Patent Application: US-23809988-A

Abstract:
the invention relates to certain sulfonylurea compounds having a carbocyclic or heterocyclic ring ortho to the sulfonylurea linkage , compositions thereof and a method of their use as herbicides or plant growth regulants .

Description:
compounds of formula i , wherein e is ch 2 or a single bond , can be synthesized by one or more of the procedures outlined in equation 1 . ## str17 ## wherein j , r , and a are as previously defined , provided e is ch 2 or a single bond . the reaction of equation 1a can be carried out according to procedures described in u . s . pat . no . 4 , 127 , 405 . the sulfonyl isocyanates ii are prepared from the corresponding sulfonamides of formula iv according to procedures described in u . s . pat . no . 4 , 238 , 621 or by the procedure of h . ulrich , b . tucker , and a . sayigh , j . org . chem ., 34 , 3200 ( 1969 ). sulfonyl isothiocyanates ( ii , w is s ) are known in the art and are prepared from the corresponding sulfonamides ( iv ) by reaction with carbon disulfide and potassium hydroxide followed by treatment of the resulting dipotassium salt vi with phosgene . such a procedure is described in arch . pharm . 299 , 174 ( 1966 ). alternatively compounds of formula i can be prepared according to equation 1b or by the reaction of equation 1c as described in u . s . pat . no . 4 , 443 , 243 . the sulfonylureas of formula i , wherein e is o , can be prepared by one or both of the procedures described in equation 2 . ## str18 ## wherein j is as previously defined , provided e is o . phenols of formula vii react with chlorsulfonylisocyanate ( csi ) under elevated temperatures ( equation 2a ) to provide the sulfonyl isocyanates ii , which react with heterocyclic amines of formula iii to yield the sulfonylureas i according to the procedure in u . s . pat . no . 4 , 475 , 944 . alternatively , the reaction of equation 2b may be employed according to the procedure described in u . s . pat . no . 4 , 391 , 976 . agriculturally suitable salts of compounds of formula i are also useful herbicides and can be prepared in a number of ways known to the art . for example , metal salts can be made by contacting compounds of formula i with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion ( e . g ., hydroxide , alkoxide or carbonate ). salts of compounds of formula i can also be prepared by exchange of one cation for another . cationic exchange can be effected by direct contact of an aqueous solution of a salt of a compound of formula i ( e . g ., alkali or quaternary amine salt ) with a solution containing the cation to be exchanged . this method is most effective when the desired salt containing the exchanged cation is insoluble in water and can be separated by filtration . exchange may also be effected by passing an aqueous solution of a salt of a compound of formula i ( e . g ., an alkali metal or quaternary amine salt ) through a column packed with a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column . this method is particularly useful when the desired salt is water - soluble , e . g ., a potassium , sodium or calcium salt . acid addition salts , useful in this invention , can be obtained by reacting a compound of formula i with a suitable acid , e . g ., p - toluenesulfonic acid , trichloroacetic acid or the like . the synthesis of heterocyclic amines such as those represented by formula iii has been reviewed in &# 34 ; the chemistry of heterocyclic compounds ,&# 34 ; a series published by interscience publ ., new york and london . aminopyrimidines are described by d . j . brown in &# 34 ; the pyrimidines ,&# 34 ; vol . xvi of the series mentioned above which is herein incorporated by reference . the 2 - amino - 1 , 3 , 5 - triazines of formula iii , where a is a - 1 and z is n , can be prepared according to methods described by e . m . smolin and l . rapaport in &# 34 ; s - triazines and derivatives ,&# 34 ; vol . xiii . pyrimidines of formula iii , where a is a - 1 and y is an acetal or thioacetal substituent , can be prepared by methods taught in european patent application no . 84 , 224 ( published july 27 , 1983 ). pyrimidines of formula iii , where a is a - 1 and y is cyclopropyl of ocf 2 h can be synthesized according to the methods taught in u . s . pat . no . 4 , 515 , 626 and u . s . pat . no . 4 , 540 , 782 , respectively . compounds of formula iii , where a is a - 2 or a - 3 , can be prepared by procedures disclosed in u . s . pat . no . 4 , 339 , 267 . compounds of formula iii , where a is a - 4 , can be prepared by methods taught in u . s . pat . no . 4 , 487 , 626 . additional references dealing with the synthesis of bicyclic pyrimidines of formula iii , where a is a - 2 , a - 3 , or a - 4 are braker , sheehan , spitzmiller and lott , j . am . chem . soc ., 69 , 3072 ( 1947 ); mitler and bhattachanya , quart . j . indian chem . soc ., 4 , 152 ( 1927 ); shrage and hitchings , j . org . chem ., 16 , 1153 ( 1951 ); caldwell , kornfeld and donnell , j . am chem . soc ., 63 , 2188 ( 1941 ); and fissekis , myles and brown , j . org . chem ., 29 , 2670 ( 1964 ). compounds of formula iii , where a is a - 5 , can be prepared by methods taught in u . s . pat . no . 4 , 421 , 550 . compounds of formula iii , where a is a - 6 , can be prepared by methods taught in the u . s . pat . no . 4 , 496 , 392 . the required sulfonamides of formula iv , provided e is not oxygen , can be conveniently prepared by amination of the corresponding sulfonyl chlorides with ammonia or ammonium hydroxide by methods known to those skilled in the art . alternatively deprotection of n - t - butylsulfonamides with polyphosphoric acid ( ppa ) or trifluoroacetic acid ( tfa ) as described by j . d . lombardino , j . org . chem ., 36 , 1843 ( 1971 ) or j . d . catt and w . l . matier , j . org . chem ., 39 , 566 ( 1974 ), respectively , provides compounds of formula iv . in addition , deprotection of n - t - butyldimethylsilylsulfonamides with fluoride ion , provides sulfonamides of formula iv , wherein e is not oxygen . the intermediate sulfonyl chlorides of formula x , as depicted in equation 3 , can be prepared from aromatic amines via a diazotization process , as described in epo publication nos . 83 , 975 and 85 , 476 ; or by oxidative chlorination of thiols or thioethers with chlorine and water as reviewed in gilbert , &# 34 ; sulfonation and related reactions ,&# 34 ; pp . 202 - 214 , interscience publishers , new york , 1965 ; when r 7 = h or benzyl , the oxidative chlorination may be effected by sodium hypochlorite following procedures described by l . h . mckendry and n . r . pearson in south african patent application no . 84 / 8845 ( november 13 , 1984 ); or by metal halogen exchange or directed lithiation of appropriately substituted aryl or heterocyclic substrates followed by trapping with sulfuryl chloride . the lithiation can be performed according to the procedure of s . h . bhattacharya , et al ., j . chem . soc . ( c ), 1265 ( 1968 ) or by procedures reviewed by h . gscwend and h . rodriquez in organic reactions , vol . 