HERBICIDAL SULFONAMIDES

Abstract: Compounds are of formula (I), wherein E is CH2 or a single bond; W is O or S; R is H or CH3; RX is H, F, Cl, CH3, OCH3, N(CH3)2 or OCHF2; R1 and R2 are selected from various organic groups, and A is selected from various heterocyclic groups, are useful as herbicides and plant growth regulators.

Description: Title HERBICIDAL SU FONAMIDES Related Applications This is a continuation-in-part of my co-pending application of U.S. 920.051. filed October 17. 1986. Background of the Invention The compounds of this invention are highly active, novel 3-substituted methyl sulfonylureas which are useful as herbicides and plant growth regulants. EP-A-44,209 (Cognate) discloses herbicidal sulfonamides of formula wherein R is H. F. Cl. Br. NO . CF . C -C alkyl or C -C alkoxy; R is H, Cl or C -C ' alkyl: R„ is H or CH,: and 2 3 is. among other values. CO E , CONR R . CN. __» __L -9 " Cl. Br. NR,R Λ . S(O) R„. SO^R ^ R, . OR_ 3 4 n 7 2 3 4 9 and OC(0)R 11 . EP-A-112.803 discloses, in part, herbicidal sulfonamides of formula South African Patent Application 84/2722 discloses herbicidal sulfonamides of formula wherein A is CRgR 7 XRg. CR 9 R 10 R ι;L or CHR 7 SCQR 21 ; R g and R... are. among other values, H or CH- : R L1 is COR . or a C..-C alkyl group substituted with, among other values. CN. NO . OH. C -C alkoxy. C.-C alkyl hio. C -C. alkylsulfinyl. C -C alkylsulfonyl.. C -C haloalkoxy. NR 12 R 13 S0 2 NR 15 R 16 , SC(0)R and OS0 2 R._; R includes H. halogen. NO,. CN. C 1 -C 4 haloalkyl and COR 18; and R includes " H. halogen. C.-C. alkyl and C.-C. alkoxy. EP-A-162.723 discloses 2.5-substituted herbicidal sulfonamides of formula wherein R is H or CH.: R is C -C_ alkyl: and R 2_ is C2.-CO. alkoxy. C.l.-Cb. alkylthio. Cj_-Cb. alkenyl. C. ό-C. _ alkynyloxy, C 3.-C6. alkenylthio. C3.-CD. alkynylthio. OCH 2 CH 2 OCH 3 . OCH 2 CH 2 SCH 3 . CH 2 F. CHF 2 . OCF 2 H. OCH 2 CH 2 F. OCH 2 CHF 2 . OCH 2 CF 3 . OCH 2 CH 2 Cl. c 2_- c _6 : alkyl substituted with 1-3 atoms of F or Cl or C -C alkyl substituted with C.-C 2 alkoxy or C.-C 2 alkylthio: South African Patent Application 84/5216 discloses herbicidal sulfonylureas of the formula (0) n E β wherein R. and R independently include H. C.-C. alkyl. C1-C4., alkoxy or C1-4„ alkylthio which are optionally substituted by halogen. NO . OS0 2 (C l " 4 alkvl) ' OS0 2 CF 3 0E C l "C 4 alkoxycarbonyl: X is CH or N: Rg and R_ include H or C..-C. alkyl: and R is C,-C. alkyl, C -C alkenyl or benzyl. EP-A-204.513. published 12/10/86 discloses herbicidal sulfonylureas of the formula wherein G is O. s. SO or SO __>: m is 0 or 1: n is 0. 1 or 2; E is a single bond. CH or O; Q is a tetrazole or tetrazolinone; A includes pyrimidines and triazineε: and R.. includes H. C., to C_ alkyl. C to C halo¬ alkyl and C -C- alkyl substituted by C -C alkoxy. C -C_ haloalkoxy. C -C alkylthio. C -C haloalkylthio. C -C haloalkylthio or CN. EP-A-205.348. published December 17. 1986. discloses herbicidal sulfonylureas of the formula « 2 ES0 2 NHCNA * wherein R includes halogen. C -C alkyl, C -C alkoxy, CO R„, CONR R . SO R,R r and 2 3 4 5 2 4 5 certain heterocyclic aromatic moieties; includes a variety of substituted methyl moieties; and A is one of seven heteroaromatic radicals. U.S. 4,515.626 discloses herbicidal 4-cyclopropyl pyrimidinyl and triazinyl benzenesulfonylureas. U.S. 4.545.811 discloses herbicidal 4-(haloalkoxy or haloalkylthio)pyrimidinyl and triazinyl benzenesulfonylureas. U.S. 4.510,325 discloses herbicidal compounds of the formula wherein X is O.S.SO or S0 2 : A includes substituted C. 1-Co. alkyl and optionally substituted C -C, alkenyl: and 2 o R 2- includes H. halogen. C.J.-C.b alkyl and C1-C. haloalkyl. EP-A-192.489 discloses herbicidal compounds of the formula wherein J is NHR 2,, . NR- 3R 4. or NR 2' NR 3' R 4' U.S. 4.594.097 discloses herbicidal alkynyl- substituted benzenesulfonylureas. U.S. 4.443,243 discloses herbicidal alkoxyalkynyl and thioalkynyl benzenesulfonylureas. South African Patent Application 82/7439 discloses 4-aminopyrimidinyl and triazinyl benzenesulfonylureas. South African Patent Application 83/6449 discloses herbicidal substituted-alkenyl benzene¬ sulfonylureas. EP-A-1 .442 discloses herbicidal ortho- heterocyclic benzenesulfonylureas. South African Patent Application 84/2245 discloses herbicidal compounds of the formula wherein iis C.-Co, haloalkyl; provided that A is not CF. i or CR a R b R c ; is H, Cl or C.-C. alkyl; R is H or CH 3 ; and R c is Cl or Br. U.S. 4,310.346 discloses herbicidal p_-sulfon- a ide sulfonylureas. Summary of the Invention This application pertains to novel compounds of Formula I, agriculturally suitable compositions containing them and their method-of-use as preemergent and/or postemergent herbicides or plant growth regulants. R wherein E is CH, or a single bond; W is 0 or S; R is H or CH 3 : R χ is H. F. Cl, CH 3 . OCH 3 , N(CH_.) 2 or OCHF 2 ; R1- is F. Cl. Br. NO2_. C.1-C4,, alkyl. C2--C4 Λ alkenyl.- C -C haloalkenyl. C -C alkynyl, C 1 -C. haloalkyl, C -C alkoxy. OCH-CH-OCH-. C.-C, haloalkoxy, C,-C Λ 2 2 3 1 4 3 4 alkenyloxy, C -C haloalkenyloxy. C -C alkynyloxy, C0 2 R 3 , CONR 4 R 5 . S0 2 . S(0) n R 6 . OS0 2 R 7 . C.-C 2 alkyl substituted with C..-C alkoxy. OH or C ] .-C 2 alkylthio. CH 2 CN. C H_. ° CR '8 Q ,' CR8 β ( X O~R Q 9)'2,,' R-^F R-^-G R.--H R^I R 1 -J R--K R.-L ___ R j -N R.--0 Ξ_ ! R j^ -Q R-^S R^-T __!__! R^-U R χ -W R χ -X _ _ χ -AC ___ O II R. is -CH(R 16 )CN. -CH(R 17 )SCN. -CH(R 17 )PR 10 R 11 . -CH R 17 )PR 10 R 11 . -CH R 17 )NR 12 R 13 . -CH(R 1? )SeR 14 . O II -CH(R 17 )N 3 -CH(R 17 ) 0 2 -CH(R 17 )NC. -CR 17' - C N OR ° ° -COR... T • -CH(0CCH )_. -CHOCR-- , , "19 3' 2 22 R R 17 R 17 17 -C(R 17 )C1. -C(R 1? )Br or -CHOS0 2 CH 3 ; R 23 R 24 R 17 R is C.-C. alkyl. < ~ 2 ~ C A a fc eι *yl. C _-C alkynyl. -CH 2 ] . CH 2 CH 2 C1. CH 2 CH 2 F. or C.-C. alkyl substituted with OCH_. SCH or CN: R is C -C alkyl or C -C- alkoxy: R4 is C1-C3 alkyl or Cχ-C 2 alkoxy; R5 is H or C1-C3 alkyl; R5 is H or C1-C3 alkyl; R4 and R5 may be taken together to form -(CH 2 > 3 - or -(CH 2 ) 4 -: R4 and R5 may be taken together to form -(CH 2 ) 3 - or -(CH 2 ) 4 -: R 6 is Cχ-C 3 alkyl. -CH CH=CH 2 or CH C≡CH; R7 is C1-C3 alkyl or N(CH3) 2 ; e is H. C3.-C4 alkyl, C3-C4 alkenyl, C3-C4 alkynyl. CH 2 CH 2 C1. CH 2 CH 2 F, C].-C 2 alkyl substituted with OCH3 or SCH3 or C3-C6 cycloalkyl; R9 is Cι~C 2 alkyl; RlO and Ru are independently Cι~C alkyl, c l~ 2 alkoxy, C 1 -C 2 alkylthio, NHCH3 or N(CH 3 ) 2 ; R^ 2 and R13 are independently H or C^-C 2 alkyl; R 14 is C l~ C 3 alkvl: R is H or CH ; R-lb, is H, C. L-C2- alkyl or F; R 17 is H or C -C alkyl: R{ 7 is H. C]_-C 2 alkyl. CN. Cl. OCH 3 . SCH 3 or N(CH 3 ) 2 ; R ID is C -C2- alkyl; R χ9 is H. si(CH 3 ) 3 or C -c alkyl: R 2Q is H or Cl -C 2 alkyl; R 21 is H. Cl -Cg alkyl or allyl; R 22 is C.-C alkyl or C.-C, haloalkyl; A-l A-2 ______ A-4 =3. &z&. h=l X is H. C.1-C4. alkyl, . C.1-C4. alkoxy • '. C1.-C4,, halo- alkoxy, C -C haloalkyl, C -C haloalkylthio. C --Cτ_- alkylthio. halogen. C *ζ_-C3 alkoxyalkyl, C 2-Cb_ alkoxyalkoxy, amino. C.1-C,3 alkylamino or di(C,-C alkyl)amino; Y is H. C1-C4 Λ alkyl. C1-C4, alkoxy. C1,-C4„ halo- alkoxy, C1-C4, haloalkylthio. C,1-C4_ alkylthio, C -C alkoxyalkyl, C -C_ alkoxyalkoxy, amino, 2 5 2 5 C J-C■_! alkylamino. di(C_-C•_> alkyl)amino. C * _ι-Ct alkenyloxy, C -C alkynyloxy. C -C alkyl- thioalkyl, C_-C_ alkylsulfinylalkyl, C ^ -C,, 2 b 2 5 alkylsulfonylalkyl, C -C haloalkyl, C -C alkynyl. C,.j-Cb_ cycloalkyl, azido, cyano. Q j^ and Q_ are independently O or S; Ra„ is H or C,1-C,3 alkyl; R. D and RC are independently CJL-C,<5 alkyl; 3.0 Z is CH. N. CCH 3 , CC 2 H 5 . CC1 or CBr; Y χ is O or CH 2 ; X χ is CH 3 . OCH 3 , OC 2 H 5 or OCF 2 H; 2 is CH 3 . C 2 H 5 or CH 2 CF 3 ; Y 2 is OCH 3 . OC 2 H g . SCH 3 . SC^. CH 3 or 15 CH 2 OCH 3 or Cl; or Cl; 20 an their agriculturally suitable salts; provided that 1) when X is halogen, then Z is CH and Y is OCH 3 . OC 2 H 5 . H 2 . NHCH 3 . (CH 3 > 2 . OCF 2 H. OCF 2 Br or 25 N(OCH 3 )CH 3 ; 2) when X or Y is C haloalkoxy. then Z is CH; 3) when H is S, then R is H. A is A-l. Z is CH or N. and Y is CH 3 . O H 3 « OC 2 H 5 . CH 2 O H 3 . C 2 H 5 . 