Patent Abstract:
a compound having the structural formula ## str1 ## wherein : y is selected from o and s ; r 1 and r 4 are independently selected from fluorinated methyl , chlorofluorinated methyl , and c 1 - c 4 alkyl , provided that not both r 1 and r 4 may be c 1 - c 4 alkyl ; r 2 is selected from hydrogen , lower alkyl , haloalkyl , alkenyl , alkynyl , haloalkenyl , and a cation ; r 3 is selected from c 1 - c 5 alkyl , cycloalkyl , cycloalkylalkyl , hydroxy , and alkoxy ; and x is selected from ## str2 ## in which r 8 is selected from h , alkyl and cf 3 and r 10 is selected from f , cl , -- or 1 , -- sr 1 , -- nhr 1 , -- n 2 , phenyl , substituted phenyl , and -- p 2 where r 1 is as defined above ; ## str3 ## wherein r 1 is as defined above ; ## str4 ## wherein r 14 and r 15 are independently selected from hydrogen and alkyl ; and -- n ═ c ═ o and their use as herbicides .

Detailed Description:
the schemes shown below schematically depict a method whereby the pyridine monocarboxylate compounds of this invention may be prepared from compounds which are known in the art . starting with a pyridinedicarboxylate compound such as those described in european patent publication no . 133 , 612 , the dicarboxylic acid chloride is prepared by treating with a chlorinating agent such as pcl 5 or socl 2 . the or 5 - amino - monocarboxylate is then prepared from the 3 - or 5 - chlorocarbonyl compound by treatment with nan 3 followed by a curtis rearrangement . the 3 - or 5 - amino compound so produced is then transformed into a 3 - or 5 - halogen substituted pyridinemonocarboxylate or a compound in which the atom linked to the pyridine ring at the 3 - or 5 - position is a nitrogen atom as shown in schemes 2 , 3 and 4 . reference to the examples will provide greater detail about the steps shown in schemes 1 - 4 . ## str11 ## preparation of further compounds of this invention will become clear by reference to the scheme in conjunction with the following examples . as used throughout the specification , including the examples , the following abbreviations have the following meanings : as used in the following examples , the terms &# 34 ; workup as usual &# 34 ;, or &# 34 ; normal workup &# 34 ;, or equivalent language refer to the process of washing the organic extract with brine , drying by pouring through a cone of anhydrous sodium sulfate , and concentrating in vacuo . 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - isobutyl - 2 -( trifluoromethyl )-, ethyl ester . six grams ( 15 . 1 mmol ) of product of example 32 of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 0 . 95 g of 89 % potassium hydroxide ( 15 . 1 mmol ) and 35 ml of ethanol and was stirred at room temperature for 1 day . the reaction mixture was poured into 135 ml of water , washed with ether ( 2 × 20 ml ) and acidified with concentrated hydrochloric acid . the product was extracted into ether ( 2 × 50 ml ), which was worked up as usual to afford 4 . 91 g ( 88 %) of the desired mono - acid as an off - white solid suitable for further transformation . this was refluxed overnight with thionyl chloride ( 25 ml ). the excess thionyl chloride was removed in vacuo and the resulting acid chloride was added dropwise to a rapidly - stirred slurry of 1 . 8 g of sodium azide in 15 ml of 4 : 1 acetone : water . this was stirred at room temperature for the weekend , then diluted with 75 ml of water and extracted with ether 3 × 20 ml . workup as usual afforded 4 . 66 g ( 91 % overall yield ) of product as a tan solid . recrystallization from cyclohexane gave analytically pure material , mp 68 °- 70 ° c . ______________________________________elemental analysis c h n______________________________________calculated 49 . 41 5 . 04 8 . 23found 49 . 23 4 . 97 8 . 26______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 35 . 0 g ( 0 . 103 mol ) of product of example 55 of european patent application no . 133 , 612 published feb . 27 , 1985 , and 60 ml of thionyl chloride was refluxed overnight . the excess thionyl chloride was removed in vacuo , and the acid chloride was diluted with 10 ml of acetone and added to a slurry of 14 . 3g of nan 3 25 ml of h 2 o and 90 ml of acetone . an exothermic reaction occurred with vigorous gas evolution . after the reaction mixture cooled to room temperature , 300 ml of water was added and the product was extracted into chloroform . normal workup gave 30 . 9 g ( 96 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 92 °- 94 ° c . ______________________________________elemental analysis c h n______________________________________calculated 46 . 16 4 . 20 8 . 97found 46 . 08 4 . 23 8 . 94______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( methoxycarbonyl ) amino ]- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 13 . 7g ( 0 . 037 mol ) of ethyl 6 -( difluoromethyl )- 5 -( chlorocarbonyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl ) - 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , and 40 ml of thionyl chloride was stirred at reflux for 7 hours , then was concentrated in vacuo . the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 13 . 4g ( 93 %) of the corresponding acid chloride as a yellow oil . to a 0 ° c . solution of 5 . 0 g ( 0 . 013 mol ) of this acid chloride in 50 ml of chloroform was added dropwise a solution of 1 . 03 g ( 0 . 013 mol ) of pyridine and 14 . 5 ml 0 . 0149 mol ) of 1 . 025 m hydrazoic acid in chloroform . after the addition was complete , the reaction mixture was stirred 30 min at room temperature , diluted with 20 ml of methanol and heated on a hot plate until gas evolution ceased . this was then poured into 100 ml of water and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 5 . 03 g ( 97 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 109 °- 110 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 25 4 . 81 7 . 03found 48 . 03 4 . 76 7 . 21______________________________________ 3 - pyridinecarboxylic acid , 5 -([ bis ( 1 - methylethyl ) amino ] carbonylamino )- 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 13 . 7g ( 0 . 037 mol ) of ethyl 6 -( difluoromethyl )- 5 -( chlorocarbonyl )- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , and 40 ml of thionyl chloride was stirred at reflux for 7 hours , then was concentrated in vacuo . the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 13 . 4g ( 93 %) of the corresponding acid chloride as a yellow oil . a 0 ° c . solution of 5 . 0 g ( 0 . 013 mmol ) of this acid chloride in 50 ml of chloroform was added dropwise to a solution of 1 . 03 g ( 0 . 013 mol ) of pyridine and 14 . 5 ml ( 0 . 015 mol ) of 1 . 025 m hydrazoic acid in chloroform . after the addition was complete , it was stirred at room temperature for 30 min . then 20 ml of diisopropylamine was added causing an exothermic reaction to occur . the reaction was allowed to cool to room temperature and diluted with 100 ml of water . the product was extracted into chloroform ( 3 × 40 ml ). normal workup afforded 5 . 54 g 91 ) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 137 °- 139 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 53 . 96 6 . 47 8 . 99found 53 . 91 6 . 46 8 . 95______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . a mixture of 45 . 0g ( 0 . 132 mol ) of methyl 5 - carboxy - 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl ) - 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , 8 . 91g ( 0 . 135 mol ) of 85 % potassium hydroxide , 125 ml of methanol and 15 ml of water was stirred at room temperature for 24 hours . the reaction mixture was poured into water ( 500 ml ), washed with chloroform ( 2 × 200 ml ), and then was acidified with concentrated hydrochloric acid . extraction with ethyl acetate ( 3 × 150 ml ) followed by workup as usual afforded 38 . 2g ( 88 %) of the corresponding carboxylic acid as a white solid . a solution of 38 . 2g ( 0 . 117 mol ) of this acid and 50 ml of thionyl chloride was refluxed for 3 h . the excess thionyl chloride was removed in vacuo and the remaining acid chloride was dissolved in acetone ( 15 ml ). this was added to a rapidly stirred slurry of 17 . 8 g ( 0 . 27 mol ) of sodium azide , 30 ml of water and 100 ml of acetone , resulting in an exothermic reaction with vigorous gas evolution . after 2 h , the reaction mixture was diluted with 200 ml of water and extracted with chloroform ( 3 × 70 ml ). normal workup afforded 33 . 0 g ( 86 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 92 °- 93 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 59 3 . 83 9 . 16______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxycarbonyl ] amino ]- 2 -( trifluoromethyl ) -, ethyl ester . a solution of 5 . 0 g ( 0 . 015 mol ) of product of example 28 of european patent application no . 133 , 612 published feb . 27 , 1985 , and 15 ml of thionyl chloride was refluxed overnight . the excess thionyl chloride was then removed in vacuo and the resulting acid chloride was diluted with 25 ml of methylene chloride and cooled to 0 ° c . to this stirred solution was added dropwise a mixture of 1 . 16 g of pyridine and 16 ml of 1 . 0 m hydrazoic acid in chloroform . after the addition was complete , the reaction mixture was warmed to room temperature for 10 min . then , 35 ml of methanol was added and the reaction mixture was warmed on a hot plate until gas evolution ceased . this was then diluted with 100 ml of water and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 5 . 6 g ( quantitative ) of product as an off - white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 84 °- 86 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 51found 45 . 17 4 . 08 8 . 14______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl ]- 5 - l ( trifluoroaoetyl ) amino ]- 2 - itrifluoromethyl )-, ethyl ester . to a slurry of 1 . 08 g ( 0 . 027 mol ) of 60 % sodium hydride and 10 ml of anhydrous tetrahydrofuran was added a solution of 8 . 0 g ( 0 . 023 mol ) of product of example 1 in 10 ml of tetrahydrofuran . this was refluxed for 2 h , then stirred overnight at room temperature . to this was added 5 . 5 g ( 0 . 026 mol ) of trifluoroacetic anhydride dropwise . this was stirred for 1 h then poured into 100 ml of 5 % hydrochloric acid and extracted with chloroform ( 3 × 50 ml ). normal workup afforded 11 . 0 g of brown solid . recrystallization from ethyl acetate / cyclohexane afforded 9 . 53 g ( 90 %) of product as a white solid , mp 102 °- 104 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 45 3 . 76 6 . 44______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - isobutyl - 6 - itrifluoromethyl )-, ethyl ester . to a mixture of 2 . 96 g ( 0 . 022 mol ) of cupric chloride , 2 . 26 g ( 0 . 018 mol ) of t - butyl nitrite and 40 ml of acetonitrile is added dropwise to a solution of 5 . 0 g ( 0 . 015 mol ) of product of example 1 in 10 ml of acetonitrile . this was stirred overnight at room temperature , then poured into 100 ml of 2 . 5 m hydrochloric acid . the product was extracted into 3 × 50 ml of ether . workup as usual afforded 5 . 26 g of dark brown oil . this was chromatographed on the prep - 500 using 2 % ethyl acetate / cyclohexane as elution solvent . fraction 1 afforded 2 . 14 g ( 41 %) of product as a colorless oil material ; n d 25 1 . 456 ______________________________________elemental analysis : c h n cl______________________________________calculated 46 . 75 4 . 20 3 . 89 9 . 86found 46 . 82 4 . 24 3 . 86 9 . 90______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - isobutyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012mol ) of product of example 1 , 2 . 16 g ( 0 . 012 mol ) of 48 % fluoroboric acid and 30 ml of acetonitrile was added 1 . 34 g ( 0 . 013 mol ) of t - butyl nitrite . this was allowed to stir at 0 ° c . for 30 min , then it was added to a solution of 30 g potassium iodide in 150 ml of water . after stirring for 30 min , the reaction mixture was extracted with chloroform ( 4 × 40 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 50 ml ) and dried through a cone of sodium sulfate . concentration in vacuo afforded 4 . 82 g of orange oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . the first fraction contained 1 . 98 g ( 37 %) of product as a colorless oil ; n d 25 1 . 493 . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 27 3 . 35 3 . 10found 37 . 55 3 . 42 3 . 13______________________________________ the second fraction contained 1 . 65 g ( 31 %) of product as a light yellow oil ; n d 25 1 . 488 . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 27 3 . 35 3 . 10found 37 . 57 3 . 40 3 . 09______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, ethyl ester . to a slurry of 2 . 55 g ( 0 . 019 mol ) of cupric chloride , 2 . 48 g ( 0 . 024 mol ) of t - butyl nitrite and 70 ml of anhydrous acetonitrile was added a solution of 5 . 0 g ( 0 . 016 mol ) of product of example 2 in 5 ml acetonitrile . this was stirred at room temperature for 2 h , diluted with 200 ml of 10 % hydrochloric acid and extracted into chloroform ( 3 × 40 ml ). normal workup afforded an orange oil which was kugelrohr distilled ( 120 ° c . @ 1 . 0 torr ) to give 4 . 57 g ( 86 %) of product as a colorless liquid . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 46 3 . 34 4 . 22 10 . 69found 43 . 44 3 . 41 4 . 30 10 . 81______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 23 g ( 0 . 024 mol ) of cupric chloride , 3 . 09 g ( 0 . 030 mol ) of t - butyl nitrite and 65 ml of acetonitrile was added to a solution of 6 . 0 g of product of example 5 in 10 ml of acetonitrile . after stirring at room temperature for 3 h , the reaction mixture was poured into 200 ml of 10 % hydrochloric acid and extracted with chloroform ( 3 × 70 ml ). normal workup afforded 6 . 32 g of an orange oil which was chromatographed on the prep - 500 using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 12 g 66 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 62 °- 62 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 57 2 . 79 4 . 34 11 . 18______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 5 . 09 g ( 0 . 023 mol ) of cupric bromide , 2 . 94 g ( 0 . 029 mol ) of t - butyl nitrite and 70 ml of anhydrous acetonitrile was added a solution of 6 . 0 g ( 0 . 019 mol ) of product of example 2 in 5 ml acetonitrile . this was stirred at room temperature for 2 h , then poured into 10 % hydrochloric acid ( 200 ml ) and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 6 . 95 g of a light yellow oil . kugelrohr distillation ( 125 ° c . @ 1 . 0 torr ) gave 6 . 35 g ( 89 %) of product as a white solid . recrystallization from cyclohexane gave analytically pure material , mp 39 °- 41 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 38 . 32 2 . 95 3 . 72 21 . 25found 38 . 47 2 . 99 3 . 77 21 . 40______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 5 . 36 g ( 0 . 024 mol ) of cupric bromide , 3 . 09 g ( 0 . 030 mol ) of t - butyl nitrite and 6 . 5 ml of acetonitrile was added a solution of 6 . 0 g ( 0 . 020 mol ) of product of example 5 in 10 ml of acetonitrile . after stirring for 3 h at room temperature , the reaction mixture was added to 200 ml of 10 % hydrochloric acid and extracted with chloroform . normal workup afforded 7 . 05 g of brown oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 83 g ( 68 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 61 °- 62 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 36 . 56 2 . 55 3 . 86 22 . 16______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 2 . 0 g ( 6 . 40 mmol ) of product of example 2 , 1 . 18 g ( 6 . 40 mmol ) of 48 % fluoroboric acid and 10 ml of acetonitrile was added to 0 . 72 g of t - butyl nitrite . this solution was stirred at 0 ° c . for 15 min then was added to a rapidly stirred solution of 12 g of potassium iodide in 100 ml of water . this was stirred for 30 min , then was extracted with chloroform ( 3 × 40 ml ). the combined chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 100 ml ), brine ( 50 ml ), and dried through a cone of sodium sulfate . concentration in vacuo afforded an orange oil which was filtered through a short plug of silica gel ( 5 % ethyl acetate / cyclohexane as eluant ) to afford 2 . 10 g ( 78 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 63 °- 65 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 34 . 06 2 . 62 3 . 31found 34 . 32 2 . 68 3 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 2 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 6 . 25 g ( 0 . 021 mol ) of product of example 5 , 3 . 84 g ( 0 . 021 mol ) of 48 % fluoroboric acid and 55 ml of acetonitrile was slowly added 2 . 38 g 0 . 023 mol ) of t - butyl nitrite . this was stirred at 0 ° c . for 30 min , then added to a rapidly stirred solution of 55 g of potassium iodide in 200 ml of water . after 20 min , this was diluted with water 20 ( 200 ml ) and extracted with chloroform ( 3 × 50 ml ). this was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 100 ml ) and dried through sodium sulfate . concentration in vacuo afforded 7 . 80 g of brown oil , which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 58 g ( 56 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 62 °- 63 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 32 . 30 2 . 22 3 . 42found 32 . 37 2 . 26 3 . 38______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred slurry of 41 . 3 g of sodium azide , 75 ml of water and 260 ml of acetone was slowly added a solution of 109 g ( 0 . 292 mol ) of product of example 47 of european patent application no . 133 , 612 published feb . 27 , 1985 , in 30 ml of acetone . an exothermic reaction took place with vigorous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with water ( 500 ml ) and extracted into chcl 3 ( 3 × 150ml ). normal workup afforded 94 . 8g ( quantitative ) of product as an offwhite solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 73 °- 75 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 79 4 . 