26 , wiley , new york , 1979 , and references cited within ; or finally , when e is a ch 2 moiety , by a two step procedure involving the conversion of aromatic chloromethyl or bromomethyl compounds to isothiouronium salts , as described by johnson and spraque , j . am . chem . soc ., 58 , 1348 ( 1936 ); 59 , 1837 and 2439 ( 1937 ); 61 , 176 ( 1939 ), followed by oxidative chlorination by the procedure of johnson as described in j . am . chem . soc ., 61 , 2548 ( 1939 ) to provide the sulfonyl chlorides x . ## str19 ## wherein j is as previously defined provided e is not oxygen , g is h . nh 2 , sr 7 , br , ch 2 cl , ch 2 br , and r 7 is h , c 1 - c 3 alkyl , benzyl . amines of the formula ix , wherein g is nh 2 , can be prepared from the corresponding nitro compounds by various reduction procedures as described in u . s . pat . nos . 3 , 846 , 440 and 3 , 846 , 439 and in ep - a no . 83 , 975 and references cited therein . phenols of formula vii can be prepared from amines of formula ix ( g ═ nh 2 ) via a diazotization process , as described in a . i . vogel , &# 34 ; practical organic chemistry ,&# 34 ; p . 595 ( 1956 ), 3rd ed ; u . s . pat . no . 3 , 270 , 029 ; j . h . finley , et al ., j . het . chem ., 6 , 841 ( 1969 ); and m . ohta , et al ., j . pharm . soc . japan , 73 , 701 ( 1953 ). compounds of the formula xii , which serve as intermediates to compounds of the formula i as illustrated in equations 1 - 3 , can be prepared from precursors of the formula xi by one or more of the procedures outlined below . ## str20 ## wherein q and r 1 are as originally defined ; r 8 is h or ch 3 , provided that when n is 2 or 3 , r 8 is h ; m is 0 or 1 , provided when m = 1 , n must be 0 ; n is 0 , 1 , 2 , or 3 , provided that m and n cannot both be 0 ; g is cl , br , ch 2 cl , ch 2 br , oh , nh 2 , no 2 , sr 7 , so 2 nh 2 , so 2 nh - t - butyl or so 2 nhsi ( ch 3 ) 2 - t - butyl ; m is cl , br , i , nh 2 , nhoh , nhnh 2 , cooch 3 , conhnh 2 , cn , cocl , cho or h or suitable leaving group , provided that when m = 1 , m is not br or i ; r 7 is h , c 1 - c 3 alkyl or benzyl . e 1 is o , s , so , so 2 or a single bond provided that when m = 1 , e 1 is a single bond . the ten procedures are based on established literature methods precedented by the references cited in table 2 . the references cited have direct applicability to compounds of the formula xii , wherein j is j - 1 . however , the procedures and experimental methods described in these references are equally applicable to the synthesis of compounds of formula xii , wherein j is j - 2 through j - 5 , by analogous procedures or slight modifications thereof . the chemistry of the thiophene , pyridine and pyrazole ring systems has been reviewed in &# 34 ; chemistry of heterocyclic compounds ,&# 34 ; volumes 3 , 14 , and 5 , respectively . wiley , new york 1952 and later . it should be noted that the chemical compatibility of the wide variety of reactions and reaction conditions described throughout this disclosure with j , r 1 , q , and g must be taken into account and as such requires a judicious choice of the appropriate methods for preparing compounds described within this disclosure . in addition , circumvention of instances of incompatibility may be achieved by the suitable selection of a protecting group , obvious to one skilled in the art . for a compilation of references describing the wide variety of protecting groups available , see t . w . greene , &# 34 ; protective groups in organic synthesis ,&# 34 ; john wiley and sons , inc ., new york , 1981 . the synthesis of the starting materials of formula xi are known in the general literature or can be prepared , by those skilled in the art , by simple modifications of established routes . procedure 1 : direct n - alkylation of intact heterocyclic compounds , containing an n -- h moiety , with compound substrates of the formula xi , wherein m = 0 and m is cl , br , or iodine ; or n - benzoylation of heterocyclic , containing an n -- h moiety , with benzoyl chlorides of the form xi , wherein m = 1 , m is cl , and g is cl , br , ch 2 cl , ch 2 br , no 2 or sr 7 . procedure 2 : c - alkylation of heterocyclic compounds containing an acidic c -- h moiety , i . e ., activated by a carbonyl or sulfonyl group , by substrates of the formula xi wherein m is cl , br , or iodine ; or c - benzoylation with benzoyl chlorides of the formula xi , wherein m = 1 , m is cl , and g is cl , br , ch 2 cl , ch 2 br , no 2 or sr 7 . procedure 3 : reactions of derivatives of formula xi , wherein m is nh 2 , nhoh , or nhnh 2 , as nucleophiles with bifunctional acrylic and cyclic reagents , which ultimately are converted to various q values . procedure 4 : use of acid - derivatives of formula xi , wherein m is cooch 3 , cohnnh 2 , cn , or cocl ; see example 4 . procedure 5 : synthesis from dianions derived from n - protected -( o - methyl aromatic sulfonamides ) of formula xi , wherein m is h , n = 1 , r 8 = h , and g is so 2 nh - t - butyl or so 2 nhsi ( ch 3 ) 2 - t - butyl . these benzyl or benzyl - like dianions can be prepared by reaction of the appropriate sulfonamide , as defined above , with two equivalents of n - butyllithium at low temperatures in an inert solvent . in some instances , conversion of the lithium dianions to copper - lithium species is dictated by the literature and can be accomplished by known procedures . procedure 6 : reactions of acyclic anions with aldehydes of the formula xi , wherein m is cho ( m = 0 ). further transformations , as described in the cited literature ( table 2 ) provide compounds of the formula xii . procedure 7 : reactions of anions derived from aromatic heterocycles such as thiophene , furan , pyrrole , and pyridine ( or simple substituted analogues ) which act as &# 34 ; masked &# 34 ; heterocycles of the form q . for example , alkylation reactions of such anions with compounds of the formula xi , wherein m is cl , br , or iodine , provide intermediates which upon reduction ( see for example conversions b and k in table 1 ) yield compounds of the formula xii . procedure 8 : synthesis of compounds of the formula xii wherein m is a vinyl group ( m = 0 ): see reference 37 . procedure 9 : this procedure involves the use of compounds which are related to xi , but are outside the defined limits of xi . these compounds may be prepared by literature procedures from compounds of the formula xi as defined . additional functional group manipulation is then required , the procedures of which are described in the references cited in table 2 , to convert these compounds to compounds of the formula xii . procedure 10 : this procedure is the conversion of the q value , contained in the formula xii to a different q value . these conversion procedures are summarized in table 1 . when