30 CF 3 . SCH 3 . OCH 2 CH-CH 2 . OC^C≡CH. O H 2 CH 2 OCH 3 . 35 4) when the total number of carbon atoms of X and Y is greater than four, then the combined number of carbons of R and R is less than or equal to six; 5 5) when R 2 is -C(0)R 1? . -C(R 23 ) (R 1? )C1 or -C(R )(R )Br then Y is other than cyclo- propyl; 6) when Y is C 2-Cb, alkylthioalkyl, C2.-C,b alkyl- sulfinylalkyl or C_-C, alkylsulfonylalkyl, then 2 b 10 2 is other than CH(R 17 )N0 2 and CH(R 17 )OSθ 2 CH 3 ; 7) X 4, and Y4„ are not simultaneously Cl; 8) when R4 is Cι-C alkoxy and R5 is H, then R 2 is other than CH(Ri7)CN, C(R 3) (R 17 )C1 and C(R 24 )(R L7 )Br; I 5 9) when R 2 is C(0)R 1? . C(R 23 ) (R 1? )C1 or C(R_.) (R )Br, then R is other than C.-C haloalkyl or C alkyl substituted with C -C alkoxy, OH or C..-C- alkylthio; 10) when R 2 is C(R 23 ) (R 1? )C1 or C(R 24 ) (R 1? )Br. 0 then X and Y are other than C..-C. haloalkoxy or C,-C haloalkylthio; 11) when 2 is C(R 23 ) (R 1? )C1 or C(R 24 ) (R 1? )B . then R1, is other than C1-C4, haloalkoxy. C -C alkenyloxy, C -C haloalkenyloxy, 5 2 ~ 4 allς Y n Y 1 ' C--C alkynyloxy. C -C haloalkenyl and R -A through R -W: 12) when R is R -X. R -Y. R -Z. R -AA. R -AB. R -AC or R -AD, then R is other than CH(R 16 )CN. C(R 23 )-( 17 )C1 and 0 C(R 24 )(R 1? )Br; 13) when R is C(0)R , then is other than S0 2 R 4 g; and 14) when R is CO R then both R and R are other than H. 5 In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl". denotes straight chain or branched alkyl. e.g.. methyl, ethyl, ri-propyl, isopropyl or the different butyl isomers. Alkoxy denotes methoxy, ethoxy. ri-propoxy, iso- propoxy and the different butoxy isomers. Alkenyl denotes straight chain or branched alkenes, e.g.. vinyl. 1-propenyl, 2-propenyl. 3-pro- penyl and the different butenyl isomers. Alkynyl denotes straight chain or branched alkynes. e.g.. ethynyl. 1-propynyl, 2-propynyl and the different butynyl isomers. Cycloalkyl denotes cyclopropyl. cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen", either alone or in compound words such as "haloalkyl". denotes fluorine, chlorine. bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be mono- halogenated or fully substituted with halogen atoms. which may be the same or different. Examples of haloalkyl include CH 2 CH 2 F. CF 2 CF 3 and CH 2 CHFC1. Similarly, haloalkoxy. haloalkylthio. haloalkenyl and haloalkenyloxy would be defined as mono- or poly-substituted with the same or different halogen atoms. The total number of carbon atoms in a substituent group is indicated by the C.-C. prefix where i and j are numbers from 1 to 5. For example. C.-C. alkylsul- fonyl would designate methylsulfonyl through propylsul- fonyl. C 2 alkoxyalkoxy would designate OCH 2 OCH 3 : C. alkoxyalkoxy would designate the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH2_OCH2_CH_2CH,3 and OCH2_CH*2__OCH2_CH_3; as a further example. C cyanoalkyl would designate CH CN and C cyanoalkyl would designate CH CH CN and CH(CN)CH . Preferred Compounds Preferred for reasons of increased ease of synthesis and/or greater herbicidal efficacy are: 5 ι. compounds of Formula I where is O. 2. Compounds of Preferred 1 where E is a single bond; X is C.-C 2 alkyl. C.-C 2 alkoxy. Cl. F. Br. 0 I. OCF 2 H. CH 2 . C 3 . OCH 2 CH 2 . OCH2„CHF2_.. OCH2„CF3„. CH2„C1 or CH2„Br; and Y is H. C.^^ alkyl. C χ -C 2 alkoxy. CH 2 O H 2 CH 3 . NHCH 3 . N(OCH 3 >CH 3 . 5 N(CH 3 ) 2 . C 3 . SCH 3 . OCH 2 CH-CH 2 . OCH C≡CH. OCH CH OCH , CH SCH . ° SCF 2 H. OCF 2 Br. cyclopropyl. C≡CH or C≡CCH 3 ; Z is CH or N; R is H or CH,; R-_ is H; and 5 3. Compounds of Preferred 2 where o R 2 is -CH 2 CN. -CH 2 3 . -CH 2 P(OC 1 -C 2 alkyl) 2 . o o 0 CR 22 or -CH(R 1? )N0 2 : an RΪ7 is H. C ! -C2 alkyl. Cl or CN. 4. Compounds of Preferred 3 where A is A-l. 5 5. Compounds of Preferred 4 where R L is F. Cl, Br. N0 2 . C 1 -C 3 alkyl. C L -C 2 alkyl substituted with 1-3 F or Cl or 1 Br. C 2 -C 3 alkenyl. C -C alkenyl substituted with 1-3 F or Cl. C -C alkoxy. C -C alkoxy substi¬ tuted with 1-3 F or Cl or 1-Br. allyloxy. propargyloxy. 0C(C1)»CHC1, CO CH . C0 2 C 2 H 5 * C0 2 CH 2 CH " CH 2' C0 2 CH 2 CH 2 C1* C0 2 CH 2 CH 2 OCH 3 , CONH(C 1 -C 2 alkyl). CONCH^C^^ alkyl). S0 2 (OCH 3 )CH 3 . S0 2 NH(C 1 -C 2 alkyl). S0 2 N(C 1 -C 2 alkyl) 2 . S(0) n C 1 -C 3 alkyl. OS0 2 C L -C 3 alkyl. C l" C 2 alkyl substituted with OCH 3 or SCH 3 . C,H 5 and R--A. R.-B. R.—C, R.—D, R-—E« R,—F, R,—G, R_—H» R.°°I t R.— J, R_—K, Ec_— i, R.—M, R,— » R L -0. L - . R L -Q. R χ -R. L -S. R χ -T. K_—U» R_- . R_—W. Ec_— . R_— , R.— . R -AA. R -AB. R -AC or R -AD; 6. Compounds of Preferred 5 where X is CH 3 . OCH 3 . OCH 2 CH 3 . Cl. OCF 2 H or OCH 2 CF 3 ; and Y is CH 3 . O H 3 . C 2 Hg. CH 2 OCH 3 . NHCH 3 or CH(OCH 3 ) 2 . 7. Compounds of Preferred 6 where R is H; R L is F. Cl, Br. N0 2 . CH 3 . CF 3 <-^-C 2 alkoxy. allyloxy. 0C(C1)»CHC1. C0 2 CH 3 , C0 2 C 2 H 5 . C0 2 NHCH 3 . C0 2 N CH 3 2 . S0 2 NHCH 3 S0 2 N CH 3 ) 2 . S0 2 CH 3 . S0 2 C 2 H 5 . 0S0 2 CH 3 . OS0 2 C 2 H 5 . R-^A. R.-B. R.-C. R--X. R.-Z or R.-AB; and R χ is H. 17 Specifically Preferred foe treasons of greatest ease of synthesis and/or greatest herbicidal efficacy are: • 2- (cyanomethyl)-6- [[(4.6-dimethoκypy imidin- 2- yl)- arainocarbonyljaminosulfonylJbenzoic acid, ethyl ester, m.p. 201°-204°C: and • 2-(acetoxymethyl)-6-[[ (4-methoxy-6-methyl- 1.3.5- riazin-2-y1)aminoca bon l]aminosuIfonylJbenzoic acid, ethyl ester, m.p. 175°-176°C. DETAILED DESCRIPTION OF THE INVENTION Synthesis The compounds of Formula I can be prepared from sulfonamides of Formula II and heterocyclic amines of Formula III by one or more methods described in the literature. H ϋi Several representative routes are described below. • U.S. Patent 4,394.506 (issued 7/19/83) teaches the conversion of sulfonamides to sulfonyl isocyanateε and sulfonyl isothio- cyanates. and their subsequent coupling with heterocyclic amines of Formula III to give sulfonylureas. • U.S. Patent 4.398.939 (issued 8/16/83) teaches the formation of n-butylsulfonylureas from sulfonamides followed by phosgenation to give the sulfonyl isocyanates. Alternatively, the sulfonamides can be treated with thionyl chloride followed by phosgenation to afford the sulfonyl isocyanates. Additionally, ethylcarbamate derivatives of compounds of Formula III react with sulfonamides in the 5 presence of trimethylaluminum to give sulfonylureas. • U.S. Patent 4.443.245 (issued 4/17/84) teaches two methods for the synthesis of sulfonylureas. Either a phenyl carbamate 3-° of a sulfonamide and a heterocyclic amine, or a sulfonamide and a phenyl carbamate of a heterocyclic amine couple to give a sulfonylurea in an inert solvent with base. The preparation of sulfonamides from sulfonyl I 5 chlorides is widely reported in the literature; for reviews see: F. Hawking and J. S. Lawrence. "The Sulfonamides." H. K. Lewis and Co.. London. 1950 and E. H. Northey. "The Sulfonamides and Allied Compounds." Reinhold Publishing Corp.. New York. 1948. 20 Additionally, primary sulfonamides. such as those of Formula II. can be formed by removal of an N_t-butyl protecting group from the corresponding secondary sulfonamide with trifluoroacetic acid (J. D. Catt and W. L. Matier, J. Orq. Chem.. 39, 566 (1974)) 25 or polyphosphoric acid (J. G. Lombardino. J. Orq. Chem.. 36 (1971). 