66 8 . 59______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( ethoxymethylene ) amino ]- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 20 . 0 g ( 0 . 061 mol ) of product of example 16 , 22 . 7 g ( 0 . 153 mol ) of triethyl orthoformate and 300 mg of p - toluenesulfonic acid was heated at 110 ° c . with removal of ethanol by distillation . after 4 h , the excess orthoformate was removed in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to afford 23 . 3 g ( quantitative ) of product as a colorless liquid ; n d 25 1 . 462 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 18 5 . 01 7 . 29______________________________________ 3 - pyridinecarboxylic acid , s - amino - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 19 . 2 g ( 0 . 054 mol ) of 3 - t - butyl 5 - ethyl 4 - ethyl - 2 - methyl - 6 -( trifluoromethyl )- 3 , 5 - pyridinedicarboxylate prepared by methods shown in european patent application no . 133 , 612 , and 40 ml of 97 % formic acid was stirred overnight at 85 ° c . the reaction mixture was then concentrated in vacuo to give an orange oil which was diluted with 50 ml of thionyl chloride and refluxed for 3 h . the excess thionyl chloride was removed in vacuo and the residue was kugelrohr distilled to give 13 . 4 g ( 78 %) of the acid chloride . this was taken up in 5 ml of acetone and added to a stirred slurry of 7 . 5 g of sodium azide , 13 ml of water and 50 ml of acetone . an exothermic reaction occurred with vigouous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with 200 ml of water and extracted with chloroform ( 3 × 75 ml ). normal workup afforded an oily solid which was chromatographed on silica gel using 20 % ethyl acetate / cyclohexane to give 6 . 35 ( 55 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 107 °- 109 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 17 5 . 47 10 . 14found 52 . 26 5 . 54 10 . 11______________________________________ 3 - pyridinecarboxylic acid , 4 - ethyl - 6 - methyl - 5 - nitro - 2 -( trifluoromethyl )-, ethyl ester . to a 55 ° c . slurry of 7 . 82 g of sodium perborate ( 0 . 051 mol ) and 40 ml of glacial acetic acid was added a solution of 3 . 5 g ( 0 . 013 mol ) of product of example 18 in 15 ml of glacial acetic acid . the reaction mixture was maintained at 55 ° c . for 2 h , then was poured into 150 ml of water and extracted with chloroform ( 3 × 40 ml ). workup as usual afforded a dark oil which was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 1 . 57 g of product as a light yellow oil . the residue which did not distill was chromatographed on silica gel ( 1 % etoac / cyclohexane ) to afford an additional 1 . 00 g of product to give a total of 2 . 57 % ( 66 %); n d 25 1 .% 65 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 07 4 . 28 9 . 15found 47 . 01 4 . 29 9 . 23______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - nitro - 2 -( trifluoromethyl ), ethyl ester . to a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 in 100 ml of concentrated sulfuric acid at 0 ° c . was carefully added 10 ml of 90 % hydrogen peroxide . this was slowly warmed to room temperature over a 3 - hour period and then stirred there overnight . the reaction mixture was diluted with ice ( 300 g ) and extracted with chloroform . normal workup gave a white solid which was chromatographed on silica gel using 1 % ethyl acetate / cyclohexane . workup of the first fraction gave 2 . 02 g ( 46 %) of product as a white solid , mp 44 °- 46 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 12 3 . 24 8 . 19found 42 . 28 3 . 25 8 . 15______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - nitro - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester to a 0 ° c . solution of 15 . 0 g ( 0 . 046 mol ) of product of example 16 and 360 ml of concentrated sulfuric acid was carefully added 36 ml of 90 % hydrogen peroxide . this was slowly warmed to room temperature over a 3 - hour period and stirred there overnight . the reaction mixture was quenched with ice ( 300 g ) and extracted into chloroform ( 3 × 100 ml ). workup as usual gave a white solid which was chromatographed on silica gel using 1 % ethyl acetate / cyclohexane . workup of the first fraction gave 9 . 35 g ( 57 %) of product as a white solid , mp 63 °- 65 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 83 3 . 68 7 . 86found 43 . 83 3 . 69 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 2 -( trifluoromethyl ) - 4 -( 2 - methylpropyl ]- 5 - nitro - 6 -( difluoromethyl )-, ethyl ester . to a 0 ° c . solution 6 . 0 g ( 0 . 018 mol ) of product of example 1 and 135 ml of concentrated sulfuric acid was carefully added 13 . 5 ml of 90 % hydrogen peroxide , dropwise . this was slowly warmed to room temperature over a period of 3 h , then was stirred overnight . to this was added 200 g of ice chips and the resulting aqueous solution was extracted with chloroform ( 3 × 75 ml ). workup as usual gave a brown oil which was chromatographed on silica gel ( 1 % ethyl acetate / cyclohexane ). workup gave 3 . 53 g ( 54 %) of product as a white solid , mp 44 °- 46 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 57found 45 . 47 4 . 03 7 . 75______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - methyl - 5 - nitro - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 15 . 0 g ( 0 . 050 mol ) of product of example 71 and 360 ml of concentrated sulfuric acid was carefully added 36 ml of 90 % hydrogen peroxide dropwise . this was slowly warmed to room temperature over a 3 - hour period and allowed to stir there overnight . then , 300 g of ice chips were added and the product was extracted into chloroform ( 3 × 75 ml ). workup as usual afforded an off - white solid which was kugelrohr distilled ( 140 ° c . @ 1 torr ) to give 11 . 8 g ( 72 %) of product as a white solid , mp 93 °- 95 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 26 2 . 76 8 . 54found 40 . 43 2 . 75 8 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - nitro - 2 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 5 . 0 g ( 0 . 017 mol ) of product of example 5 and 120 ml of concentrated sulfuric acid was carefully added 12 ml of 90 % hydrogen peroxide dropwise . this was stirred at 0 ° c . for 3 h , then slowly warmed to room temperature and stirred overnight . the reaction mixture was then diluted with 200 g of ice and extracted with chloroform . workup as usual gave a white solid which was chromatographed on silica gel ( 1 % ethyl acetate / cyclohexane ). workup of the first fraction afforded 2 . 73 g ( 50 %) of product as a white solid , mp 65 °- 67 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 26 2 . 76 8 . 54found 40 . 30 2 . 76 8 . 54______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( trifluoroacetyl ) amino - 2 -( trifluoromethyl )-, ethyl ester . a solution a 4 . 0 g ( 0 . 16 mol ) of product of example 2 , 35 ml of trifluoroacetic anhydride and 20 ml of methylene chloride was stirred at room temperature for 3 h . the reaction mixture was then concentrated in vacuo ( 50 ° c . @ 20 torr ) affording 6 . 19 g ( 95 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 98 °- 100 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 19 2 . 96 6 . 86found 41 . 49 3 . 09 6 . 95______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - methyl - 5 -( trifluoroacetyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 7 . 44 g ( 0 . 025 mol ) of product of example 71 , 20 g of trifluoroacetic anhydride and 20 ml of chloroform was stirred at room temperature for 2 h . the reaction mixture was concentrated in vacuo to afford a white solid which was recrystallized from ethyl acetate / cyclohexane to give 8 . 5 g ( 90 %) of product , mp 112 °- 114 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 39 . 61 2 . 56 7 . 14found 39 . 55 2 . 58 7 . 11______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( pentafluoropropionyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g 0 . 0128 mol ) of product of example 71 , 15 ml of dichloromethane and 5 . 0 g ( 0 . 16 mol ) of pentafluoropropionic anhydride was stirred at room temperature for 1 day . the reaction mixture was then concentrated in vacuo and kugelrohr distilled ( 150 ° c . @ 5 torr ) to give 4 . 8 g ( 82 %) of product as a white solid , mp 113 °- 115 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 39 . 32 2 . 64 6 . 11found 39 . 72 2 . 68 6 . 17______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( pentafluoropropionyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 0 g ( 0 . 010 mol ) of product of example 5 , 9 ml of pentafluoropropionic anhydride and 14 ml of chloroform was stirred at room temperature for 3 h . the reaction mixture was concentrated in vacuo affording a white solid . recrystallization from ethyl acetate / cyclohexane gave 4 . 07 g ( 92 %) of product as a white solid , mp 96 °- 98 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 85 2 . 27 6 . 31found 38 . 10 2 . 41 6 . 50______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( formylamino )- 4 - methyl - 2 - itrifluoromethyl ) -, ethyl ester . to 43 . 2 g ( 0 . 42 mol ) of acetic anhydride at 0 ° c . was added 24 . 4 g ( 0 . 53 mol ) of formic acid . this was warmed to room temperature , then heated at 50 ° c . for 15 min . this was then immediately cooled to 0 ° c . and 4 . 68 g 0 . 016 mol ) of product of example 71 was added . after stirring at room temperature for 40 min , the reaction mixture was concentrated in vacuo and the resulting solid was recrystallized from ethyl acetate to give 3 . 51 g ( 67 %) of product as a white solid , mp 151 °- 152 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 18 3 . 40 8 . 59found 44 . 11 3 . 43 8 . 57______________________________________ 3 - pyridinecarboxylic acid , 5 -[( α - chloroacetyl ) amino - 6 -( difluoromethyl ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 1 . 50 g ( 0 . 013 mol ) of chloroacetyl chloride and 10 ml of acetonitrile was stirred overnight at room temperature . a small amount of starting material remained , as determined by gas chromatography , so another 75 mg of chloroacetyl chloride was added and the reaction was stirred another 4 h . concentration of the reaction mixture in vacuo gave 5 . 10 g ( quantitative ) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 104 °- 106 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 26 3 . 63 7 . 21 9 . 12found 43 . 40 3 . 67 7 . 26 9 . 10______________________________________ 3 - pyridinecarboxylic acid , 5 -[( α , α - dichloropropionyl ) amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 2 . 42 g ( 0 . 015 mol ) of 2 , 2 - dichloropropionyl chloride , 1 . 18 g ( 0 . 015 mol ) of pyridine and 10 ml of acetonitrile was refluxed for 24 h . the reaction mixture was then poured into 50 ml of 1m hydrochloric acid and extracted with chloroform . normal workup afforded a dark solid which was kugelrohr distilled ( 160 ° c . @ 1 torr ) to give 4 . 52 g ( 81 %) of product as an off - white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 145 °- 146 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 21 3 . 46 6 . 41 16 . 22found 41 . 26 3 . 46 6 . 37 16 . 15______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0 g ( 0 . 0168 mol ) of product of example 71 , 7 . 0 g of triethyl orthoformate and 100 mg of p - toluenesulfonic acid was heated at 110 ° c . with removal of ethanol by distillation . after 3 h , the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to afford 5 . 10 g ( 86 %) of product as a colorless liquid ; n d 25 1 . 46s . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 47 4 . 29 7 . 89______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 5 . 7 g ( 0 . 038 mol ) of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 2 h with removal of the ethanol formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 86 g ( 82 %) of product as a colorless oil ; n d 25 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 78 4 . 62 7 . 51______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 4 . 0 g ( 0 . 038 mol ) of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the methanol formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to afford 3 . 90 g ( 86 %) of product a colorless oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 67 4 . 36 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl )- 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 75 g ( 0 . 011 mol ) of product of example 1 , 4 . 90 ( 0 . 033 mol ) of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the ethanol which formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 83 g ( 88 %) of product as a colorless liquid ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 52 5 . 34 7 . 07found 51 . 80 5 . 48 7 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 - methyl - 2 -{ trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 71 , 4 . 2 g ( 0 . 040 mol ) of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the methanol which formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 4 . 01 g ( 88 %) of product as a light yellow oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 45 . 89 3 . 94 8 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 50 g ( 0 . 012 mol ) of product of example 5 , 3 . 82 g ( 0 . 036 mol ) of trimethyl orthoformate and 30 mg of p - toluenesulfonic acid was stirred at reflux for 2 h , then concentrated in vacuo . the residue was kugelrohr distilled ( 145 ° c . @ 1 torr ) to give 3 . 47 g ( 84 %) of product as a colorless oil which slowly solidified , mp 29 °- 30 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 46 . 04 3 . 82 8 . 11______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 0 g ( 0 . 0092 mol ) of product of example 16 , 10 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 2 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 135 ° c . ° c . @ 1 torr to give 3 . 13 g ( 92 %) of product as a colorless oil ; n d 25 1 . 465 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 66 4 . 57 7 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 10g ( 0 . 012 mol ) of product of example 1 , 7 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred overnight at 100 ° c . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr to give 4 . 07 g ( 89 %) of product as a colorless oil ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 16 5 . 19 7 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 1 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 3 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to give 4 . 18 g ( 88 %) of product as a colorless oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 41 4 . 29 7 . 80______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( 2 - methylpropoxy ] methylene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g (. 012 mol ) of product of example 16 , 10 ml of tri - i - butyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 16 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to afford 4 . 6 % ( 81 %) of product as a colorless oil ; n d 25 1 . 503 . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 68 5 . 65 6 . 83found 52 . 65 5 . 69 6 . 82______________________________________ 3 - pyridinecarboxylic acid , 5 -[( n - butoxymethylene ) amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 8 . 7 g of tri - n - butyl orthoformate , 4 . 0 g ( 0 . 013 mol ) of product of example 2 and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 18 h . the reaction was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . 1 torr ) to give a yellow oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) afforded 1 . 98 g ( 39 %) of product as a colorless oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 52 5 . 34 7 . 07found 51 . 76 5 . 42 7 . 00______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[[ n - propoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0 g ( 0 . 016 mol ) of product of example 2 , 10 ml of tri - n - propyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 1 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . ° c . @ 1 torr ) to give 4 . 25 g ( 69 %) of product as a light yellow oil ; n d 25 1 461 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 24 5 . 02 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 2 - methylpropoxy ) methylene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 10 ml of triisobutyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 110 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . ° c . @ 1 torr ) to afford 3 . 8 g ( 75 %) of product as a light yellow oil , which slowly crystallized , mp 34 °- 34 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 51 5 . 34 7 . 07found 51 . 37 5 . 35 7 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( n , n - dimethylamino ) methylene ] amino }- 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a slurry of 5 . 0 g ( 0 . 168 mol ) of product of example 71 , 4 . 0 g ( 0 . 34 mol ) of dimethylformamide dimethylacetal and 100 mg of p - toluenesulfonic acid was heated at reflux for 1 h . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to give 5 . 20 g ( 88 %) of product as a white solid , mp 70 °- 71 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 50 4 . 57 11 . 89found 47 . 61 4 . 43 11 . 64______________________________________ 3 - pyridinecarboxylic acid , 5 -[( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl )- 4 - methyl - 2 - itrifluoromethyl )-, ethyl ester . a mixture of 4 . 0 g ( 0 . 010 mol ) of product of example 26 and 2 . 11 g ( 0 . 010 mol ) of phosphorous pentachloride was heated to 140 ° c . and stirred there for 16 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c .° c . @ 1 torr ) to give 3 . 24 g of product as a colorless oil ; n d 25 1 . 435 . ______________________________________elemental analysis : c h n cl______________________________________calculated 37 . 84 2 . 20 6 . 79 8 . 59found 38 . 15 2 . 26 6 . 82 8 . 