applicable , the conversion procedures of table 1 are cited by their letter designation in table 2 . table 1______________________________________conversion proceduresconversiondesignation from to references______________________________________a lactone lactam 1 - 3b thiophene tetrahydro 4 - 6 furan derivative pyrrolec sulfide sulfoxide or 7 sulfoned lactone , lactam , α - unsaturated 8 , 84 sulfone or derivative sultame lactam cyclic amine 9 - 11f cycloketone lactone 12 - 14g dihydro - γ - tetrahydro - γ - 15 - 19 pyrone pyroneh dihydro - γ - tetrahydro - γ - 20 - 22 pyridone pyridonei γ - pyrone γ - pyridone 23 - 25j lactone tetrahydrofuran 26 or tetrahydropyrank pyridine piperidine or 27 - 28 ( including n -- substituted quaternary piperidines salts ) l anhydride succinimide______________________________________ table 2 sumarizes selected synthetic procedures viable for the synthesis of compounds of formula xii . table 2 is not meant to be all inclusive , but does provide synthetic routes , which are well established and precedented in the literature , through the known chemical procedures ( 1 - 10 ), conversions ( a - l ), and methods described in the references ( 1 - 84 ) or slight modifications thereof . for example , the preparation of a compound of formula xii , where q is q 1 and x b is nr 5 can be carried out according to the procedure outlined in line number 2 table 2 . thus alkylation ( procedure 2 ) of butyrolactone ( qh = q - 1 where x b = 0 ) with an appropriately substituted alkyl halide as described in references 29 - 31 , followed by conversion of the lactone moiety to a lactam ( conversion procedure a ) provides the desired compound of formula xii . finally , compounds of formula xii are converted to the desired sulfonylureas of formula i via one or more of the procedures outlined in equation 1 through 3 . table 2__________________________________________________________________________preparative schemes for compounds of the formula xii conv .. sup . 3no . q x . sub . b x . sub . c proc .. sup . 1 qh ( x . sub . b ( c )). sup . 2 proc . ref . comments__________________________________________________________________________1 q - 1 o -- 2 1 ( o ) -- 29 - 312 q - 1 nr . sub . 5 -- 2 1 ( o ) a 29 - 313 q - 1 nr . sub . 5 -- 2 1 ( nr . sub . 5 ) 32 - 354 q - 2 o -- 5 365 q - 2 nr . sub . 5 -- 5 a 366 q - 3 o 8 377 q - 3 nr . sub . 5 8 a 378 q - 4 -- -- 1 4 -- see example 19 q - 5 -- -- 2 5 38 , 3910 q - 6 5 18 40 - 42 1 , 4 - addition11 q - 7 -- -- 2 43 - 45 3812 q - 8 9 cyclize a halo - sulfonamide with base13 q - 9 9 -- cyclize a halo - sulfonamide with base14 q - 10 -- -- 1 -- 46 analogous to example 115 q - 11 nr . sub . 5 2 4916 q - 11 s 2 38 , 5017 q - 11 so 2 c 38 , 5018 q - 11 so . sub . 2 2 c 38 , 5019 q - 11 -- o 6 51 , 5220 q - 12 -- nr . sub . 5 2 4921 q - 12 -- s 9 53 , 54 see also ref 5022 q - 12 -- so 9 c 53 , 54 see also ref 5023 q - 12 -- so . sub . 2 9 c 53 , 54 see also ref 5024 q - 12 -- o 9 5525 q - 13 o 9 5526 q - 13 s 9 50 , 52 - 5427 q - 13 so 9 c 50 , 52 - 5428 q - 13 so . sub . 2 9 c 50 , 52 - 5429 q - 13 nr . sub . 5 5 in addition to to appropriate pyrrolidinone see also ref . 5630 q - 14 -- -- 1 protection of co may be necessary31 q - 15 o -- 5 d 3632 q - 15 nr . sub . 5 -- 5 d , a 36 conversion d then a33 g - 16 o 8 d 3734 q - 16 nr . sub . 5 8 d , a 37 conversion d then a35 q - 17 -- -- 1 4 d see example 136 q - 17 -- -- 1 17 see example 137 q - 18 -- -- 5 20 d 58 - 60 1 , 4 addition to qh - 18 followed by in situ conversion d38 q - 19 -- -- 1 use α , β unsaturated propane sultam39 q - 20 o 2 29 - 3140 q - 20 nr . sub . 5 2 32 - 35 see ref 35 . r = h41 q - 21 o 9 57 ref 57 discusses lactonization of hydroxy - acids42 q - 21 nr . sub . 5 9 d 5743 q - 22 o 9 5744 q - 22 nr . sub . 5 9 a 5745 q - 23 o 2 5 f 38 , 3946 q - 23 -- -- 2 5 f , a procedure e then a47 q - 24 -- -- 1 24 modification of example 148 q - 25 -- -- 2 25 37 , 3949 q - 26 5 40 - 42 1 , 4 addition50 q - 26 -- -- 9 cyclization of halo - sulfonamides with base51 q - 27 -- -- 2 27 43 - 4552 q - 28 -- -- 1 modification of example 153 q - 29 nr . sub . 5 2 29 ( nr . sub . 5 ) 4954 q - 29 s 2 , 9 53 , 54 , 5855 q - 29 so 2 , 9 c 38 , 53 , 5456 q - 29 so . sub . 2 2 , 9 c 38 , 53 5457 q - 29 o 2 , 9 3858 q - 30 -- o 5 41 ( o ) 40 - 42 1 , 4 addition59 q - 30 -- nr . sub . 5 5 41 ( nr . sub . 5 ) 40 - 42 1 , 4 addition60 q - 30 -- s 5 41 ( s ) 40 - 42 1 , 4 addition61 q - 30 -- so 5 41 ( s ) c 40 - 42 1 , 4 addition62 q - 30 -- so . sub . 2 5 41 ( s ) c 40 - 42 1 , 4 addition63 q - 31 -- s 9 -- 53 - 5464 q - 31 -- so 9 -- c 53 - 5465 q - 31 -- so . sub . 2 9 -- c 53 - 5466 q - 31 -- o 9 -- -- -- 67 q - 31 -- nr . sub . 5 9 -- -- -- 68 q - 32 -- nr . sub . 5 2 -- -- 4969 q - 32 -- o 2 38 modification of ref . 4970 q - 32 -- s 2 38 modification of ref . 4971 q - 32 -- so 2 38 modification of ref . 4972 q - 32 -- so . sub . 2 2 38 modification of ref . 4973 q - 33 1 33 c ═ o protection may be necessary74 q - 34 o 2 34 ( o ) 3875 q - 34 s 2 34 ( s ) 3876 q - 34 so 2 34 ( s ) c 3877 q - 34 so . sub . 2 2 34 ( s ) c 3878 q - 34 nr . sub . 5 2 34 ( nr . sub . 5 ) 3879 q - 35 o 4 g 5980 q - 35 nr . sub . 5 9 h 6181 q - 35 s 9 6282 q - 35 so 9 c 6283 q - 35 so . sub . 2 9 c 6284 q - 36 1 36 c ═ o protection may be necessary85 q - 37 o 2 5 f , d 38 , 3986 q - 37 nr . sub . 5 2 5 f , d , a 38 , 3987 q - 38 -- -- 2 38 modification of example 188 q - 39 -- -- 2 25 d 38 , 3989 q - 39 -- -- 2 39 3890 q - 40 -- -- 1 modification of example 191 q - 41 nr . sub . 5 2 30 ( nr . sub . 5 ) d 4992 q - 41 o d 3893 q - 41 s d 3894 q - 41 so d , c 3895 q - 41 so . sub . 2 d , c 3896 q - 42 s 9 d 6297 q - 42 nr . sub . 5 9 6198 q - 42 so 9 d , c 6299 q - 42 so . sub . 2 9 d , c 6100 q - 42 -- o 2 38101 q - 43 -- -- 1 35 d102 q - 44 o -- 9 63 - 65103 q - 44 nr . sub . 5 -- 9 63 - 65104 q - 45 3 reaction of amine with γ - pyrone105 q - 46 4 66106 q - 47 4 67 - 69 ref 69 contains n -- alkylation procedures107 q - 48 4 70108 q - 49 4 71109 q - 50 4 72 - 73110 q - 51 4 74111 q - 52 4 75 - 77112 q - 53 4 78113 q - 54 1 54 79 , 80114 q - 55 1 55 81115 q - 56 1 56116 q - 57 9 82117 q - 58 8 83118 q - 59 1 59119 q - 60 1 60120 q - 61 9121 q - 62 1 62122 q - 63 3 m = nhoh123 q - 64 2 64 38 r . sub . 5 = 16124 q - 65 1 65125 q - 66 2 66 38126 q - 67 1 67127 q - 68 2 68 38128 q - 69 1 69129 q - 69 3 m = nhoh130 q - 70 2 70 38131 q - 71 9132 q - 72 1 72133 q - 73 1 73134 q - 74 1 74135 q - 75 6 l136 q - 76 1 76137 q - 77 6 l , d138 q - 78 6 anion from ch . sub . 3 co . sub . 2 ch . sub . 2 ch . sub . 2 -- co . sub . 2 ch . sub . 3 then ring close with acid139 q - 79 1 79140 q - 80 1 80141 q - 81 2 81 38142 q - 82 1 82143 q - 83 1 83144 q - 84 1 84145 q - 85 2 85 38146 q - 86 2 86 38147 q - 87 2 87 38__________________________________________________________________________ . sup . 1 procedures of 1 - 10 . sup . 2 for example when qh ( x . sub . b ) = 1 ( o ); qh is q . sub . 