Abstract:
There is provided a new class of derivatives of 2-nitro-5-(substituted-phenoxy) benzoyl compounds that have pre- and post-emergence herbicidal activity. The derivatives include certain substituted phenyl esters, phenyl thioesters; heterocyclic esters; substituted alkyl and alkylthio esters; carbonates and thiocarbonates; benzoyl phosphonates; substituted alkanones and substituted amides.

Description:
CROSS-REFERENCES TO RELATED APPLICATIONS 
     This is a division of application Ser. No. 282,316 filed July 10, 1981, which is a continuation-in-part application No. Ser. No. 117,732 filed Feb. 1, 1980, now abandoned. 
    
    
     Applicant Theissen herein has been granted a series of patents relating to 2-nitro-5-(substituted-phenoxy) benzoic acid derivatives including the salt, alkyl and cycloalkyl esters, alkylthio esters, phenyl ester, alkyl and dialkyl amido and benzoyl chloride forms. Illustrative of those patents are U.S. Pat. Nos. 3,652,645; 3,784,635; 3,873,302; 3,983,168 and 3,907,866. 
     BRIEF SUMMARY OF THE INVENTION 
     This invention provides certain herbicidal compounds falling within the general formula: ##STR1## wherein X 1  is halogen, X 2  is selected from halogen and hydrogen, and Z is a polyhalo 1-9  alkyl 1-4  group such as CF 3 , CHF 2 , C 4  F 9 , CF 2  CH 2  CH 3  and CH 2  Cl. Preferably, X 1  is chloro, Z is CF 3  and X 2  is hydrogen. QA in the formula includes certain groups more fully described below. 
    
    
     DETAILED DESCRIPTION 
     The specific 2-nitro-5-(substituted-phenoxy) benzoyl compounds are described below. One method for preparing these compounds is the use of the Ullman ether synthesis reaction between the alkali metal (e.g., Na, K) salt of a suitable substituted phenol, e.g., m-hydroxy benzoic acid or m-cresol with an active halogen-substituted aromatic, e.g., 3,4-dichlorobenzotrifluoride. The intermediate obtained may be nitrated and subsequently derivatized by known procedures to the desired benzoyl compound. Where m-cresol is used as a starting material, the product obtained can be oxidized and subsequently nitrated before the aforementioned derivatization. 
     A. Substituted phenyl esters, phenylthio ester, substituted phenylthio esters 
     Illustrative compounds of this class are those of the formula: ##STR2## where 
     Q is O or S, 
     n is an integer from 1 to 5, and 
     X is selected from NO 2  ; lower alkyl of C 1-4  ; halogen; phenyl; COOR where R is lower alkyl of C 1-4 , H or a cation selected from alkali metals, alkaline earth metals, ammonium and lower alkyl and di-lower alkyl ammonium; CN; lower alkyl thio of C 1-4  ; lower alkoxy of C 1-4  ; trifluoromethyl; and combinations thereof. X can be hydrogen when Q is sulfur. 
     Compound 1 
     Preparation of 2,4-dinitro-6-sec-butylphenyl 5-[-2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate. 
     To a stirred solution of 2,4-dinitro-6-sec-butylphenol (3.60 g, 0.015 mole) and 5-[-2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (5.68 g, 0.015 mole) in toluene (25 ml) was added triethylamine (1.50 g, 0.015 mole). The temperature exothermed to 45° C. and there was an immediate precipitation of triethylamine hydrochloride. The reaction was stirred and heated to 110° F. for 15 hours. The precipitate was filtered from the cooled solution, washed and dried to give triethylamine hydrochloride (1.8 g). The toluene solution was washed with 10% sodium hydroxide (3×25 ml). The toluene was then stripped off on a rotary evaporator to give 5.5 g (62%) of a crude brown oil which slowly crystallized. Recrystallization from methanol gave 2.1 g of an off white solid, mp. 109°-110° C. 
     I.R. (nujol): C═O, 1765 cm -1   
     NMR (D6 Acetone): triplet 0.9 ppm (3H, J=7.0 Hz): doublet 1.37 ppm (3H, J=7.0 Hz): multiplet 1.82 ppm (2H); multiplet 3.35 ppm (1H); multiplet 7.5-8.2 (5H); doublet 8.45 ppm (1H, J=9.0 Hz); doublet 8.82 ppm (1H, J=2.4 Hz); doublet 9.02 ppm (1H, J=2.4 Hz). 
     In a similar manner the following compounds were prepared as defined according to Formula II: 
     
         ______________________________________    Q          Phenyl SubstitutionCompound (O or S)   X.sub.n        m.p., °C.______________________________________2        O          2-NO.sub.2     137-93        O          3-NO.sub.2     93.54        O          4-NO.sub.2     115-75        O          5-CH.sub.3 --2NO.sub.2                              88-906        O          2-Cl--4NO.sub.2                              99-1017        O          4-Cl           135-78        O          4-Cl--2-CH.sub.3                              121-29        O          2-Cl--4-CH.sub.3                              105-710       O          2-Cl--4-phenyl 128-3011       O          2,4-(Cl).sub.2 144-712       O          4-COOCH.sub.3  103-613       O          4-CN           103-514       O          4-SCH.sub.3    94-515       O          3-OCH.sub.3    95-716       O          4-OCH.sub.3    128-917       O          3-CF.sub.3     oil18       O          4-COONa        215-2019       O          4-COOH         191-820       S          H              oil21       S          4-Cl           128-3022       S          4-CH.sub.3     90-323       S          4-OCH.sub.3    oil24       S          3,4-(Cl).sub.2 oil______________________________________ 
    
     Other compounds of this class include: 
     
         ______________________________________ ##STR3##       Compound______________________________________ ##STR4##      2,6-diethylphenyl 5-[2-chloro-4- (trifluoromethyl)          phenyoxy]-2- nitrobenzoate ##STR5##      S[2-carboxyphenyl) 5-[2-chloro- 4-(trifluoromethyl)          phenoxy]-2- nitrobenzenecarbothioate ##STR6##      4-cyano-2,6-dibromophenyl 5-[2-chloro-4-(trifluoromethyl)          phenoxy]-2-nitrobenzoate ##STR7##      3,6-dichloro-2-methoxycarbonyl- phenyl 5-[2-chloro-4-          (trifluoromethyl) phenoxy]-2- nitrobenzoate ##STR8##      (2,6-di-6-butyl) phenyl 5-[2- chloro-4-(trifluoromethyl)          phenoxy]-2-nitrobenzoate ##STR9##      pentachlorophenyl 5-[2-chloro- 4-(trifluoromethyl)          phenoxy]-2- nitrobenzoate______________________________________ 
    
     B. Heterocyclic Esters 
     Illustrative compounds of this class are those of the formula: ##STR10## where Q is O or S and Het is a substituted or unsubstituted heterocyclic ring of 5 to 7 members comprising carbon in combination with one or more of sulfur, oxygen and nitrogen where a carbon atom on the ring is bound directly to Q. 
     Compound 25 
     Preparation of 3-pyridyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate: To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (3.79 g, 0.01 mole) and triethyl amine (1.01 g, 0.01 mole) in toluene (50 ml) was added 3-hydroxypyridine (0.95 g, 0.01 mole). The temperature exothermed to 33° C. and there was an immediate precipitate. The reaction was then refluxed for 24 hours, cooled to room temperature and the triethylamine hydrochloride precipitate collected by filtration. The toluene solution was washed with dilute sodium hydroxide solution and then with saturated sodium chloride solution. After drying and evaporation of the solvent there was obtained 3.1 g of brown oil which solidified. This was triturated with hexane and the solid filtered and dried to give a tan product, m.p. 65°-68° C. 
     I.R. (nujol): C═O, 1765 cm -1   
     NMR(D 6  -acetone): complex multiplet 7.2-8.1 ppm (7H); doublet 8.50 ppm (1H, J=4.5 Hz); multiplet 8.75 ppm (2H). 
     Compound 26 
     This compound is defined in accordance with Formula III as &#34;Q&#34; is O and &#34;Het&#34; is ##STR11## The compound was prepared by the procedure shown for Compound 25. Compound 26 has an m.p. of 153°-161° C. 
     Other compounds of this class include: 
     