63______________________________________ 3 - pyridinecarboxylic acid , 5 -( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino - 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 33 . 5 g ( 0 . 082 mol ) of product of example 25 and 17 . 08 g ( 0 . 082 mol ) of phosphorous pentachloride was heated at 140 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 31 . 7 g ( 91 %) of product as a colorless oil ; n d 25 1 . 436 ______________________________________elemental analysis : c h n cl______________________________________calculated 39 . 41 2 . 60 6 . 57 8 . 31found 39 . 81 2 . 65 6 . 59 8 . 35______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( 1 - ethoxy - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to an ethanolic sodium ethoxide solution , prepared from 0 . 25 g ( 0 . 011 mol ) of sodium metal and 5 ml of absolute ethanol , was added a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of ethanol . a white precipitate formed immediately . after stirring for 15 min the reaction mixture was poured into water and extracted with chloroform . workup gave a light yellow oil which was kugelrohr distilled ( 130 ° c . ° c . @ 1 torr ) to give 3 . 67 ( 89 %) of product as a colorless oil ; n d 25 1 . 440 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 46 3 . 76 6 . 48______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( 1 - methoxy - 2 , 2 ,- 2 - trifluoroethylidine ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a methanolic sodium methoxide solution , prepared from 0 . 23 g ( 0 . 010 mol ) of sodium metal and 4 ml of methanol was added a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of methanol . a white precipitate formed immediately . after 15 min , the reaction mixture was poured into water and extracted with chloroform . workup as usual gave a yellow oil which was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 3 . 63 g ( 91 %) of product as a colorless oil which slowly solidified , mp 49 °- 51 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 67 3 . 34 6 . 63found 43 . 03 3 . 39 6 . 65______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 1 -( ethylthio )- 2 , 2 , 2 - trifluoroethylidine ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 0 . 38 g ( 0 . 0094 mol ) of 60 % sodium hydride in 10 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere was added 0 . 59 g ( 0 . 0094 mol ) of ethanethiol . after gas evolution ceased , a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 , 5 ml of tetrahydrofuran was added dropwise . after 15 min , the reaction mixture was poured into water and extracted with chloroform . workup as usual gave a yellow oil which was kugelrohr distilled ( 135 ° c . @ 1 torr ) to give 3 . 87 g ( 91 %) of product as a colorless liquid ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n s______________________________________calculated 42 . 48 3 . 57 6 . 19 7 . 09found 42 . 86 3 . 64 6 . 24 7 . 24______________________________________ 3 - pyridinecarboxylic acid , 5 -{[ 1 -( diethoxyphosphinyl )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 2 . 5 g ( 0 . 0059 mol ) of product of example 47 and 0 . 98 g of triethylphosphite was heated at 160 ° c . for 30 min . the reaction mixture was then cooled to room temperature where solidification occurred . trituration of this solid with cyclohexane gave 3 . 03 g ( quantitative ) of product as a light yellow solid , mp 73 °- 75 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 92 4 . 01 5 . 30found 40 . 72 4 . 00 5 . 19______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 5 -[ 5 -( trifluoromethyl ) - 1h - tetrazol - 1 - yl ]-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 and 0 ml of tetrahydrofuran was added 0 65 g ( 0 . 01 mol ) of sodium azide . this was stirred at room temperature and 4 ml of water was added . the reaction mixture became warm immediately . after 5 min , the reaction mixture was diluted with water ( 25 ml ) and extracted with chloroform ( 3 × 20 ml ). workup as usual afforded a thick oil which was kugelrohr distilled ( 150 ° c . ° c . @ torr ) to give 3 . 83 g ( 94 %) of product as a light yellow oil ; n d 25 1 . 444 . ______________________________________elemental analysis : c h n______________________________________calculated 38 . 81 2 . 56 16 . 16found 39 . 12 2 . 68 15 . 92______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 5 -{[ 1 -( trifluoromethyl ) ethylidene ] amino }-, ethyl ester . to a solution of 2 . 3 g ( 0 . 0054 mol ) of product of example 47 in 5 ml of anhydrous tetrahydrofuran at 0 ° c . under a dry nitrogen atmosphere was added dropwise 1 . 7 ml ( 0 . 0054 mol ) of 3 . 2 m methyl magnesium bromide in ether . this was stirred at 0 ° c . for 30 min , then was poured into 10 ml of saturated ammonium chloride . the reaction mixture was suction filtered and the filtrate was extracted with ether ( 3 × 25 ml ). workup as usual gave an oil which was chromatographed on silica gel using 5 % ethyl acetate / cyclohexane . workup of the first fraction afforded 1 . 0 g ( 46 %) of product as a colorless oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 35 3 . 47 6 . 89found 43 . 35 3 . 40 6 . 70______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - isocyanato - 2 -( trifluoromethyl )-, ethyl ester . the product of example 46 ( 50 . 4g , 0 . 14 mol ) of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 17 . 3 g of azidotrimethyl silane ( 0 . 15 mol ) and 100 ml of carbon tetrachloride and heated at reflux until gas evolution ceased (˜ 4 h ). the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to give 35 . 2 g ( 74 %) of product as a light yellow oil ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 16 3 . 28 8 . 28found 45 . 88 3 . 40 8 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - isocyanato - 2 -( trifluoromethyl )-, methyl ester . methyl 5 - chlorocarbonyl - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate ( 84 . 1 g , 0 . 243 mol ) was added to 150 ml of carbon tetrachloride and 30 g ( 0 . 26 mol ) of azidotrimethyl silane and stirred overnight at 55 ° c . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled to give 57 . 3 g ( 72 %) of product as a white solid , mp 55 °- 57 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 46 2 . 80 8 . 64found 44 . 32 2 . 94 8 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - isocyanato - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . ethyl 5 - chlorocarbonyl - 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate ( 64 . 1 g , 0 . 165 mol ) was added to 21 . 06 ( 0 . 182 mol ) of azidotrimethyl silane and 120 ml of carbon tetrachloride and heated at reflux for 4h , at which time , gas evolution ceased . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 100 ° c . @ 1 torr to give 29 . 4 g ( 65 %) of product as a light yellow oil ; n d 25 1 . 455 . ______________________________________elemental analysis : c h n______________________________________calculated 49 . 19 4 . 13 7 . 65found 48 . 95 4 . 02 7 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( ethylthio ] carbonyl ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 5 g ( 0 . 013 mol ) of product of example 54 and 20 ml of methylene chloride was added 15 ml of ethanethiol . to this was added 30 mg of potassium t - butoxide causing an exotherm . the reaction mixture was allowed to stir overnight then was concentrated in vacuo affording a light yellow solid . recrystallization from ethyl acetate / cyclohexane gave 4 . 63 g ( 90 %) of product as a white solid , mp 124 °- 126 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 45 . 00 4 . 28 7 . 00 8 . 01found 44 . 73 4 . 14 6 . 80 7 . 83______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( ethylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a slurry of 0 . 49 g ( 0 . 012 mol ) of 60 % sodium hydride in 10 ml of anhydrous tetrahydrofuran was added a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 in 25 ml of anhydrous tetrahydrofuran . this was stirred at room temperature for 1 h then 50 ml of water was added and the product was extracted into ethyl acetate ( 3 × 25 ml ). workup as usual gave 3 . 95 g ( 83 %) of product as a white solid , mp 143 °- 145 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 43 . 52 3 . 91 7 . 25 8 . 30found 43 . 42 3 . 97 7 . 21 8 . 38______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( methylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . a solution of 15 . 0 g ( 0 . 046 mol ) of product of example 55 and 50 ml of tetrahydrofuran was cooled to 0 ° c . and 10 g of methanethiol was added . to this mixture was added 100 mg of potassium t - butoxide . the reaction mixture was slowly warmed to room temperature and stirred overnight . the reaction mixture was concentrated in vacuo and the residue taken up in chloroform ( 100 ml ). workup as usual afforded 15 . 21 % ( 89 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 134 °- 135 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 41 . 94 3 . 52 7 . 52 8 . 61found 42 . 01 3 . 53 7 . 57 8 . 57______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( ethylthio ) carbonyl ] amino }- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 50 g ( 0 . 0095 mol ) of product of example 56 , 0 . 93 g ( 0 . 015 mol ) of ethanethiol and 20 ml of tetrahydrofuran was added 15 mg of potassium t - butoxide . this was stirred for 2 h at room temperature , then was concentrated in vacuo . this solid was dissolved in 75 ml of chloroform and worked up as usual to give 3 . 54 g ( 86 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 113 °- 114 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 47 . 66 4 . 94 6 . 54 7 . 48found 47 . 65 4 . 96 6 . 52 7 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxycarbonyl ) amino ]- 4 - ethyl - 2 -( trifluoro - methyl )-, methyl ester . a solution of 4 . 1 g ( 0 . 013 mol ) of product of example 55 , 25 ml of chloroform and 25 ml of ethanol was stirred at reflux for 15 min . the reaction mixture was concentrated in vacuo to give 4 . 53 g ( 97 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 100 °- 101 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 75found 45 . 31 4 . 11 7 . 63______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethoxy ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g (. 012 mol ) of product of example 55 , 25 ml of chloroform and 25 ml of 2 - propanol was refluxed for 15 min . the reaction mixture was concentrated in vacuo to give 4 . 63 g ( 85 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 130 °- 132 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 88 4 . 46 7 . 29found 46 . 67 4 . 47 7 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 , 5 . 0 g ( 0 . 066 mol ) of 2 - propanethiol and 20 ml of tetrahydrofuran was added 20 mg of potassium t - butoxide . the reaction mixture was stirred at room temperature for 2 hours then concentrated in vacuo to give a white solid . recrystallization from ethyl acetate / cyclohexane afforded 4 . 37 ( 89 %) of product as a white solid , mp 139 °- 140 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 45 . 00 4 . 28 7 . 00 8 . 01found 45 . 04 4 . 30 7 . 00 8 . 06______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -({[( 1 , 1 - dimethylethyl ) thio ] carbonylamino )- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 60 g ( 0 . 011 mol ) of product of example 55 , 20 ml of chloroform and 20 ml of t - butanol was stirred at reflux for 15 min . the reaction mixture was concentrated in vacuo and the resulting solid was recrystallized from ethyl acetate / cyclohexane to give 4 . 01 g ( 91 %) of product as a white solid , mp 99 °- 100 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 25 4 . 81 7 . 03found 48 . 31 4 . 93 7 . 00______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxycarbonyl ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 0 g ( 0 . 0093 mol ) of product of example 55 , 20 ml of chloroform and 20 ml of methanol was stirred at reflux for 15 min , then concentrated in vacuo . the resulting solid was recrystallized from ethyl acetate / cyclohexane to give 3 . 08 g ( 93 %) of product as a white solid , mp 111 °- 113 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 83 3 . 68 7 . 86found 44 . 21 3 . 75 8 . 12______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) carbonyl ] amino }- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 0 g ( 0 . 0093 mol ) of product of example 55 , 20 ml of dioxane was added 10 ml of 26 % aqueous dimethylamine . this was stirred at 60 ° c . for 10 min , then was poured into 100 ml of water and extracted with chloroform ( 3 × 40 ml . workup as usual afforded 3 . 06 g ( 89 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 177 °- 178 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 53 4 . 37 11 . 38found 45 . 64 4 . 41 11 . 29______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( n - methylamino ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 57 g ( 0 . 011 mol ) of product of example 55 and 20 ml of dioxane was added 7 ml of 40 % aqueous methylamine . a white preciptiate formed immediately . this was stirred at 50 ° c . for 10 min , cooled to room temperature , and suction filtered . air drying afforded 3 . 56 g ( 91 %) of product as a white solid , mp 202 °- 203 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 95 3 . 97 11 . 83found 43 . 82 4 . 02 11 . 78______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( 4 , 5 - dihydro - 5 - oxo - 1h - tetrazol - 1 - yl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 54 and 2 . 72 g 0 . 024 mol ) of azidotrimethyl silane was refluxed for 1 . 5 days then was concentrated in vacuo . the reaction mixture slowly solidified over a period of 3 days . trituration with ethyl acetate / cyclohexane gave 2 . 20 g ( 49 %) of product as a white solid , mp 139 °- 141 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 95 3 . 17 18 . 37found 40 . 88 3 . 21 18 . 33______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( 2 - chloroethoxy ) carbonyl ] amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 12 mol ) of product of example 54 , 9 ml of chloroform and 9 ml of 2 - chloroethanol was heated at reflux for 1 . 5 days . the reaction mixture was concentrated in vacuo and the residue slowly solidified over 3 days . trituration with ethyl acetate / cyclohexane gave 3 . 27 g ( 66 %) of product as a white solid , mp 102 °- 103 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 02 3 . 85 6 . 69 8 . 47found 43 . 21 3 . 87 6 . 68 8 . 50______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( diethoxyphosphinyl ) carbonyl ] amino }- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 and 3 drops of triethylamine in 20 ml of toluene was added 1 . 70 g of diethyl phosphite . this was heated at 80 ° c . for 1 . 5 day , then was concentrated in vacuo . the residue was dissolved in chloroform , washed with water 20 ml , 1 m hydrochloric acid ( 20 ml ) and brine ( 20 ml ). workup as usual afforded 5 . 1 g ( 90 %) of product as a white solid , mp 91 °- 94 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 57 4 . 36 6 . 06found 41 . 24 4 . 28 6 . 29______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - methyl - 2 - itrifluoromethyl )-, ethyl ester . to a slurry of 50 g of sodium azide , 90 ml of water and 315 ml of acetone was added 0 . 474 mol of ethyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 - methyl - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 35 ml of acetone with rapid stirring . an exothermic reaction resulted with vigorous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with 200 ml of water and extracted with chloroform . normal workup afforded 86 . 3 g ( 82 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 71 °- 72 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 30 3 . 73 9 . 40______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a rapidly - stirred solution of 21 g of sodium azide , 35 ml of water and 140 ml of acetone was added a solution of 0 . 096 mol of product of example 44 of european patent application no . 133 , 612 published feb . 27 , 1985 , in 20 ml of acetone . an exothermic reaction followed with gas evolution . after the reaction mixture cooled to room temperature , it was diluted with water ( 300 ml ) and extracted with chloroform ( 3 × 100 ml ). normal workup afforded 28 . 4 g ( 91 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 56 °- 58 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 92 4 . 68 8 . 58______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 76 g ( 0 . 028 mol ) of cupric chloride , 3 . 61 g ( 0 . 035 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 7 . 0g ( 0 . 023 mol ) of product of example 71 in 7 ml of acetonitrile . this was stirred at room temperature for 90 min , then poured into 200 ml of 1 m hydrochloric acid and extracted with chloroform . normal workup afforded an orange oil which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . concentration in vacuo afforded 5 . 92 g ( 81 %) of product as a colorless liquid ; n d 25 1 . 452 . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 60 2 . 87 4 . 39 11 . 15______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 6 . 25 g ( 0 . 028 mol ) of cupric bromide , 3 . 61 g ( 0 . 035 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 7 . 0 g ( 0 . 023 mol ) of product of example 71 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , then poured into 200 ml of 10 % hydrochloric acid and extracted with chloroform ( 3 × 50 ml ). normal workup gave a yellow oil which was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ) to give 7 . 54 g ( 91 %) of product as a colorless liquid ; n d 25 1 470 . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 36 . 47 2 . 53 3 . 86 21 . 99______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 7 . 0 g ( 0 . 023 mol ) of product of example 71 , 4 . 21 g 0 . 023 mol ) of 48 % fluoroboric acid and 60 ml of acetonitrile was added 2 . 