1 , and x . sub . b is oxygen which suggests butyrolactone would be a viable starting material . sup . 3 conversion procedures ( a - l ) are described in table i . the preparation of the compounds of this invention is further illustrated by the following specific examples . to a solution of 1 . 35 g of potassium - tert - butoxide in 25 ml of dimethylformamide , cooled to 0 ° c ., was added 0 . 92 ml of 2 - pyrrolidinone . as a white precipitate formed , the mixture was stirred for 10 minutes , and 3 . 0 g of 2 - phenylmethylthio chloromethyl benzene was added in one portion . the resulting solution was allowed to warm to room temperature , stirred for 1 hour , poured into water , and extracted with methylene chloride . the organic layer was washed well with water , dried over magnesium sulfate , filtered , and the filtrate evaporated to leave 3 . 0 g of a yellow oil . ______________________________________nmr ( cdcl . sub . 3 ) ppm : 7 . 3 ( m , 9h , arh ) 4 . 5 ( s , 2h , ch . sub . 2 ) 4 . 0 ( s , 2h ch . sub . 2 ) 3 . 05 ( t , 2h , -- ch . sub . 2 --) 2 . 3 ( t , 2h , -- ch . sub . 2 --) 1 . 7 - 2 . 05 ( m , 2h , ch . sub . 2 ) ______________________________________ to a solution of 2 . 6 g of the compound of example 1 dissolved in 100 ml of acetic acid , containing 0 . 5 ml of water , and cooled to 15 ° c ., was bubbled in chlorine gas for 15 minutes . a slight exotherm of 5 ° c . was noted . the reaction was stirred for an additional 5 minutes , poured into ice water , and extracted with methylene chloride . the organic layer was washed with saturated sodium bicarbonate , dried over magnesium sulfate , filtered , and evaporated to an oil . the oil was immediately dissolved in 100 ml of tetrahydrofuran and treated with 2 ml of concentrated ammonium hydroxide and stirred for 1 hour . the tetrahydrofuran was removed on the rotaryevaporator to give a semisolid . the residue was then triturated with water to form a sticky solid which was filtered off and triturated with ether to provide 1 . 1 g of an off - white solid ; m . p . 149 °- 151 ° c . ir ( nujol ) 1660 ( c ═ o ) cm - 1 . to a suspension of 254 mg of the product of example 2 in 10 ml of acetonitrile , containing 275 mg of phenyl ( 4 , 6 - dimethoxypyrimidin - 2 - yl ) carbamate , was added 0 . 15 ml of 1 , 8 - diazabicyclo [ 5 . 4 . 0 ] undec - 7 - ene ( dbu ). the resultant solution was stirred for 2 hours , diluted with 20 ml of water and acidified with 5 drops of concentrated hydrochloric acid . n - butylchloride ( 10 ml ) was added , stirred , and the white precipitate was filtered . the collected white solid was washed with a little water , suction dried and finally dried in vacuo @ 70 ° c . overnight to afford 200 mg of a white solid , m . p . 185 °- 187 ° c . ______________________________________ir ( nujol ) 1730 ( c = o ) 1668 ( c = o ) cm . sup .- 1 ; nmr ( cdcl . sub . 3 ) ppm 12 . 76 ( bs , 1h , nh ) 8 . 21 ( m , 1h , arh ) 7 . 36 - 7 . 7 ( m , 3h , arh ) 7 . 22 ( bs , 1h , nh ) 5 . 80 ( s , 1h , pyh ) 5 . 01 ( s , 2h , ch . sub . 2 ) 3 . 96 ( s , 6h , och . sub . 3 ) 3 . 32 ( t , 2h , ch . sub . 2 ) 2 . 46 ( t , 2h , ch . sub . 2 ) 2 . 03 ( m , 2h , ch . sub . 2 ) ______________________________________ for purposes of expediency and avoidance of voluminous pages of tables each sulfonylurea is divided into three structural pieces as illustrated below . ## str21 ## each structural piece a , j , and q is fully defined separately in tables a , j and q respectively and requires the designation of a particular structure from one of the structure ( s ) assigned to each of these tables . thus to fully delineate a complete structure for a unique sulfonylurea it requires the information from one entry in each of the tables a , j , and q and a designation of one of the structures assigned to that table . note that only one structure , namely structure a , is assigned to table a and need not be specifically designated . the use of tables a , j , and q provides an alternative to listing individual compounds line by line as is done in a conventional table . it is the applicant &# 39 ; s intent to specifically disclose each and every compound that can be constructed from tables a , j and q using the procedure described above and illustrated below . the use of tables a , j , and q can be illustrated by the following . for example , specifically claimed is compound of formula xiii and is ## str22 ## listed in tables a , j , and q as entry number 4 of table a ; entry number one of table j -- structure b ; and entry number seven of table q -- structure j . as a shorthand notation , compound of formula xiii can be listed in a matrix form as : this provides a convenient method for listing the melting point of compounds as is done in the melting point table ( ajq ) ( see line number one of table ajq ). each compound for which a melting point is available is simply listed in the melting point table ( ajq ) as the entry number of table a ; entry number - structure for table j ; and entry number - structure for table q in that order . also specifically claimed is compound of formula xiv shown below . ## str23 ## compound of formula xiv is found in tables a , j , and q as entry number four of table a ; entry number one of table j - structure b ; and entry number one of table q - structure j or in the convenient matrix form as : by analogy compounds of formula xv and xvi having structures as shown below ## str24 ## have matrix designations of 2 ; 1 - b ; 19 - l and 4 ; 1 - b ; 76 - j respectively . the structures assigned to tables a , j , and q are shown below followed by tables a , j , and q and finally the melting point table ajq . ## str25 ## ______________________________________table a for structure aentry x y z______________________________________1 ch . sub . 3 ch . sub . 3 ch2 ch . sub . 3 och . sub . 3 ch3 ch . sub . 3 och . sub . 3 n4 och . sub . 3 och . sub . 3 ch5 och . sub . 3 och . sub . 3 n6 cl och . sub . 3 ch7 ch . sub . 3 c . sub . 2 h . sub . 5 ch8 ch . sub . 3 ch . sub . 2 och . sub . 3 ch9 ch . sub . 3 ch . sub . 2 och . sub . 3 n10 ch . sub . 3 nhch . sub . 3 ch11 ch . sub . 3 nhch . sub . 3 n12 ch . sub . 3 ch ( och . sub . 3 ). sub . 2 ch13 ch . sub . 3 ch ( och . sub . 3 ). sub . 2 n14 ch . sub . 3 cyclopropyl ch15 ch . sub . 3 cyclopropyl n16 och . sub . 3 c . sub . 2 h . sub . 5 ch17 och . sub . 3 c . sub . 2 h . sub . 5 n18 och . sub . 3 ch . sub . 2 och . sub . 3 ch19 och . sub . 3 ch . sub . 2 och . sub . 3 n20 och . sub . 3 nhch . sub . 3 ch21 och . sub . 3 nhch . sub . 3 n22 och . sub . 3 ch ( och . sub . 3 ). sub . 2 ch23 och . sub . 3 ch ( och . sub . 3 ). sub . 2 n24 och . sub . 3 cyclopropyl ch25 och . sub . 3 cyclopropyl n26 och . sub . 2 ch . sub . 3 ch . sub . 3 ch27 och . sub . 2 ch . sub . 3 ch . sub . 3 n28 och . sub . 2 ch . sub . 3 och . sub . 3 ch29 och . sub . 2 ch . sub . 3 och . sub . 3 n30 och . sub . 2 ch . sub . 3 ch . sub . 2 och . sub . 3 ch31 och . sub . 