1843). The requisite sulfonyl chlorides may be synthe¬ sized by known methods or with slight modifications thereof, by one skilled in the art. Several repre- 30 sentative teachings are listed below. • Aromatic nitro groups may be transformed into sulfonyl chlorides by reduction, diazotization and coupling with sulfur dioxide/cupric chloride as taught in U.S. 35 Patent 4.310,346 (issued 1/12/82). • European Publication No. 94,821 (published 11/23/83) describes the displacement of aromatic halides with thiolate anions and subsequent oxidative chlorination to yield sulfonyl chlorides. • Halogen-metal exchange of aromatic halides or proton-metal exchange of aromatics fol¬ lowed by quenching with sulfur dioxide gives sul inate salts. These salts yield sulfonyl chlorides upon reaction with N-chlorosuccin- imide as taught in U.S. Patent 4.481.029 (issued 11/6/84). Directed proton-metal exchange of aromatic compounds has been reviewed by Gschwend and Rodriguez. Orq. Reactions. 26 (1979). 1. Directed lithiation of arγl-N-t,-butylsulfonamides is described by J. G. Lo bardino. j. Orq. Chem.. 36 (1971) . 1843. Also, aryllithiu s may be converted directly to arylsulfonyl chlorides with sulfuryl chloride as described in S. N. Bhattacharya. et. al.. J. Chem. Soc. C. (1968). 1265. • Electrophilic chlorεulfonation of an aromatic ring to give a sulfonyl chloride is well known in the literature. This technique works best for alkyl aryl ethers and alkyl aromatics. Its application is described by E. H. Huntress and F. H. Carten, J. Am. Chem. Soc.. 62 (1940). 511-14 and 603-4. • Transformation of phenols to sulfonyl chlorides can be accomplished by the formation of a thiocarba ate. rearrangement, hydrolysis and oxidative chlorination as described by M. S. Newman and H. A. ames. J. Orq. Chem.. 31 (1966), 3980. Compounds of Formula II can be prepared by a variety of methods known in the literature. The most universal scheme, where benzyl halides of Formula IV are reacted with the appropriate reagent, is shown below. IV Λ II wherein U is SO-NH or a previously described sulfon- amide precursor, and X is Cl. Br or I and R is of the structure -CH(R )-. Some specific methods are listed below. NITRILES (R 2 =CH(R 17 )CN) • Nitrilβs can be prepared by nucleophilic displacement of benzyl halides, usually benzyl chlorides or bromides, with potassium or sodium cyanide. Many solvents are appli¬ cable, but frequently dimethylsulfoxide is used. Thus, a benzyl bromide of formula IV can be contacted with potassium cyanide in dimethylsulfoxide for 0.5h to 24h at 20° to 140°C. For a review of this reaction, refer to Friedrich and Wallenfels, in Rappoport. "The Chemistry of the Cyano Group", pp. 77-86, Interscience Publishers. New York, 1970. ISONITRILES (R_.-CH(R ? )NC) • Heavy metal cyanides and benzylhalides react to give isonitriles. The reaction is best carried out in the dark using silver cyanide and a benzyl iodide. Typical procedures are given by A. Gautier. Ann. Chem.. 142 (1867). 28 and H. L. Jackson and B. C. McKusick, Orq. Svn.. Col. Vol. IV. 438. AZIDES (R 2 -CH(R 17 )N 3 ) • Compounds of Formula II may be prepared by reacting an azide anion with a benzyl halide. Typically sodium azide in alcohol or wet acetone is mixed with a benzyl bromide at 20-100°C. This nucleophilic displacement is reviewed in Biffin, Miller and Paul, in Patai. "The Chemistry of the Azido Group," pp. 57-119. Interscience Pub., New York. 1971. PHOSPHONATES (R «CH(R )P(0)R R ) • Alkyl phosphites are heated with benzylic halides to give phosphonates. The reaction is known as the Arbuzov reaction and it is reviewed by Arbuzov. Pure Appl. Chem. , .9 (1964). 307-335. AMINES (R 2 -CH(R 17 )NR 12 R 13 ) • Tertiary amines are prepared by alkylation of a secondary amine with a benzylic halide. The reaction is well documented in the liter¬ ature. • Primary amines can be prepared by reduction of compounds of Formula II where R_ is azide. Generally lithium aluminum hydride or hydrogen and palladium catalyst are used. NITRO (R 2 =_CH(R 17 )N0 2 ) • Nitrites react with benzylic halides to give benzylic nitro compounds. The reaction is usually carried out with sodium nitrite on a benzylic bromide in dimethylformamide or dimethylsulfoxide. When silver nitrite is used, diethyl ether at 0°-25°C are the preferred reaction conditions. The reaction is exhaustively discussed by N. ornblura. Orq. Reactions. 12 (1962). 101. SELENO ETHERS (R 2 «CH(R 17 SeR 14 ) • Alkali alkylselenides can be prepared by in situ combination of an alkali metal — t-butoxide with the selenol HSeR,14. in the solvent to be used for the displacement reaction. The selenols. HSeR, 14., can be prepared by a variety of methods reviewed by D. L. Klayman. "Selenols and their Deriva¬ tives" in Organic Selenium Compounds; Their Chemistry and Biology. D. L. Klayman. W. H. H. Gunther ed.. New York. 1973, and K. J. I golic and M. V. Kudchadker. "Organic Chemistry of Selenium" in Selenium. R. A. Zingaro. W. C. Cooper ed.. Van Nostrand Reinhold. New York. 1974. Benzyl halides may be formed through a variety of methods described in the literature. Several are listed below. BENZYLIC CHLORIDES (X L -C1) • Treatment of alkyl benzene derivatives with N-chlorosuccinimide. NCS. in a suitable solvent, such as carbon tetrachloride or dichloromethane. and catalyzed by light or a free radical initiator, such as azoiso- butyronitrile or benzoyl peroxide, gives the benzylic chloride. • Treatment of a benzylic alcohol with thionyl chloride, either neat or in the presence of a base such as pyridine, gives the benzylic chloride. For typical examples, see H. Gil- man and J. E. Kirby. J. Am. Chem.. Soc.. 51. 3475 (1929) and M. S. Newman. J. Am. Chem. SOC.. 62, 2295 (1940). BENZYLIC BROMIDES (X 1 «Br) • Treatment of alkyl benzene derivatives with N-bromosuccinimide by a method analogous to the case of N-chlorosuccinimide gives the benzylic bromide. Benzylic alcohols in an inert solvent such as benzene or dichloro- methane react with phosphorus tribromide to give benzylic bromides. BENZYLIC IODIDES X 1 -!) • Treatment of a benzylic chloride or benzylic bromide with sodium iodide gives the benzylic iodide. The reaction, known as the Finkel- stein reaction, works well in refluxing acetone. • Benzylic alcohols may be treated with iodine and phosphorus (red) or phosphorus (red) and phosphorus (yellow) to give the benzylic iodide. ESTERS ( 2 -CH(R L7 )OCOR 22 • Reaction of a benzyl bromide or iodide with a carboxylic acid salt in a dipolar aprotic solvent, results in good yields of the carboxylic esters. For a leading reference see Parker. Adv. Orq. Chem.. 5_. (1965) 1-46. METHANESULFONATES (R 2 «CH( 17 >OS0 2 CH 3 ) • Primary and secondary alcohols react with methanesulfonyl chloride in dry pyridine at room temperature to give mesylates, usually in good yield. The reaction is well documented in the literature. Compounds of Formula II. where R_ contains an oxygen functionality, such as an aldehyde or ketone. may be prepared by a variety of methods known to one skilled in the art. Two such routes are shown below. /05 24 IV VI V Primary and secondary benzylic halides may be oxidized to aldehydes and ketones. respectively using dimethylsulfoxide. For reviews of this reaction see Durst. Adv. Orq. Chem.. 285-388 (1969) pp. 343-356 and W. Epstein and F. Sweat. Chem. Rev.. 67 (1967). 