         ______________________________________QHet            Compound Name______________________________________ ##STR12##      3-(1,2,5 thiadiazoloyl)-5-[2- chloro-4-trifluoromethyl)           phenoxy]-2-nitrobenzoate ##STR13##      1,2-dihydro-1,6-dimethyl-2-oxo 4-pyridinyl 5-[2-chloro-4-           trifluoromethyl) phenoxy]-2- nitrobenzoate ##STR14##      6(2,3-dihydro-3-oxo-pyridazinyl) 5-[2-chloro-4-(trifluorom           ethyl) phenoxy]-2-nitrobenzoate ##STR15##      2-chloro-6-pyridinyl 5-[2-chloro- 4-(trifluoromethyl)           phenoxy]-2- nitrobenzoate ##STR16##      s-(2,6-dichloro-4-s-triazinyl) 5-[2-chloro-4-(trifluoromet           hyl) phenoxy]-2-nitrobenzoate ##STR17##       S(2-methyl 1,3,4,-thiadiazol- 5-yl) 5-[2-chloro-4-trifluo           ro- methyl) phenoxy]-2-nitrobenzene- carbothioate ##STR18##      S(2-pyridinyl) 5-[-2-chloro-4- (trifluoromethyl)           phenoxy]-2- nitrobenzenecarbothioate Noxide ##STR19##      S[4-methyl-3-thioxo-3H1,2- dithiol-5-yl] 5-[2-chloro-4-           (trifluoromethyl) phenoxy]-2- nitrobenzene-carbothioate ##STR20##      S[3,5-bis-(diethylamino)-s-tri- azinyl] 5-[2-chloro-4-(tri           fluoro- methyl) phenoxy]-2-nitrobenzene- carbothioate______________________________________ 
    
     Substituted C 1-4  Alkyl Esters 
     Illustrative compounds of this class are those of the formula: ##STR21## wherein the substituents on the straight or branched C 1-4  alkyl group are selected from cyano; phenyl; ##STR22## where n is 1 to 5 and X is selected from NO 2 , lower alkyl or C 1-4 , halogen, phenyl, CN, lower alkyl thio of C 1-4 , lower alkoxy of C 1-4 , trifluoromethyl and combinations thereof; ##STR23## phenoxy; nitro; SR 1  ; SOR 1  ; SO 2  R 1  ; where R 1  is an alkyl of 1 to 3 carbons and R 2  is an alkyl or alkenyl of up to 3 carbons and wherein one or more of said substituents can be attached to any one or more of the carbons on said straight or branched C 1-4  alkyl group. 
     The compounds of this class may be prepared by the methods shown above or alternatively by displacement of an active halogen (e.g., Haloalkyl X) with the salt of an acid (e.g., ##STR24## 
     The following substituted C 1-4  alkyl esters as defined by Formula IV were prepared: 
     
         ______________________________________Compound   Substituted Alkyl Group                        m.p. °C.______________________________________27      C(CH.sub.3).sub.2 CN oil28      CH(CH.sub.3)CN       oil29      CH.sub.2 COCH.sub.3  83-530    ##STR25##           oil  31    ##STR26##           oil  32    ##STR27##           oil  33    ##STR28##           oil  34    CH.sub.2CH.sub.2CN   oil35  36    ##STR29##           86-8  37    ##STR30##           112-3  38    CH.sub.2 C(CH.sub.3).sub.2NO.sub.2                        oily semisolid39      CH.sub.2CH.sub.2SCH.sub.3                        oil40      CH.sub.2CH.sub.2SO.sub.2 CH.sub.3                        97-9______________________________________ 
    
     Other compounds of this class include: 
     
         ______________________________________Substituted alkyl          Compound Name______________________________________CH.sub.2SCH.sub.2 CH.sub.3          (ethylthio)methyl 5-[2-chloro-4-          (trifluoromethyl) phenoxy]-2-          nitro-benzoate ##STR31##     (ethylsulfinyl)methyl 5-[2-chloro- 4-(trifluoromethyl)          phenoxy]-2- nitro-benzoate ##STR32##     (ethylsulfinyl)methyl 5-[2-chloro- 4-(trifluoromethyl)          phenoxy]- 2-nitrobenzoate ##STR33##     1-acetylethyl 5-[2-chloro-4-tri- fluoromethyl)          phenoxy]-2-nitro- benzoate ##STR34##     3-acetylpropyl 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-n          itrobenzoate ##STR35##     2-(methylsulfinyl) ethyl 5-[2- chloro-4-(trifluoromethyl)          phenoxy]-2-nitrobenzoate ##STR36##     (3-fluorophenyl) methyl 5-[2-chloro-4-(trifluoromethyl)          phenoxy]-2-nitrobenzoate______________________________________ 
    
     D. Carbonates and Thiocarbonates 
     Illustrative compounds of this class are those of the formula: ##STR37## where Q is O or S and Y is a straight or branched alkoxy or alkylthio of 1 to 6 carbons, a dialkylamino of 2 to 6 carbons, or a heterocyclic amine such as morpholine. 
     Compound 41 
     Preparation of S[(ethylthio)carbonyl]5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate. 
     To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid (3.0 g, 0.0083 mole) in ether (15 ml) was added triethylamine (0.84 g, 0.0083 mole). A precipitate formed. The reaction was cooled to 4° C. and a solution of ethylchlorothioformate (1.03 g, 0.0083 mole) in ether was added dropwise. Cooling was maintained during initial exotherm. The reaction was then stirred at room temperature for twenty hours. The precipitate of triethyl amine hydrochloride was filtered. The ether was washed consecutively with 10% hydrochloric acid solution, 5% sodium hydroxide solution and water. The dried solution was evaporated to give 3.04 g of a yellow oil. 
     I.R. (neat): C═O, 1675 and 1800 cm -1   
     NMR (CDCl 3 ): triplet 1.37 ppm (3H, J=7.0 Hz); quartet 3.12 ppm (2H, J=7.0 Hz); complex multiplet 7.0-8.0 ppm (5H); doublet 8.15 ppm (1H, J=9.6 Hz). 
     In a similar manner, the following compounds, as defined in accordance with Formula V, were prepared: 
     
         ______________________________________Compound Q       Y             m.p. °C.______________________________________42       O       OCH.sub.3     oil43       O       OCH.sub.2 CH.sub.3                          oil44       O       OCH.sub.2 CH.sub.2 CH.sub.3                          oily semi-solid45       O       OCH(CH.sub.3).sub.2                          oily semi-solid46       O       OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                          oil47       O       OCH.sub.2 CH(CH.sub.3).sub.2                          oil48       S       OCH.sub.3     oil49       S             ##STR38##    137-8°______________________________________ 
    