2 ch . sub . 3 ch . sub . 2 och . sub . 3 n32 och . sub . 2 ch . sub . 3 nhch . sub . 3 ch33 och . sub . 2 ch . sub . 3 nhch . sub . 3 n34 och . sub . 2 ch . sub . 3 ch ( och . sub . 3 ). sub . 2 ch35 och . sub . 2 ch . sub . 3 ch ( och . sub . 3 ). sub . 2 n36 cl ocf . sub . 2 h ch37 ocf . sub . 2 h ch . sub . 3 ch38 ocf . sub . 2 h och . sub . 3 ch39 ocf . sub . 2 h c . sub . 2 h . sub . 5 ch40 ocf . sub . 2 h ch . sub . 2 och . sub . 3 ch41 ocf . sub . 2 h nhch . sub . 3 ch42 ocf . sub . 2 h ch ( och . sub . 3 ). sub . 2 ch43 ocf . sub . 2 h cyclopropyl ch______________________________________ ______________________________________table j for structures b - i . sup . ( a ) . sup . r 1 no . refers to positionentry e in structure b only______________________________________1 -- h ( single bond ) 2 -- 5 - ch . sub . 33 -- 5 - ch . sub . 2 cl4 -- 5 - och . sub . 35 -- 5 - sch . sub . 36 -- 5 - sch . sub . 2 ch . sub . 37 -- 5 - cl8 -- 6 - f9 -- 5 - no . sub . 210 -- 6 - so . sub . 2 n ( ch . sub . 3 ). sub . 211 -- 5 - soch . sub . 312 -- 3 - cl13 -- 6 - so . sub . 2 ch . sub . 314 -- 5 - ch . sub . 2 cn15 -- 5 - cn16 -- 6 - cn - 17 -- 5 - co . sub . 2 ch . sub . 318 -- 5 - cf . sub . 319 ch . sub . 2 h20 ch . sub . 2 5 - cn21 ch . sub . 2 5 - sch . sub . 322 ch . sub . 2 5 - och . sub . 323 ch . sub . 2 5 - cl24 o h25 o 5 - sch . sub . 3______________________________________ . sup . ( a ) w = o , r = h ______________________________________table q for structures j - q proviso ( see end ofentry . sup . q . sup . x b . sup . x c . sup . r 5 . sup . r 6 table ) ______________________________________1 q - 1 o -- -- -- a2 q - 1 nr . sub . 5 -- ch . sub . 3 -- -- 3 q - 2 o -- -- -- -- 4 q - 2 nr . sub . 5 -- ch . sub . 3 -- -- 5 o - 3 o -- -- -- -- 6 q - 3 nr . sub . 5 -- ch . sub . 3 -- -- 7 q - 4 -- -- -- -- -- 8 q - 5 -- -- -- -- -- 9 q - 6 -- -- -- -- -- 10 q - 7 -- -- ch . sub . 3 -- -- 11 q - 8 -- -- ch . sub . 3 -- -- 12 q - 9 -- -- ch . sub . 3 -- -- 13 q - 10 -- -- -- -- -- 14 q - 11 -- o -- -- -- 15 q - 11 -- nr . sub . 5 ch . sub . 2 ch . sub . 3 -- -- 16 q - 12 -- nr . sub . 5 ch . sub . 2 ch . sub . 3 -- -- 17 q - 12 -- o -- -- -- 18 q - 13 -- o -- -- -- 19 q - 14 -- -- -- -- -- 20 q - 15 o -- -- -- -- 21 q - 15 nr . sub . 5 -- ch . sub . 3 -- -- 22 q - 16 o -- -- -- b23 q - 16 nr . sub . 5 -- ch . sub . 3 -- b24 q - 17 -- -- -- -- -- 25 q - 18 -- -- -- -- -- 26 q - 19 -- -- -- -- -- 27 q - 20 o -- -- -- -- 28 q - 20 nr . sub . 5 -- ch . sub . 3 -- -- 29 q - 21 o -- -- -- -- 30 q - 22 o -- -- -- -- 31 q - 23 o -- -- -- -- 32 q - 23 nr . sub . 5 -- ch . sub . 3 -- -- 33 q - 24 -- -- -- -- -- 34 q - 25 -- -- -- -- -- 35 q - 26 -- -- ch . sub . 3 -- -- 36 q - 27 -- -- ch . sub . 3 -- -- 37 q - 28 -- -- -- -- -- 38 q - 29 -- nr . sub . 5 ch . sub . 3 -- -- 39 q - 30 -- o -- -- -- 40 q - 31 -- o -- -- -- 41 q - 32 -- nr . sub . 5 ch . sub . 3 -- -- 42 q - 33 -- -- -- -- -- 43 q - 33 -- o -- -- -- 44 q - 34 -- nr . sub . 5 ch . sub . 3 -- -- 45 q - 35 -- o -- -- -- 46 q - 36 -- -- -- -- -- 47 q - 37 o -- -- -- b48 q - 38 nr . sub . 5 -- ch . sub . 3 -- -- 49 q - 38 -- -- -- -- -- 50 q - 39 -- -- -- -- -- 51 q - 40 -- -- -- -- -- 52 q - 41 -- nr . sub . 5 ch . sub . 3 -- b53 q - 41 -- o -- -- b54 q - 42 -- o -- -- b55 q - 42 -- nr . sub . 5 -- -- b56 q - 43 -- -- -- -- -- 57 q - 44 -- o -- -- b58 q - 44 -- nr . sub . 5 ch . sub . 3 -- b59 q - 45 -- -- -- -- b60 q - 46 -- -- ch . sub . 3 -- b61 q - 46 -- -- h -- b62 q - 47 -- -- ch . sub . 3 -- b63 q - 48 -- -- ch . sub . 3 -- b64 q - 49 -- -- ch . sub . 3 -- b65 q - 50 -- -- ch . sub . 3 ch . sub . 3 b66 q - 51 -- -- -- -- b67 q - 52 -- -- -- -- b68 q - 53 -- -- -- ch . sub . 3 b69 q - 54 -- -- -- -- -- 70 q - 54 -- -- -- -- a71 q - 55 -- -- -- -- a72 q - 56 -- -- -- -- -- 73 q - 57 -- -- ch . sub . 3 -- -- 74 q - 58 -- -- h -- -- 75 q - 58 -- -- ch . sub . 3 -- -- 76 q - 59 -- -- -- -- -- 77 q - 60 -- -- ch . sub . 3 -- -- 78 q - 61 -- -- ch . sub . 3 ch . sub . 3 -- 79 q - 62 -- -- ch . sub . 3 -- -- 80 q - 63 -- -- -- -- -- 81 q - 63 -- -- -- -- c82 q - 64 -- -- ch . sub . 3 -- -- 83 q - 65 -- -- -- -- -- 84 q - 66 -- -- ch . sub . 3 -- -- 85 q - 67 -- -- -- -- -- 86 q - 68 -- -- ch . sub . 3 -- -- 87 q - 69 -- -- -- -- -- 88 q - 70 -- -- ch . sub . 3 -- -- 89 q - 71 -- -- -- -- -- 90 q - 72 -- -- ch . sub . 3 -- -- 91 q - 73 -- -- ch . sub . 3 -- -- 92 q - 74 -- -- -- -- -- 93 q - 75 -- -- ch . sub . 3 -- -- 94 q - 76 -- -- -- -- -- 95 q - 77 -- -- ch . sub . 3 -- b96 q - 78 -- -- -- -- -- 97 q - 79 -- -- -- -- -- 98 q - 80 -- -- -- -- -- 99 q - 81 -- -- ch . sub . 3 -- -- 100 q - 82 -- -- -- -- -- 101 q - 83 -- -- -- -- -- 102 q - 84 -- -- ch . sub . 3 -- -- 103 q - 85 -- -- -- -- -- 104 q - 86 -- -- -- -- -- 105 q - 87 -- -- -- -- -- ______________________________________ . sup . a q . sub . 1 is substituted by a 4methyl group . sup . b structure b of table j is excluded with the use of the q value designated in this entry . sup . c substituted by α , dimethyl ______________________________________melting point table ( ajq ) des - table a : table j : table qignations : entry #: entry # entry # structure structureno . matrix designation mp ° c . ______________________________________1 4 : 1 - b : 7 - j 185 - 872 5 : 1 - b : 7 - j 194 - 953 1 : 1 - b : 72 - j 184 - 854 4 : 1 - b : 72 - j 139 - 425 5 : 1 - b : 72 - j 184 - 856 1 : 1 - b : 70 - j 192 - 947 2 : 1 - b : 70 - j 177 - 788 4 : 1 - b : 70 - j 183 - 859 6 : 1 - b : 70 - j 202 - 0410 3 : 1 - b : 70 - j 185 - 8611 5 : 1 - b : 70 - j 195 - 9612 2 : 1 - b : 1 - j 202 - 04 . 513 6 : 1 - b : 1 - j 178 - 82 . 514 1 : 1 - b : 1 - j 193 - 9615 5 : 1 - b : 1 - j 182 - 8516 3 : 1 - b : 1 - j 188 - 9417 4 : 1 - b : 1 - j 178 - 8218 1 : 1 - e : 7 - j 174 - 7619 2 : 1 - e : 7 - j 163 - 6520 4 : 1 - e : 7 - j 137 - 3921 6 : 1 - e : 7 - j 182 - 8322 3 : 1 - e : 7 - j 171 - 7223 5 : 1 - e : 7 - j 169 - 7124 1 : 1 - e : 72 - j 159 - 6125 2 : 1 - e : 72 - j 146 - 5526 4 : 1 - e : 72 - j 157 - 6027 6 : 1 - e : 72 - j 146 - 5028 3 : 1 - e : 72 - j 155 - 6129 1 : 1 - e : 70 - j 190 - 9130 2 : 1 - e : 70 - j 169 - 7231 4 : 1 - e : 70 - j 129 - 3132 6 : 1 - e : 70 - j 168 - 7533 3 : 1 - e : 70 - j 154 - 5934 5 : 1 - e : 70 - j 170 - 7335 4 : 1 - e : 33 - j 150 - 6036 5 : 1 - e : 33 - j 170 - 72______________________________________ useful formulations of the compounds of formula i can be prepared in conventional ways . they include dusts , granules , pellets , solutions , suspensions , emulsions , wettable powders , emulsifiable concentrates and the like . many of these may be applied directly . sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare . high strength compositions are primarily used as intermediates for further formulation . the formulations , broadly , contain about 0 . 1 % to 99 % by weight of active ingredient ( s ) and at least one of ( a ) about 0 . 1 % to 20 % surfactant ( s ) and ( b ) about 1 % to 99 . 