247-60. Primary benzylic alochols may be oxidized to aldehydes and secondary benzylic alcohols may be oxidized to ketones by one skilled in the art. One or more of a variety of methods, such as an oxidizing agent, catalytic dehydrogenation, Oppenauer oxidation or halosuccinimide oxidation may be used. Acetals. thioacetals. ketals and thioketals are easily prepared by one skilled in the art from com¬ pounds of Formula V. Oxi es. and oxi e ethers of Formula Va are easily prepared by one skilled in the art from com¬ pounds of Formula V and hydroxylamine or o-alkyl- hydroxylamine with or without an appropriate base. 25 Va wherein R{ is H or C 1 -C 2 alkyl. Additionally, compounds of the Formula la. can be prepared from VII by treatment with an appropriate salt or amine. VII Va wherein M is Na + or K + Q is CN. OCH 3 and SCH 3 - The reaction is effected by reacting VII with at least one molor equivalent of M-Q in an inert solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide or methanol. The reaction is carried out at 0°C to 80 β C for one to twenty-four hours. Compounds of the Formula VII are themselves readily prepared from the corresponding carboxylic acids, VIII. VIII VII The carboxylic acids are converted to their acid chlorides which are in turn converted to N-alkoxyamides. Subsequent reaction of the amides with a suitable halogenating agent provides compounds of the Formula VII. Benzylic alcohols and alkyl benzene derivatives are either known or may be prepared by one skilled in the art. The heterocyclic amines A-l to A-7 are either known, disclosed in this application or can be pre¬ pared by methods obvious to one skilled in the art. For a review of the synthesis and reactions of 2-aminopyrimidines (A-l, Z=CH) see The Chemistry of Heterocyclic Compounds. Vol 16, Wiley-Interscience, New York (1962). For a review of the synthesis and reactions of 2-amino-1.3,5-triazines (A-l. Z»N) see The Chemistry of Heterocyclic Compounds. Vol. 13, Wiley-Interscience. New York (1959). F. C. Schaefer. U.S. Patent 3.154.537 and F. C. Schaefer and K. R. Huffman J. Orq. Chem.. 28 (1963). 1812. The synthesis of bicyclic amines A-2 and A-3 is taught in U. S. Patent 4.339.267. The synthesis of amino furo[2.3-d]pyrimidines. A-4. is taught in U.S. Patent 4.487.626. The synthesis of aminotriazoles. A-5. is taught in U.S. Patent 4.421.550. The synthesis of aminomethylheterocycles. A-6. is taught in U.S. Patent 4.496.392. The synthesis of aminocyano heterocycles. A-7, iβ taught in European Publication No. 125.864 (published 11/21/84). 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 com¬ pounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g. hydroxide, alkoxide, carbonate or hydride). Quaternary amine salts can be made by similar techniques. Salts of compounds of Formula I can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct contacting of an aqueous solution of a salt of a compound of Formula I (e.g.. alkali metal 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, e.g.. a copper salt, 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. In this method. the cation of the resin is exchanged for that of the original salt of the resin is 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 preparation of the compounds of this invention is further illustrated by the following examples. Example 1 Ethyl 2-Amino-β-methγlbenzoate A reaction mixture of 185 g of ethyl 6-mβthyl-2- nitrobenzoate and 176 g of powdered iron in 343 mL of glacial acetic acid and 2200 mL of ethanol was heated at reflux for 5 hours. The reaction mixture was allowed to cool, diluted with excess water and extracted with ethyl acetate. The organic layer was dried over sodium sulfate. filtered and concentrated § to an orange oil 148.3 g. NMR (CDC1 3 . 90 MHz): 1.32 (t. CH 3 . 3H) ; 2.40 (s. CH 3 . 3H); 4.25 (q. CH 2 . 2H): 6.25 (br s. NH 2 . 2H); 0 6.50 (d. ArH. 2H): and 7.05 (dd. ArH. 1H) . Example 2 2-Carboethoxy-N-(1.1-dimethylethyl)-3-methylbenzene- 5 sulfonamide To 31.5 g of ethyl 2-amino-6-methylbenzoate in 65 L of concentrated hydrochloric acid and 185 L of glacial acetic acid at 0°C was added a solution of 13.0 g of sodium nitrite in 28 mL of H_0. keeping the temperature below 5°C. The solution was stirred an additional one-half hour and then poured portion- wise into a suspension of 7.8 g of cupric chloride dihydrate. 16.0 mL of anhydrous sulfur dioxide and 140 mL of glacial acetic acid at 15°C. The resulting reaction mixture was warmed to room temperature and stirred an additional 3.5 hours. The reaction mixture was poured into 1 liter of ice/water and the solids filtered to give 35.5 g of a yellow solid. The solids were dissolved in 350 mL of tetrahydrofuran and treated at -50 to -60 β C with 46 mL of tert-butyl amine. The reaction mixture was warmed to 0°C over 2 hours and then the solids were removed by filtration. Removal of the solvent provided 31.0 g of an orange solid. Recrystallization from ethanol/water provided 30 g of a pale yellow solid, m.p. 89-91°C. X HNMR (90 MHz. CDC1 3 ): 1.15 (s. CH 3 . 9H) : 1.34 (t. CH 3 . 3H); 2.31 (s. CH , 3H) ; 4.40 (q. CH 2 . 2H); 5.22 (br s. NH. 1H); 7.44 (d. ArH. 2H) : and 7.85 (dd. ArH. 1H) . Example 3 2-Bromomethyl-2-carboethoxy-N-(l,l-dimethylethyl)- benzenesulfonamide A mixture of 67.0 g of 2-carboethoxy-N-(l.1- dimethylethyl)-3-methylbenzenesulfonamide and 47.6 g of NBS and 0.5 g of azobisisobutyronitrile in 700 mL of carbontetrachloride was heated at reflux for 3 hours. The resulting reaction mixture was allowed to cool and the solids removed by filtration. Concentra¬ tion provided a waxy yellow solid which was washed with 1:1 hexane/n-butyl chloride to yield 44.36 g of a white solid, m.p. 74-75 β C. 1 HNMR (200 MHZ. CDCl j : 1.25 (β. CH 3 . 9H); 1.47 (t. CH 3 . 3H); 4.50 (q. CH 2 . 2H); 4.54 (s. CH 2 . 2H); 5-20 (s. NH. 1H): 7.43-7.65 (m. ArH. 2H); and 8.02 (d. ArH. 1H). Example 4 3-Bromomethyl-2-carboethoχybenzenesulfonamide A solution of 5.7 g of 3-bromomethyl-2-carbo- ethoxy-N-(l. -dimethylethyl)benzenesul onamide in 60 mL of trifluoroacetic acid was stirred at room temperature for 16 hours. Concentration provided a viscous oil which was triturated with ri-butyl chloride. The solids were collected to yield 3.91 g of a white solid, m.p. 138-140 β C. X HNMR (90 MHz. CDC1 3 ): 1.40 (t. CH 3 , 3H); 4.48 (q. CH 2 . 2H) 4.62 (s. CH 2 . 2H); 6.95 (br s, H 2 . 2H); and 7.4-8.2 (m, ArH. 3H). Example 5 3-Azidomethy1-2-carboethoxybenzenesulfonamide A solution of 1.64 g of 3-bromomethyl-2-carbo- ethoxybenzenesulfonamide and 0.43 g of sodium azide in ethanol was heated to reflux for 3 hours. The resulting reaction mixture was cooled to room temperature and the ethanol was removed on the rotovap. The residue was partitioned between water and ethyl acetate. The organic phase was dried over magnesium sulfate. filtered and concentrated to give 1.32 g of a waxy solid. L HNMR (200 MHz. CDC1 3 ): 1.40 (t. CH 3 . 3H) ; 4.46 (q. CH 2 . 2H) ; 4.47 (s. CH 2 . 2H); 5.49 (br s. NH 2 . 2H); 7.75-7.85 (m. ArH. 2H) ; and 7.98 (dd. ArH. 1H) . Example 6 2-(Azidomethyl)-6-[ ( (4.6-dimethoxypyrimidin-2-yl)- aminocarbonvDaminosulfonyπbenzoic acid, ethyl ester To a suspension of 0.21 g of the compound from Example 5 and 0.23 g of 4.6-dimethoxy-2-pyrimidinyl- carbamic acid, phenyl ester in 4.0 mL of dry aceto- nitrile was added 0.12 mL of 1.8-diazabicyclo[5.4.0]- undec-7-ene (DBU) . After being stirred at room temperature for 2 hours, the resulting reaction mixture was diluted with 4.0 mL of water, acidified with IN hydrochloric acid to pH 2 and the solidε collected by vacuum filtration. The solids were further washed with ether and then air dried to give 0.21 g of a white βolid. m.p. 158-160 β C. L HNMR (200 MHZ. CDC1 3 : 1.41 (t. CH 3 . 3H) ; 3.98 (S. OCH 3 . 6H); 4.43 (q. CH 2 . 2H) ; 4.44 (S. CH 2 . 