61 g of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 1 h , then added to a rapidly stirred solution of 60 g of potassium iodide in 200 ml of water . after 15 min , the reaction mixture was diluted with 200 ml of water and extracted with chloroform ( 3 × 100 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml , brine ( 50 ml ) and dried through sodium sulfate . concentration in vacuo afforded an orange oil which was filtered through a short plug of silica gel . the resulting oil was kugelrohr distilled ( 150 ° c . @ 1 torr ) to afford 1 . 73 g ( 18 %) of product as a white solid , mp 41 °- 43 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 32 . 30 2 . 22 3 . 42found 32 . 51 2 . 12 3 . 60______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a mixture of 2 . 69 g ( 0 . 02 mol ) of cupric chloride , 2 . 58 g ( 0 . 025 mol ) of t - butyl nitrite and 40 ml of acetonitrile was added a solution of 5 . 44 g ( 0 . 017 mol ) of product of example 72 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , poured into 150 ml of 1 m hydrochloric acid and extracted into chloroform ( 3 × 50 ml ). normal workup gave 5 . 73 g of a brown oil which was passed through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . @ 2 torr ) of the resulting oil afforded 4 . 32 g ( 75 %) of product as a colorless liquid ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n cl______________________________________calculated 45 . 17 3 . 79 4 . 05 10 . 26found 45 . 31 3 . 81 4 . 06 10 . 28______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 47 g ( 0 . 020 mol ) of cupric bromide , 2 . 58 g ( 0 . 025 mol ) of t - butyl nitrite and 40 ml of acetonitrile was added a solution of 5 . 49 g ( 0 . 17 mol ) of product of example 72 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , poured into 150 ml of 1 m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). normal workup afforded a brown oil which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . @ 2 torr ) of the resulting oil afforded 5 . 13 g ( 78 %) of product as a colorless liquid ; n d 25 1 . 473 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 05 3 . 38 3 . 57 20 . 40______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 6 . 0 q 0 . 018 mol ) of product of example 72 , 3 . 29 g 0 . 018 mol ) of 48 % fluoroboric acid and 45 ml of acetonitrile was added 2 . 04 g ( 0 . 02 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 15 min , then was added to a rapidly stirred solution of 60 g of potassium iodide in 150 ml of water . the reaction mixture was stirred for 30 min , then was diluted with water ( 200 ml ) and extracted with chloroform ( 3 × 50 ml ). the chloroform extract was washed with 100 ml of 10 % sodium thiosulfate , 100 ml of brine , and dried though sodium sulfate . concentration in vacuo afforded a red - orange oil that was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 160 ° c . @ 2 torr ) of the resulting oil afforded 4 . 3 g ( 55 %) of product as a light yellow oil ; n d 25 1 . 498 . ______________________________________elemental analysis : c h n i______________________________________calculated 35 . 72 3 . 00 3 . 20 29 . 03found 35 . 83 3 . 00 3 . 15 28 . 94______________________________________ 3 ™ pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 4 . 97 g ( 0 . 037 mol ) of cupric chloride , 4 . 84 g ( 0 . 047 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 10 . 0 g ( 0 . 031 mol ) of product of example 16 in 10 ml of acetonitrile . gas evolution occurred immediately . after the reaction was stirred at room temperature for 90 min , it was poured into 250 ml of 1 m hydrocholoric acid and extracted with chloroform . normal workup afforded 10 . 45 g of a brown oil which was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ) and kugelrohr distilled 130 ° c . @ 2 torr ) to afford 7 . 33 g ( 68 %) of product as a colorless liquid ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n cl______________________________________calculated 45 . 17 3 . 79 4 . 05 10 . 26found 45 . 19 3 . 81 4 . 02 10 . 34______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 8 . 26 g ( 0 . 037 mol ) of cupric bromide , 4 . 84 g ( 0 . 047 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added 10 . 0 g ( 0 . 031 mol ) of product of example 16 in 10 ml of acetonitrile , resulting in immediate gas evolution . after 90 min the reaction mixture was poured into 250 ml of 1m hydrochloric acid . extraction with chloroform ( 3 × 75 ml ) and workup as usual afforded 11 . 81 g of a brown oil . this material was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ), then kugelrohr distilled ( 135 ° c . @ 1 . 5 torr ) to afford 8 . 7 g ( 72 %) of product as a colorless oil ; n d 25 1 . 467 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 14 3 . 38 3 . 58 20 . 58______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 10 . 0 g 0 . 031 mol ) of product of example 16 , 5 . 67 g of 48 % fluoroboric acid 0 . 031 mol ) and 55 ml of acetonitrile was added 3 . 50 g ( 0 . 034 mol ) of t - butyl nitrite dropwise . after 20 min at 0 ° c ., the reaction mixture was added to a rapidly - stirred solution of 80 g of potassium iodide in 175 ml of water . this was stirred for 45 min , diluted with 200 ml of water and extracted with chloroform ( 3 × 75 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 100 ml ) and dried through sodium sulfate . normal workup afforded 12 . 8 g of an oily brown solid which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . at 1 . 5 torr ) afforded 9 . 32g ( 69 %) of product as a white solid , mp 45 °- 48 ° c . ______________________________________elemental analysis : c h n i______________________________________calculated 35 . 72 3 . 00 3 . 20 29 . 03found 35 . 77 3 . 00 3 . 17 28 . 96______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred slurry of 2 . 92 g ( 0 . 022 mol ) of cupric chloride , 2 . 80 g ( 0 . 027 mol ) of t - butyl nitrite and 50 ml of acetonitrile was added a solution of 5 . 0 g ( 0 . 018 mol ) of product of example 18 in 10 ml of acetonitrile . this was stirred at room temperature for 2 h , then was poured into 150 ml of 1 m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). workup as usual afforded a brown oil that was kugelrohr distilled ( 120 ° c . @ 1 torr to give 4 . 73 g ( 88 %) of product as a yellow liquid ; n d 25 1 .% 70 . ______________________________________elemental analysis : c h n cl______________________________________calculated 48 . 74 4 . 43 4 . 74 11 . 99found 48 . 83 4 . 20 5 . 11 12 . 26______________________________________ 3 - pyridinecarobxylic acid , 5 - bromo - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 85 g ( 0 . 022 mol ) of cupric bromide , 2 . 80 g ( 0 . 027 mol ) of t - butyl nitrite and 50 ml of acetonitrile was added a solution of 5 . 0 g ( 0 . 018 mol ) of product of example 18 in 10 ml of acetonitrile . this was stirred at room temperature for 2 h , then was diluted with 200 ml of 1m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). normal workup afforded an orange oil that was kugelrohr distilled ( 120 ° c . @ 1 torr ) to give 5 . 21 g ( 84 %) of product as a light yellow oil ; n d 25 1 . 484 . ______________________________________elemental analysis : c h n br______________________________________calculated 42 . 37 3 . 85 4 . 12 23 . 49found 42 . 43 3 . 88 4 . 11 23 . 41______________________________________ 3 - pyridinecarboxylic acid , 4 - ethyl - 5 - iodo - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 66 g ( 0 . 017 mol ) of product of example 18 , 3 . 08 g of 48 % fluoroboric acid and 35 ml of acetonitrile was added 1 . 91 g ( 0 . 019 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 25 min , then was added to a rapidly stirred solution of 40 g of potassium iodide in 120 ml of water . after 30 min , 120 ml of water was added and the reaction mixture was extracted with chloroform ( 3 × 70 ml ). the chloroform extracts were washed with 10 % sodium thiosulfate ( 2 × 50 ml , brine ( 50 ml and dried through sodium sulfate . workup as usual afforded an orange oil that was kugelrohr distilled ( 120 ° c . @ 1 torr ) to give 4 . 88 ( 75 %) of product as a light yellow oil ; n d 25 1 . 504 . ______________________________________elemental analysis : c h n i______________________________________calculated 37 . 23 3 . 38 3 . 62 32 . 78found 37 . 35 3 . 42 3 . 55 32 . 50______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 2 . 34 g ( 0 . 013 mol ) of 48 % fluoroboric acid and 30 ml of acetonitrile was added 1 . 46 g ( 0 . 014 mol ) of t - butyl nitrite dropwise . after 30 min , a solution of 1 . 7 g ( 0 . 026 mol ) of sodium azide in 9 ml of water was added dropwise , resulting in vigorous gas evolution . this was stirred at room temperature for 30 min , diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). workup as usual afforded a yellow oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) afforded 2 . 44 g ( 55 %) of product as a light yellow oil ; n d 25 1 . 476 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 61 3 . 28 16 . 56found 42 . 76 3 . 33 16 . 49______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethoxy ) methylene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 10 ml of triisopropyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 4 h . the temperature was then raised to 130 ° c . and stirring was continued for another 18 hours . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 1 . 58 g ( 32 %) of product as a colorless oil ; n d 25 1 . 502 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 49 . 97 4 . 95 7 . 67______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( 2 - methylpropoxy ) methylene ] amino - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 10 ml of triisobutyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 18 h , then at 120 ° c . for another 18 h . the reaction mixture was concentrated in vacuo . the residue was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 1 . 93 g ( 39 %) of product as a light yellow oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 53 . 77 5 . 94 6 . 60found 54 . 30 6 . 00 6 . 34______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 5 -( propoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 10 ml of tripropyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 71 g ( 56 %) of product as a colorless oil ; n d 25 1 . 458 . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 68 5 . 65 6 . 83found 52 . 85 5 . 76 6 . 43______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 2 , 2 , 2 - trifluoro - 1 -( dimethylamino ) ethylidene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a rapidly stirred solution of 4 . 3 g ( 0 . 010 mol ) of product of example 47 in 5 ml of dioxane was added 4 . 5 ml ( 0 . 025 mol ) of 26 % aqueous dimethylamine . an exothermic reaction occurred . when the reaction cooled to room temperature , 50 ml of water was added and the product was extracted into methylene chloride ( 3 × 25 ml ). workup as usual afforded a dark oil that was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 2 . 35 g 54 %) of product as a yellow oil ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 15 3 . 94 9 . 65found 44 . 17 3 . 77 9 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 2 , 2 , 2 - trifluoro - 1 -( methylamino ) ethylidene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 and 5 ml of dioxane was added 2 ml of 40 % aqueous methylamine . after 30 min , 50 ml of water was added and the product was extracted with methylene chloride . workup as usual , followed by kugelrohr distillation ( 170 ° c . @ 1 torr ) gave 3 . 07 g ( 78 %) of product as a white solid , mp 95 °- 97 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 77 3 . 59 9 . 97found 42 . 59 3 . 63 9 . 98______________________________________ 3 - pyridinecarboxylic acid , 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 5 g 0 . 013 mol ) of product of example 18 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for the weekend . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 73 g ( 88 %) of product as a colorless oil ; n d 25 1 . 477 . ______________________________________elemental analysis : c h n______________________________________calculated 54 . 21 5 . 76 8 . 43found 54 . 16 5 . 80 8 . 23______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( dimethylamino ) methylene ] amino }- 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 70 g ( 0 . 013 mol ) of product of example 18 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 55 g ( 80 %) of product as a yellow solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material as a white solid , mp 71 °- 73 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 54 . 37 6 . 08 12 . 68found 54 . 38 6 . 13 12 . 62______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 2 . 16 g 0 . 012 mol ) of ( 48 %) fluoroboric acid and 40 ml of acetonitrile was added 1 . 34 g of t - butyl nitrite dropwise . this was stirred at 0 ° c . for - 20 min then a solution of 2 . 1 g of sodium azide in 11 ml of water was added slowly , causing immediate gas evolution . after 10 min , 50 ml of water was added and the product was extracted into chloroform . workup as usual afforded a yellow oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction gave 2 . 85 g ( 66 %) of product as a light yellow oil ; n d 25 1 . 470 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 91 4 . 13 15 . 30found 45 . 71 4 . 21 15 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -({ 1 -[( 1 - methylethyl ) thio ]- 2 , 2 , 2 - trifluoroethylidene } amino )- 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 0 . 40g ( 0 . 010 mol ) of 60 % sodium hydride in 7 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere was added 0 . 74 g ( 0 . 0097 mol ) of 2 - propanethiol . this was stirred at room temperature for 30 min , then a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of tetrahydrofuran was added dropwise . this was stirred for 30 min , diluted with 25 ml of water and extracted with ether ( 3 × 15 ml ). workup as usual , followed by kugelrohr distillation ( 150 ° c . @ 1 torr ) afforded 2 . 92 g ( 67 %) of product as a yellow liquid ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n s______________________________________calculated 43 . 78 3 . 89 6 . 01 6 . 87found 44 . 09 3 . 90 5 . 90 6 . 89______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( methylamino )- 2 -( trifluoromethyl ) ethyl ester . to 40 ml of acetic anhydride at 0 ° c . was added 20 ml of formic acid . this was warmed to room temperature , then was heated to 50 ° c . for 15 min . the flask was immediately re - cooled to 0 ° c . and 5 . 0g ( 0 . 016 mol ) of product of example 2 was added . this was stirred at room temperature for 18 hours , then was concentrated in vacuo to afford a yellow oil . this was dissolved in 15 ml of anhydrous tetrahydrofuran , and stirred at 0 ° c . under a dry nitrogen atmosphere . to this , 20 ml ( 0 . 04 mol ) of 2 . 0 m borane - dimethyl sulfide complex in tetrahydrofuran was added dropwise . after the addition was complete , the reaction mixture was stirred at 70 ° c . for 3 . 5 hours . the reaction mixture was then cooled to 0 ° c . and 10 ml of methanol was added slowly . after frothing ceased , the mixture was warmed to room temperature and stirred for 1 hour . the 7 ml of concentrated hydrochloric acid was added and the mixture was refluxed for 1 hour . the reaction mixture was concentrated in vacuo to afford a yellow solid , which was slurried with ethyl acetate and stirred with 25 ml of 10 % sodium hydroxide solution . the organic layer was separated and workup as usual gave a yellow oil . chromatography on silica gel using 5 % ethyl acetate / cyclohexane gave 2 . 77g of product as a yellow oil which slowly solidified , mp 38 °- 40 ° c . ______________________________________elemental analysi : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 88 4 . 63 8 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( 2 , 2 , 2 - trifluoroethyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 5 . 16g ( 0 . 0128 mol ) of product of example 25 in 12 ml of anhydrous tetrahydrofuran at 0 ° c . under a nitrogen atmosphere , was added 16 ml of 2 . om borane - dimethyl sulfide complex in tetrahydrofuran dropwise . the reaction mixture was heated at 70 ° c . for 3 hours . then the mixture was cooled to 0 ° c . and 10 ml of methanol was added carefully . after frothing ceased 10 ml of concentrated hydrochloric acid was added and the mixture was refluxed for 1 hour . the reaction mixture was concentrated in vacuo and the residue was slurried with 50 ml of ethyl acetate and stirred with 25 ml of 10 % sodium hydroxide . workup of the ethyl acetate solution afforded a yellow oil that was chromatographed on silica gel with 5 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 15g ( 43 %) of product as a colorless oil ; n d 25 1 . 439 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 65 3 . 58 7 . 11found 42 . 93 3 . 58 7 . 13______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0g 0 . 0134 mol ) of product of example 71 , 2 . 45g 0 . 0134 mol ) of 48 % fluoroboric acid and 45 ml of acetonitrile was stirred at 0 ° c . and 1 . 44g 0 . 014 mol ) of t - butyl nitrite was added dropwise . this was allowed to stir at 0 ° c . for 20 minutes , then a solution of 2 . 1 g of sodium azide in 11 ml of water was added dropwise , resulting in immediate gas evolution . after stirring for an additional 10 minutes the reaction mixture was diluted with water and extracted with chloroform . workup as usual gave a yellow oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 27g ( 52 %) of product as a yellow oil ; n d 25 1 . 474 . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 75 2 . 80 17 . 28found 40 . 96 2 . 71 17 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0g ( 0 . 015 mol ) of product of example 72 , 10 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 2 hours . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . at 1 torr ) to afford 5 . 05g ( 90 %) of product as a colorless oil which slowly crystallized , mp 57 °- 59 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 91 4 . 66 7 . 59______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ] 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0g ( 0 . 015 mol ) of product of example 72 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 145 ° c . 1 torr ) to give 5 . 07 g 8 %) of product as a colorless oil ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 26 5 . 05 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) 4 - ethyl - 5 -{[( dimethylamino ) methylene ] amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 145 ° c . at 1 torr ) to afford 3 . 90 g ( 83 %) of product as a yellow solid , mp 50 °- 52 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 49 . 05 4 . 94 11 . 44found 49 . 02 4 . 93 11 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl - 5 -{[( dimethylamino ) methylene ] amino }- 4 -( 1 - methylethyl ) - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 25 g ( 0 . 013 mol ) of product of example 72 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was heated overnight at 100 ° c . the reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel using 5 % ethyl acetate / cyclohexane . workup of the correct fraction afforded 4 . 17 g ( 84 %) of product as a yellow oil ; n d 25 1 . 487 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 33 5 . 22 11 . 28______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012 mol ) of product of example 72 , 2 . 25 g ( 0 . 012 mol ) of 48 % fluoroboric acid and 40 ml of acetonitrile was added 1 . 40 g ( 0 . 013 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 20 minutes , then a solution of 2 . 1 g of sodium azide in 11 ml of water was added slowly , resulting in vigorous gas evolution . after stirring for 10 minutes , 100 ml of water was added and the product was extracted into chloroform ( 3 × 50 ml ). workup as usual afforded an orange oil which was chromatrographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 41g ( 56 %) of product as a slightly yellow oil ; n d 25 1 . 472 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 33 3 . 72 15 . 91found 44 . 11 3 . 72 15 . 91______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( sulfinylamino )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g of product of example 2 and 15 ml of thionyl chloride was stirred at reflux overnight . the excess thionyl chloride was removed in vacuo and the residue was kugelrohr distilled ( 145 ° c . at 1 torr ) to give 4 . 21 g ( 92 %) of product as a bright yellow oil ; n d 25 1 . 477 . ______________________________________elemental analysis : c h n s______________________________________calculated 40 . 23 3 . 09 7 . 82 8 . 95found 40 . 30 3 . 11 7 . 80 8 . 87______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - isocyanato - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . the product of example 47 ( 5 . 0 g , 0 . 0134 mol ) of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 1 . 66 g ( 0 . 0144 mol ) of azidotrimethyl silane and 10 ml of carbon tetrachloride and stirred at reflux until gas evolution ceased (˜ 45 minutes ). the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 2 . 65 g ( 50 %) of product as a light yellow oil ; n d 25 1 . 459 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 74 3 . 72 7 . 95found 47 . 74 3 . 89 7 . 80______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 5 -[( 2 , 2 , 2 - trifluoro - 1 - methoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 2 . 16 g ( 0 . 01 mol ) of 25 % methanolic sodium methoxide in 5 ml of methanol was added a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 5 ml of methanol , resulting in the immediate formation of a white precipitate . the reaction mixture was stirred for 1 hour , then was poured into water ( 50 ml ) and extracted with ether ( 3 × 15 ml ). workup as usual afforded a colorless oil which was kugelrohr distilled ( 130 ° at 1 . 5 torr ) to give 3 . 27 g ( 82 %) of product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 13 3 . 69 6 . 44______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 16 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was stirred at reflux overnight . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 165 ° c . at 1 . 5 torr to give 4 . 10 g ( 87 %) of product as a yellow oil ; n d 25 1 . 486 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 50 5 . 29 10 . 99______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( trifluoroacetyl ) amino ]- 4 - propyl ™ 2 ™( trifluoromethyl )-, ethyl ester . a solution of 35 . 0 g ( 0 . 107 mol ) of product of example 16 , 100 ml of methylene chloride and 30 g ( 0 . 14 mol ) of trifluoroacetic anhydride was stirred at room temperature overnight . concentration in vacuo afforded 45 . 7 g 100 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 95 °- 97 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 67 3 . 34 6 . 63found 42 . 80 3 . 20 6 . 74______________________________________ 3 - pyridinecarboxylic acid , 5 -[( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 39 . 58 g ( 0 . 0937 mol ) of product of example 107 and 19 . 51 g ( 0 . 0937 mol ) of phosphorous pentachloride was heated at 135 ° c . for 3 hours . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 40 . 07 g ( 97 %) of product as a colorless oil ; n d 25 1 . 434 . ______________________________________elemental analysis : c h n cl______________________________________calculated 40 . 88 2 . 97 6 . 36 8 . 04found 40 . 53 2 . 73 6 . 26 8 . 08______________________________________ 3 - pyridinecarboxylic aoid , 5 -[[ 1 -( diethoxyphosphinyl ) - 2 , 2 , 2 - trifluoroethylidene ] amino ]- 6 -( difluoromethyl )- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 6 . 0 g ( 0 . 0136 mol ) of product of example 108 and 2 . 26 g ( 0 . 0136 mol ) of triethyl phosphine was stirred at 160 ° c . for 30 min . the reaction mixture was then cooled to room temperature affording 7 . 35 g (˜ quant .) of product as a yellow oil ; n d 25 1 . 437 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 08 4 . 27 5 . 17found 41 . 68 4 . 29 5 . 14______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 5 -[( 2 , 2 , 2 - trifluoro - 1 - ethoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 24 g ( 0 . 010 mol ) of 21 % ethanolic sodium ethoxide and 5 ml of ethanol was added a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 5 ml of ethanol . this was stirred at room temperature for 15 minutes during which time a white precipitate formed . the reaction mixture was poured into water ( 50 ml ) and extracted with ether . workup as usual gave a yellow oil which was kugelrohr distilled ( 150 ° at 1 . 5 torr to give 3 . 87 g ( 84 %) of product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 34 4 . 03 6 . 22found 45 . 44 4 . 00 6 . 26______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )- 5 -[ 5 -( trifluoromethyl ) - 1h - tetrazol - 1 - yl ]-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 20 ml of tetrahydrofuran was added 0 . 65 g ( 0 . 01 mol ) of sodium azide followed by the addition of 4 ml of water . the reaction mixture was stirred at room temperature for 30 minutes , then was diluted with water 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave 3 . 87 g ( 86 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 66 °- 68 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 28 2 . 93 15 . 66found 40 . 07 2 . 87 15 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 1 -( dimethylamino )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 and 10 ml of dioxane was added 4 . 5 ml of 26 % aq . dimethylamine . the solution became warm immediately . this was allowed to stir for 30 minutes , then was diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave an orange oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 3 . 77 g ( 84 %) of product as a colorless 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 44 4 . 26 9 . 35found 45 . 42 4 . 18 9 . 19______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 2 , 2 , 2 - trifluoro - 1 ( methylamino ) ethylidene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 and 10 ml of dioxane was added 2 ml of 40 % aq . methylamine . the reaction mixture became warm . this was allowed to stir for 30 minutes , then was diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave a yellow oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 3 . 53 g ( 89 %) of product as a thick colorless oil ; n d 25 1 . 461 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 15 3 . 94 9 . 65found 44 . 25 3 . 77 9 . 38______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 209 , 7 . 8 ml of triethyl orthoformate and 78 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 6 hours . the reaction mixture was concentrated in vacuo to give 5 . 39 g ( 100 %) of product as a colorless oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) ave analytically pure material ; n d 25 1 . 462 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 50 5 . 09 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred slurry of 14 . 3 g of sodium azide , 25 ml of water and 75 ml of acetone was slowly added a solution of 35 . 77 g ( 0 . 103 mol ) of methyl 5 - chlorocarbonyl - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )- 3 - pyridinecarboxylic in 20 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction mixture was allowed to cool to room temperature and diluted with water ( 300 ml ) and extracted into chloroform ( 3 × 100 ml ). normal workup afforded 26 . 61 g ( 82 %) of product as a light yellow solid . trituration with cyclohexane gave analytically pure material , mp 54 °- 56 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 37 3 . 72 9 . 37______________________________________ 3 - pyridinecarboxylic acid , 2 -{ difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 7 . 4 ml of trimethyl orthoformate and 74 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was then concentrated in vacuo and the residue kugelrohr distilled ( 150 °- 165 ° c . at 1 torr ) to give 4 . 24 g ( 98 %) of product as white solid , mp 67 °- 69 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 45 . 92 3 . 85 8 . 21______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 7 . 8 ml of triethyl orthoformate and 78 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 °- 165 ° c . at 1 torr ) to give 4 . 3 g ( 0 . 012 mol ) of product as a white solid . trituration with cyclohexane gave analytically pure material , mp 68 °- 69 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 37 4 . 30 7 . 90______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . a solution of 3 . 5 g ( 0 . 011 mol ) of product of example 209 , 6 . 7 ml of trimethyl orthoformate , and 67 mg of p - toluenesulfonic acid was refluxed for 2 hours . reaction mixture was then concentrated in vacuo and the residue kugelrohr distilled ( 150 °- 160 ° c . at 1 torr ) to give 3 . 67 g ( 93 %) of product as a colorless oil ; n d 25 1 466 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 98 4 . 66 7 . 61______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 3 . 41 g ( 0 . 015 mol ) of copper ( ii ) bromide and 1 . 96 g ( 0 . 019 mol ) of t - butyl nitrite in 36 ml of acetonitrile was added a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 in 7 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour , then was poured into 180 ml of 20 % aqueous hydrochloric acid and extracted with ether ( 3 × 50 ml ). normal workup followed by kugelrohr distillation ( 130 °- 145 ° c . at 1 torr ) gave 3 . 63 g ( 79 %) of product as a colorless oil . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave an analytically pure white solid , mp 25 49 °- 51 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 37 . 14 2 . 59 3 . 92 22 . 39______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 2 . 05 g ( 0 . 015 mol ) of copper ( ii ) chloride and 1 . 96 g (. 019 mol ) of t - butyl nitrite in 36 ml of acetonitrile was added a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 in 7 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour . the reaction mixture was poured into 180 ml of 20 % aqueous hydrochloric acid and extracted with ether ( 3 × 50 ml ). workup as usual followed by kugelrohr distillation ( 130 °- 145 ° c .) gave 3 . 28 g ( 81 %) of product as a colorless oil . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave analytically pure material ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 72 2 . 88 4 . 47 11 . 20______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 3 . 98 g ( 0 . 013 mol ) of product of example 115 , 2 . 32 g ( 0 . 013 mol ) of 48 % fluoroboric acid and 33 ml of acetonitrile in an ice bath was slowly added 1 . 44 g 0 . 014 mol ) of t - butyl nitrite . the solution was stirred at 0 ° c . for 30 minutes and then added to a rapidly stirred solution of 33 . 17 g ( 0 . 20 mol ) of potassium iodide in 120 ml water . after 30 minutes , the reaction mixture was diluted with 120 ml of water and extracted with chloroform ( 3 × 75 ml ). the chloroform solution was washed with 10 % sodium thiosulfate solution ( 2 × 75 ml ). workup as usual followed by kugelrohr distillation ( 140 °- 165 ° c . at 1 torr ) gave 3 . 75 g ( 72 %) of product as an off - white solid , mp 63 °- 65 ° c . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane gave an analytically pure white solid , mp 72 °- 73 ° c . ______________________________________elemental analysis : c h n i______________________________________calculated 32 . 30 2 . 22 3 . 42 31 . 02found 32 . 12 2 . 23 3 . 37 30 . 98______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 2 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl ) -, methyl ester . to a stirred solution of 16 . 22 g ( 0 . 072 mol ) of copper ( ii ) bromide and 9 . 32 g ( 0 . 091 mol ) of t - butyl nitrite in 170 ml of acetonitrile was added a solution of 19 . 71 g ( 0 . 060 mol ) of product of example 209 in 34 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour . the reaction mixture was poured into 856 ml of 20 % hydrochloric acid and then extracted with ether . normal workup yielded 20 . 22 g ( 86 %) of product as a bright yellow oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) yielded 12 . 24 g ( 52 %) of product as a colorless oil ; n d 25 1 . 472 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 15 3 . 37 3 . 58 20 . 42______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl ) -, methyl ester . to a stirred slurry of 26 . 9 g ( 0 . 414 mol ) of sodium azide , 47 ml of water and 158 ml acetone was slowly added a solution of 62 . 53 g ( 0 . 168 mol ) of methyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 21 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction was allowed to cool to room temperature and diluted with 565 ml water and extracted with chloroform ( 3 × 100 ml ). workup as usual gave 52 . 9 g ( 97 %) of product as a light yellow solid . chromatography on silica gel ( 20 % ethyl acetate / cyclohexane to elute product ) gave 37 . 25 g ( 68 %) of analytically pure material , mp 104 °- 106 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 78 4 . 68 8 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 25 g ( 0 . 01 mol ) of product of example 123 , 6 . 0 ml of trimethyl orthoformate , and 60 mg of p - toluenesulfonic acid was stirred for 28 hours at 100 ° c . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 145 °- 155 ° c . at 1 torr ) to yield 3 . 39 g ( 92 %) of product as a colorless oil . chromatography of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave analytically pure material ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 84 4 . 69 7 . 61______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 25 g ( 0 . 010 mol ) of product of example 123 , 6 . 2 ml of triethyl orthoformate and 62 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 8 hours . an additional 62 mg of p - toluenesulfonic acid was added and the reaction was complete 20 hours later . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 135 °- 145 ° c . at 1 torr ) to give 3 . 8 g ( 99 %) of product as a colorless oil ; n d 25 1 . 4655 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 32 5 . 02 7 . 23______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[[( dimethylamino ) methylene ] amino ]- 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . a stirred solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 170 °- 185 ° c . at 1 torr ) to give 3 . 98 g of product as a yellow solid , mp 89 °- 91 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 60 4 . 56 11 . 89found 47 . 63 4 . 59 11 . 88______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, methyl ester . a stirred solution of 4 . 0 g ( 0 . 012 mol ) of product of example 123 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue kugelrohr distilled ( 170 °- 185 ° c . at 1 torr ) to give 4 . 11 g ( 88 %) of product as yellow liquid that slowly solidified , mp 59 °- 60 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 41 5 . 28 10 . 98______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino }- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g of product of example 1 , 9 ml of dimethylformamide dimethyl acetal , and 91 mg of p - toluenesulfonic acid was stirred at reflux for 3 hours . the reaction mixture was concentrated in vacuo and the residue kugelrohr distilled ( 185 °- 200 ° c . at 1 torr ) to yield a brown oil . chromatography on silica gel ( 7 % ethyl acetate / cyclohexane ) gave 3 . 29 g ( 71 %) of product as a colorless oil ; n d 25 1 . 486 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 64 5 . 61 10 . 63found 51 . 73 5 . 62 10 . 61______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 5 . 0 g ( 0 . 016 mol ) of product of example 115 , 2 . 9 g ( 0 . 