9 % solid or liquid inert diluent ( s ). more specifically , they will contain these ingredients in the following proportions : ______________________________________ weight percent * active ingredient diluent ( s ) surfactant ( s ) ______________________________________wettable powders 20 - 90 0 - 74 1 - 10oil suspensions , 3 - 50 40 - 95 0 - 15emulsions , solutions ,( including emulsifiableconcentrates ) aqueous suspension 10 - 50 40 - 84 1 - 20dusts 1 - 25 70 - 99 0 - 5granules and pellets 0 . 1 - 95 5 - 99 . 9 0 - 15high strength 90 - 99 0 - 10 0 - 2compositions______________________________________ * active ingredient plus at least one of a surfactant or a diluent equals 100 weight percent . lower or higher levels of active ingredient can , of course , be present depending on the intended use and the physical properties of the compound . higher ratios of surfactant to active ingredient are sometimes desirable , and are achieved by incorporation into the formulation or by tank mixing . typical solid diluents are described in watkins , et al ., &# 34 ; handbook of insecticide dust diluents and carriers &# 34 ;, 2nd ed ., dorland books , caldwell , n . j ., but other solids , either mined or manufactured , may be used . the more absorptive diluents are preferred for wettable powders and the denser ones for dusts . typical liquid diluents and solvents are described in marsden , &# 34 ; solvents guide ,&# 34 ; 2nd ed ., interscience , new york , 1950 . solubility under 0 . 1 % is preferred for suspension concentrates ; solution concentrates are preferably stable against phase separation at 0 ° c . &# 34 ; mccutcheon &# 39 ; s detergents and emulsifiers annual &# 34 ;, mc publishing corp ., ridgewood , new jersey , as well as sisely and wood , &# 34 ; encyclopedia of surface active agents &# 34 ;, chemical publishing co ., inc ., new york , 1964 , list surfactants and recommended uses . all formulations can contain minor amounts of additives to reduce foaming , caking , corrosion , microbiological growth , etc . the methods of making such compositions are well known . solutions are prepared by simply mixing the ingredients . fine solid compositions are made by blending and , usually , grinding as in a hammer or fluid energy mill . suspensions are prepared by wet milling ( see , for example , littler , u . s . pat . no . 3 , 060 , 084 ). granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques . see j . e . browning , &# 34 ; agglomeration &# 34 ;, chemical engineering , dec . 4 , 1967 , pp . 147ff , and &# 34 ; perry &# 39 ; s chemical engineer &# 39 ; s handbook &# 34 ;, 5th ed ., mcgraw - hill , new york , 1973 , pp . 8 - 57ff . for further information regarding the art of formulation , see for example : h . m . loux , u . s . pat . no . 3 , 235 , 361 , feb . 15 , 1966 , col . 6 , line 16 through col . 7 , line 19 and examples 10 through 41 ; r . w . luckenbaugh , u . s . pat . no . 3 , 309 , 192 , mar . 14 , 1967 , col . 5 , line 43 through col . 7 , line 62 and examples 8 , 12 , 15 , 39 , 41 , 52 , 53 , 58 , 132 , 138 - 140 , 162 - 164 , 166 , 167 and 169 - 182 ; h . gysin and e . knusli , u . s . pat . no . 2 , 891 , 855 , june 23 , 1959 , col . 3 , line 66 through col . 5 , line 17 and examples 1 - 4 ; g . c . klingman , &# 34 ; weed control as a science &# 34 ;, john wiley and sons , inc ., new york , 1961 , pp . 81 - 96 ; and j . d . fryer and s . a . evans , &# 34 ; weed control handbook &# 34 ;, 5th ed ., blackwell scientific publications , oxford , 1968 , pp . 101 - 103 . in the following examples , all parts are by weight unless otherwise indicated . ______________________________________wettable powder______________________________________n --[[( 4 , 6 - dimethoxypyrimidin - 2 - yl ) aminocarbonyl ]- 2 -( 2 - 80 % oxo - 1 - pyrrolidinylmethyl ) benzenesulfonamidesodium alkylnaphthalenesulfonate 2 % sodium ligninsulfonate 2 % synthetic amorphous silica 3 % kaolinite 13 % ______________________________________ the ingredients are blended , hammer - milled until all the solids are essentially under 50 microns , reblended , and packaged . ______________________________________wettable powder______________________________________n --[[ 4 - methoxy - 6 - methyl - 1 , 3 , 5 - triazin - 2 - yl )- 50 % aminocarbonyl ]- 2 -( 2 - oxo - 1 - pyrrolidinylmethyl )- benzenesulfonamidesodium alkylnaphthalenesulfonate 2 % low viscosity methyl cellulose 2 % diatomaceous earth 46 % ______________________________________ the ingredients are blended , coarsely hammermilled and then air - milled to produce particles essentially all below 10 microns in diameter . the product is reblended before packaging . ______________________________________granule______________________________________wettable powder of example 5 5 % attapulgite granules 95 %( u . s . s . 20 - 40 mesh ; 0 . 84 - 0 . 42 mm ) ______________________________________ a slurry of wettable powder containing 25 % solids is sprayed on the surface of attapulgite granules while tumbling in a double - cone blender . the granules are dried and packaged . ______________________________________extruded pellet______________________________________n --[[( 4 , 6 - dimethoxypyrimidin - 2 - yl ) aminocarbonyl ]- 2 -( 2 - 25 % oxo - 1 - pyrrolidinylmethyl ) benzenesulfonamideanhydrous sodium sulfate 10 % crude calcium ligninsulfonate 5 % sodium alkylnaphthalenesulfonate 1 % calcium / magnesium bentonite 59 % ______________________________________ the ingredients are blended , hammer - milled and then moistened with about 12 % water . the mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long . these may be used directly after drying , or the dried pellets may be crushed to pass a u . s . s . no . 20 sieve ( 0 . 84 mm openings ). the granules held on a u . s . s . no . 40 sieve ( 0 . 42 mm openings ) may be packaged for use and the fines recycled . ______________________________________oil suspension______________________________________n --[[( 4 - methoxy - 6 - methyl - 1 , 3 , 5 - triazin - 2 - yl ) aminocar - 25 % bonyl ]- 2 -( 2 - oxo - 1 - pyrrolidinylmethyl ) benzene - sulfonamidepolyoxyethylene sorbitol hexaoleate 5 % highly aliphatic hydrocarbon oil 70 % ______________________________________ the ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns . the resulting thick suspension may be applied directly , but preferably after being extended with oils or emulsified in water . ______________________________________wettable powder______________________________________n --[[( 4 - methoxy - 6 - methyl - 1 , 3 , 5 - triazin - 2 - yl ) amino - 20 % carbonyl ]- 2 -( 2 - oxo - 1 - pyrrolidinylmethyl )- benzenesulfonamidesodium alkylnaphthalenesulfonate 4 % sodium ligninsulfonate 4 % low viscosity methyl cellulose 3 % attapulgite 69 % ______________________________________ the ingredients are thoroughly blended . after grinding in a hammer - mill to produce particles essentially all below 100 microns , the material is reblended and sifted through a u . s . s . no . 