     S[(propylthio)thionocarbonyl]5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzenecarbothioate is a further illustrative compound of this class wherein Q is S and Y is --SC 3  H 7 . 
     Benzoyl Phosphonates 
     Illustrative compounds of this class are those of the formula: ##STR39## where R 3  is straight or branched alkyl of 1 to 6 carbons. 
     Compound 50 
     Preparation of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl-phosphonic acid, diisopropyl ester. 
     To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (3.8 g, 0.01 mole) in ether (100 ml) was added triisopropyl phosphite (2.1 g, 0.01 mole). The reaction was refluxed for one hour and the disappearance of phosphite monitored by v.p.c.. The ether was stripped off and the resulting oil placed under vacuum (1.0 mm) at 40° C. for two hours. The resulting amber liquid amounted to 5.2 g. 
     I.R. (neat): C═O, 1692 and 1730 cm -1   
     NMR (CDCl 3 ): doublet 1.29 ppm (3H, J=6.0 Hz); doublet 1.37 ppm (3H, J=6.0 Hz); multiplet 4.88 ppm (1H); complex multiplet 6.9-8.0 ppm (5H); broad doublet 8.37 ppm (1H, J=9.0 Hz). 
     In a similar manner, the following compound was prepared as an additional example of a benzoyl phosphonate. 
     Compound 51 
     5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoy-phosphonic acid diethyl ester was prepared and was an oil. 
     F. Substituted Alkanone Compounds 
     Illustrative compounds of this class are those of the formula: ##STR40## where A is an alkyl of 1-3 carbons or hydrogen. 
     Compound 52 
     Preparation of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl ethanone (A is --CH 3 ). 
     A stirred solution of 3-[2-chloro-4-(trifluromethyl)phenoxy]phenyl ethanone (15.7 g, 0.05 mole) in dichloroethane (40 ml) was cooled to 0.5° C. Nitric acid (95%) (4.95 g, 0.075 mole) was added, followed by the dropwise addition of 95% sulfuric acid (12.3 g, 0.125 mole) while maintaining the temperature below 5°-10° C. Allowed reaction to warm to room temperature. The progress of the reaction was monitored by v.p.c. The reaction solution was poured onto ice water and the organic solution separated, washed with water and dried. The solvent was evaporated to give 16 g of a brown oil, which was extracted with hot heptane. Upon cooling, the heptane solution furnished an oil fraction which solidified to give 8.8 g of a brown solid, m.p. 58°-60° C. 
     I.R. (nujol mull): C═O, 1710 cm -1  ; NO 2 , 1530 and 1315 cm -1 . 
     Compound 53 
     5-[2-chloro-4-trifluoromethyl)phenoxy]-2-nitrobenzaldehyde (&#34;A&#34; is hydrogen in Formula VII) was prepared. It had a melting point of 99°-100° C. 
     G. Amides 
     Illustrative compounds of this class include those of the formula: ##STR41## wherein 
     R 4  is selected from hydrogen and straight or branched chain alkyl of 1-4 carbon: 
     R 5  is selected from: phenyl; ##STR42## where n is 1 to 5 and X is selected from NO 2 , lower alkyl of C 1-4 , halogen, phenyl, COOR where R is lower alkyl of C 1-4  or H or a cation, CN, lower alkyl thio of C 1-4 , lower alkoxy of C 1-4 , trifluoromethyl and combinations thereof; heterocyclicalkyl and heterocyclic, heterocyclics of a 5 to 7 member ring comprising carbon in combination with one or more of sulfur, oxygen and nitrogen; hydroxyl; alkoxy of 1-3 carbons; --R 6  CO 2  R 6 , where R 6  is an alkyl or alkenyl of up to 3 carbons; --R 6  CONH 2  ; R 6  CON(R 2 ) 2  ; alkoxyalkyl where the alkoxy and alkyl may each contain a straight or branched C 1-3  alkyl chain; or 
     where R 4  and R 5  together form a heterocyclic ring as hereinabove defined. 
     Compound 54 
     Preparation of N-phenyl 5-[2-chloro-4-(trifluoromethyl)phenoxyl]-2-nitrobenzamide. 
     To a stirred solution of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride (5.68 g, 0.015 mole) in toluene (35 ml) was added aniline (2.8 g, 0.30 mole). The temperature immediately rose to 45° C. The reaction was then heated to reflux for twelve hours. The cooled reaction was poured into dilute hydrochloric acid solution. The residual solids were filtered, washed with warm water and dried to give 4.1 g of a gray solid m.p. 190°-4° C. Recrystallization from methanol gave 3.8 g, m.p. 191°-4° C. 
     I.R. (nujol): C═O, 1660 cm -1   
     NMR (D 6  -Acetone): complex multiplet 7.0-8.1 ppm (10H); doublet 8.32 ppm (1H, J=9.0 Hz); broad singlet 9.95 ppm (1H). 
     In a similar manner, the following compounds were prepared: 
     
         ______________________________________Compound R.sub.4   R.sub.5         m.p. °C./oil______________________________________55       H               ##STR43##      145-8  56     H               ##STR44##      179-81  57     H               ##STR45##      155-8  58     H               ##STR46##      169-71  59     H               ##STR47##      185-7  60     CH(CH.sub.3).sub.2               ##STR48##      144-6  61     H               ##STR49##      140-1  62     H         OH              oil  63     H         OCH.sub.3       171-4  64     CH.sub.3  OH              oil  65     CH.sub.3  OCH.sub.3       oil  66     H         CH.sub.2 COOC.sub.2 H.sub.5                              136-7  67     H               ##STR50##      oil68       H               ##STR51##      160-3  69     H         CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                              86-8  70     H         CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                              102-4  71     H               ##STR52##      158-60______________________________________Compound R.sub.4 and R.sub.5   m.p. °C./oil______________________________________72     ##STR53##            107-8  73     ##STR54##            128-32  74     ##STR55##            124-6  75     ##STR56##            169-72  76     ##STR57##            oil  77     ##STR58##            125-8______________________________________ ##STR59##        Compound Name______________________________________ ##STR60##       N[2-(5-t-butyl-1,3,4 thiadia- zolyl)]5-[2-chloro-4-(trifl            uoro- methyl)phenoxy]-2-nitro- benzamide ##STR61##       5-[2 chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl            2,5-dioxopyrolidine ##STR62##       N[2-(4,6,6-trimethyl-1,3- thiazinyl)]5-[2-chloro-4-(tri-            luoromethyl)phenoxy]-2-nitro benzamide ##STR63##       N(carboxymethyl)5-[2- chloro-4-(trifluoro- methyl)phenoxy            ]-2-nitro benzamide ##STR64##       Ncarboxymethyl-Nmethyl 5-[2-chloro-4-(tri- fluoromethyl)p            henoxy]-2- nitrobenzamide ##STR65##       N(2,5-dichloro-3-methoxy- carbonyl)phenyl 5-[2-chloro-4-            trifluoromethyl)phenoxy]- 2-nitrobenzamide ##STR66##       N[4-[6-(1,1-dimethylethyl)-3- methylthio-1,2,4-triazin-5(            4H) onyl]]5-[2-chloro-4-(trifluoro- methyl)phenoxy]-2-            nitrobenzamide ##STR67##       N(3,4-dimethyl-2,6- dinitrophenyl)- N(1-methylethyl)            5-[2-chloro-4-(tri- fluoromethyl)phenoxy]- 2-nitrobenzami            de ##STR68##       N[2,6-dinitro-4-(tri- fluoromethyl)phenyl]- Nethyl            5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzamid            e______________________________________ 
    
     H. Other Benzoyl Compounds 
     The following 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-benzoyl compounds do not readily fall within the defined classes A-G above and are therefore listed below: 
     Compund 78 
     2-chloro-cyclohexyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate (oil). 
     Compound 79 ##STR69## [m.p. 134°-6° C.] 
     Compound 80 
     S-(4-chloro-benzyl) 5-[(2-chloro-4-trifluoromethyl)phenoxy]-2-nitro-benzene carbothioate. [oil] 
     Compound 81 ##STR70## 
     Additional illustrative compounds are listed below according to the structural formula: 
     