2H); 5.78 (s. Het-H. 1H); 7.22 (br s. NH. 1H); 7.60-7.80 ( . ArH. 2H) : 8.36 (dd. ArH. 1H) : and 12.52 (br S. NH. 1H). Example 7 3-Acetoxymethyl-2-carboethoxy-N-(l.l-dimethγlethyl)- benzenesulfonamide A solution of 5.0 g of 3-bromomethyl-2-carbo- ethoxy-N-(l.1-dimethylethyl)benzenesulfonamide and 1.5 g of potassium acetate in 50 mL of dimethyl¬ sulfoxide was stirred at room temperature for 6 hours. The resulting reaction mixture was poured onto ice and extracted with ethyl acetate. The organic phase was washed with a solution of saturated sodium chloride and then dried over magnesium sulfate. Removal of the drying agent by filtration and concentration provided a white solid. Chromatography on silica gel with 1:1 ethyl acetate/hexane provided 2.58 g of a white solid, m.p. 81-82 β C. 1 HNMR (90 MHz. CDC1 3 ): 1.22 (s. CH 3 . 9H); 1.40 (t. CH 3 , 3H); 2.20 (s. CH 3 . 3H); 4.48 (q. CH 2 . 2H)ϊ 5.23 (br s. NH. CH 2 . 3H): 7.53-7.70 ( . ArH. 2H) : and 8.00-8.16 (m. ArH. 1H). Example 8 3-Acetoχymethyl-2~carboethoχybenzenesulfonamide A solution of 2.58 g of 3-acetoxymethyl-2-carbo- ethoxy-N-(l.l-dimethylethyl)benzenesulfonamide in 25 mL of trifluoroacetic acid was stirred at room temperature overnight. Removal of the solvent on the rotovap followed by trituration with n-butyl chloride provided 2.0 g of a white solid, m.p. 98-100°C. L HNMR (90 MHZ. CDC1 3 ): 1.51 (t. CH 3 . 3H) ; 2.20 (s. CH 3 . 3H); 4.48 (q. CH 2 . 2H); 5.23 (s. NH, CH 2 . 2H); 5.35 (br s. H 2< 2H) ; 7.50-7.70 (m, ArH. 2H) ; and 7.98-8.15 (m. ArH. 1H) . Example 9 2-Acetoxymethyl-6-[((4.6-dimethoxypyrimidin-2-yl)- aminocarbonyDaminosulfonyπbenzoic acid, ethyl ester To a suspension of 0.25 g of the compound from Example 8 and 0.23 g of 4.6-dimethoxy-2-pyrimidinyl- carbamic acid, phenyl ester in 4.0 L of dry aceto- nitrile was added 0.12 mL of l,8-diazabicyclo[5.4.0]- undec-7-ene (DBU) . After being stirred at room temperature for 2 hours, the reaction mixture was diluted with 4.0 mL of water and then acidified with IN hydrochloric acid to pH 2. The solids were collected by vacuum filtration and washed with ether to yield 0.28 g of a white solid, m.p. 162-163°C. I HNMR (200 MHZ. DMSO-dg): 1.22 (t. CH 3 , 3H) ; 2.00 (S. CH 3 . 3H); 3.90 (s. OCH . 6H); 4.28 (q. CH . 2H) ; 5.08 (s. CH . 2H); 5.60 (S. Het-H. 1H); 7.70-7.90 ( . ArH, 2H) : and 8.03-8.10 (m. ArH. 1H) . Example 10 3-Bromomethyl-6-[((4.6-dimethoxypyrimidin-2-yl)- aminocarbonyDaminosulfonyπbenzoic acid, ethyl ester To a suspension of 0.31g of the compound from Example 4 and 0.28g of 4,6-dimethoxy-2-pyrimidinyl- carbamic acid, phenyl ester in 5.0ml of dry acetonitrile was added 0.15ml of DBU. After stirring 296 34 at room temperature for three hours, the reaction mixture was diluted with 5.0 ml of water and then acidified with IN hydrochloric acid to pH3. The solids were collected by vacuum filtration and washed with n-butylchloride to yield 0.38g of a white solid; m.p. 195-197°C; HNMR (200mhz. DMSO-dg) 1.28 (t. CH 3 . 3H); 3.90 (S. OCH 3 . 6H); 4.35 (q. CH 2 . 2H); 4.68 (S. CH . 2H); 6.00 (S. CH. 1H); 7.75 (d. d. ARH. 1H) ; 7.94 (d. ARH. IH) ; 8.15 (d. ARH. IH); 10.68 (br. s. N-H. IH) and 12.65 (brs. N-H. IH). The invention is further exemplified, but not limited to the compounds in Tables I-VII. The com- pounds depicted in these tables may be prepared by methods described in Examples 1-10, or by modifications thereof apparent to those skilled in the art. General structures General Formula I R General Structures (Cont'd) General Formula II ) General Formula III ) General Formula IV General Formula V General Formula VI General Formula VII R. R. _!__. F CH CN F CH CH F CH CH F CH SCH F CH SCH F CH-SCH F CH 2 P(0) (OCH 3 ) 2 F CH 2 PCOXOCH 3 ) 2 F CH 2 P(0) <OCH 3 ) 2 F CH 2 P(0) (CH 3 ) 2 Cl CH CH Cl CH CH Cl CH CH Cl CH SCH Cl CH 2 SCH Cl CH SCH Cl CH SCH Cl CH SCH Cl CH-SCH Cl CH 2 P(OXOCH 3 ) 2 Cl CH 2 PCO) (OCH 3 ) 2 Cl CH 2 P(0>(OCH 3 > 2 Cl CH„P(0)COCH 2-CH3«,) Br CH CH Br CH CH Br CH-CH Br CH-SCH Be CH-SCH Bc CH 2 SCH Br CH P(0)(OCH 3,)'2 37 TABLE I Continued TABLE I (Continued) R. CF 3 CF 3 C 3 C 3 CF 3 C 3 CH„CHC1CH-C1 2 2 CH-CF- 2 3 0CH 3 0CH 3 OCH 3 0CH 3 OCH 3 0CH 3 0CH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH j OCH 3 OCH„ TABLE I (Continued) BLE I Continued 5296 42 TABLE I Continued TABLE I (Continued) R„ *1 CO,CH, 2 3 2 3 CO CH CH,H, 2 3 2 3 CO,CH, CH,N, 2 3 2 3 CO,CH, 2 3 2 3 CO,CH, CH,H, 2 3 2 3 CO,CH, 2 3 2 3 C0 2 CH 3 CH,H, 2 3 CO,CH, CH,NO, 2 3 2 2 CO,CH, CH,NO, 2 3 2 2 CO,CH, CH,HO, 2 3 2 2 CO,CH, CH,NO, 2 3 2 2 CO,CH, CH,HO, 2 3 2 2 CO„CH, CH,HO, 2 3 2 2 C0 2 CH 3 CH HC C0 2 CH 3 CH 2 HC CO-CH CH CH CH 2 2 3 CO,CH,CH, CH CH 2 2 3 CO,CH,CH, CH,CN 2 2 3 2 CO,CH,CH, CH,CH 2 2 3 2 CO,CH,CH, CH SCN 2 2 3 CO,CH,CH, CH,SCN 2 2 3 2 C0 2 CH 2 CH 3 CH,CN 2 CO^CH,CH, CH,CH 2 2 3 2 CO,CH CH„ CH,CN 2 2 3 2 CO,CH,CH, CH,SCN 2 2 3 2 CO CH, CH, CH,SCH • 2 2 3 2 CO,CH,CH, CH SCH 2 2 3 CO,CH,CH, CH,SCN 2 2 3 2 CO,CH,CH, CH 2 P 0) (0CH 3 2 2 2 3 CO,CH,CH, CH PCOXOCH ) 2 2 3 CO,CH,CH, CH 2 P 0) OCH 3 ) 2 2 2 3 C0 2 CH 2 CH 3 CH 2 H 3 C0 2 CH 3 CH 2 N 3 TABLE I (Continued) R- C0 2 CH 2 CH 3 CH 2 H 3 C0 2 CH(CH 3 ) 2 CH CH C0 2 CH(CH 3 ) 2 CH CH CO Λ CH,CH»CH n CH CH 2 2 2 CO Λ CH,CH«CH, CH,SCN 2 2 2 2 CO,CH,CH-CH, CH,SCN 2 2 2 2 CO CH C≡CH CH 2 P(0X0CH 3 2 C0,CH,CH,C1 CH 2 P(0)(0CH 3 ) 2 2 2 2 CO,CH,CH Cl CH,CH 2 2 2 2 CO,CH, CH F CH,CH 2 2 2 2 C0 2 CH 2 CH 2 F CH,SCH 2 C0 2 CH 2 CF 3 CH SCH CO,CH,CH,OCH, CH 2 P(0X0CH 3 ) 2 2 2 2 3 C0 2 CH 2 CH 2 OCH 3 CH 2 P(0)(0CH 3 ) 2 C0 2 CH 2 CH 2 SCH 3 CH 2 CH CO Λ CH,CH,SCH, CH SCH 2 2 2 3 CCONHCH CH 2 CN CCO)HHCH CH SCH C(0)HHCH CH SCN CCO)HHCH, CH 2 P(0)(OCH 3 ) 2 3 C(0)H(CH 3 2 CH,CN 2 C(0)H(CH 3 ) 2 CH,CH 2 C(0 H<CH 3 2 CH,CN 2 C 0)H(CH 3 ) 2 CH,CH 2 C(0)H(CH 3 2 CH,SCN 2 CO ,CH CH, 2 2 3 23 CO,CH,CH, 2 2 3 23 CO,CH,CH, 2 2 3 23 C0,CH,CH, CH,N, 2 2 3 23 C(0)N(CH 3 ) 2 CH SCN C(0)N(CH 3 ) 2 CH 2 SCN C(0)H(CH 3 ) 2 CH 2 P(0 (0CH 3 2 TABLE I (Continued) OJ OJ t t H H Ul o in o l o Ul X X X X X X X X X X X X X X X X X X x X X X X X X X X X X O O O O P P P P P P P P P P P P P P P P P P P P P P P P P P O IC X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X IX Ω Ω X Ω Ω Ω Ω X Ω X Ω Ω X Ω Ω X Ω Ω Ω Ω X X X X X X X TABLE I (Continued) R. R_, SO,CH„CH, CH,P(0)(0CH,) 2 2 3 3'2 SO-CH-CH-CH- CH CN 2 2 2 3 SO-CH-CH-CH, CH CN 2 2 2 3 SO-CH-CH-CH- CH-CN 2 2 2 3 2 SO„CH.CH,CH, CH CN 2 2 2 3 SO,CH,CH,CH, CH CN 2 2 2 3 SO„CH,CH,CH, CH CN 2 2 2 3 SO Λ CH.CH,CH, CH-H, 2 2 2 3 2 3 SO,CH,CH,CH, CH-H, 2 2 2 3 2 3 SO,CH,CH,CH, CH 2 H 3 2 2 2 3 SO-CH-CH-CH- 2 2 2 3 SO,CH,CH,CH, CH 2 N 3 2 2 2 3 S0 2 CH 2 CH 2 CH 3 CH 2 N 3 SCH 3 CH CH SCH,CH,CH, CH,CN 2 2 3 2 S<0)CH CH CH SCN S<0)CH 2 CH 2 CH 3 CH PCOXOCH,) 3'2 OS0 2 CH 3 CH 2 CN OS0 2 CH 3 CH CH OSO-CH- CH CH 2 3 OSO-CH- CH CH 2 3 OSO-CH, CH-CH . 2 3 2 OSO-CH, CH 2 SCN 2 3 OSO.CH. CH SCN 2 3 OS0 2 CH 3 CH SCN OS0 2 CH 3 CH.SCN 0S0 2 CH 3 CH 2 P(OXOCH 3 2 OS0 2 CH 3 CH 2 P 0XOCH 3 ) 2 OS0 2 CH 2 CH 3 CH 2 CH 0S0 2 CH 2 CH 3 CH 2 CN 0S0 2 CH 2 CH 3 CH CN 0S0 2 CH 2 CH 3 CH CN 48 TABLE I (Continued) R- R„ OS0 2 CH 2 CH 3 CH CH OSO,CH,CH, CH SCH 2 2 3 OSO,CH.CH. CH 2 SCN 2 2 3 OS0 2 CH 2 CH 3 CH SCN OS0 2 CH 2 CH 3 CH 2 P(0) (OCH 3 ) 2 OS0 2 CH 2 CH 3 CH 2 P(0) (OCH 3 > 2 OS0 2 CH 2 CH 3 CH 2 P(0) (OCH 3 ) 2 OSO.CH-CH-CH- CH CH 2 2 2 3 OS0 2 CH 2 CH 2 CH 3 CH 2 CN OS0 2 CH 2 CH 2 CH 3 CH 2 CH OSO,CH,CH,CH- CH CH 2 2 2 3 CH-OCH- CH 2 P(0) (OCH 3 ) 2 2 3 CH 2 SCH 3 CH 2 P(0) (OCH 3 ) 2 CH 2 CH 3 OCH 3 CH 2 P(OXOCH 3 > 2 CH-CH-OCH- 2 2 3 CH-CH-SCH-CH- 2 2 2 3 CH 2 CH C 2 H 5 C 2 H 5 C 2 H 5 C 2 H 5 COCH 3 COCH 2 CH 3 COC≡CC-L COCH CH 2 C1 C(0)-cyclo- propyl C(0)-cyclo- CH 2 CH propyl c(0)-cyclo- CH 2 SCH propyl 49 TABLE I (Continued) 50 TABLE I (Continued) 51 TABLE I (Continued) Ω P to Ω x CJ io to X X X X X X X x x x x a a a a a a a a a a x a .x x x x x x IX 8 0 0 0 0 0 8 Ω 0 p P P Ω O O IM Ω Ω Ω Ω Ω ___.. w Q Ω Ω Ω Ω Ω _ Ω._ Ω_. Ω_. b- Ω Ω X X X X X X 8 X 8 ... 