016 mol ) of 48 % fluoroboric acid , and 52 ml of acetonitrile was added 1 . 75 g ( 0 . 017 mol ) of t - butyl nitrite dropwise . the reaction mixture was stirred at 0 ° c . for 20 minutes , then a solution of 2 . 72 g 0 . 042 mol ) of sodium azide in 14 ml of water was added . vigorous gas evolution followed . the reaction was stirred for 10 minutes at room temperature , then diluted with 100 ml of water and extracted with chloroform ( 3 × 25 ml ). normal workup afforded 5 . 07 g ( 98 %) of product as an orange oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) gave 2 . 61 g ( 50 %) of product as a colorless oil ; n d 25 1 . 570 . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 75 2 . 80 17 . 28found 40 . 82 2 . 77 17 . 10______________________________________ 3 - pyridinecarboxylic acid , 5 -( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl )- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 37 . 65 g ( 0 . 086 mol ) of product of example 7 and 17 . 97 g ( 1 equivalent ) of pcls was stirred overnight at 130 ° c . in a flask fitted with a reflux condenser and a drying tube . the reaction mixture was concentrated in vacuo , then kugelrohr distilled at 90 ° c . to remove low - boiling impurities and finally at 130 ° c . to afford 35 . 78 g ( 0 . 078 mol ) of product as a yellow oil which gradually solidified . yield was 91 %. mp 33 . 0 °- 34 . 0 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 42 . 26 3 . 32 6 . 16 7 . 80found 42 . 69 3 . 39 6 . 22 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 5 - ( 2 , 2 , 2 - trifluoro - 1 - methoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 2 . 09 g ( 0 . 010 mol ) of 25 % sodium methoxide / methanol and 5 ml of methanol was added a solution of 4 . 0 g 0 . 009 mol ) of product of example 130 in 4 . 7 ml methanol . a yellow precipitate formed immediately and the reaction mixture was stirred at room temperature for 1 hour , then diluted with 25 ml of water and extracted with ether ( 3 × 20 ml . workup as usual followed by kugelrohr distillation ( 135 ° c . at 1 torr ) gave 2 . 57 g ( 65 %) of product as a colorless oil . chromatography on silica gel ( 0 . 5 % ethyl acetate / cyclohexane ) gave 1 . 89 g ( 48 %) of pure product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 34 4 . 03 6 . 22found 45 . 32 3 . 91 6 . 25______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )- 5 -[( 2 , 2 , 2 - trifluoro - 1 - ethoxyethylidine ) amino ]-, ethyl ester . to a solution of 3 . 24 g ( 0 . 010 mol ) of 21 % sodium ethoxide / ethanol and 5 ml of ethanol was added a solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 in 5 ml ethanol . the reaction was stirred at room temperature for 15 minutes . the reaction mixture was diluted with 100 ml water and extracted with ether ( 3 × 25 ml ) which was worked up as usual . kugelrohr distillation ( 135 °- 145 ° c . at 1 torr ) gave 2 . 87 g ( 70 %) of product as a colorless oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) gave 1 . 89 g ( 46 %) of product as a colorless oil ; n d 25 1 . 439 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 56 4 . 34 6 . 03found 46 . 64 4 . 34 6 . 14______________________________________ 3 - pyridinecarboxylic acid , 5 -{[ 1 -( dimethylamino ) - 2 , 2 , 2 - trifluoroethylidene ] amino - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 and 10 ml of dioxane was added 4 . 5 ml ( 0 . 026 mol ) of 26 % aqueous solution of dimethylamine . the solution became warm and was stirred for 30 minutes . the reaction mixture was diluted with 250 ml of water and extracted with chloroform ( 3 × 30 ml ). workup as usual gave a brown oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 2 . 06 g ( 50 %) of product as a yellow oil ; n d 25 1 . 467 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 66 4 . 57 9 . 07found 46 . 44 4 . 56 9 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 1 -( methylamino )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 in 10 ml dioxane was added 2 ml ( 0 . 026 mol ) of 40 % aqueous methylamine . the reaction became warm and was stirred for 30 minutes . the reaction mixture was diluted with 250 ml of water and extracted with chloroform ( 3 × 30 ml ). normal workup gave a yellow oil which was kugelrohr distilled ( 175 ° c . at 1 torr ) to yield product as a thick yellow oil ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 44 4 . 26 9 . 35found 45 . 54 4 . 27 9 . 18______________________________________ ethyl 2 , 6 - bis - trifluoromethyl )- 5 - bromo - 4 - hydroxy - 3 - pyridinecarboxylate . the precursor ethyl 2 , 6 - bis ( trifluoromethyl )- 4 - hydroxy - 3 - pyridinecarboxylate was prepared as follows : to a flame dried 3 - liter , four - necked flask equipped with nitrogen inlet , low temperature thermometer , 500 ml addition funnel and mechanical stirrer was charged 91 . 0 g ( 126 ml , 0 . 899 mol ) of diisopropylamine and 500 ml of dry tetrahydrofuran . the resulting solution was cooled to - 78 ° c . using an acetone - dry ice bath . to this was slowly added 383 ml ( 0 . 880 mol ) of 2 . 3m n - buli in hexane at such a rate that the reaction temperature was kept below - 60 ° c . after stirring at - 78 ° c . for 1 hour , a solution of 90 . 0 g ( 0 . 400 mol ) of ethyl 2 - acetyl - 3 - amino - 4 , 4 , 4 - trifluoro 2 - butenoate in 150 ml of dry tetrahydrofuran was added in such a rate that the reaction temperature was kept below - 60 ° c . the reaction mixture turned yellow and a solid suspension formed . after 1 hour of stirring at - 78 ° c ., the reaction mixture was treated with 184 . 7 g ( 155 ml , 1 . 300 mol ) of ethyl trifluoroacetate in such rate that the reaction temperature was kept below - 60 ° c . this reaction mixture was left at - 78 ° c . for 1 hour , then warmed to room temperature ( the yellow suspension disappeared and a brown solution was formed ) and stirred for 18 hours . the resulting solution was poured into 1 . 5 l of 10 % hcl ( aqueous ) and extracted 3 times with methylene chloride . the combined methylene chloride layers were dried ( mgso 4 ) and reduced in vacuo affording a thick brown oil . the residue was kugelrohr distilled at 47 pa . the earlier fraction ( pot temperature 50 ° c .) was discarded . the later fraction ( pot temperature 80 ° c .) afforded 80 . 0 g ( 66 %) of the pyridine intermediate ; mp 70 °- 77 ° c . to a solution of 5 . 0 g ( 0 . 165 mol ) of the compound prepared above in 50 ml of 10 % naoh was added 5 ml of bromine . an exothermic reaction occurred instantly . the reaction mixture was stirred for 5 minutes and poured into a mixture of 20 ml of concentrated hcl and 50 ml of water . to the above mixture was added sodium sulfite until all red bromine color disappeared . the white oil precipitate was extracted into ether . the ether solution was dried and concentrated . the residue was kugelrohr distilled at 0 . 8 mm ( pot temperature 95 ° c .) to give 5 . 7 g of an oil which was crystallized from petroleum ether at low temperature to give 3 . 5 g ( 55 . 9 %) of product , mp 30 °- 32 ° c ., which turned into a liquid upon standing , n d 25 1 . 4646 . ______________________________________elemental analysis : c h n br______________________________________calculated 31 . 44 1 . 58 3 . 67 20 . 92found 31 . 30 1 . 59 3 . 64 20 . 86______________________________________ using preparative techniques similar to those set out in detail above in examples 1 through 136 , additional compounds were prepared . these additional compounds are shown in the following table 1 , along with a physical property for each where available . table 1__________________________________________________________________________ ## str12 ## example r . sub . 1 r . sub . 2 r ra x mp (° c .) n . sub . d . sup . 25__________________________________________________________________________136 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 3 cyclobutyl 59 . 8 - 64 . 8137 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 br isobutyl 1 . 473138 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 2 ch . sub . 3 cyclobutyl139 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 nh . sub . 2 methoxy 70 . 0 - 71 . 0140 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 br methoxy 1 . 449141 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 i methoxy 39 . 0 - 40 . 0142 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str13 ## isobutyl 1 . 518143 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclopropylmethyl 1 . 480144 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str14 ## isobutyl 96 . 0 - 97 . 0145 cf . sub . 3 cf . sub . 2 h och . sub . 3 br cyclobutyl 50 . 0 - 54 . 0146 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str15 ## cyclobutyl 83 . 0 - 83 . 7147 cf . sub . 3 cf . sub . 2 h och . sub . 3 br isobutyl 1 . 471148 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nh . sub . 2 isobutyl 94 . 0 - 96 . 0149 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nchoch . sub . 3 isobutyl 1 . 477150 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 br isobutyl 1 . 483151 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str16 ## propyl 82 . 0 - 84 . 0152 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str17 ## cyclobutyl153 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nso propyl 1 . 476154 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str18 ## isobutyl 1 . 493155 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str19 ## isobutyl 1 . 442156 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 54 . 0 - 57 . 0157 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 1 . 497158 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nhch . sub . 3 isobutyl 1 . 473159 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 no . sub . 2 isobutyl 1 . 465160 cf . sub . 2 h cf . sub . 3 och . sub . 3 no . sub . 2 ethyl 1 . 451161 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str20 ## isobutyl 1 . 502162 cf . sub . 3 cf . sub . 2 h och . sub . 3 nco isobutyl 1 . 466163 cf . sub . 3 cf . sub . 2 h och . sub . 3 nso isobutyl 1 . 479164 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str21 ## propyl 64 . 0 - 66 . 0165 cf . sub . 2 h cf . sub . 3 och . sub . 3 nso isobutyl 1 . 482166 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str22 ## isobutyl 168 . 0 - 171 . 0167 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str23 ## isobutyl 1 . 418168 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nh . sub . 2 isobutyl 108 . 0 - 110 . 0169 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str24 ## isobutyl 90 . 0 - 92 . 0170 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 70 . 0 - 71 . 0171 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 3 isobutyl 1 . 494172 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 2 ch . sub . 3 isobutyl 1 . 492173 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nchsch . sub . 3 isobutyl 1 . 4925174 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str25 ## isobutyl 118 . 0 - 120 . 0175 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nso isobutyl 1 . 477176 cf . sub . 3 cf . sub . 2 h sch . sub . 3 br isobutyl 37 . 0 - 38 . 0177 ## str26 ## 177 ( cont .) cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str27 ## isobutyl178 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 3 isobutyl 1 . 493179 cf . sub . 3 cf . sub . 2 h och . sub . 3 n ( cho ). sub . 2 isobutyl 1 . 457180 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 2 ch . sub . 3 isobutyl 1 . 493181 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str28 ## isobutyl 182 . 0 - 184 . 0182 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str29 ## isobutyl 1 . 488183 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str30 ## isobutyl 1 . 494184 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str31 ## isobutyl 112 . 0 - 114 . 0185 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str32 ## isobutyl 1 . 483186 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str33 ## isobutyl 160 . 0 - 161 . 0187 cf . sub . 2 h cf . sub . 3 sch . sub . 3 br isobutyl 1 . 507188 cf . sub . 3 cf . sub . 2 h sch . sub . 2 ch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 1 . 511189 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str34 ## isobutyl 1 . 470190 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str35 ## isobutyl 1 . 4845191 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str36 ## isobutyl 1 . 462192 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str37 ## isobutyl 1 . 477193 cf . sub . 3 cf . sub . 2 h och . sub . 3 ncfch . sub . 3 isobutyl 158 . 0 - 160 . 0194 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str38 ## isobutyl 1 . 492195 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str39 ## isobutyl 118 . 0 - 119 . 0196 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchsch . sub . 3 isobutyl 1 . 523197 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nhcoch . sub . 3 isobutyl 140 . 0 - 142 . 0198 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nh . sub . 2 cyclopropylmethyl 90 . 0 - 92 . 0199 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclopropylmethyl 109 . 0 - 112 . 0200 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchoch . sub . 3 cyclobutyl 64 . 0 - 66 . 0201 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclobutyl 48 . 0 - 52 . 0202 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclobutyl 86 . 6 - 88 . 4203 cf . sub . 3 cf . sub . 2 h och . sub . 3 nh . sub . 2 cyclobutyl 88 . 8 - 90 . 5204 cf . sub . 2 h cf . sub . 3 och . sub . 3 nh . sub . 2 cyclobutyl 89 . 0 - 92 . 8205 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchoch . sub . 3 cyclobutyl206 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclobutyl207 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclobutyl 69 . 0 - 74 . 0208 cf . sub . 2 h cf . sub . 3 och . sub . 3 br cyclobutyl__________________________________________________________________________ pg , 85 3 - pyridinecarboxylic acid , 5 - amino - 2 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . to a stirred slurry of 27 . 8 g of sodium azide , 50 ml of water and 164 ml of acetone was slowly added a solution of 65 . 2 g ( 0 . 183 mol ) of methyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 16 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction mixture was allowed to cool to room temperature and diluted with water ( 500 ml ) and extracted into chloroform ( 3 × 100 ml ). normal workup afforded 51 . 93 g ( 94 %) of product as green solid . chromatography on silica gel ( 10 % ethyl acetate / cyclohexane ) gave analytically pure material , mp 48 °- 50 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 81 4 . 63 8 . 58______________________________________ as noted above , many of the compounds of this invention have been found to be effective as pre - emergent and post - emergent herbicides . table 2 summarizes results of tests conducted to determine the pre - emergent herbicidal activity of the compounds of this invention on common weeds . top soil is placed in aluminum pans and compacted to a depth of 0 . 95 to 1 . 27 cm . from the top of the pan . on the top of the soil is placed a predetermined number of seeds or vegetative propagules of various plant species . the soil required to level fill the pans after seeding or adding vegetative propagules is weighed into a pan . a known amount of the active ingredient applied in acetone as a solvent is thoroughly mixed with the soil , and the herbicide / soil mixture is used as a cover layer for prepared pans . in table 3 below the amount of active ingredient is equal to the rate of 11 . 2 kg / ha . after treatment , the pans are moved to a greenhouse bench where they are watered from below as needed to give adequate moisture for germination and growth . approximately 10 - 14 days ( usually 11 days ) after seeding and treating , the pans are observed and the results recorded . in some instances , a second observation is made approximately 24 - 28 days after seeding and treating , and these observations are indicated in the following tables by an asterisk (*) immediately following the example number . table 2 below summarizes the results of the pre - emergent herbicidal activity tests of compounds of this invention in weeds . the herbicidal rating is obtained by means of a fixed scale based on the percent inhibition of each plant species . the symbols in the table are defined as follows : ______________________________________ % inhibition rating______________________________________ 0 - 24 025 - 49 150 - 74 2 75 - 100 3not planted -- species planted , nno data______________________________________ the plant species usually regarded as weeds which are utilized in one set of tests , the data for which are shown in table 3 , are identified by letter headings above the columns in accordance with the following legend : ______________________________________ a - canada thistle * b - cocklebur c - velvetleaf d - morningglory e - common lambsquarters f - pennsylvania smartweed g - yellow nutsedge * h - quackgrass * i - jonhsongrass * j - downy brome k - barnyardgrass______________________________________ * grown from vegetative propagules table 2______________________________________pre - emergent activity for weedsexample no . kg / ha a b c d e f g h i j k______________________________________ 1 11 . 2 0 0 1 2 3 3 0 3 0 3 3 2 11 . 2 0 0 3 3 3 3 0 2 -- 3 3 3 11 . 2 0 0 1 2 3 2 0 3 3 1 3 4 11 . 2 0 0 0 0 1 3 0 0 3 0 1 5 11 . 2 3 2 3 3 3 3 2 2 3 3 3 6 11 . 2 0 0 3 1 3 3 0 0 3 3 3 7 11 . 2 3 0 2 3 3 2 0 0 3 2 2 8 11 . 2 0 0 0 0 0 1 0 3 3 3 3 9 11 . 2 3 0 2 3 3 3 0 1 n 3 3 10 11 . 2 3 n 2 3 3 2 1 3 3 3 3 11 11 . 2 0 1 1 3 2 2 0 3 3 3 3 12 11 . 2 3 1 1 3 3 3 0 3 -- 3 3 13 11 . 2 3 1 2 3 3 3 0 3 3 3 3 14 11 . 2 3 0 2 3 3 3 3 3 -- 3 3 15 11 . 2 1 1 3 3 3 3 2 3 3 3 3 16 11 . 2 3 0 3 3 3 3 0 2 0 2 3 17 11 . 2 -- 1 3 3 3 3 0 3 2 3 3 18 11 . 2 -- n 0 0 3 0 0 0 0 0 1 19 11 . 2 -- 0 1 2 3 3 0 3 3 3 3 20 11 . 2 -- 1 0 0 0 1 0 0 0 0 1 21 11 . 2 -- 0 0 0 0 0 0 0 0 2 0 22 11 . 