         __________________________________________________________________________ ##STR71##QA                  Compound Name__________________________________________________________________________ ##STR72##          4-(2,4-difluorophenyl)-2-(methoxy- carbonyl)phenyl               5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoa               te ##STR73##          4-(ethoxycarbonylethyl)-2-hydroxy- phenyl 5-[2               chloro-4(tri- fluoromethyl)phenoxy]-2- nitrobenzoate ##STR74##          3,5-dinitro-4-dipropylaminophenyl 5-[2-chloro-4-(trifl               uoromethyl) phenoxy]-2-nitrobenzoate ##STR75##          2,6-bis(hydroxymethyl)-4-methyl- phenyl               5-[2-chloro-4-(trifluoro- methyl)phenoxy]-2-nitrobenzo               ate ##STR76##          3-(1,2,5,6-diisopropylidene-D-  glucosyl)5-[2-chloro-4               -(tri- fluoromethyl)phenoxy]-2-nitro- benzoate ##STR77##          2-chloro-9-(methoxycarbonyl) 9Hfluoran-9-yl               5-[2-chloro-4- (trifluoromethyl)phenyl]-2- nitrobenzoa               te ##STR78##          α-benzoyl (phenylmethyl)5-[2- chloro-4-(trifluor               omethyl)phenoxy]- 2-nitrobenzoate ##STR79##          2-(acetylamino)ethyl 5-[2-chloro- 4-(trifluoromethyl)p               henoxy]-2- nitrobenzoate ##STR80##          2-(2-methylpropanoyl- amino)ethyl 5-[ 2-chloro-4-               (trifluoromethyl)phenoxy]- 2-nitrobenzoate ##STR81##          [3-(dimethylamino)-2-methyl propionyloxy]ethyl 5-[2-               chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoate ##STR82##          2-(2-methylpropenoyloxy)-2- methylethyl               5-[2-chloro-4-(tri- fluoromethyl)phenoxy]-2-nitro-               benzoate ##STR83##          (1-cyano-1 methyl)ethoxymethyl 5-[2-chloro-4-(trifluor               omethyl) phenoxy]-2-nitrobenzoate ##STR84##          (ethoxycarbonyl)(acetyl)methyl 5-[2-chloro-4-(trifluor               omethyl) phenoxy]-2-nitrobenzoate ##STR85##          diethoxyphosphonylmethyl 5-[2- chloro-4-(trifluorometh               yl)phenoxy]- 2-nitrobenzoate ##STR86##          dimethoxyphosphonylethyl 5-[2- chloro-4-(trifluorometh               yl)phenoxy]- nitrobenzoate ##STR87##          dimethoxyphosphonylethoxy ethyl 5-[2-chloro-4-(tri-               fluoromethyl) phenoxy]-2-nitrobenzoate ##STR88##          2-(chloroacetyl)ethyl 5-[2-chloro- 4-(trifluoromethyl)               phenoxy]-2- nitrobenzoate  OCHF.sub.2        difluoromethyl 5-[2-chloro-               4-(trifluoromethyl)phenoxy]-2-               nitrobenzoate ##STR89##          propenoylaminomethyl 5-[2-chloro- 4-(trifluoromethyl)p               henoxy]- 2-nitrobenzoate ##STR90##          cyano(ethoxycarbonyl)methyl 5-[2- chloro-4-(trifluorom               ethyl)phenoxy]- nitrobenzoate ##STR91##          4-(3-chlorophenylcarbamoyloxy) butyn-2-yl               5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzo               ate ##STR92##          N(Chloroacetyl)-N(2,6-diethyl- phenylamino)methyl               5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoa               te  OCH.sub.2 CHCHCN  3-cyanopropen-2-yl               5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrobenzoateSCN                 5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrobenzoic acid               anhydride with thiocyanic acid ##STR93##          S(phenylsulfonylaminoethyl)5-[2- chloro-4-(trifluorome               thyl)phenoxy] 2-nitrobenzenecarbothioate ##STR94##          S(2,3-Dihydroxypropyl)5-[2-chloro- 4-(trifluoromethyl)               phenoxy]-2- nitrobenzenecarbothioate  SCH.sub.2 COOC.sub.2 H.sub.5               S(ethoxycarbonylmethyl)5-[2-               chloro-4-(trifluoromethyl)               phenoxy]-2-nitrobenzenecarbothioate  SCH.sub.2 COOH    S(carboxymethyl)5-[2-chloro-4-               (trifluoromethyl)phenoxy]-2-               nitrobenzenecarbothioate ##STR95##          S[(3-fluorophenyl)methyl]5-[2- chloro-4-(trifluorometh               yl)phenoxy]- 2-nitrobenzenecarbothioate ##STR96##          S[(ethylthiocarbonyl)methyl] 5-[2-chloro-4-(trifluorom               ethyl) phenoxy]-2-nitrobenzene- carbothioate ##STR97##          S[2,3-dihydroxypropoxycarbonyl) methyl]5-[2-chloro-4-(               trifluoro- methyl)phenoxy]-2-nitro- benzenecarbothioat               e  SCH.sub.2 CHCHCOOC.sub.2 H.sub.5               S[(3-ethoxycarbonyl)propen-2-yl]               5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrobenzene-               carbothioate ##STR98##          1,1 dimethyl-2,2,2-trichloro- ethoxycarbonyl               5-[2-chloro-4- (trifluoromethyl)phenoxy]-2- nitrobenzo               ate ##STR99##          5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoy               l Oethylphosphonic acid ammonium salt  CCl.sub.3         1-{5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrophenyl}2,2,2,-               trichloroethanone  CF.sub.3          1-{5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrophenyl}2,2,2,-               trifluoroethanone ##STR100##         dimethyl 5-[2-chloro-4-trifluoro- methyl)phenoxy]-2-ni               trobenzoyl- methylphosphonate ##STR101##         {5-[2-chloro-4-(trifluoromethyl) phenoxy]2-nitrophenyl               }4-methoxy- 3-methylphenyl methanone ##STR102##         1-{5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrophe               nyl}2-(di- methoxyphosphonylmethyl- amino)ethanone   CN               5-[2-chloro-4-(trifluoromethyl)               phenoxy]-2-nitrobenzoyl cyanide__________________________________________________________________________ 
    
     
         ______________________________________Miscellaneous - AmideQA              Compound Name______________________________________NHCH.sub.2 CH(OCH.sub.3).sub.2           N(2,2-dimethoxyethyl)5-           [2-chloro-4-trifluoromethyl)           phenoxy]-2-nitrobenzamide ##STR103##     N(carboxymethyl)-N (phosphonomethyl)5-[2-chloro-4-           (trifluoromethyl)phenoxy]-2- nitrobenzamide ##STR104##     N(carboxymethoxy)5-[2-chloro-4- (trifluoromethyl)phenoxy]-           2- nitrobenzamide ##STR105##     N(1-methylethyl)-N phenylmethyl)5-[2-chloro-4- (trifluorom           ethyl)phenoxy]-2- nitrobenzamide ##STR106##     3{5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl}           4-chloro- 2-oxobenzothiazoline ##STR107##     N[1,3-dihydroxy-2-methylpropyl) 5-[2-chloro-4-(trifluorome           thyl) phenoxy]-2-nitrobenzamide ##STR108##     N(diethoxyphosphonyl)5-[2- chloro-4-(trifluoromethyl)pheno           xy]- 2-nitrobenzamide  NHCH.sub.2 CH.sub.2 SO.sub. 3 Na           N(2-sulfoethyl)5-[2-chloro-4-           (trifluoromethyl)phenoxy]-2-           nitrobenzamide sodium salt  NHCH.sub.2 SO.sub.3 C.sub.6 H.sub.13           N(2-hexyloxysulfonyl)ethyl           5-[2-chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzamide ##STR109##     N(trifluoroacetyl)5-[2-chloro-4- (trifluoromethyl)phenoxy]           -2- nitrobenzamide ##STR110##     N(4-sulfophenyl)5-[2-chloro- 4-(trifluoromethyl)phenoxy]-2           - nitrobenzamide  NHC(CH.sub.3).sub.2 CN           N[(1-cyano-1-methyl)-2-ethyl]           4-[2-chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzamide ##STR111##     N(ethoxycarbonyl)5-[2-chloro- 4-(trifluoromethyl)phenoxy]-            2-nitrobenzamide ##STR112##     N[2-methyl-4-(phenylsulfonyl) phenyl]5-[2-chloro-4-(triflu           oro- methyl)phenoxy]-2-nitrobenzamide ##STR113##     N(4-aminophenylsulfonyl)-N (methoxycarbonyl) 5-[2-chloro-4           -(trifluoromethyl) phenoxy]-2-nitrobenzamide  NHCHNOH       N[(hydroxyimino)methyl]           5-[2-chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzamide  NHNH.sub. 2   5-[2-chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzoic acid           hydrazide ##STR114##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoic           acid methyl hydrazide ##STR115##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl(2-           chloro- acetyl)hydrazide ##STR116##     5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoyl           2-(carbox- amido)hydrazide  NHCN          5-[2-chloro-4-(trifluoromethyl)-           phenoxy]-2-nitrobenzoylcyanamide ##STR117##     5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoylcy           anamide sodium salt  N.sub.3       5-[2-chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzoyl amide  ONCHNH.sub.2  aminomethyleneamino 5-[2-chloro-           4-(trifluoromethyl)phenoxy]-2           nitrobenzoate  ONC(CH.sub.3).sub.2           1-methylethylideneimino 5-[2-           chloro-4-(trifluoromethyl)           phenoxy]-2-nitrobenzoate ##STR118##     1-(methylthio)ethylideneamino 5[2-chloro-4-(trifluoromethy           l) phenoxy]-2-nitrobenzoate______________________________________ 
    