8 X 8 8 tr X X X X X X X X X X OJ CJ CJ OJ OJ OJ OJ OJ a OJ .. OJ . CJ OJ OJ J " W S P p O p OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ^ OJ 33 * 3 3 3 3 8 Ω x xΩ Ωx X Ω x Ωa Ωa Ωa Ωa X Ω Ω Ω X x Ω Ω x a a X aΩ xΩ X aΩ X Ω x xΩ xΩ IN a Ω TABLE I (Continued) to _ o _-> l o-> Ul ΩS O ΩS O ΩS O ΩS O g> o Q s -* Q- ~* Q" ~* Q~ —* S S O CJ OJ OJ io x Ω Ω a Ω a x 3 Ω IN X X 56 TABLE I (Continued) 57 TABLE I (Continued) 58 TABLE I (Continued) 59 TABLE I Continued 60 TABLE I (Continued) 61 TABLE I (Continued) 8 X X to 8 to 8 to 2f If If If IJ I-f IJ* If IJ If IJ I t f If If If If IJ I-f If If IJ I*J I* t J I'>l I-f Ij I*j I> CJ a to to t x Ω Ω CJ CJ a OJ x oj 8oj3888 OJx OJx CJa 8 OJa 8a 888 OJ CJa OJao x x x a x a x a a x x x B a a a a a a a x x x x x x x IN 63 TABLE I (Continued) 96 64 TABLE I (Continued) 65 66 TABLE I (Continued) TABLE I Continued h NO, NO N0 2 N0 2 N0 2 N0 2 NO 2 N0 2 NO_ NO, CM CM CM CM CM CM X X B ■ a __.<*> X X X o O O j x o CM o δ o o te 70 m.p. CO TABLE III General Formula III TABLE III (cont.) O„ F Cl CF 3 N0 2 OCH 3 OCH 3 O H 2 CH 3 OCH 2 CH 3 C0 2 CH 3 C0 2 CH 3 C0 2 CH 3 C0 2 CH 3 C0 2 CH 2 CH 3 C0 2 H 2 CH 3 C0 2 M(CH 3 ) 2 S0 2 NHCH 3 S0 2 N CH 3 ) 2 S0 2 N(CH 3 ) 2 S0 2 CH 3 S0 2 CH 3 S0 2 CH 2 CH 3 S0 2 CH 2 CH 3 OSO CH OS0 2 CH 3 OS0 2 CH 2 CH 3 R -A R χ -A R 1 -B R χ -C F OCH, TABLE V cont. TABLE V (cont.) TABLE VI General Formula VII F CH,CN H OCH 2 Cl CH SCN H OCH CF 3 CH 2 P(0)(OCH 2 CH 3 ) 2 H OCH 3 N0 2 CH CH H CH 3 OCH 3 CH CH H OCH OCH CH SCN H CH 3 OCH-CH, CH SCN H OCH 2 3 OCHCH, CH CN H CH 3 2 3 C0 2 CH 3 CH CN H OCH, 3 C0 2 CH 3 CH,CN H CH, 2 3 C0 2 CH 3 CH SCN H OCH CO,CH CH 2 P(0)(OCH ) H CH, 2 3 3 CO,CH,CH, CH,P(0)(OCH,) H OCH 2 2 3 2 32 C0 2 CH 2 CH 3 CH CN H CH 3 C0 2 N CH 3 2 CH,CN H OCH 2 SO NHCH CH,CH H CH 3 2 S0 2 N CH 3 ) 2 CH,CH H OCH 2 S0 2 NCCH 3 ) 2 CH SCN H CH 3 S0 2 CH 3 CH SCN H OCH S0 2 CH 3 CH CN H OCH S0 2 CH 2 CH 3 CH CN H CH 3 SO,CH,CH, CH 2 P(0)(OCH 3 ) 2 H CH 3 2 2 3 OS0 2 CH 3 CH 2 P 0 OCH 3 2 H CH 3 OS0 2 CH 3 CH CN H OCH, OS0 2 CH 2 CH 3 CH 2 SCN H OCH R -A CH CN H CH 3 R_-A CH SCN H OCH, B CH 2 P 0 OCH 3 2 H CH 3 " R -C CH CN H OCH, CH-NOH H OCH, OCH, CH=NOCH„ H OCH, TABLE VI (CQtt. ) TABLE VI (eont.) TABLE VI I Genera l Formula VI I 5 __1 __2 F CH 2 CN Cl CH 2 SCN C 3 CH 2 P(0)(0CH 2 CH 3 ) 2 N0 2 CH 2 CN 10 OCH 3 CH 2 CN OCH 3 CH 2 SCN OCH 2 CH 3 CH 2 SCN OCH CH CH 2 CN C0 2 CH 3 CH 2 CN 15 C0 2 CH 3 CH 2 C CO CH CH SCN C0 2 CH 3 CH 2 P(0)(OCH 3 ) 2 C0 2 CH 2 CH 3 CH 2 (O) (OCH 3 ) 2 C0 2 CH 2 CH 3 CH 2 CN 20 C0 2 (CH 3 ) 2 CH 2 CN S0 2 NHCH 3 CH 2 C S0 2 CH 3 ) 2 CH 2 CN S0 2 N(CH 3 ) 2 CH 2 SCN S0 2 CH 3 CH 2 SCN 25 S0 2 CH 3 CH 2 CN S0 2 CH 2 CH 3 CH 2 CN S0 2 CH 2 CH 3 CH 2 P(0)(OCH 3 ) 2 OS0 2 CH 3 CH 2 P(0)(OCH 3 ) 2 OS0 2 CH 3 CH 2 CN 30 OS0 2 CH 2 CH 3 CH 2 SCN R χ -A CH 2 CN R -A CH 2 SCN R L -B CH 2 P(0)(OCH 3 ) 2 R L -C CH 2 CN 35. F CH-NOH OCH, CH-NOCH, TABLE VII (cont.) 86 Formulations 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 approximate proportions: Weight Percent* Active Ingredient Diluent(s) Surfactant(s) Wettable Powders 20-90 0-74 1-10 Oil Suspensions. 3-50 40-95 0-15 Emulsions. Solutions. (including Emulsifiable Concentrates) * 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 βomtimes desirable, and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins. et al.. "Handbook of Insecticide Dust Diluents and Carriers". 2nd Ed.. Dorland Books. Caldwell. New Jersey, but other solids, either rained or manufac¬ tured, 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. "Solvents Guide." 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 β C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents". 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. Patent 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. "Agglomeration". Chemical Engineering. December 4. 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook". 5th Ed.. McGraw-Hill. New York. 1963. pp. 8-57ff. 88 For further information regarding the art of formulation, see for example: H. M. Loux. U.S. Patent 3.235.361. February 15. 1966. Col. 6. line 16 through Col. 7. line 19 and Examples 10 through 41; R. W. Luckenbaugh. U.S. Patent 3.309.192. March 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. Patent 2.891.855. June 23. 1959. Col. 3. line 66 through Col. 5. line 17 and Examples 1-4; G. C. Klingman. "Weed Control as a Science". John Wiley and Sons. Inc., New York. 1961. pp. 81-96; and J. D. Fryer and S. A. Evans, "Weed Control Handbook". 5th Ed.. Blackwell Scientific Publications. Oxford. 1968. pp. 101-103. Tn the following examples, all parts are by weight unless otherwise indicated. Example 11 High Strength Concentrate 2-(cyanoraethyl)-6-[[(4,6-diraethoxypyrimidin-2-yl)- aminocarbonyl]aminosulfonyl]benzoic acid, ethyl ester 99% trimethylnonyl polyethylene glycol ether 1% The surfactant is sprayed upon the active ingredient in a blender and the mixture sifted through a U. S. S. no. 40 sieve (0.42 mm openings) prior to packaging. The concentrate may be formulated further for practical use. 89 Example 12 Wettable Powder 2-(acetoxymethyl)-6-[[(4-methoxy-6-raethyl-1.3.5- triazin-2-yl)aminocarbonyl]aminosulfonylJbenzoic acid, ethyl ester 65% dodecylphenol polyethylene glycol ether 2% sodium ligninsulfonate 4% sodium silicoaluminate 6% montmorillonite (calcined) 23% The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below loo microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged. Example 13 Aqueous Suspension 2-(cyanomethyl)-6-[[(4.6-dimethoxypyrimidin-2-yl)- aminocarbonyl]aminosulfonyl]benzoic acid, ethyl ester 50.0% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1* mo osodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. Example 14 Oil Suspension 2-(acetoxymethyl)-6-CC(4-methoxy-6-methyl-1.3.5- triazin-2-yl)aminocarbonyl]aminosulfonyljbenzoic acid, ethyl ester 35% blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6% xylene 59% The ingredients are combined and ground together in a sand mill to produce particles essentially all below 3 microns. The product can be used directly, extended with oils, or emulsified in water. Example 15 Oil Suspension 2-(cyanomethyl)-6-[C(4.6-dimethoxypyrimidin-2-yl)- aminocarbonyljaminoβul onylJbenzoic acid, ethyl ester 25% polyoxyethylene 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. Example 16 Aqueous Suspension 2-(acetoxymethyl)-6-[[(4-methoxy-6-methyl-l.3.5- triazin-2-yl)aminocarbonyl]aminosulfonyl]benzoic acid, ethyl ester 25% hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5% The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns. Example 17 Wettable Powder 2-(cyanomethyl)-6-[C(4.6-dimethoxypyrimidin-2-yl)- arainocarbonyl]aminosulfonylJbenzoic acid, ethyl ester 40% dioctyl sodium βulfoβuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54% The ingredients are thoroughly blende, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging. All compounds of the invention may be formulated in the same manner. Example 18 Granule wettable powder of Example 17 15% gypsum 69% potassium sulfate 16% The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 cm (U.S.S.#18 to 40 sieves), the granules are removed, dried, and screened. Oversized material is crushed to produce additional material in the desired range. These granules contain % active ingredient. Example 19 Wettable Powder 2-(acetoxymethyl)-6-[[(4-methoxy-6-methyl-l.3.5- triazin-2-yl)aminocarbonyl]aminosulfonylJbenzoic acid, ethyl ester 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46% The ingredients are blended, coarsely hammer- milled and the air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. Example 20 Extruded Pellet 2-(cyanomethyl)-6-[[(4.6-dimethoxypyrimidin-2-yl)- aminocarbonyl a inosulfonylJbenzoic acid, ethyl ester 25% anhydrous 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. Example 21 Wettable Powder 2-(acetoxymethyl)-6-[[(4-methoxy-6-methyl-l.3.5- triazin-2-yl)aminocarbonyljarainosulfonylJbenzoic acid, ethyl ester 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13% The ingredients are blended and then ground in a hammermill to produce particles with an average particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before being packaged. Example 22 High Strength Concentrate 2-(cyanomethyl)-6-CC(4.6-dimethoxypyrimidin-2-yl)- aminocarbonyljaminosulfonylJbenzoic acid, ethyl ester 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0% The ingredients are blended and ground in a hammer mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways. Util ity 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, 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 barley, corn, soybeans, sugarbeets and cotton. 