2 -- 0 0 0 0 2 0 0 0 2 2 23 11 . 2 -- 1 1 0 0 1 1 0 1 0 1 24 11 . 2 -- 0 0 0 0 0 0 0 3 0 0 25 11 . 2 1 n 1 0 3 1 0 0 0 0 2 26 11 . 2 -- 0 2 0 3 2 0 0 0 1 2 26 * 11 . 2 -- 0 2 0 3 1 0 0 0 1 2 27 11 . 2 -- 0 3 3 n 3 0 0 0 0 0 28 11 . 2 -- 2 3 3 3 3 0 1 1 1 1 29 11 . 2 -- 0 0 0 2 2 0 0 0 3 3 30 11 . 2 -- 0 0 0 0 0 0 0 0 1 0 31 11 . 2 -- 2 2 0 0 3 0 0 0 1 3 32 11 . 2 -- 3 3 3 3 3 0 3 3 3 3 33 11 . 2 -- 1 3 3 3 3 0 3 3 3 3 34 11 . 2 -- 0 3 3 3 3 0 3 3 3 3 35 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 36 11 . 2 -- 0 3 3 3 3 0 3 0 3 3 37 11 . 2 -- 0 3 3 3 2 0 3 0 3 3 38 11 . 2 -- 1 3 3 3 3 1 3 3 3 3 39 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 40 11 . 2 -- 0 3 3 3 3 0 3 3 3 3 41 11 . 2 -- 0 0 0 3 3 0 0 n 0 3 42 11 . 2 -- 0 2 0 2 3 0 0 n 1 3 43 11 . 2 -- 0 0 0 3 3 0 0 0 3 3 44 11 . 2 -- 0 0 0 3 3 0 0 0 0 3 45 11 . 2 -- 0 1 0 3 3 0 0 0 3 3 46 11 . 2 -- 1 0 0 3 3 1 0 0 1 0 47 11 . 2 -- 0 0 2 1 3 0 1 0 3 3 49 11 . 2 -- 1 1 1 3 3 0 3 3 3 3 50 11 . 2 -- 0 0 0 1 2 0 1 2 3 3 51 11 . 2 -- 0 1 0 3 1 0 0 0 0 0 52 11 . 2 -- 0 1 1 3 3 0 2 0 3 3 53 11 . 2 -- 0 2 3 3 3 0 3 1 3 3 54 11 . 2 -- 3 3 3 3 3 1 3 1 3 3 55 11 . 2 -- 0 2 2 1 2 0 3 0 3 3 56 11 . 2 -- 0 1 3 3 3 0 2 0 3 3 57 11 . 2 -- 1 3 3 3 3 0 3 1 3 3 58 11 . 2 -- 0 2 1 3 2 0 3 0 3 3 59 11 . 2 -- 1 2 1 2 2 0 0 0 1 3 60 11 . 2 -- 0 2 1 3 3 0 0 0 3 3 61 11 . 2 -- 0 0 0 1 0 0 0 0 0 3 62 11 . 2 -- 0 0 0 0 0 0 0 0 0 2 63 11 . 2 -- 0 1 0 3 2 0 2 0 2 3 64 11 . 2 -- 0 0 0 0 1 0 3 1 0 3 65 11 . 2 -- 0 3 0 1 1 0 2 0 0 3 66 11 . 2 -- 3 0 0 0 0 0 0 3 0 0 67 11 . 2 -- 0 2 0 0 0 0 1 n 0 0 68 11 . 2 -- 3 3 3 3 3 0 0 0 3 3 69 11 . 2 -- 3 0 3 3 2 0 0 0 1 3 70 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 71 11 . 2 0 1 3 3 3 3 0 1 1 2 3 72 11 . 2 1 0 3 3 3 3 0 3 0 3 3 73 11 . 2 0 3 0 3 1 1 0 3 3 3 3 74 11 . 2 0 3 0 3 3 3 0 3 0 3 3 75 11 . 2 0 3 1 3 3 3 0 1 0 3 3 76 11 . 2 -- 0 2 3 3 3 0 3 3 3 3 77 11 . 2 -- 0 2 3 3 3 0 3 0 3 3 78 11 . 2 -- 1 2 3 3 3 0 3 0 3 3 79 11 . 2 -- 0 1 3 3 3 0 3 1 3 3 80 11 . 2 -- 0 1 3 3 3 0 3 0 3 3 81 11 . 2 -- 0 3 3 3 3 1 3 0 3 3 82 11 . 2 -- 1 0 3 2 1 0 3 3 3 3 83 11 . 2 -- 0 1 3 3 3 0 3 0 3 3 84 11 . 2 -- 1 2 3 3 3 0 3 1 3 3 85 11 . 2 -- 1 3 3 3 3 2 3 3 3 3 86 11 . 2 -- 0 3 3 3 3 0 3 2 3 3 87 11 . 2 -- 0 1 1 1 1 0 0 n 1 3 88 11 . 2 -- 0 2 2 3 3 0 2 n 3 3 89 11 . 2 -- 0 3 3 3 3 0 2 2 3 3 90 11 . 2 -- 0 3 3 3 3 0 0 0 2 3 91 11 . 2 -- 0 2 3 3 1 0 0 n 2 3 92 11 . 2 -- 0 2 3 3 2 0 1 0 2 3 93 11 . 2 -- 0 0 1 3 3 0 0 0 3 3 94 11 . 2 -- 1 0 0 1 0 0 0 0 3 3 95 11 . 2 -- 1 2 3 3 3 0 3 2 3 3 96 11 . 2 -- 0 3 3 3 3 0 3 0 3 3 97 11 . 2 -- 0 2 3 3 3 0 3 3 3 3 98 11 . 2 3 1 3 3 3 3 1 3 2 3 3 99 11 . 2 -- 1 3 3 3 3 0 3 0 3 3 100 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 101 11 . 2 3 0 3 3 3 3 0 3 0 3 3 102 11 . 2 0 1 3 3 3 3 1 3 0 3 3 103 11 . 2 1 1 3 2 3 3 0 1 0 3 3 104 11 . 2 0 0 1 2 3 3 0 0 0 1 3 105 11 . 2 0 1 2 3 3 3 0 3 3 3 3 106 11 . 2 2 2 3 3 3 3 0 3 0 3 3 107 11 . 2 2 0 1 1 3 1 0 0 0 0 1 108 11 . 2 1 1 0 2 3 2 0 0 0 0 0 109 11 . 2 0 1 0 3 3 3 1 0 0 0 3 110 11 . 2 1 0 1 1 2 1 0 0 0 3 3 111 11 . 2 1 0 0 0 2 1 0 0 2 1 3 112 11 . 2 3 0 3 3 3 3 0 0 0 3 3 113 11 . 2 0 0 3 3 3 3 0 0 3 3 3 114 11 . 2 3 3 3 3 3 3 3 3 3 3 3 115 11 . 2 0 1 3 3 3 3 0 0 3 3 3 116 11 . 2 1 3 3 3 3 3 1 3 1 3 3 117 11 . 2 3 1 3 3 3 3 1 3 3 3 3 118 11 . 2 3 3 3 3 3 3 3 3 3 3 3 119 11 . 2 0 0 2 3 3 3 3 3 0 3 3 120 11 . 2 0 0 1 2 2 3 0 3 0 3 3 121 11 . 2 3 0 3 3 3 3 1 3 3 3 3 122 11 . 2 1 0 3 3 3 3 2 3 0 3 3 123 11 . 2 1 1 3 2 3 3 0 0 0 3 3 124 11 . 2 3 2 3 3 3 3 3 3 3 3 3 125 11 . 2 3 3 3 3 3 3 3 3 3 3 3 126 11 . 2 1 1 3 3 3 3 0 3 2 3 3 127 11 . 2 3 3 3 3 3 3 3 3 3 3 3 128 11 . 2 3 2 3 3 3 3 3 3 3 3 3 129 11 . 2 3 1 3 3 3 3 3 3 3 3 3 130 11 . 2 2 1 3 3 3 3 0 3 0 2 3 131 11 . 2 0 1 3 3 3 3 0 3 3 3 3 132 11 . 2 0 0 1 0 0 0 0 2 1 3 3 133 11 . 2 0 0 3 3 3 3 0 2 0 3 3 134 11 . 2 0 0 3 3 3 3 0 2 0 3 3 135 11 . 2 0 1 2 2 3 3 0 n 0 0 0 135 * 11 . 2 0 0 1 2 3 2 0 n 0 0 0 136 11 . 2 3 2 3 3 3 3 1 3 3 -- 3 137 11 . 2 3 1 0 1 2 2 0 3 -- 3 3 138 11 . 2 0 0 1 2 3 3 0 2 3 -- 3 139 11 . 2 0 0 0 1 0 0 0 0 0 0 3 140 11 . 2 3 0 0 2 0 0 0 0 n 0 0 141 11 . 2 0 0 0 2 3 3 0 0 n 3 3 142 11 . 2 3 3 3 3 3 3 2 3 3 -- 3 143 11 . 2 3 2 3 3 3 3 2 3 3 -- 3 144 11 . 2 3 0 3 3 3 3 1 3 3 -- 3 145 11 . 2 1 0 2 2 3 3 1 3 0 -- 3 146 11 . 2 3 1 3 3 3 3 2 3 3 -- 3 147 11 . 2 1 0 1 3 3 3 0 3 1 3 3 148 11 . 2 0 0 2 0 3 2 1 0 0 1 3 149 11 . 2 3 1 3 3 3 3 0 3 3 3 3 150 11 . 2 3 0 0 2 3 0 0 3 3 1 3 151 11 . 2 3 0 3 3 3 3 1 0 0 2 3 152 11 . 2 3 0 3 3 3 3 0 3 0 -- 3 153 11 . 2 2 0 3 3 3 3 0 0 0 2 3 154 11 . 2 3 2 3 3 3 3 3 3 3 3 3 155 11 . 2 3 0 1 3 3 2 0 0 0 0 3 156 11 . 2 3 3 3 3 3 3 2 3 3 3 3 157 11 . 2 3 0 3 3 3 3 1 3 1 3 3 158 11 . 2 0 0 3 3 3 3 0 3 0 3 3 159 11 . 2 0 0 0 0 3 1 0 3 1 3 3 160 11 . 2 0 0 0 0 0 0 0 1 0 0 3 161 11 . 2 3 0 3 3 3 3 0 0 0 -- 3 162 11 . 2 0 0 1 2 3 3 0 0 0 3 3 163 11 . 2 1 0 1 1 3 3 0 0 0 3 3 164 11 . 2 3 0 3 3 3 3 0 3 0 3 3 165 11 . 2 1 0 3 3 3 3 1 3 0 3 3 166 11 . 2 3 0 1 1 3 3 0 3 0 3 3 167 11 . 2 3 0 2 3 3 3 1 3 0 1 3 168 11 . 2 3 1 3 3 3 3 2 3 1 3 3 169 11 . 2 1 0 3 3 3 3 0 0 0 1 3 170 11 . 2 3 3 3 3 3 3 3 3 3 3 3 171 11 . 2 3 2 3 3 3 3 2 3 3 3 3 172 11 . 2 3 2 3 3 3 3 1 3 1 3 3 173 11 . 2 3 2 3 3 3 3 3 3 2 3 3 174 11 . 2 0 0 1 0 2 0 0 0 0 0 3 175 11 . 2 1 0 3 3 3 3 0 1 0 3 3 176 11 . 2 0 0 3 3 3 3 0 3 0 3 3 177 11 . 2 0 0 0 0 3 1 0 2 0 0 3 178 11 . 2 3 2 3 3 3 3 3 3 3 3 3 179 11 . 2 1 0 0 0 3 1 0 0 0 0 3 180 11 . 2 3 1 3 3 3 3 0 3 3 3 3 181 11 . 2 0 0 0 2 2 1 0 1 3 0 3 182 11 . 2 0 0 0 0 3 3 0 0 0 1 3 183 11 . 2 1 0 3 3 3 3 0 3 0 3 3 184 11 . 2 0 0 2 1 3 3 0 1 0 3 3 185 11 . 2 0 0 2 1 3 3 0 0 0 3 3 186 11 . 2 0 0 0 0 0 0 0 0 0 0 3 187 11 . 2 1 0 2 3 3 3 0 3 0 3 3 188 11 . 2 2 1 3 3 3 3 1 3 0 3 3 189 11 . 2 0 0 0 0 0 0 0 0 0 0 0 190 11 . 2 3 1 3 3 3 3 1 3 3 3 3 191 11 . 2 3 3 3 3 3 3 3 3 3 n 3 192 11 . 2 0 0 2 3 3 1 0 1 0 n 3 193 11 . 2 0 0 1 0 0 0 0 0 0 n 3 194 11 . 2 3 1 3 3 3 3 2 3 3 3 3 195 11 . 2 0 0 0 1 2 0 0 0 3 1 3 196 11 . 2 3 3 3 3 3 3 3 3 3 3 3 197 11 . 2 0 0 0 0 2 0 0 0 n 0 3 198 11 . 2 1 1 2 3 3 3 0 0 0 3 3 199 11 . 2 3 2 3 3 3 3 3 3 2 3 3 200 11 . 2 3 0 3 3 3 3 2 3 3 3 3 201 11 . 2 0 0 3 3 3 3 1 3 3 3 3 202 11 . 2 3 0 3 3 3 3 1 3 3 3 3 203 11 . 2 0 0 3 3 3 3 0 0 3 1 3 204 11 . 2 3 0 3 3 3 3 1 3 3 3 3 205 11 . 2 3 3 3 3 3 3 1 3 3 3 3 206 11 . 2 3 2 3 3 3 3 1 3 3 3 3 207 11 . 2 3 0 3 3 3 3 0 3 3 3 3 208 11 . 2 3 0 3 3 3 3 1 3 3 3 3______________________________________ the compounds were further tested by utilizing the above procedure on the following plant species , i . e ., on weeds in the presence of crop plants . ______________________________________l - soybean r - hemp sesbaniam - sugarbeet e - common lambsquartersn - wheat f - pennsylvania smartweedo - rice c - velvetleafp - grain sorghum j - downy bromeb - cocklebur s - panicum spp . q - wild buckwheat k - barnyardgrassd - morningglory t - large crabgrass______________________________________ table 3__________________________________________________________________________pre - emergent activity for weeds in crop plantsexample no . kg / ha l m n o p b q d r e f c j s k t__________________________________________________________________________ 1 5 . 6 0 3 0 0 2 0 0 1 1 3 3 1 1 2 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 0 0 . 28 0 0 0 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3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 28 2 3 3 3 3 0 3 3 2 3 3 2 3 3 3 3 0 . 056 2 0 1 2 3 0 3 0 1 2 1 1 2 3 3 3 0 . 0112 0 0 0 1 1 0 0 0 0 1 0 0 0 1 1 3128 5 . 6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 2 3 3 3 3 3 3 3 0 . 28 1 2 1 1 2 0 3 2 2 3 3 1 3 3 3 3 0 . 056 0 0 0 0 1 0 0 0 1 0 0 0 2 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0129 5 . 6 2 2 3 3 3 0 2 3 3 3 3 1 3 3 3 3 1 . 12 0 0 1 0 1 0 1 1 0 0 1 0 3 1 2 1 0 . 28 0 0 0 0 0 0 1 0 0 1 0 0 0 0 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0130 5 . 6 0 3 0 0 2 0 0 2 0 3 3 0 2 1 2 2 1 . 12 0 3 0 0 0 0 n2 0 2 1 0 2 0 0 0 0 . 28 0 1 0 0 0 0 1 0 0 0 0 0 2 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0131 5 . 6 0 0 3 2 3 0 0 0 0 0 0 0 3 3 3 3 1 . 12 0 0 1 0 2 0 0 0 0 0 0 0 3 1 2 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0132 5 . 6 0 1 3 1 0 0 0 0 1 2 1 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 2 1 0 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 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12 0 1 0 0 0 0 3 1 0 2 1 0 3 1 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0149 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 1 2 2 3 0 3 2 2 3 3 2 3 3 3 3 0 . 28 0 0 0 0 1 0 3 0 1 3 0 0 0 1 3 3 0 . 056 0 0 0 0 0 0 2 0 0 1 0 0 1 0 0 1 0 . 0112 0 0 0 0 0 0 2 0 0 1 0 0 1 1 0 1150 5 . 6 2 0 3 2 1 0 1 1 1 3 3 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0151 5 . 6 0 1 0 1 3 0 1 2 1 3 2 0 3 3 3 3 1 . 12 0 0 0 1 1 0 0 0 0 1 0 0 1 0 0 1 0 . 28 0 0 0 0 0 0 0 0 0 1 0 0 0 1 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0153 5 . 6 n 2 0 2 2 0 2 2 2 3 3 1 3 3 3 3 1 . 12 0 1 0 1 1 0 0 0 0 1 1 0 1 0 2 2 0 . 28 0 1 0 0 1 0 0 0 0 1 0 0 0 1 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1155 5 . 6 0 3 0 0 1 0 2 3 0 2 2 0 3 0 0 1 1 . 12 0 2 0 0 0 0 1 2 0 2 1 0 1 0 1 0 0 . 28 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0156 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 2 2 3 3 3 3 3 3 3 0 . 28 1 1 2 2 3 0 2 1 2 3 3 2 2 3 3 3 0 . 056 0 0 0 0 1 0 1 0 1 2 1 0 0 1 2 3 0 . 0112 0 0 0 0 0 0 0 0 0 1 0 0 0 0 1 1157 5 . 6 3 3 3 3 1 0 3 3 3 3 3 2 3 3 3 3 1 . 12 3 2 1 2 0 0 0 2 2 3 3 2 2 3 3 3 0 . 28 1 1 0 0 0 0 0 1 0 0 0 0 0 2 2 3 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0158 5 . 6 0 1 2 1 3 0 1 3 2 2 2 0 3 3 3 3 1 . 12 0 0 1 1 0 0 3 0 0 0 1 0 0 2 3 2 0 . 28 0 0 0 0 0 0 3 1 0 0 0 0 2 0 0 0 0 . 056 0 0 0 0 0 0 3 1 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 2 0 0 0 0 0 1 0 0 0159 5 . 6 0 0 1 1 2 0 1 2 1 1 2 0 2 3 3 3 1 . 12 0 0 0 0 0 0 1 1 0 1 0 0 0 0 0 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0160 5 . 6 0 1 1 0 0 0 0 0 0 0 0 0 1 0 2 0 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0162 5 . 6 0 1 0 0 3 0 0 1 1 3 2 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 n 0 0 1 0 0 0 2 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0163 5 . 6 0 0 0 0 1 0 1 n 1 3 2 0 2 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0164 5 . 6 2 3 1 0 3 0 3 3 3 3 3 2 3 3 3 3 1 . 12 0 1 0 0 2 0 0 n 0 3 1 1 3 3 3 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0165 5 . 6 0 3 3 3 3 0 1 2 2 3 3 2 3 3 3 3 1 . 12 0 1 0 1 2 0 0 1 0 0 1 0 2 3 3 3 0 . 28 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0166 5 . 6 3 2 3 0 2 0 3 1 0 3 3 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 n 0 2 1 0 0 0 0 2 0 . 56 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 014 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0167 5 . 6 1 3 1 2 0 0 2 2 0 3 2 1 3 0 1 2 1 . 12 0 1 0 0 0 0 1 0 0 2 0 0 1 0 0 0 0 . 28 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0168 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 3 2 2 3 0 3 3 2 3 3 2 3 3 3 3 0 . 28 0 0 1 1 0 0 0 1 0 3 1 0 2 2 3 3 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0169 5 . 6 0 3 0 1 0 0 1 0 0 3 1 0 1 1 0 3 1 . 12 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0170 5 . 6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 0 . 28 1 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 056 0 3 2 3 3 0 3 0 3 3 3 3 3 3 3 3 0 . 0112 0 2 0 0 1 0 1 0 0 3 2 1 0 1 3 3171 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 0 . 28 0 2 3 3 3 0 2 2 2 3 3 2 3 3 3 3 0 . 056 0 0 1 1 3 0 0 0 0 2 2 0 2 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 1 0 0 0 0 2 3172 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 28 0 2 2 2 3 0 2 0 1 3 3 1 3 3 3 3 0 . 056 0 0 0 1 0 0 1 0 0 0 0 0 2 2 2 3 0 . 0112 0 0 0 0 0 0 0 0 1 1 1 1 1 0 0 0173 5 . 6 3 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1 . 12 0 3 1 1 3 0 3 3 3 3 3 1 3 3 3 3 0 . 28 0 2 0 0 3 0 0 1 2 2 3 0 3 3 3 3 0 . 056 0 1 0 0 0 0 0 0 1 0 1 0 1 2 3 2 0 . 0112 0 0 0 0 0 0 0 n 0 0 1 0 0 0 0 0174 5 . 6 0 2 0 1 0 0 0 0 0 3 1 0 3 0 0 2 1 . 12 0 0 0 0 0 0 0 0 0 1 0 0 2 0 0 1175 5 . 6 0 3 1 1 3 0 0 1 1 2 3 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 1 0 2 1 3 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0176 5 . 6 1 3 3 3 3 0 3 2 3 3 3 2 3 3 3 3 1 . 12 0 3 2 1 3 0 2 0 1 3 2 0 3 3 3 3 0 . 28 0 1 0 0 0 0 0 0 0 0 0 0 3 0 2 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0177 5 . 6 2 3 1 1 0 0 2 0 1 3 2 1 3 1 3 3 1 . 12 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1178 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 0 . 28 0 3 1 1 3 0 3 2 2 3 3 0 3 3 3 3 0 . 056 0 0 0 0 0 0 3 0 0 0 0 0 3 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 2179 5 . 6 0 3 0 0 0 0 0 0 0 2 1 0 2 1 2 2 1 . 12 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0180 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 0 2 2 2 2 0 2 2 2 3 3 2 2 3 3 3 0 . 56 0 0 2 0 1 0 1 1 0 2 3 0 2 3 3 3 0 . 28 0 0 1 0 1 0 0 0 0 0 2 0 2 3 3 3 0 . 14 0 0 0 0 0 0 0 0 0 0 1 0 1 1 3 3 0 . 07 0 1 1 0 0 0 0 0 0 1 0 0 1 0 1 1 0 . 035 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0182 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0818 5 . 6 0 3 0 0 0 0 2 0 0 2 2 0 1 1 3 2 1 . 12 0 2 0 0 0 0 0 0 0 2 2 0 0 0 0 0 0 . 56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0182 5 . 6 0 1 0 1 3 0 1 1 1 2 2 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 1 0 0 0 2 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1183 5 . 6 1 3 3 3 3 0 3 2 3 3 3 1 3 3 3 3 1 . 12 0 0 2 1 3 0 0 1 1 2 1 n 1 3 3 3 0 . 28 1 0 0 0 1 0 0 0 0 0 1 0 0 0 3 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1184 5 . 6 1 0 1 0 2 0 0 0 0 0 2 0 2 3 3 3 1 . 12 0 0 1 0 0 0 0 0 0 0 1 0 0 0 1 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1185 5 . 6 0 1 0 1 3 0 1 1 1 0 2 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1186 5 . 6 0 3 0 1 0 1 0 2 2 2 2 1 1 0 1 3 1 . 12 0 2 0 0 0 0 0 0 1 2 2 1 0 0 0 1188 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 3 2 2 2 0 2 2 3 2 3 3 2 3 3 3 0 . 56 0 3 1 1 2 0 2 2 2 2 3 2 2 3 3 3 0 . 28 0 2 0 1 1 0 1 1 2 1 3 0 1 3 3 3 0 . 14 0 1 0 0 1 0 0 0 0 0 2 0 0 2 3 3 0 . 07 0 1 0 0 0 0 0 0 0 0 1 0 0 0 1 2190 5 . 6 1 3 1 2 2 1 3 2 2 3 3 2 3 3 3 3 1 . 12 1 3 1 1 1 1 2 1 0 3 2 1 3 2 3 3 0 . 56 0 0 1 0 1 0 2 0 0 1 1 0 2 1 1 2 0 . 28 0 1 1 1 0 0 2 0 0 0 0 0 0 0 0 0 0 . 14 0 1 0 0 0 0 2 0 0 0 0 0 0 0 0 1 0 . 07 0 1 0 0 0 0 2 0 0 1 0 0 2 0 0 1 0 . 035 0 1 2 1 0 0 1 0 0 1 1 0 1 0 0 0191 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 1 3 3 3 3 0 3 2 2 3 3 3 3 3 3 3 0 . 56 0 3 3 3 3 0 2 1 2 3 3 2 3 3 3 3 0 . 28 0 1 2 2 3 0 1 0 1 2 2 0 3 3 3 3 0 . 14 0 1 1 1 3 0 1 0 0 0 2 0 2 2 3 2 0 . 07 0 0 0 1 1 0 0 0 0 0 1 0 3 3 3 1 0 . 035 0 0 0 0 0 0 0 0 0 0 1 0 1 0 1 0 0 . 0182 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 009 0 0 0 0 0 0 0 0 0 0 0 n 0 0 0 0192 5 . 6 0 2 1 0 3 0 2 2 1 3 3 3 3 3 3 3 1 . 12 0 1 0 0 0 0 0 0 1 3 1 0 0 1 3 3 0 . 56 0 1 0 0 0 0 0 0 0 1 2 1 1 0 0 1 0 . 28 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 . 14 0 0 0 0 0 0 1 0 0 2 0 0 1 0 0 0193 5 . 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 . 12 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0__________________________________________________________________________ the post - emergence herbioidal activity of some of the various compounds of this invention was demonstrated by greenhouse testing in the following manner . top soil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0 . 95 to 1 . 27 cm . from the top of the pan . a predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and / or vegetative propagules for the perennial plant species were placed on the soil and pressed into the soil surface . the seeds and / or vegetative propagules are covered with soil and leveled . the pans are then placed on a bench in the greenhouse and watered from below as needed . after the plants reach the desired age ( two to three weeks ), each pan , is removed individually to a spraying chamber and sprayed by means of an atomizer , operating at a spray pressure of 170 . 3 kpa ( 10 psig ) at the application rates noted . in the spray solution is an amount of an emulsifying agent mixture to give a spray solution or suspension which contains about 0 . 4 % by volume of the emulsifier . the spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates of the active ingredient corresponding to those shown in the tables while applying a total amount of solution or suspension equivalent to 1870 l / ha ( 200 gallons / acre ). the pans were returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately 10 - 14 days ( usually 11 days ) and in some instances observed again at 24 - 28 days ( usually 25 days ) after spraying . these latter observations are designated by an asterisk (*) following the column of example numbers in the table . the post - emergent herbicidal activity index used in table 4 is as follows : ______________________________________plant response index______________________________________0 - 24 % inhibition 025 - 49 % inhibition 150 - 74 % inhibition 275 - 99 % inhibition 3100 % inhibition 4species not planted -- species planted , no data n______________________________________ table 4______________________________________post - emergent activity for weedsexample no . kg / ha a b c d e f g h i j k______________________________________ 1 11 . 2 0 0 0 0 0 0 0 0 0 0 0 2 11 . 2 0 0 0 0 0 0 0 0 0 0 0 3 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 4 11 . 2 0 0 0 0 0 0 1 0 -- 0 1 5 11 . 2 0 n 0 1 0 0 0 0 0 0 0 6 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 7 11 . 2 n 3 1 3 4 1 0 0 0 0 2 7 * 11 . 2 n 4 1 3 4 1 0 0 0 0 1 7 * 11 . 2 n 3 1 3 3 0 0 0 0 0 1 8 11 . 2 0 0 0 0 0 0 0 0 0 0 0 9 11 . 2 0 0 0 0 0 0 0 0 0 0 0 10 11 . 2 n 0 1 0 0 0 0 0 0 0 0 11 11 . 2 0 n 0 0 0 0 0 0 0 0 0 12 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 13 11 . 2 0 n 0 0 0 0 0 0 0 0 0 14 11 . 2 0 0 0 0 0 0 0 0 n 0 0 15 11 . 2 0 n 0 0 0 0 0 0 0 0 0 16 11 . 2 0 0 0 0 0 0 0 0 n 0 0 17 11 . 2 -- 0 1 1 n 0 0 0 0 0 1 18 11 . 2 -- 0 0 0 0 0 0 1 0 0 1 19 11 . 