     Primary Herbicide Screening 
     The compounds of this invention can be applied in various ways to achieve herbicidal action. They can be applied per se, as solids or in vaporized form, but are preferably applied as the toxic components in pesticidal compositions of the compound and a carrier. These compositions are preferably applied directly to the soil and often incorporated therewith. The compositions can be applied as granulars or dusts; as liquid sprays, or as gas-propelled sprays and can contain, in addition to a carrier, additives such as emulsifying agents, binding agents, gases compressed to the liquid state, odorants, stabilizers, and the like. A wide variety of liquid and solid carriers can be used. Non-limiting examples of solid carriers include talc, bentonite, diatomaceous earth, pyrophyllite, fullers earth, gypsum, flours derived from cotton seeds and nut shells, and various natural and synthetic clays having a pH not exceeding about 9.5. Non-limiting examples of liquid carriers include water, organic solvents such as alcohols, ketones, light oils, and medium oils and vegetable oils such as cottonseed oil. 
     In practice, herbicidal application is measured in terms of pounds of herbicide applied per acre. The compounds of this invention are effective herbicides when applied in herbicidal amounts, i.e., at rates between about 0.03 pounds and about 10 pounds per acre. 
     HERBICIDAL EFFECTIVENESS 
     Method of Propagating Test Species 
     Crop and weed species are planted in 8&#34;×10&#34; disposable fiber flats containing potting soil to provide each flat with a 4&#34; row of all test species. Crop species consist of field corn (CN), crabgrass (CG), cotton (CT), and soybeans (SB). The weed species consist of foxtail millet (FM), green foxtail (CF), velvetleaf (VL), cocklebur (CB), wild mustard (WM) and pigweed (FW). 
     Cotton, corn, soybean, and cocklebur plantings consist of 4 to 5 seeds per row depending upon species. The smaller seeded species (velvetleaf, wild mustard, pigweed, foxtail millet and green foxtail) are planted in an uncounted but sufficient number to provide a solid row of seedlings. 
     Plantings for the pre- and post-emergence portions of the test are identical as to seeding. The initial watering until emergence is done from the top. The post-emergence phase is propagated in advance so as to provide plants of the proper stage of development at the time of treatment. Plantings for the pre-emergence phase are made not more than one day in advance of treatment. 
     The desired stage of development for treatment of the post-emergence broadleaf species (CT, SB, CB, VL, WM, PW) is the one true leaf or first trifoliate leaf stage. The desired stage for corn would be a height of 3-4&#34;, while a 2&#34; height would be adequate for the grasses. 
     Method of Treatment 
     Spray applications are made with a handgun sprayer (aspirator type) simultaneously to one flat of established plants for the post-emergence phase and one newly seeded flat for the pre-emergence phase. The 10 lb./acre treatment rate consists of the uniform application of 116 milligrams of test compound to the combined area of the two flats (160 sq. inches). Application is made in a solvent mixture consisting of 40 ml acetone and 40 ml water and a surfactant concentration of 0.1%. 
     Following spray application, flats are returned to the greenhouse where watering of the post-emergence phase is done only by subirrigation. The pre-emergence phase is top watered by sprinkling until after test species have emerged. Subsequent watering is by-subirrigation. 
     Two weeks after treatment, the pre- and post-emergence injury and control is rated on a 0-100% injury and control scale. Special physiological effects are rated as to intensity also at this time. 
     The herbicidal test data reported for compounds 1-81 was obtained at application rates of 10 lbs. down to 1/4 lb./acre. The following lists the metric equivalents for each rate. 
     
         ______________________________________Application RateUS - lb./acre Metric - kg/ha______________________________________10.0          11.24.0           4.482.0           2.241.0           1.120.5           0.560.25          0.28______________________________________ 
    
     Test results are set forth in Table I (pre-emergence) and Table II (post-emergence). 
     