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, formula- tions selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.010 to 20 kg/ha. the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modificaton or for situations where only short-term persistence is required such as herbicide for fallow land. The compounds of the invention may be used in combination with any other commercial herbicide; non-limiting examples of which are those of the sulfonylurea. triazine. triazole. uracil. urea, amide, diphenyl ether, carbamate and imidazolinone. cineole and bipyridylium types. The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow. Com ounds Continued 98 Test A Seeds of crabgrass (Digitaria spp. ) . barnyard- grass (Echinochloa crusgalli) . cheatgrass (Bromus Secalinus). giant foxtail (Setaria faberii). wild oats (Avena fatua). velvetleaf (Abutilon theophrasti) . morningglory (Ipomoea spp. . cocklebur (Xanthium pensylvanicum) . sorghum, corn, barley, soybean, sugar- beet, 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: B - burn; C - chlorosis/necrosis; D 3 defoliation; E - emergence inhibition; G - growth retardation; H - formative effect; U - unusual pigmentation; X - axillary stimulation; S = albinism; and 6Y = abscised buds or flowers. (TEST A) CUP. 1 CHPIf 2 OiPB 3 CMP. 4 RATE RAT£=KG/HA 6.65 θ.δi 6.65 6.6f 6.65 6.61 6.65 6.61 SUBSTITUTE SHEET BARLEY 9G 8G 2C.7G 3G 8G 5G SUBSTITUTE SHEET (TEST A) CKFD 9 CHPD 16 CHPD I I QIPD 12 SUBSTITUTE SHEET (TEST A) CHPD 13 CHPD 14 CHPD 15 CHPD <6 RATE RATE=KG/HA 6.Θ5 6.61 6.65 6.61 6.65 6.61 6.65 ..01 SUBSTITUTE SHEET 104 10 15 20 25 30 35 SUBSTΪTISTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) j u B sτi T uτe SHE£T TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUEO) SUBSTITUTE SHEE TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUR STITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A t CONTINUED) SUBSTITUTE SHEET SUBSTITUTE SHEET TEST A <CONTINUED! CMPO 79 SUBSTITUTE SHEET TEST A (CONTINUED) SUBSTITUTE SHEET TEST A (CONTXtMCD) SUBSTITUTE SHEET TEST A ICONTINUED) SUBSTITUTE SHEET TEST A (CONTINUED ) It is noted that certain compounds (i.e., 77, 78. etc.) do not show activity at the rate tested. It is thought that these compounds would show activity at higher rates. SUBSTITUT Test B Postemerσence Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge (Cyperus rotundus) tubers, crabgrass (Di itaria sanguinalis) . sicklepod (Cassia obtusifolia) . jimsonweed (Datura stramonium) . velvetleaf (Abutilon theophrasti) . lambsquarters (Chenopodium album) . rice (Oryza sativa) and teaweed (Sida spinosa). The second pot was planted with green foxtail (Setaria viridis) . cocklebur (Xantium pensyl- vanicum) . morningglory (Ipomoea hederacea). cotton (Gossypium tiirsutum) . johnsongrass (Sorghum halepense) . barnyardgrass (Echinochloa crusgalli). corn (Zea mays) . soybean (Qlycine max) and giant foxtail (Setaria faberi) . The third pot was planted with wheat (Triticum aestivum). barley (Hordeum vulgare). wild buckwheat (Polgohum convolvulus .), cheatgrass (Bromus secalinus L;), sugarbeet (Beta vulgaris) . wild oats fAvβna fatua). viola (Viola arvensis). blackgrass (Alopecurus mvosuroides) . and rape (Brassica napus) . The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a non-phytotoxic solvent. Preemergence Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutεedge tubers, crabgrass, sicklepod. jimsonweed. velvetleaf. lambsquarters. rice and teaweed. The second pot was planted with green foxtail, cocklebur. morningglory, cotton, johnsongrass, barnyardgrass. corn, soybean and giant foxtail. The third pot was planted with wheat, barley, wild buck- wheat, cheatgrass. sugarbeet. wild oat. viola, black¬ grass and rape. The three pans were sprayed pree er- 126 gence with the chemicals dissolved in a non-phytotoxic solvent. Treated plants and controls were maintained in the greenhouse for 24 days, then all rated plants were compared to controls and visually rated for plant response. Response eatings are based on a scale of 0 to 100 where 0 « no effect and 100 - complete control. A dash (-} response means no test. Response ratings are contained in Table B. (TEST B) CKN 3 RATE 9091 ΘΘΘ4 9011 994? 9256 SUBSTITUTE SHEET (TEST B) CHPD 4 SUBSTITUTE SHET • TEST B) c 5 RATE RATE-G/hή 900: 990< 901έ 096? Θ25C (TEST B> HPD ε SUBSTITUTE SHEET (TEST B) CHPI- o ' ATI RATE=G/HA 905! 9904 0016 9062 0250 M-TBERGEN-E C HT FOXTAIL 39 59 90 VELVETLEAF 59 79 199 SUGAR BEETS 79 100 190 CRABGRASS 39 79 TEAWEED 39 70 JI/ISONWEED 9 30 79 RICE 39 79 196 COCKLEBUR 59 79 199 COTTON 9 9 79 SOYBEAN 79 96 190 BARNYARD CRASS 39 59 99 WILD OATS 9 39 79 MORNINGGLORY 9 9 59 WHEAT 9 0 79 CASSIA 9 30 70 JOHNSONGRASS 9 30 80 NUTSEDGE 9 50 CORN 39 50 79 WILD BUCKWHEAT 29 40 SO PftEE«ERG_KCE WANTFOXTAIL 39 79 190 VELVETLEAΓ 30 89 100 SUGAR BEETS 60 30 99 CRABGRASS 39 76 90 TEAWEED 30 79 90 JIKSOWEE- 30 79 190 RICE 59 ? 9 99 COCKLED-!. 39 79 96 COTTON 39 60 SOYBEAN 39 6i 89 BARNYARD CRASS 39 79 59 WILD OATS 39 50 79 ΛORNINCCL-RY 9 50 76 WHEAT 39 59 79 CASSIA 9 50 79 JOHNSαVSRASS 5θ 90 199 MIT-EKE 9 59 90 CORN 9 50 89 WILD BUCKWHEAT 39 79 (60 E SHEET (TEIT ..' CMPD »9 SUBSTITUTE SH ET ( TEST B) CMPD 11 RATE RATE=C/HA 6991 9904 9916 9962 ft POSTE-OCENCE 259 UMR FOXTAIL 9 VELVETLEAF • 9 SUGAR BEETS 9 CMKBUr e TEAWEED 6 JΓΛSONWEED 39 RICE 9 COCKLEBU.. 39 COΠON A SOYBEAN 39 * BARNYARD CRASS 6 WILD OATS 9 MORNINKLORY i WHEAT 9 CASSIA 9 JOHNSONGRASS 9 NUTSEDGE CORN WILD BUCKWHEAT PREEMERGENCE CIAHT FOXTAIL - VELVETLEAF SUGAR BEETS CRABGRASS TEAWEED JIMSONWEED RICE CBttUXF. COTTON SOYBEAN •ARNYARD CRASS - rfILD OATJ" MORNINCCLOfir WHEAT CASSIA JOHNSONGRASS' NUTSEDGE CORN WILD BUCKWHEAT - ITUTE SHEET SUBSTITUTE SHEET (TEST B) CMPD 13 SUBSTITUTE SHEET (TEST B ) CMPD 14 (TEST B) CMPD (5 UBSTITUTE SHEET L39 (TEST B ) am 16 50 (TEST B) CMPD 17 RATE ft_TE=G/HA 0991 9094 9616 9962 9256 (TEST B) CMPD 18 25Θ