2 -- 0 0 0 0 0 0 0 1 0 0 20 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 21 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 22 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 23 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 24 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 25 11 . 2 n 0 0 1 1 0 1 1 0 0 1 26 11 . 2 -- 0 1 3 3 0 1 0 0 0 1 26 * 11 . 2 -- 1 0 3 3 0 0 0 0 0 1 27 11 . 2 -- 1 1 1 1 0 1 0 0 0 1 28 11 . 2 -- 1 0 1 3 0 0 0 0 0 0 29 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 30 11 . 2 -- 0 0 1 n 0 0 0 0 0 0 31 11 . 2 -- 0 0 1 0 0 0 0 0 0 1 32 11 . 2 -- 0 0 0 0 0 0 0 2 0 1 33 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 34 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 35 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 36 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 37 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 38 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 39 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 40 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 41 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 42 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 43 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 44 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 45 11 . 2 -- 0 0 1 1 0 0 0 0 0 0 46 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 47 11 . 2 -- 0 0 0 2 0 0 0 0 0 1 48 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 49 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 50 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 51 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 52 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 53 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 54 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 55 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 56 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 57 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 58 11 . 2 -- 0 0 0 1 0 0 0 0 0 1 59 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 60 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 61 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 62 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 63 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 64 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 65 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 66 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 67 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 68 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 69 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 70 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 71 11 . 2 0 1 1 1 1 0 0 0 0 0 0 72 11 . 2 0 0 0 0 0 0 0 0 n 0 0 73 11 . 2 n 0 0 0 0 0 0 0 0 0 0 74 11 . 2 n 0 0 0 0 0 0 0 0 0 0 75 11 . 2 0 0 0 0 0 0 0 0 0 0 0 76 11 . 2 0 0 0 0 0 0 0 0 0 0 0 77 11 . 2 0 0 0 0 0 0 0 0 0 0 0 78 11 . 2 0 0 0 0 0 0 0 0 0 0 0 79 11 . 2 0 0 0 0 0 0 0 0 0 0 0 80 11 . 2 0 0 0 0 0 0 0 0 0 0 0 81 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 82 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 83 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 84 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 85 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 86 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 87 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 88 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 89 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 90 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 91 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 92 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 93 11 . 2 -- 0 0 0 0 0 0 0 0 0 1 94 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 95 11 . 2 -- 0 1 0 0 0 0 1 0 0 0 96 11 . 2 -- 0 1 1 0 0 0 0 0 0 0 97 11 . 2 -- 0 0 0 1 0 0 0 0 0 0 98 11 . 2 -- 0 0 1 0 0 0 0 0 0 0 99 11 . 2 -- 0 1 1 0 0 0 1 0 0 0 100 11 . 2 -- 0 1 1 0 0 0 0 0 0 0 101 11 . 2 -- 0 0 n 0 0 0 0 0 0 1 102 11 . 2 -- 1 0 0 0 0 0 0 0 0 1 103 11 . 2 0 0 0 1 0 0 0 0 0 0 0 104 11 . 2 0 0 0 0 0 0 0 0 0 0 0 105 11 . 2 0 0 1 1 0 0 0 0 0 0 0 106 11 . 2 0 1 1 1 0 0 0 0 0 0 1 107 11 . 2 1 1 0 1 4 0 1 0 0 0 1 107 * 11 . 2 2 1 1 2 4 0 1 0 0 0 1 108 11 . 2 0 1 1 1 3 0 0 0 0 0 1 109 11 . 2 0 0 0 0 1 0 0 1 0 0 1 110 11 . 2 0 0 0 0 0 0 0 0 0 0 0 111 11 . 2 0 0 0 0 1 0 0 0 0 0 0 112 11 . 2 0 1 1 0 1 0 0 0 0 0 1 113 11 . 2 1 1 1 1 0 0 0 0 0 0 0 114 11 . 2 1 1 0 1 0 0 0 0 0 0 0 115 11 . 2 0 0 0 0 0 0 0 0 0 0 0 116 11 . 2 0 0 0 0 0 0 0 0 0 0 0 117 11 . 2 0 0 0 0 0 0 0 0 0 0 0 118 11 . 2 0 n 1 2 1 1 1 0 0 0 2 119 11 . 2 0 0 0 0 0 0 0 0 0 0 0 120 11 . 2 0 0 0 0 0 0 0 0 0 0 0 121 11 . 2 0 0 0 0 1 0 0 0 0 0 0 122 11 . 2 0 0 0 0 0 0 0 0 0 0 0 123 11 . 2 0 0 0 n 0 0 0 0 0 0 0 124 11 . 2 0 0 2 1 1 0 0 0 0 0 1 125 11 . 2 0 0 1 n 1 0 0 0 1 0 2 126 11 . 2 0 1 0 n 0 0 0 0 0 0 0 127 11 . 2 n 2 1 1 0 1 1 0 0 0 2 128 11 . 2 0 1 0 0 1 0 0 0 0 0 1 129 11 . 2 0 0 0 0 0 0 0 0 0 0 0 130 11 . 2 0 1 1 1 0 0 0 0 0 0 1 131 11 . 2 0 0 0 0 0 0 0 0 0 0 0 132 11 . 2 0 0 0 0 0 0 0 0 0 0 0 133 11 . 2 0 0 0 0 0 0 0 0 0 0 0 134 11 . 2 0 0 0 0 0 0 0 0 0 0 0 135 11 . 2 n 3 2 3 3 1 1 3 1 0 2 135 * 11 . 2 n 3 2 3 3 2 0 3 1 0 1 136 11 . 2 4 0 0 2 3 0 0 0 0 -- 0 137 11 . 2 n 0 0 0 0 0 0 0 0 0 0 138 11 . 2 0 0 0 0 4 0 0 0 0 -- 0 139 11 . 2 0 0 0 0 0 0 0 0 0 0 0 140 11 . 2 0 0 0 0 0 0 0 0 n 0 0 141 11 . 2 n 0 0 0 0 0 0 0 n 0 0 142 11 . 2 0 0 0 1 0 0 0 0 0 0 0 143 11 . 2 0 1 1 1 0 0 0 0 n 0 0 144 11 . 2 0 0 0 0 0 0 0 0 0 0 0 145 11 . 2 0 0 0 0 2 0 0 0 0 0 0 146 11 . 2 0 0 0 0 0 0 0 0 n 0 1 147 11 . 2 0 0 0 0 0 0 0 0 0 0 0 148 11 . 2 0 0 1 0 1 0 0 0 0 0 0 149 11 . 2 0 0 0 0 1 0 0 0 0 0 0 150 11 . 2 0 0 0 0 0 0 0 0 0 0 0 151 11 . 2 0 0 0 1 0 0 0 0 0 0 0 152 11 . 2 0 0 1 1 0 0 0 0 n 0 0 153 11 . 2 0 0 0 0 0 0 0 0 0 0 0 154 11 . 2 0 0 0 0 0 0 0 n 0 0 0 155 11 . 2 0 0 1 1 0 0 0 0 0 0 0 155 11 . 2 n 0 1 0 0 0 0 0 0 0 1 157 11 . 2 1 0 1 0 0 0 0 0 0 0 0 158 11 . 2 0 0 0 0 0 0 0 0 0 0 0 159 11 . 2 0 0 0 0 0 0 0 0 0 0 0 160 11 . 2 0 0 0 0 0 0 0 0 0 0 1 161 11 . 2 0 0 0 0 0 0 0 0 n 0 0 162 11 . 2 0 0 0 0 0 0 0 0 0 0 0 163 11 . 2 0 0 0 0 0 0 0 0 0 0 0 164 11 . 2 n 0 0 0 0 0 0 0 1 0 0 165 11 . 2 0 0 1 0 0 0 0 0 0 1 0 166 11 . 2 0 0 0 0 0 0 0 0 0 0 0 167 11 . 2 1 1 1 1 2 0 0 0 0 0 1 168 11 . 2 0 0 1 1 0 0 0 0 0 0 0 169 11 . 2 n 0 1 0 0 0 0 0 0 0 0 170 11 . 2 1 1 1 1 0 0 0 0 0 0 1 171 11 . 2 n 0 0 0 0 0 0 0 0 0 1 172 11 . 2 n 0 0 0 0 0 0 0 0 0 0 173 11 . 2 0 0 1 0 0 0 0 0 0 0 0 174 11 . 2 0 0 0 0 0 0 0 0 0 0 0 175 11 . 2 0 0 0 0 0 0 0 0 0 0 0 176 11 . 2 0 0 1 0 n 0 0 0 0 0 0 177 11 . 2 0 0 0 0 0 0 0 0 0 0 0 178 11 . 2 0 0 0 0 0 0 0 0 0 0 0 179 11 . 2 0 0 0 0 0 0 0 0 0 0 0 180 11 . 2 0 0 1 0 0 0 0 0 0 0 1 181 11 . 2 0 0 0 0 0 0 0 0 0 0 0 182 11 . 2 0 0 0 0 n 0 0 0 0 0 0 183 11 . 2 0 0 0 0 0 0 0 0 0 0 0 184 11 . 2 0 0 1 0 n 0 0 0 0 0 0 185 11 . 2 0 0 0 0 n 0 0 0 0 0 0 186 11 . 2 0 0 0 0 0 0 0 0 0 0 0 187 11 . 2 0 0 0 0 0 0 0 0 0 0 0 188 11 . 2 1 2 1 1 1 0 0 0 0 0 1 189 11 . 2 0 0 0 0 0 0 0 0 0 0 0 190 11 . 2 0 0 0 0 0 0 0 0 0 0 0 191 11 . 2 0 0 0 0 0 0 0 0 0 0 0 192 11 . 2 0 0 0 0 0 0 0 0 0 0 0 193 11 . 2 0 0 0 0 0 0 0 0 0 0 0 194 11 . 2 0 0 0 0 0 0 0 0 n 0 1 195 11 . 2 0 0 0 0 0 0 0 0 n 0 0 196 11 . 2 0 0 0 0 0 0 0 0 n 0 0 197 11 . 2 0 0 0 0 0 0 0 0 0 0 0 198 11 . 2 0 0 0 0 0 0 0 0 0 0 0 199 11 . 2 0 0 0 0 0 0 0 0 0 0 0 200 11 . 2 0 0 0 0 0 0 0 0 0 0 0 201 11 . 2 0 0 0 0 0 0 0 0 0 0 0 202 11 . 2 0 0 0 0 0 0 0 0 0 0 0 203 11 . 2 0 0 0 0 0 0 0 0 0 0 0 204 11 . 2 0 0 0 0 0 0 0 0 0 0 0 205 11 . 2 0 0 0 0 0 0 0 0 0 0 0 206 11 . 2 0 0 0 0 0 0 0 0 0 0 0 207 11 . 2 0 0 0 0 1 0 0 0 0 0 0 208 11 . 2 0 0 0 0 0 0 0 0 n 0 0______________________________________ as can be seen from the data above , some of the compounds appear to be quite safe on certain crops and can thus be used for selective control of weeds in these crops . the herbicidal compositions of this invention , including concentrates which require dilution prior to application , may contain at least one active ingredient and an adjuvant in liquid or solid form . the compositions are prepared by admixing the active ingredient with an adjuvant including diluents , extenders , carriers , and conditioning agents to provide compositions in the form of finely - divided particulate solids , granules , pellets , solutions , dispersions or emulsions . thus , it is believed that the active ingredient could be used with an adjuvant such as a finely - divided solid , a liquid of organic origin , water , a wetting agent , a dispersing agent , an emulsifying agent or any suitable combination of these . suitable wetting agents are believed to include alkyl benzene and alkyl naphthalene sulfonates , sulfated fatty alcohols , amines or acid amides , long chain acid esters of sodium isothionate , esters of sodium sulfosuccinate , sulfated or sulfonated fatty acid esters , petroleum sulfonates , sulfonated vegetable oils , ditertiary acetylenic glycols , polyoxyethylene derivatives of alkylphenols ( particularly isooctylphenol and nonylphenol ) and polyoxyethylene derivatives of the mono - higher fatty acid esters of hexitol anhydrides ( e . g ., sorbitan ). preferred dispersants are methyl , cellulose , polyvinyl alcohol , sodium lignin sulfonates , polymeric alkyl naphthalene sulfonates , sodium naphthalene sulfonate , and polymethylene bisnaphthalene sulfonate . wettable powders are water - dispersible compositions containing one or more active ingredients , an inert solid extender and one or more wetting and dispersing agents . the inert solid extenders are usually of mineral origin such as the natural clays , diatomaceous earth and synthetic minerals derived from silica and the like . examples of such extenders include kaolinites , attapulgite clay and synthetic magnesium silicate . the wettable powders compositions of this invention usually contain from above 0 . 5 to 60 parts ( preferably from 5 - 20 parts ) of active ingredient , from about 0 . 25 to 25 parts ( preferably 1 - 15 parts ) of wetting agent , from about 0 . 25 to 25 parts ( preferably 1 . 0 - 15 parts of dispersant and from 5 to about 95 parts ( preferably 5 - 50 parts ) of inert solid extender , all parts being by weight of the total composition . where required , from about 0 . 1 to 2 . 0 parts of the solid inert extender can be replaced by a corrosion inhibitor or anti - foaming agent or both . other formulations include dust concentrates comprising from 0 . 1 to 60 % by weight of the active ingredient on a suitable extender ; these dusts may be diluted for application at concentrations within the range of from about 0 . 1 - 10 % by weight . aqueous suspensions or emulsions may be prepared by stirring a nonaqueous solution of a water - insoluble active ingredient and an emulsification agent with water until uniform and then homogenizing to give stable emulsion of very finely - divided particles . the resulting concentrated aqueous suspension is characterized by its extremely small particle size , so that when diluted and sprayed , coverage is very uniform . suitable concentrations of these formulations contain from about 0 . 1 - 60 % preferably 5 - 50 % by weight of active ingredient , the upper limit being determined by the solubility limit of active ingredient in the solvent . concentrates are usually solutions of active ingredient in water - immiscible or partially waterimmiscible solvents together with a surface active agent . suitable solvents for the active ingredient of this invention include dimethylformamide , dimethylsulfoxide , n - methyl - pyrrolidone , hydrocarbons , and water - immiscible ethers , esters , or ketones . however , other high strength liquid concentrates may be formulated by dissolving the active ingredient in a solvent then diluting , e . g ., with kerosene , to spray concentration . the concentrate compositions herein generally contain from about 0 . 1 to 95 parts ( preferably 5 - 60 parts ) active ingredient , about 0 . 25 to 50 parts ( preferably 1 - 25 parts ) surface active agent and where required about 4 to 94 parts solvent , all parts being by weight based on the total weight of emulsifiable oil . granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert , finely - divided particulate extender . in order to aid leaching of the active ingredient from the particulate , a surface active agent such as those listed hereinbefore can be present in the composition . natural clays , pyrophyllites , illite , and vermiculite are examples of operable classes of particulate mineral extenders . the preferred extenders are the porous , absorptive , preformed particules such as preformed and screened particulate attapulgite or heat expanded , particulate vermiculite and the finely - divided clays such as kaolin clays , hydrated attapulgite or bentonitic clays . these extenders are sprayed or blended with the active ingredient to form the herbicidal granules . the granular compositions of this invention may contain from about 0 . 1 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay . the compositions of this invention can also contain other additaments , for example , fertilizers , other herbicides , other pesticides , safeners and the like used as adjuvants or in combination with any of the above - described adjuvants . chemicals useful in combination with the active ingredients of this invention included , for example , triazines , ureas , carbamates , acetamides , acetanilides , uracils , acetic acid or phenol derivatives , thiolcarbamates , triazoles , benzoic acids , nitriles , biphenyl ethers and the like such as : fertilizer useful in combination with the active ingredients include , for example ammonium nitrate , urea , potash and superphosphate . other useful additaments include materials in which plant organisms take root and grow such as compost , manure , humus , sand and the like . herbicidal formulations of the types described above are exemplified in several illustrative embodiments below . ______________________________________ weight percent______________________________________i . emulsifiable concentratesa . compound of example no . 3 11 . 0free acid of complex organic 5 . 59phosphate or aromatic oraliphatic hydrophobe base ( e . g ., gafac re - 610 , registeredtrademark of gaf corp .) polyoxyethylene / polyoxypropylene 1 . 11block copolymer with butanol ( e . g ., tergitol xh , registeredtrademark of union carbide corp .) pheno1 5 . 34monochlorobenzene 76 . 96 100 . 00b . compound of example no . 14 25 . 00free acid of complex organic 5 . 00phosphate of aromatic oraliphatic hydrophobe base ( e . g ., gafac re - 610 ) polyoxyethylene / polyoxypropylene 1 . 60block copolymer with butanol ( e . g ., tergitol xh ) phenol 4 . 75monochlorobenzene 63 . 65 100 . 00ii . flowablesa . compound of example no . 24 25 . 00methyl cellulose 0 . 3silica aerogel 1 . 5sodium lignosulfonate 3 . 5sodium n - methyl - n - oleyl taurate 2 . 0water 67 . 7 100 . 00b . compound of example no . 18 45 . 0methyl cellulose . 3silica aerogel 1 . 5sodium lignosulfonate 3 . 5sodium n - methyl - n - oleyl taurate 2 . 0water 47 . 7 100 . 00iii . wettable powdersa . compound of example no . 5 25 . 0sodium lignosulfonate 3 . 0sodium n - methyl - n - oleyl - taurate 1 . 0amorphous silica ( synthetic ) 71 . 0 100 . 00b . compound of example 21 80 . 00sodium dioctyl sulfosuccinate 1 . 25calcium lignosulfonate 2 . 75amorphous silica ( synthetic ) 16 . 00 100 . 00c . compound of example no . 6 10 . 0sodium lignosulfonate 3 . 0sodium n - methyl - n - oleyl - taurate 1 . 0kaolinite clay 86 . 0 100 . 00iv . dustsa . compound of example no . 13 2 . 0attapulgite 98 . 0 100 . 00b . compound of example no . 10 60 . 0montmorillonite 40 . 0 100 . 00c . compound of example no . 54 30 . 0ethylene glycol 1 . 0bentonite 69 . 0 100 . 00d . compound of example no . 62 1 . 0diatomaceous earth 99 . 0 100 . 00v . granulesa . compound of example no . 52 15 . 0granular attapulgite ( 20 / 40 mesh ) 85 . 0 100 . 00b . compound of example no . 70 30 . 0diatomaceous earth ( 20 / 40 ) 70 . 0 100 . 00c . compound of example no . 58 1 . 0ethylene glyco1 5 . 0methylene blue 0 . 1pyrophyllite 93 . 9 100 . 00d . compound of example no . 46 5 . 0pyrophyllite ( 20 / 40 ) 95 . 0 100 . 00______________________________________ when operating in accordance with the present invention , effective amounts of the compounds of this invention are applied to the soil containing the seeds , or vegetative propagules or may be incorporated into the soil media in any convenient fashion . the application of liquid and particulate solid compositions to the soil can be carried out by conventional methods , e . g ., power dusters , boom and hand sprayers and spray dusters . the compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages . the exact amount of active ingredient to be employed is dependent upon various factors , including the plant species and stage of development thereof , the type and condition of soil , the amount of rainfall and the specific compounds employed . in selective preemergence application or to the soil , a dosage of from about 0 . 02 to about 11 . 2 kg / ha , preferably from about 0 . 1 to about 5 . 60 kg / ha , is usually employed . lower or higher rates may be required in some instances . one skilled in the art can readily determine from this specification , including the above examples , the optimum rate to be applied in any particular case . the term &# 34 ; soil &# 34 ; is employed in its broadest sense to be inclusive of all conventional &# 34 ; soils &# 34 ; as defined in webster &# 39 ; s new international dictionary , second edition , unabridged ( 1961 ). thus , the term refers to any substance or media in which vegetation may take root and grow , and includes not only earth but also compost , manure , muck , humus , sand , and the like , adapted to support plant growth . although the invention is described with respect to specific modifications , the details thereof are not to be construed as limitations .