50 sieve ( 0 . 3 mm opening ) and packaged . the active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender . after spraying of the solution has been completed , the blender is allowed to run for a short period and then the granules are packaged . ______________________________________aqueous suspension______________________________________n --[[( 4 - methoxy - 6 - methyl - 1 , 3 , 5 - triazin - 2 - yl ) amino - 40 % carbonyl ]- 2 -( 2 - oxo - 1 - pyrrolidinylmethyl ) benzene - sulfonamidepolyacrylic acid thickener 0 . 3 % dodecylphenol polyethylene glycol ether 0 . 5 % disodium phosphate 1 % monosodium phosphate 0 . 5 % polyvinyl alcohol 1 % water 56 . 7 % ______________________________________ the ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size . the salt is added directly to the water with stirring to produce the solution , which may then be packaged for use . the active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double - cone blender . after spraying of the solution has been completed , the material is warmed to evaporate the solvent . the material is allowed to cool and then packaged . ______________________________________ granule______________________________________n --[[( 4 , 6 - dimethoxypyrimidin - 2 - yl ) aminocarbonyl ]- 2 -( 2 - 80 % oxo - 1 - pyrrolidinylmethyl ) benezenesulfonamidewetting agent 1 % crude ligninsulfonate salt ( containing 10 % 5 - 20 % of the natural sugars ) attapulgite clay 9 % ______________________________________ the ingredients are blended and milled to pass through a 100 mesh screen . this material is then added to a fluid bed granular , the air flow is adjusted to gently fluidize the material , and a fine spray of water is sprayed onto the fluidized material . the fluidization and spraying are continued until granules of the desired size range are made . the spraying is stopped , but fluidization is continued , optionally with heat , until the water content is reduced to the desired level , generally less than 1 %. the material is then discharged , screened to the desired size range , generally 14 - 100 mesh ( 1410 - 149 microns ), and packaged for use . the ingredients are blended and ground in a hammer - mill to produce a material essentially all passing a u . s . ser . no . 50 screen ( 0 . 3 mm opening ). the concentrate may be formulated further if necessary . the ingredients are blended and ground in a hammer - mill to produce particles essentially all below 100 microns . the material is sifted through a u . s . ser . no . 50 screen and then packaged . the ingredients are thoroughly blended , coarsely hammer - milled and then air - milled to produce particles essentially all below 10 microns in size . the material is reblended and then packaged . ______________________________________oil suspension______________________________________n --[[( 4 , 6 - dimethoxypyrimidin - 2 - yl ) aminocarbonyl ]- 2 -( 2 - 35 % oxo - 1 - pyrrolidinylmethyl ) benzenesulfonamide . blend of polyalcohol carboxylic 6 % esters and oil soluble petroleumsulfonatesxylene 59 % ______________________________________ the ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns . the product can be used directly , extended with oils , or emulsified in water . the active ingredient is blended with attapulgite and then passed through a hammer - mill to produce particles substantially all below 200 microns . the ground concentrate is then blended with powdered pyrophyllite until homogeneous . test results indicate that the compounds of the present invention are highly active preemergent or postemergent herbicides or plant growth regulants . many of them have utility for broad - spectrum pre and / or post - emergence weed control in areas where complete control of all vegetation is desired , such as around fuel storage tanks , ammunition depots , industrial storage areas , parking lots , drive - in theaters , around billboards , highway and railroad structures . some of the compounds have utility for selective weed control in crops such as wheat , second barley . alternatively , the subject compounds are useful to modify plant growth . the rates of application for the compounds of the invention are determined by a number of factors , including their use as plant growth modifiers or as herbicides , the crop species involved , the types of weeds to be controlled , weather and climate , formulations selected , mode of application , amount of foliage present , etc . in general terms , the subject compounds should be applied at levels of around 0 . 005 to 10 kg / ha , the lower raters being suggested for use on lighter soils and / or those having a low organic matter content , for plant growth modification or for situations where only short - term persistence is required . the compounds of the invention may be used in combination with any other commercial herbicides , examples of which are those of the triazine , triazole , uracil , urea , amide , diphenylether , carbamate and bipyridylium types . the herbicidal properties of the subject compounds were discovered in a number of greenhouse tests . the test procedures and results follow . ______________________________________compounds______________________________________ ## str26 ## compound q x y z______________________________________ ## str27 ## och . sub . 3 och . sub . 3 ch2 ## str28 ## och . sub . 3 och . sub . 3 n3 ## str29 ## ch . sub . 3 ch . sub . 3 ch4 ## str30 ## och . sub . 3 och . sub . 3 ch5 ## str31 ## och . sub . 3 och . sub . 3 n6 ## str32 ## ch . sub . 3 ch . sub . 3 ch7 ## str33 ## ch . sub . 3 och . sub . 3 ch8 ## str34 ## cl och . sub . 3 ch9 ## str35 ## ch . sub . 3 och . sub . 3 ch10 ## str36 ## och . sub . 3 och . sub . 3 n11 ## str37 ## ch . sub . 3 och . sub . 3 n12 ## str38 ## och . sub . 3 och . sub . 3 ch______________________________________ ## str39 ## compound q x y z______________________________________13 ## str40 ## ch . sub . 3 och . sub . 3 ch14 ## str41 ## och . sub . 3 och . sub . 3 ch15 ## str42 ## cl och . sub . 3 ch16 ## str43 ## ch . sub . 3 ch . sub . 3 ch17 ## str44 ## ch . sub . 3 och . sub . 3 ch18 ## str45 ## och . sub . 3 och . sub . 3 ch19 ## str46 ## cl och . sub . 3 ch20 ## str47 ## ch . sub . 3 och . sub . 3 n21 ## str48 ## ch . sub . 3 och . sub . 3 ch22 ## str49 ## och . sub . 3 och . sub . 3 ch______________________________________ seeds of crabgrass ( digitaria , spp . ), barnyard - grass ( echinochloa crusgalli ), wild oats ( avena fatua ), cheatgrass ( bromus secalinus ), velvetleaf ( abutilon theophrasti ), morningglory ( ipomoea spp . ), cocklebur ( xanthium pensylvanicum ), sorghum , corn , soybean , sugarbeet , cotton , rice , wheat , and purple nutsedge ( cyperus rotundus ) tubers were planted and treated preemergence with the test chemicals dissolved in a non - phytotoxic solvent . at the same time , these crop and weed species were treated with a soil / foliage application . at the time of treatment , the plants ranged in height from 2 to 18 cm . treated plants and controls were maintained in a greenhouse for sixteen days , after which all species were compared to controls and visually rated for response to treatment . the ratings , summarized in table a , are based on a numerical scale extending from 0 = no injury , to 10 = complete kill . the accompanying descriptive symbols have the following meanings : table a______________________________________ cmpd . 