Claims: 142 WHAT IS CLAIMED IS: 1. A compound selected from wherein E is CH or a single bond; W is O or S; R is H or CH : R χ is H. F. Cl. CH 3 . OCH 3 . N(CH ) or OCHF '. R χ is F, Cl. Br. N0 2 . C -C 4 alkyl. C -C 4 alkenyl. _-C 4 haloalkenyl. C_-C. alkynyl, C -C haloalkyl. C -C alkoxy. OCH 2 CH 2 OCH 3 . C χ -C 4 haloalkoxy. C -C alkenyloxy. C -C haloalkenyloxy, C -C alkynyloxy. CO _;R3, CONR4Rb. S(O) R e o. OSO„2R„7. C,1-C2 alkyl substituted with C -C alkoxy. OH or C -C alkylthio. CH ^ CN. C R . 2 6 5 R,-A R^B χ -C R- ^ -D R- ^ -E L43 _± R.-G R j^ -H ___£ ____ R.-K R^M R^» R.-O *___ R ι- U R, R.-W R.-X xl R -Z R -AA R--AB ' R.-AC R -AD II R 2 is -CH(R 16 )CN. -CH(R L7 )SCN. -CH(R 17 )PR 10 R 1; .. S II -CH(R 17 )PR 10 R 1;L . -CH( 17 )NR 12 R 13 , -CH(R 17 )SeR 14 , -CH(R 17 )N 3 . -CH(R 17 )N0 2 . -CH(R 17 )NC, -CR 1? . ■ - -CH(OCCH 3 ) 2 . -CHOCR 22 -C(R 1? )C1. -C(R 1? )Br or -CHOSθ 2 CH 3 ; R 23 R 24 R 17 R„3 is C1,-C. alkyl. C.3-C4,, alkenyl, C3-C4. or alkynyl. -CH 2 - ] . CH CH 2 C1. CH 2 CH 2 F. C -C alkyl substituted with OCH . SCH 3 or CN; R is -C 3 alkyl or C.-C- alkoxy; R4 is C1-C3 alkyl or C1-C2 alkoxy: R is H or C1-C 3 alkyl; R5 is H or C1-C 3 alkyl; R 4 and R5 may be taken together to form -(CH 2 ) 3 - or -(CH 2 )4-; R4 and R5 may be taken together to form -(CH 2 ) 3 - or -(CH 2 ) 4 -; R 6 is CX-C3 alkyl, -CH 2 CH=CH 2 or CH 2 C≡CH; R 7 is C L -C 3 alkyl or N(CH 3 ) 2 ; R 8 is H. C 1 -C 4 alkyl. C 3 -C4 alkenyl, C 3 -C4 alkynyl, CH 2 CH 2 C1. CH 2 CH 2 F, C 1 -C 2 alkyl substituted with OCH 3 or SCH 3 or C 3 -Cg cycloalkyl; Kg is Cι - C 2 alkyl; R^ O and R ll are independently C C 2 alkyl. C L -C 2 alkoxy, C -C 2 alkylthio. NHC_I 3 or N(CH 3 ) 2 : R^2 and R 13 ace independently H or Cj-C2 alkyl: R- 4 is -C 3 alkyl; R, Lb, is H, C-L.-C Δ- alkyl or F; R is H or C -C alkyl; R{ 7 is H. C x -C2 alkyl. CN. Cl. OCH 3 . SCH 3 or R 18 is C -C alkyl; 'l9 is H, Si(CH 3 ) 3 or C-_-C 2 alkyl; 20 is H or C 1 -C_ alkyl; 21 is H. C -C_ alkyl or allyl; 22 is C 1 -C 2 alkyl or C j -C- haloalkyl; 23 is H, CH 3 . Cl or Br; p is 1 or 2; n is 0, 1 or 2; -1 A-2 h____2. = h=5. ____£ A-7 146 X is H. C L -C 4 alkyl. C χ -C 4 alkoxy. C -C 4 halo¬ alkoxy. C 1 -C 4 haloalkyl, C -C haloalkylthio. C 1 -C 4 alkylthio. halogen. C -C alkoxyalkyl. C 2 -C 5 alkoxyalkoxy. amino. C.-C 3 alkylamino or di(C -C alkyl)amino; Y is H. C1-C4 Λ alkyl. C1.-C, alkoxy. C1-e, halo- alkoxy. C -C haloalkylthio. C -C alkylthio. C -C alkoxyalkyl. C -C alkoxyalkoxy, amino, C, 1-c,J alkylamino. di(C,-C, alkyl)amino. C3-C4, alkenyloxy, C-C alkynyloxy. C -C_ alkyl- thioalkyl. C 2 -C 8 alkylsulfinylalkyl. C -C_ alkylsulfonylalkyl. C -C 4 haloalkyl. C -C alkynyl. C,-C_ cycloalkyl, azido. cyano. - •» N(OCH 3 )CH 3 ϊ i is 2 oi 3; Q. and Q 2 are independently O or S; Ra is H or C.1-C,3 alkyl; R and R are independently C -C 3 alkyl; Z is CH. N. CCH 3 . CC 2 H 5 . CC1 or CBr; is O or CH 2, ' X is CH 3 . OCH 3 . OC 2 H 5 or OC 2 H; 2 is CH 3 . C 2 H g or CH 2 C 3 ; Y 2 is OCH 3 . OC 2 H 5 . SCH 3 . SC 2 H 5 . CH 3 or CH_CH_; X, is CH, or OCH,: 3 3 3 Y is H or CH 3 ; X 4 A is CH,3. OCH,3, OC2.H-5. CH2-OCH,3 or Cl; Y4. is CH,3. OCH,3, OC2,H c 5 or Cl; and their agriculturally suitable salts; provided that 1) when X is halogen, then z is CH and Y is OCH 3 OC 2 H 5 . H 2 . NHCH 3 , N(CH 3 ) 2 . OCF 2 H, OCF Br or N(OCH 3 )CH 3 ; 2) when X or Y is C haloalkoxy, then Z is CH: 3) when W is S. then R is H. A is A-l. Z is CH or N. and Y is CH,3. OCH,3. OC2_H_. CH-2.OCH,3. < W CF 3 . SCH 3 . OCH 2 CH=CH 2 . OCH C≡CH. 4) when the total number of carbon atoms of X and Y is greater than four, then the combined number of carbons of R and R is less than or equal to six; 5) when R 2 is -C(0)R 1? . -C(R 23 ) (R 1? )C1 or -C(R )(R )Br then Y is other than cyclo- propyl: 6) when Y is C 2 -C 5 alkylthioalkyl, C 2 -C 8 alkyl¬ sulfinylalkyl or C -C_ alkylsulfonylalkyl, then 2 b R„ is other than CH(R,„)NO,. and 2 17 2 CH(R 17 )OS0 2 CH 3 ; 7) X, and Y Λ are not simultaneously Cl; 4 . 4 I 8) when R 4 is C.-C alkoxy and R g is H, then R is other than CH(R )CN. C(R 23 )(R 1? )C1 and C(R 24 )(R 17 )Br; 9) when R 2 is C(0)R 17 . C(R 23 ) (R 1? )C1 or C(R )(R )Br. then R is other than C -C haloalkyl or C alkyl substituted with C -C alkoxy. OH or C -C alkylthio; 10) when R 2 is C(R 23 ) (R 1? )C1 or C(R 24 ) (R 1? )Br, then X and Y are other than C -C haloalkoxy or C„1-C4 Λ haloalkylthio: 11) when R 2 is C(R 23 )(R 1? )C1 or CCR 24 )(R 1? )Br. then R is other than C -C haloalkoxy, C-C, alkenyloxy. C_-C. haloalkenyloxy, 3 4 2 4 C 2 -C 4 alkynyl. 3 -C 4 alkynyloxy. 2 -C 4 haloalkenyl and R -A through R -W: 12) when R is R -X. R -Y. R -Z. R -AA, R -AB. R -AC or R -AD. then R is other than CH(R 16 )CN. C(R 23 )-( 17 )C1 and C(R 24 )(R 17 )Br; 13) when R2 is C(Q)R 17 . then ^ is other than SO2N 4 5; and 14) when 2 is CO2 3. then both R 2 and R.3 are other than H. 2. A compound of Claim 1 where is O. 3. A compound of Claim 2 where E is a single bond; X is C-C alkyl. C -C alkoxy. Cl. F. Br. I. OCF H. CH F. CF . OCH CH F. OCH 2 CHF 2 . OCH 2 CF 3 . CH 2 C1 or CH 2 Br; and Y is H. C χ -C 2 alkyl. C.-C alkoxy, CH 2 OCH 3 . CH 2 OCH 2 CH 3 . NHCH 3 . N(OCH 3 )CH 3 . (CH 3 ) 2 . C 3 . SCH 3 , OCH 2 CH=CH 2 . OCH„C≡CH. OCH ^ CH ^ OCH,. CH SCH . 2 2 2 3 2 3 SCF H. OCF Br. cyclopropyl. C≡CH or C≡CCH Z is CH or N; , A compound of Claim 3 where O 2 is -CH 2 CN. -CH 2 N 3 . -CH 2 P(OC 1 -C 2 alkyl) 2 . y- H-OR 2Q . -CR 17 . -CHOCR 22 or -CH(R 1? )N0 2 ; a R Ϊ7 Rl7 is H. C1-C2 alkyl, Cl or CN. 5. A compound of Claim 4 where A is A-l. 6. A compound of Claim 5 where R L is F, Cl. Br. N0 2 . <- 1 ~C 3 alkyl. C L -C 2 alkyl substituted with 1-3 F or Cl or 1 Br. C-C alkenyl, C -C alkenyl substituted with 1-3 F or Cl. C -C alkoxy. C -C alkoxy substi¬ tuted with 1-3 F or Cl or 1-Br, allyloxy, propargyloxy. 0C(C1)=CHC1. C0 2 CH 3 , C0 2 CH 2 CH 2 C1. C0 2 CH 2 CH 2 OCH 3 . . CONH(C -C alkyl). CONCH 3 (C -C alkyl). . S0 2 N(OCH 3 )CH 3 . S0 2 NH(C 1 -C 2 alkyl). S0 2 (C L -C 2 alkyl) 2 . S(O) C -C alkyl. OSO C -C alkyl. £1 JL •_» * 6 JL •_» C-C alkyl substituted with OCH or SCH . Co,H_b and R.1-A. R1.-B. -i—C, R_—D, R —E, R-—F, R-— , R —H, R-—I, R.— , R-—K, R_—L, R_—M, R_—N, R ι "u# R ι~ v* R ι " ' R ι ~x* R ι "γ ' R ι "z ' R -AA. R -AB. R -AC or R -AD; 7. A compound of Claim 6 where A compound of Claim 7 where R is H; L is F. Cl. Br. N0 2 . CH 3 . CF 3 C ]L -C 2 alkoxy. allyloxy. 0C(C1)-CHC1. CO CH . C0 2 C 2 H 5 . C0 2 NHCH 3 . C0 2 N(CH 3 ) 2 . S0 2 NHCH 3 S0 2 N(CH 3 ) 2 . S0 2 CH 3 . S °2 C 2 H 5' OS °2 CH 3' OS °2 C 2 H 5' R l "A ' R,-B. R,-C. R -X. R,1-Z or R,-AB; and R χ is H. 9. The compound of Claim 1 that is 2-(cyanomethyl)-6-[[(4.6-dimethoxypyrimidin-2-yl) aminocarbonyl]aminosulfonyl]benzoic acid, ethyl ester. 10.The compound of Claim 1 that is 2-(acetoxymethyl)-6-[[(4-methoxy-6-methyl-l.3.5- triazin-2-yl)aminocarbonyl]aminosulfonyl]benzoic acid, ethyl ester. 11. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 1 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 12. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 2 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 13. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 3 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 14. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 4 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 15. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 5 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 16. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 6 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of th foregoing. 17. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 7 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 18. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 8 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 19. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of the compound of Claim 9 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 20. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of the compound of Claim 10 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing. 21. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com- pound of Claim 1. 22. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 2. 23. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 3. 24. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 4. 25. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 5. 26. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com- pound of Claim 6. 27. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 7. 28. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a com¬ pound of Claim 8. 29. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 9. 30. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 10.

Inventors: GEE STEPHEN KENNETH, GEE, STEPHEN, KENNETH
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1987
Main classification: C07D239
IPC codes: A01N47, C07D491, C07D521