                                           TABLE I__________________________________________________________________________   DosageCpd.   Lbs./  Pre-EmergenceNo.   Acre  CG  FM  GF  VL  CB  WM  PW  CT CN SB__________________________________________________________________________1  10  --  100 90  90  0   100 100 10 0  0   4   --  100 90  20  --  100 --  0  0  0   2   --  100 60  10  --  100 70  0  10 10   1   --  90  90  30  0   100 100 20 0  10   1/2 --  90  80  0   0   90  100 20 0  10   1/4 --  90  70  30  0   90  80  0  10 02  10  --  20  20  10  0   70  90  0  0  0   4   --  --  --  --  --  --  --  -- -- --   2   --  --  --  --  --  --  --  -- -- --   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --3  10  --  90  90  0   0   90  100 0  0  0   4   --  100 90  30  20  90  100 10 0  0   2   --  60  10  0   10  30  80  -- 0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --4  10  --  100 90  90  20  100 100 10 0  10   4   --  100 90  0   --  100 --  0  0  10   2   --  90  40  0   --  70  60  0  0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --5  4   --  90  90  70  30  100 100 60 0  0   2   --  90  90  10  40  100 100 20 0  10   1   --  70  10  0   0   70  100 0  0  10   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --6  4   --  100 90  70  20  100 100 0  40 0   2   --  100 90  10  0   100 100 40 0  0   1   --  90  60  0   40  90  90  30 0  0   1/2 --  70  80  10  0   50  90  10 0  10   1/4 --  20  0   10  10  30  0   0  20 107  4   --  0   0   0   0   100 100 40 0  0   2   --  70  20  0   0   0   70  0  0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --8  10  --  0   0   0   0   0   0   0  30 0   4   --  --  --  --  --  --  --  -- -- --   2   --  --  --  --  --  --  --  -- -- --9  4   --  0   0   0   --  10  60  10 0  0   2   --  --  --  --  --  --  --  -- -- --   1   --  --  --  --  --  --  --  -- -- --   1/2 --  10  0   0   0   50  60  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --10 4   --  10  10  10  0   0   0   10 10 10   2   --  --  --  --  --  --  --  -- -- --11 10  --  0   0   0   0   0   0   0  0  0   4   --  --  --  --  --  --  --  -- -- --12 4   --  100 90  90  60  100 100 40 10 0   2   --  100 90  40  10  100 100 10 30 0   1   --  100 90  0   0   100 100 0  0  0   1/2 --  70  30  10  0   90  90  30 0  0   1/4 --  20  20  0   0   20  60  60 60 3013 10  --  90  90  100 80  100 100 90 10 10   4   --  90  90  70  10  90  90  10 20 0   2   --  90  70  30  0   90  90  0  0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --14 4   --  70  50  10  0   70  60  0  20 0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --15 4   --  100 90  40  20  90  90  10 0  0   2   --  90  90  10  0   90  90  0  0  0   1   --  70  60  10  0   20  80  20 0  10   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --16 4   --  90  50  10  0   90  70  10 10 0   2   --  80  10  10  0   70  0   0  0  10   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --17 4   --  100 90  40  0   100 100 0  10 0   2   --  90  90  30  0   90  90  30 0  10   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --18 10  --  100 80  70  0   100 100 10 0  0   2   --  100 40  20  10  100 100 10 0  10   1/2 --  90  20  0   10  100 90  10 10 30   1/4 --  10  10  40  10  80  60  10 0  019 10  --  100 100 80  60  100 100 30 60 0   2   --  100 70  40  10  100 100 20 10 10   1/2 --  100 60  0   0   100 60  10 0  0   1/4 --  10  10  60  20  70  50  20 0  2020 4   --  90  80  50  0   100 90  0  0  0   2   --  80  20  10  20  90  20  0  0  10   1   --  0   0   0   0   0   20  30 10 10   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --21 4   --  80  60  20  0   30  20  10 20 20   2   --  --  --  --  --  --  --  -- -- --22 4   --  90  80  20  0   90  90  0  10 0   2   --  80  70  20  0   80  60  0  20 0   1   --  90  20  10  20  30  10  40 10 50   1/4 --  --  --  --  --  --  --  -- -- --23 4   --  80  0   10  0   90  30  10 0  0   2   --  70  10  30  0   70  10  0  0  0   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --24 4   --  90  70  60  10  90  90  0  0  10   2   --  80  70  40  0   70  80  0  0  0   1/2 --  0   10  0   0   0   10  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --25 4   --  100 90  90  20  100 100 10 40 10   2   --  90  90  80  40  100 100 40 10 20   1   --  100 90  10  0   90  90  0  0  0   1/2 --  90  70  0   0   90  70  10 0  10   1/4 --  10  20  10  0   20  20  0  0  026 2   --  40  40  20  70  90  70  0  0  10   1/2 --  10  0   10  0   90  40  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --27 2   --  90  90  80  0   100 100 10 0  0   1/2 --  70  50  40  0   90  100 0  0  0   1/4 --  50  10  0   0   70  10  0  0  028 2   --  90  90  90  20  100 100 50 10 20   1/2 --  90  90  20  0   100 100 10 0  0   1/4 --  60  20  0   --  50  80  10 0  029 2   --  100 100 40  10  100 100 0  0  20   1/2 --  100 90  0   0   100 90  10 0  0   1/4 --  10  40  60  0   90  90  0  0  030 1/2 10  60  --  30  --  90  90  -- -- --   1/4 10  40  --  10  --  10  --  -- -- --31 2   --  60  50  10  0   80  90  30 20 0   1/2 --  10  0   10  0   10  50  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --32 2   --  90  70  0   0   100 100 10 0  10   1/2 --  90  90  0   0   90  80  0  0  10   1/4 --  30  10  0   0   10  0   0  0  033 2   --  100 90  50  0   90  90  10 10 40   1/2 --  80  10  0   0   20  10  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --34 2   --  100 100 10  30  90  90  30 10 0   1/2 --  20  20  20  10  80  20  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --36 2   --  50  20  40  --  20  90  10 20 30   1/2 --  0   0   0   --  20  50  10 10 10   1/4 --  --  --  --  --  --  --  -- -- --37 2   --  60  60  0   --  80  20  0  0  0   1/2 --  0   0   0   --  0   0   0  0  0   1/4 --  --  --  --  --  --  --  -- -- --38 2   --  100 90  50  10  100 100 60 0  0   1/2 --  90  50  0   0   50  40  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --39 2   --  90  90  70  20  100 100 10 20 0   1/2 --  90  70  10  10  100 100 0  0  040 2   --  100 90  90  0   100 100 10 10 0   1/2 --  90  70  20  0   100 90  10 0  041 2   --  100 90  40  0   100 90  10 0  0   1/2 --  90  30  0   0   90  70  0  0  0   1/4 --  0   0   0   0   10  10  0  0  042 2   --  100 100 90  70  100 100 90 20 30   1/2 --  100 100 80  60  100 100 90 20 30   1/4 --  80  90  10  0   60  90  10 0  1043 1/2 90  90  --  50  0   90  100 -- -- --   1/4 60  90  --  50  --  10  --  -- -- --44 2   --  100 100 90  30  100 100 60 20 30   1/2 --  90  90  80  10  100 100 20 10 20   1/4 --  20  0   0   0   90  20  0  0  1045 2   --  100 100 70  10  100 100 10 10 0   1/2 --  90  80  10  0   100 100 0  0  0   1/4 --  90  10  0   0   80  90  0  0  046 2   --  100 90  20  10  100 90  10 0  0   1/2 --  90  90  10  30  90  70  10 0  0   1/4 --  30  20  0   0   0   0   0  0  047 2   --  100 90  90  20  100 100 30 10 0   1/2 --  100 90  20  10  100 100 10 0  0   1/4 --  20  0   0   0   90  90  20 10 048 2   --  100 100 70  100 100 0   0  0  0   1/2 --  100 90  30  0   90  60  40 0  049 2   --  90  90  60  0   90  100 0  0  0   1/2 --  20  0   10  10  100 90  0  0  1050 2   --  90  90  90  50  100 100 50 10 30   1   --  90  90  20  0   100 90  0  0  0   1/2 --  80  70  10  0   100 90  10 10 20   1/4 --  90  70  20  10  90  80  0  0  051 10  --  100 100 100 50  100 100 10 30 0   4   --  100 100 90  60  100 100 20 10 20   2   --  90  90  70  10  100 100 20 0  10   1   --  100 100 10  0   100 100 0  0  10   1/2 --  90  50  0   10  70  40  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --52 10  100 100 --  90  --  100 --  -- -- --   1   60  70  --  60  0   90  --  -- -- --   1/2 40  80  --  50  10  80  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --53 10  --  90  90  50  --  100 100 50 10 0   4   --  90  90  30  --  100 100 10 0  0   1   --  90  60  0   --  90  90  0  0  0   1/2 --  10  0   10  --  20  90  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --54 4   --  0   0   0   0   0   0   0  0  0   2   --  --  --  --  --  --  --  -- -- --   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --55 4   --  0   20  40  10  90  100 60 0  20   2   --  0   0   0   0   0   0   0  0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --56 4   --  0   0   30  --  70  100 30 0  0   2   --  --  --  --  --  --  --  -- -- --57 4   --  10  0   0   --  70  90  0  0  0   2   --  --  --  --  --  --  --  -- -- --   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --58 4   --  30  0   0   --  10  100 0  0  0   2   --  --  --  --  --  --  --  -- -- --   1   --  --  --  --  --  --  --  -- -- --59 10  --  0   0   0   --  0   100 0  0  060 10  --  0   0   10  0   10  70  0  0  0   4   --  --  --  --  --  --  --  -- -- --61 2   --  50  20  60  10  90  80  20 10 20   1/2 --  0   0   0   0   50  0   0  0  0   1/4 --  --  --  --  --  --  --  -- -- --62 4   90  100 --  80  --  100 100 -- -- --   1   90  40  --  70  --  100 100 -- -- --   1/2 40  0   --  10  0   80  --  -- -- --63 4   90  90  --  100 --  100 100 -- -- --   1   60  40  --  70  --  90  0   -- -- --   1/2 20  0   --  20  0   10  0   -- -- --64 4   90  90  --  90  --  100 100 -- -- --   2   90  90  --  50  --  100 90  -- -- --   1   20  0   --  40  0   90  0   -- -- --   1/2 0   20  --  0   0   70  70  -- -- --65 4   80  90  --  90  --  100 --  -- -- --   2   --  30  70  20  0   80  100 0  0  0   1   --  90  70  80  0   90  90  10 10 0   1/2 --  10  10  50  0   100 100 0  0  0   1/4 --  30  10  10  0   70  80  0  0  066 4   90  90  --  100 --  100 100 -- -- --   1   70  40  --  70  --  100 100 -- -- --   1/2 0   10  --  20  0   60  0   -- -- --67 4   90  90  --  90  --  100 100 -- -- --   2   60  70  --  60  --  90  90  -- -- --   1   0   0   --  10  0   40  0   -- -- --   1/2 0   0   --  40  10  90  20  -- -- --68 10  100 90  --  100 --  100 100 -- -- --   4   --  100 90  90  60  100 100 0  10 0   2   --  90  90  90  10  100 100 20 20 20   1   --  90  30  90  0   100 100 40 0  0   1/2 --  70  80  70  50  100 100 10 0  0   1/4 --  80  60  0   0   100 100 20 0  --69 2   --  100 90  60  50  100 100 10 40 20   1/2 --  100 90  10  10  100 100 0  0  10   1/4 --  0   60  10  10  80  80  10 50 1070 2   --  100 90  50  50  100 100 10 10 20   1/2 --  100 90  10  30  100 100 20 0  10   1/4 --  0   10  50  0   90  90  0  40 8071 2   --  90  50  40  0   90  80  10 10 10   1/2 --  10  10  0   0   10  90  10 0  10   1/4 --  --  --  --  --  --  --  -- -- --72 10  --  90  90  --  20  90  90  -- 40 70   2   --  90  90  70  0   100 100 10 20 0   1   --  90  80  0   0   90  80  10 0  0   1/2 --  20  0   10  --  90  90  20 20 10   1/4 --  30  0   10  --  70  80  0  20 1073 10  --  100 90  90  30  100 100 20 60 0   4   --  100 90  80  60  100 90  50 70 10   2   --  80  70  70  10  100 10  10 0  0   1   --  90  60  10  0   90  60  20 0  10   1/2 --  90  50  0   0   90  80  0  0  074 2   --  90  90  70  0   100 100 10 10 0   1/2 --  90  70  0   0   90  50  10 0  0   1/4 --  0   0   10  0   70  70  10 0  1075 2   --  60  20  0   0   50  80  0  0  0   1   --  --  --  --  --  --  --  -- -- --   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --76 2   --  80  40  80  0   70  70  20 60 10   1/2 --  10  10  0   0   70  70  10 0  0   1/4 --  --  --  --  --  --  --  -- -- --77 2   --  100 90  10  0   100 90  0  0  0   1/2 --  90  70  0   10  90  60  10 0  078 10  90  90  --  100 --  100 --  -- -- --   4   --  90  90  90  0   100 100 0  0  0   2   --  90  90  80  0   90  100 10 0  0   1   --  40  60  60  10  100 100 0  0  0   1/2 --  50  70  0   --  90  90  0  0  0   1/4 --  80  50  20  0   90  60  10 30 079 10  70  90  --  50  --  90  --  -- -- --   1/4 0   0   --  0   --  0   --  -- -- --80 4   --  100 90  40  20  90  90  0  20 10   2   --  90  80  10  10  90  10  10 10 10   1   --  10  0   0   0   70  20  0  0  0   1/2 --  --  --  --  --  --  --  -- -- --   1/4 --  --  --  --  --  --  --  -- -- --81 2   --  80  50  0   0   90  80  0  0  0   1/2 --  10  0   0   0   10  60  0  0  0   1/4 --  --  --  --  --  --  --  -- -- --__________________________________________________________________________ 
    