1 cmpd . 2 cmpd . 3rate ( kg / ha ) 0 . 05 0 . 05 0 . 05______________________________________postemergencemorningglory 10c 1c , 1h 9ccocklebur 10c 1c 5c , 9gvelvetleaf 9c 0 2c , 6gnutsedge 3c , 8g , 9x 0 5gcrabgrass 4c , 9g 0 5c , 9gbarnyardgrass 9c 0 9ccheatgrass 9c 0 8gwild oats 4c , 8g 2c , 2h 9cwheat 3g 0 9ccorn 5u , 9g 8g 10csoybean 9c 3c 9crice 9c 5g 6c , 9gsorghum 9c 4g 9csugar beets 9c 3c , 3h 9ccotton 9c 2c , 2h 5c , 9gpreemergencemorningglory 9g 2h 8hcocklebur 9h 2h 9hvelvetleaf 9c 7g 7gnutsedge 8g 0 4gcrabgrass 2c , 6g 2g 2gbarnyardgrass 4c , 9h 2g 2c , 9hcheatgrass 5c , 9h 0 7hwild oats 4c , 9g 0 9cwheat 4c , 8g 0 9hcorn 4c , 9h 2g 4c , 9hsoybean 3c , 7g 0 5grice 10e 0 10esorghum 10e 0 10esugar beets 5c , 9g 10ecotton 4c , 9g 0 8g______________________________________ cmpd . 4 cmpd . 5 cmpd . 6rate ( kg / ha ) 0 . 05 0 . 05 0 . 05______________________________________postemergencemorningglory 10c 2c , 6g 2c , 5gcocklebur 9c 2c , 3h 3c , 9hvelvetleaf 10c 0 3gnutsedge 3c , 9g 0 2c , 4gcrabgrass 3c , 9h 0barnyardgrass 9c 3c 8h 3c , 5hcheatgrass 7g 0 6gwild oats 4c , 8g 4c , 8g 6gwheat 0 0 4gcorn 6c , 9g 5c , 9g 3c , 7hsoybean 6c , 9g 4c , 8g 5c , 9grice 9c 4c , 8g 5gsorghum 5c , 9g 3c , 6h 4c , 8hsugar beets 9c 4c , 7g 2hcotton 9c 4c , 6g 4c , 8hpreemergencemorningglory 9g 3g 7hcocklebur 9h 3g 2hvelvetleaf 8g 0 3gnutsedge 9g 8g 0crabgrass 9g 0 4gbarnyardgrass 5c , 9h 2c 0cheatgrass 2c , 7g 0 7gwild oats 3c , 8g 0 0wheat 7g 0 0corn 3u , 9h 2c , 5g 0soybean 4c , 8h 2g 10erice 10e 7g 0sorghum 4c , 9h 2c , 6g 3gsugar beets 10c 10c 8gcotton 5c , 9g 0 0______________________________________ cmpd . 7 cmpd . 8rate ( kg / ha ) 0 . 05 0 . 05______________________________________postemergencemorningglory 5c , 9g 4c , 9gcocklebur 6c , 9g 5c , 9gvelvetleaf 3c , 8h 5gnutsedge 5g 2gcrabgrass 3g 0barnyardgrass 3c , 8h 0cheatgrass 2c , 8g 0wild oats 2c , 5g 0wheat 2c , 5g 0corn 3c , 9g 0soybean 9c 3c , 8grice 3c , 8g 5gsorghum 2c , 9g 3c , 7gsugar beets 3c , 5g 2hcotton 3c , 6g 5gpreemergencemorningglory 9g 3gcocklebur 9h 9gvelvetleaf 9c 0nutsedge 3g 0crabgrass 2g 0barnyardgrass 2c , 5g 0cheatgrass 8g 0wild oats 2c , 6g 0wheat 7g 2gcorn 2c , 8h 2gsoybean 3c , 6h 2hrice 3c , 7h 0sorghum 3c , 9h 2csugar beets 4c , 9g 6gcotton 5g 0______________________________________ cmpd . 9 cmpd . 10 cmpd . 11rate kg / ha 0 . 05 0 . 05 0 . 05______________________________________postemergencemorningglory 10c 4c , 8g 6c , 9gcocklebur 10c 4c , 9g 4c , 9gvelvetleaf 4c , 9g 4c , 8h 4c , 9gnutsedge 0 0 0crabgrass 3g 0 0giant foxtail 4g 0 0barnyardgrass 2c , 8g 1c 0cheatgrass 2c , 8g 0 0wild oats 5g 0 0wheat 4g 0 0corn 3c , 7g 1h 0barley 2c , 7g 0 0soybean 5h 0 0rice 7g 0 2gsorghum 2c , 9g 2c , 5g 4gsugar beet 3c , 7g 9c 9ccotton 9c 8g 2c , 9gpreemergencemorningglory 9g 5g 9ccocklebur -- 9h -- velvetleaf 10c 9c 2gnutsedge 0 0 0crabgrass 7g 0 0giant foxtail 5g 0 0barnyardgrass 2c , 8g 2c 0cheatgrass 7g 0 0wild oats 5g 0 0wheat 5g 0 0corn 2c , 7g 0 0barley 8g 0 0soybean 2g 2g 2c , 5grice 7g 2g 0sorghum 2c , 8g 3g 4gsugar beet 8g 7g 4c , 8gcotton 7g 4g 5g______________________________________ compound 12 cmpd . 13 cmpd . 14rate kg / ha 0 . 05 0 . 01 0 . 05 0 . 05______________________________________postemergencemorningglory 9c 2g 10c 10ccocklebur 10c 2c , 9h 9c 9cvelvetleaf 10c 5c , 9g 4c , 8g 9cnutsedge 6g 2g 4g 4c , 8gcrabgrass 0 0 0 0giant foxtail 2g 0 4g 4c , 9gbarnyardgrass 7h 3h 8h 10ccheatgrass 7g 6g 0 7gwild oats 0 0 3c , 6g 0wheat 5g 0 4g 0corn 1h 0 3c , 8h 9gbarley 7g 3g 0 2csoybean 2c , 8g 5h 5c , 9g 9crice 8g 3g 2c , 6g 2c , 9gsorghum 2c , 8h 7g 3c , 8h 4c , 9gsugar beet 9c 5c , 9g 10c 10ccotton 3c , 9g 4c , 8g 5c , 9g 9cpreemergencemorningglory 5g 5g 8g 9gcocklebur -- 7g 9h 9hvelvetleaf 7g 6g 9g 9gnutsedge 4g 0 0 5gcrabgrass 0 0 4g -- giant foxtail 4g 2c 2g 6gbarnyardgrass 2c , 7g 2c 2g 8gcheatgrass 9h 7g 0 7gwild oats 0 0 0 0wheat 0 0 0 0corn 6g 5g 3c , 7h 3c , 8gbarley 7g 0 0 5gsoybean 0 0 3c , 7h 9hrice 6g 0 3g 6gsorghum 2c , 8h 3g 4g 4c , 9hsugar beet 8g 5g 10c 10ccotton 5g -- 3c , 7g 9g______________________________________ cmpd . 15 cmpd . 16 cmpd . 17 cmpd . 18rate kg / ha 0 . 05 0 . 05 0 . 05 0 . 05______________________________________postemergencemorningglory 5c , 9g 10c 10c 10ccocklebur 5c 9h 10c 10c 10cvelvetleaf 2g 5g 4c , 9g 9cnutsedge 0 2c , 9g 3c , 7g 5c , 9gcrabgrass 0 6g 2g 3ggiant foxtail 0 5c , 9g 4c , 8g 3c , 8gbarnyardgrass 5h 10c 4c , 9h 4c , 9hcheatgrass 0 9g 7g 4c , 9gwild oats 0 3g 0 0wheat 0 3g 3g 0corn 4g 9c 9c 10cbarley 0 2c , 5g 0 0soybean 3c , 8g 4c , 9g 4c , 9g 9crice 6g 9c 5c , 9g 8gsorghum 4c , 9h 4c , 9g 4c , 9h 9hsugar beet 4c , 8g 10c 10c 10ccotton 3c , 7g 4c , 9g 10c 10cpreemergencemorningglory 8g 9g 9g 9gcocklebur -- 9h 9h 9hvelvetleaf 7g 9g 9g 9gnutsedge 0 9g 8g 10ecrabgrass -- 6g 5g 5ggiant foxtail 3g 3c , 7g 3c , 7g 3c , 7gbarnyardgrass 2g 3c , 9h 4c , 9h 9hcheatgrass 0 8g 8g 9hwild oats 0 5g 5g 4gwheat 0 4g 2g 0corn 3g 9h 3c , 9h 3c , 9hbarley 0 2c , 8g 5g 6gsoybean 0 7h 9h 9hrice 3g 4c , 8h 8g 8gsorghum 0 8g 3c , 8g 7gsugar beet 8g 10e 10e 10ecotton 8g 9g 9g 9g______________________________________ cmpd . 19 cmpd . 20 cmpd . 21 cmpd . 22rate kg / ha 0 . 05 0 . 05 0 . 05 0 . 05______________________________________postemergencemorningglory 10c 4c , 8h 10c 4c , 9gcocklebur 10c 4c , 9g 9c 4c , 9hvelvetleaf 3c , 7g 3c , 7h 4c , 8g 4c , 8gnutsedge 4g 0 2c 2gcrabgrass 3g 0 3g 2ggiant foxtail 3c , 5g 2c , 8g 2g 0barnyardgrass 3c , 8h 5c , 9h 2c , 5h 0cheatgrass 3c , 6g 0 0 0wild oats 0 0 0 0wheat 2g 0 0 0corn 9h 10c 8h 3hbarley 0 0 0 0soybean 4c , 9g 2c , 7g 4c , 9g 4c , 9grice 8g 7g 5g 4gsorghum 4c , 9h 4c , 9h 3c , 8g 2gsugar beet 9c 4c , 8h 3c , 7g 2c , 6gcotton 10c 3c , 7g 4c , 8h 3c , 6gpreemergencemorningglory 8g 7h 9g 7hcocklebur 8h 7g 9h 7hvelvetleaf 9g 0 8g 7gnutsedge 9g 0 0 0crabgrass 2g 0 3g -- giant foxtail 2c , 4g 0 3g 0barnyardgrass 3c , 7g 0 0 0cheatgrass 5g 0 0 0wild oats 0 0 0 0wheat 0 0 0 0corn 7g 7g 5g 0barley 0 0 0 0soybean 0 0 3c , 6h 2c , 4hrice 5g 5g 2c , 5g 0sorghum 6g 0 2c , 4g 2csugar beet 4c , 9g 9c 8g 8gcotton 2c , 8g 4g 2c , 6g 7g______________________________________ 2 . jones et . al ., j . am . chem . soc ., 48 , 181 ( 1926 ). 4 . z . n . parnes et al ., izv . akad . nauk sssr , ser . khim ., ( 11 ) 2526 ( 1977 ); ca ., 88 62239k . 6 . d . s . tarbell and c . weaver , j . am . chem . soc ., 63 , 2939 ( 1941 ). 7 . h . o . house , &# 34 ; modern 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