     
                                           TABLE II__________________________________________________________________________   DosageCpd.   Lbs./  Post-EmergenceNo.   Acre  CG  FM  GF  VL  CB  WM  PW  CT  CN  SB__________________________________________________________________________1  10  --  100 100 100 100 100 100 100 80  60   4   --  90  90  100 100 100 100 90  60  50   2   --  100 100 100 --  100 --  90  50  20   1   --  100 90  100 --  100 100 90  30  50   1/2 --  100 90  90  90  100 100 80  70  10   1/4 --  50  50  40  80  100 100 60  50  402  10  --  90  90  90  80  90  100 90  10  10   4   --  100 90  90  60  90  90  90  10  10   2   --  90  90  90  80  100 100 90  20  20   1   --  90  90  80  90  90  100 90  70  70   1/2 --  80  70  60  90  100 100 90  80  30   1/4 --  90  70  70  80  100 80  90  50  603  10  --  90  90  90  90  100 100 100 30  30   4   --  100 100 90  90  100 100 90  30  10   2   --  100 90  100 90  100 100 90  90  20   1   --  90  90  90  90  100 100 80  70  60   1/2 --  90  90  90  90  100 90  90  90  60   1/4 --  90  80  90  80  100 100 90  30  104  10  --  100 100 100 100 100 100 100 90  50   4   --  100 100 100 --  100 --  100 90  30   2   --  90  90  100 100 100 100 100 20  20   1   --  100 100 100 --  100 100 100 40  50   1/2 --  100 90  90  90  100 100 100 70  10   1/4 --  50  70  30  50  90  100 40  30  505  4   --  100 90  100 100 100 100 90  0   40   2   --  90  90  100 --  100 --  90  10  20   1   --  90  90  100 0   100 100 90  50  10   1/2 --  80  70  90  80  100 100 90  20  20   1/4 --  60  60  50  70  90  100 60  30  606  4   --  100 100 100 100 100 100 100 10  60   2   --  100 100 100 100 100 100 90  80  40   1   --  70  80  70  70  100 100 60  70  60   1/2 --  90  90  90  90  100 90  80  80  20   1/4 --  80  60  80  50  90  70  90  10  107  4   --  100 80  100 80  100 100 80  0   20   2   --  90  30  100 --  90  100 90  10  20   1   --  90  70  100 --  90  100 90  --  40   1/2 --  90  90  100 --  90  100 90  10  50   1/4 --  90  90  90  50  100 100 60  30  408  10  --  90  80  100 60  90  100 40  0   20   4   --  60  30  --  --  70  --  70  20  0   2   --  80  70  50  --  70  70  90  0   109  4   --  90  90  100 40  90  100 90  10  20   2   --  90  90  90  --  90  100 90  10  30   1   --  90  90  100 80  100 100 90  0   10   1/2 --  100 90  90  70  100 100 80  10  10   1/4 --  70  80  30  50  90  100 50  50  4010 4   --  80  20  70  10  90  50  90  40  10   2   --  50  50  70  0   90  70  90  70  3011 10  --  90  90  70  30  80  100 40  0   10   4   --  30  20  30  20  70  90  80  30  1012 4   --  90  90  100 90  100 100 90  20  10   2   --  100 100 90  100 100 100 100 70  40   1   --  100 100 100 100 100 100 100 60  10   1/2 --  100 100 90  80  100 100 80  80  60   1/4 --  90  90  90  70  100 100 90  60  5013 10  --  90  90  100 100 100 100 90  80  20   4   --  100 100 100 100 100 100 100 90  90   2   --  100 100 90  90  100 100 100 90  50   1   --  90  90  90  70  100 100 90  70  50   1/2 --  90  90  80  70  100 100 90  70  60   1/4 --  90  80  80  80  100 90  90  60  6014 4   --  90  90  90  80  100 100 90  30  20   1   --  90  90  80  10  90  90  90  70  40   1/2 --  90  90  70  70  90  90  80  70  20   1/4 --  80  80  70  50  90  100 80  50  7015 4   --  90  100 100 90  100 100 100 60  10   2   --  90  90  90  90  100 90  90  70  30   1   --  90  90  80  60  90  100 90  50  30   1/2 --  90  90  90  90  100 100 90  50  30   1/4 --  90  70  60  50  70  90  70  50  7016 4   --  90  90  60  50  100 100 90  50  10   2   --  30  40  60  30  90  80  70  50  80   1   --  70  60  70  70  90  90  90  60  70   1/2 --  90  70  70  80  100 100 90  60  40   1/4 --  60  40  60  30  90  100 60  50  5017 4   --  100 100 100 90  100 100 90  70  30   2   --  100 100 100 90  100 100 100 80  40   1   --  90  90  80  60  90  100 70  70  40   1/2 --  90  90  90  90  90  90  90  70  10   1/4 --  80  80  80  50  90  60  90  40  1018 10  --  100 100 100 90  100 100 90  90  90   2   --  90  90  100 90  100 100 90  90  80   1/2 --  90  90  100 70  100 100 80  70  60   1/4 --  90  70  90  50  100 100 70  70  5019 10  --  100 100 100 90  100 100 90  80  40   2   --  90  90  100 100 100 100 90  60  40   1/2 --  90  90  90  90  100 100 90  80  40   1/4 --  90  70  70  40  100 100 50  60  2020 4   --  90  90  90  80  100 100 90  40  20   2   --  70  80  90  70  90  90  90  60  40   1   --  80  60  70  70  90  80  90  50  20   1/2 --  20  20  60  30  90  90  90  30  30   1/4 --  50  40  40  40  100 50  50  40  5021 4   --  80  70  90  40  90  90  90  50  20   2   --  10  20  70  70  80  70  70  30  3022 4   --  90  90  90  70  90  100 90  80  30   2   --  80  80  90  20  90  100 90  80  50   1   --  90  90  70  40  90  --  60  50  70   1/4 --  50  60  10  10  80  80  50  10  1023 4   --  90  90  80  60  90  100 90  80  80   2   --  90  90  90  70  90  --  90  40  40   1/2 --  20  20  20  10  90  80  80  10  10   1/4 --  70  70  30  20  80  70  80  10  3024 4   --  100 100 100 90  100 100 90  90  90   2   --  100 100 100 80  100 --  90  50  70   1/2 --  60  50  70  20  80  100 90  20  30   1/4 --  70  80  70  50  90  90  90  10  4025 4   --  100 100 100 100 100 100 100 90  80   2   --  --  --  --  --  --  --  --  --  --   1   --  100 100 100 90  100 90  100 90  70   1/2 --  90  90  90  90  100 100 100 90  90   1/4 --  80  80  90  80  90  90  90  40  3026 2   --  50  70  100 90  100 100 90  30  60   1/2 --  10  0   90  50  90  90  50  20  40   1/4 --  20  10  60  80  90  100 50  10  5027 2   --  100 100 100 100 100 100 90  70  90   1/2 --  100 100 100 90  100 100 90  60  60   1/4 --  70  60  90  70  100 60  90  50  8028 2   --  100 90  100 100 100 100 100 90  90   1/2 --  90  90  90  90  100 100 90  90  60   1/4 --  90  90  90  80  100 100 100 70  8029 2   --  100 100 100 90  100 100 100 60  90   1/2 --  90  90  100 80  100 100 90  10  80   1/4 --  90  90  100 70  100 100 90  50  8030 1/2 20  100 --  --  --  100 100 90  80  60   1/4 90  90  --  70  100 100 100 90  20  4031 2   --  90  90  100 90  100 100 90  30  60   1/2 --  90  90  100 70  90  100 90  60  30   1/4 --  80  80  100 60  80  100 80  30  7032 2   --  100 100 100 90  100 100 100 40  80   1/2 --  100 100 100 80  100 100 100 20  80   1/4 --  30  20  100 90  90  90  70  60  4033 2   --  100 100 100 90  100 100 100 70  80   1/2 --  90  90  100 70  100 100 100 70  80   1/4 --  80  70  90  90  100 100 70  10  4034 2   --  70  70  100 90  100 100 90  60  60   1/2 --  60  60  100 90  100 100 80  40  40   1/4 --  90  70  90  90  100 100 50  20  5036 2   --  100 90  90  80  100 100 90  90  50   1/2 --  90  90  90  30  90  100 90  70  60   1/4 --  20  30  90  --  90  90  90  40  1037 2   --  90  90  80  0   90  90  90  80  70   1/2 --  90  90  90  --  90  90  90  40  40   1/4 --  10  10  70  --  80  70  50  10  3038 2   --  90  90  100 90  100 100 90  50  60   1/2 --  90  90  100 90  100 100 60  10  50   1/4 --  30  20  90  80  100 100 70  10  1039 2   --  90  90  100 100 100 100 100 60  90   1/2 --  90  90  90  90  100 100 100 40  7040 2   --  100 100 100 100 100 100 100 90  90   1/2 --  90  90  100 90  100 100 100 30  7041 2   --  100 100 100 100 100 100 100 90  90   1/2 --  90  90  100 90  100 90  90  30  80   1/4 --  70  80  90  70  100 90  90  20  6042 2   --  100 100 100 100 100 100 100 100 90   1/2 --  100 100 90  90  100 100 100 90  90   1/4 --  100 100 100 80  100 100 90  50  8043 1/2 70  100 --  90  100 100 100 100 40  40   1/4 100 100 --  90  100 100 100 70  40  3044 2   --  100 100 100 100 100 100 100 90  90   1/2 --  100 100 100 90  100 100 90  80  80   1/4 --  90  90  90  70  100 100 90  60  6045 2   --  100 100 100 100 100 100 100 100 90   1/2 --  100 100 90  90  100 100 100 80  60   1/4 --  100 100 90  90  100 100 90  50  6046 2   --  100 100 100 90  100 100 100 90  90   1/2 --  100 100 100 70  90  90  100 70  50   1/4 --  90  90  90  30  90  90  90  50  5047 2   --  100 100 100 100 100 100 100 90  80   1/2 --  90  90  70  90  100 100 90  50  30   1/4 --  90  90  60  20  100 100 80  20  6048 2   --  100 100 100 90  100 100 100 90  80   1/2 --  90  90  90  90  100 100 100 40  9049 2   --  50  10  90  70  100 100 60  20  30   1/2 --  10  20  70  30  100 100 90  40  3050 2   --  90  90  60  90  100 100 90  70  40   1   --  90  90  100 100 100 100 80  90  60   1/2 --  60  80  90  70  100 100 80  0   10   1/4 --  90  80  90  70  100 100 40  0   3051 10  --  100 100 100 80  100 100 90  70  70   4   --  100 100 100 100 100 100 90  90  70   2   --  90  90  100 90  100 100 90  70  40   1   --  100 100 100 100 100 100 80  90  80   1/2 --  60  80  100 80  100 100 90  10  20   1/4 --  100 90  100 70  100 90  50  0   4052 10  70  90  --  100 --  100 100 80  30  30   1   70  40  --  100 50  100 100 80  10  40   1/2 30  20  --  70  20  90  100 40  10  10   1/4 20  90  --  30  20  100 100 70  30  1053 10  100 100 --  100 90  100 100 100 90  90   4   100 90  --  80  80  100 100 100 70  80   1   90  90  --  70  60  100 100 90  60  50   1/2 40  40  --  20  0   100 90  80  20  50   1/4 20  10  --  10  --  90  50  20  10  3054 4   --  30  30  80  30  100 100 40  10  10   2   --  20  20  10  --  90  90  20  10  10   1   --  80  80  90  40  90  90  50  10  20   1/2 --  60  50  10  --  90  90  30  10  10   1/4 --  20  40  30  50  80  60  40  40  1055 4   --  20  20  10  20  100 100 --  0   10   2   --  30  30  0   --  100 80  20  0   80   1   --  80  80  20  30  90  100 30  20  30   1/2 --  80  80  10  --  90  --  80  0   10   1/4 --  20  30  0   30  30  30  0   0   1056 4   --  80  90  50  70  100 100 20  20  10   2   --  30  10  30  --  60  80  70  0   1057 4   --  60  80  40  30  90  100 70  0   10   2   --  70  40  0   --  100 100 60  10  10   1   --  60  50  0   --  90  90  60  40  30   1/2 --  20  30  20  --  90  100 50  10  20   1/4 --  20  20  10  30  60  80  50  10  1058 4   --  40  70  0   40  90  100 30  --  20   2   --  10  10  0   --  90  100 10  0   10   1   --  50  50  30  20  70  100 30  20  3059 10  --  0   10  0   0   0   80  0   0   060 10  --  80  60  10  70  90  100 30  10  10   4   --  20  10  10  20  80  70  50  0   1061 2   --  30  20  90  60  100 100 80  30  30   1/2 --  20  30  80  50  100 100 70  20  30   1/4 --  60  60  90  70  90  100 40  20  3062 4   20  20  --  0   20  100 --  30  10  20   1   0   10  --  10  10  60  70  30  0   30   1/2 30  30  --  0   10  70  50  10  0   2063 4   0   0   --  0   0   90  --  20  20  30   1   0   30  --  20  10  50  80  10  10  20   1/2 20  0   --  0   0   70  60  10  0   3064 4   0   20  --  10  30  30  100 60  10  10   2   0   10  --  20  10  100 90  70  10  10   1   20  20  --  10  20  80  50  20  0   10   1/2 10  10  --  10  10  80  60  0   10  2065 4   10  20  --  30  --  100 100 70  20  40   2   --  70  90  100 90  100 100 90  20  10   1   --  90  90  100 90  100 100 80  30  40   1/2 --  90  90  90  --  90  100 20  10  10   1/4 --  50  40  70  70  90  100 80  30  4066 4   0   40  --  10  20  90  100 20  40  30   1   0   0   --  10  50  60  50  70  0   40   1/2 10  10  --  20  40  40  50  10  0   4067 4   20  20  --  10  60  40  100 50  40  50   2   10  10  --  30  50  100 100 80  10  20   1   20  20  --  0   10  20  100 20  10  40   1/2 20  0   --  10  40  30  100 10  20  2068 10  20  20  --  30  --  100 100 90  20  50   4   --  100 100 100 100 100 100 90  90  60   2   --  100 90  100 100 100 100 80  60  90   1   --  30  50  100 --  90  100 90  20  30   1/2 --  90  90  100 --  90  100 90  70  90   1/4 --  50  40  80  80  90  100 70  30  6069 2   --  100 90  100 80  100 100 90  80  70   1/2 --  90  90  100 70  90  90  70  40  70   1/4 --  50  40  100 60  90  90  90  50  6070 2   --  90  80  100 70  100 100 90  70  60   1/2 --  90  80  100 60  100 100 90  20  50   1/4 --  90  70  100 50  90  90  80  20  4071 2   --  40  60  100 90  100 100 90  20  60   1/2 --  40  40  100 90  100 100 90  10  50   1/4 --  20  10  60  80  90  100 50  10  5072 10  --  100 100 100 100 100 100 100 90  80   2   --  100 100 100 90  100 100 100 80  80   1   --  100 100 100 90  100 100 100 80  80   1/2 --  90  90  90  90  100 100 90  50  80   1/4 --  90  90  90  80  100 100 100 30  8073 10  --  100 100 100 70  100 100 90  80  50   4   --  90  90  100 90  100 100 90  70  40   2   --  30  50  70  40  100 100 50  10  30   1   --  40  40  50  70  90  100 50  20  30   1/2 --  90  90  80  70  100 100 70  20  2074 2   --  90  80  90  10  100 100 90  10  40   1/2 --  90  80  90  --  100 90  90  20  30   1/4 --  60  60  80  90  90  90  90  10  4075 2   --  80  70  60  20  90  100 90  10  20   1   --  90  80  80  40  100 70  70  20  20   1/2 --  20  20  50  10  90  90  90  10  10   1/4 --  10  10  70  --  60  20  50  0   2076 2   --  20  10  40  --  90  100 90  10  50   1/2 --  10  10  10  --  90  90  60  10  40   1/4 --  10  10  80  30  80  70  40  10  1077 2   --  90  90  100 90  100 100 50  20  30   1/2 --  90  90  90  80  100 100 30  10  3078 10  60  20  --  70  --  100 100 90  70  30   4   --  80  90  100 90  100 100 90  0   10   2   --  100 100 100 90  100 100 90  50  70   1   --  90  90  100 60  100 100 40  80  40   1/2 --  90  90  90  80  90  --  30  20  20   1/4 --  40  80  40  50  80  100 40  40  4079 10  50  60  --  80  --  100 100 80  10  20   1/2 70  80  --  40  80  90  100 70  10  1080 4   --  90  90  100 50  100 90  90  90  30   2   --  70  50  90  50  90  60  90  60  90   1   --  70  70  80  20  90  90  90  40  10   1/2 --  30  30  70  50  90  90  90  60  20   1/4 --  50  50  40  50  80  100 50  20  5081 2   --  40  40  90  70  100 100 90  30  60   1/2 --  30  30  100 50  100 100 90  10  40   1/4 --  40  40  90  30  90  90  50  10  30__________________________________________________________________________ 
    
     Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.