Agricultural sulfonamides

BACKGROUND OF THE INVENTION
This invention relates to novel N-(heterocyclicaminocarbonyl)arylsulfonamides in which the aryl radical is substituted by a carboxyl radical, ester, thioester or amide thereof. The compounds of this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g. plant growth regulants and herbicides.
Netherlands Pat. No. 121,788, published Sept. 15, 1966, discloses the preparation of compounds of the following Formula and their use as general or selective herbicides: ##STR1## wherein R.sub.1 and R.sub.2 may independently be alkyl of 1-4 carbon atoms; and
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2## wherein R.sub.1 is hydrogen or lower saturated aliphatic acyl and
R.sub.2 is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.
The disclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.
French Pat. No. 1,468,747 discloses the following para-substituted phenylsulfonamides as being useful as antidiabetic agents: ##STR3## wherein R=H, halogen, CF.sub.3 or alkyl.
Logemann et al. Chem Ab., 53, 18052 g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula: ##STR4## wherein R is butyl, phenyl, or ##STR5## and R.sub.1 is hydrogen or methyl.
When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon. Pharm 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: ##STR6## Based upon similarity to a known compound, the author speculated that the foregoing compound might have a hypoglycemic activity.
Substituted-pyrimidinyl sulfonylureas of the following formula, which are also para-substituted on the phenyl ring, are disclosed in Farmco Ed. Sci., 12, 586 (1957) [Chem. Ab., 53, 18052 g (1959]: ##STR7## wherein R=H or CH.sub.3.
The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomitant world food and fiber shortage demand improvements in the efficiency of producing these crops. Preventing or minimizing loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective herbicides.
SUMMARY OF THE INVENTION
According to this invention, there are provided novel compounds of Formula I and their agriculturally suitable salts, e.g. Na, K, alkyl ammonium, trichloroacetic acid, suitable agricultural compositions containing them and methods of using them as general or selective pre-emergence and post-emergence herbicides and as plant growth regulants: ##STR8## wherein Q is 0, S or ##STR9## when Q is O or S then R is C.sub.1 -C.sub.12 alkyl; C.sub.3 -C.sub.10 alkenyl; C.sub.3 -C.sub.10 alkynyl; C.sub.2 -C.sub.6 alkyl substituted with one to four substituents selected from 0-3 atoms of F, Cl, Br, 0-2 methoxy groups and 0-1 cyano groups; --CH.sub.2 CN; ##STR10## where R.sub.7 ' or CH.sub.3 ; C.sub.3 -C.sub.6 alkenyl substituted with 1-3 atoms of F, Cl, Br; C.sub.3 -C.sub.6 alkynyl substituted with one of F, Cl or Br; C.sub.5 -C.sub.8 cycloalkyl; C.sub.5 -C.sub.8 cycloalkenyl; C.sub.5 -C.sub.6 cycloalkyl substituted with OCH.sub.3, alkyl of C.sub.2 -C.sub.4, F, Cl or Br or one to four methyl groups; C.sub.4 -C.sub.10 cycloalkylalkyl; C.sub.4 -C.sub.8 cycloalkylalkyl with 1-2 CH.sub.3 ; C.sub.7 -C.sub.10 bicycloalkyl; C.sub.7 -C.sub.10 bicycloalkenyl; C.sub.10 tricycloalkyl, C.sub.10 tricycloalkenyl; ##STR11## where R.sub.9 is C.sub.1 -C.sub.3 alkyl or hydrogen, R.sub.10 and R.sub.11 are independently hydrogen, C.sub.1 -C.sub.3 alkyl, Cl, Br, --OCH.sub.3, --OC.sub.2 H.sub.5 or R.sub.10 and R.sub.11 may be taken together to form a 5 or 6 member ring: ##STR12## and n is 0, 1, 2 or 3 provided the total number of carbon atoms is .ltoreq.12; ##STR13## A is O, S; A.sub.1 is O, S, SO.sub.2 ;
when Q is O, then R is H, M, --CH.sub.2 CH.sub.2 OR.sub.7 ; --CH.sub.2 CH.sub.2 CH.sub.2 OR.sub.7, ##STR14## where R.sub.7 is --CH.sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, phenyl, --CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CCl.sub.3 ; CH.sub.2 OR.sub.8 ' where R.sub.8 ' is --CH.sub.3, --CH.sub.3 CH.sub.2, --CH(CH.sub.3).sub.2, --CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CCl.sub.3, phenyl, ##STR15## --CH.sub.2 CH.sub.2 OCH.sub.3, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 ; (CH.sub.2 CH.sub.2 O).sub.n' R.sub.8, ##STR16## where R.sub.8 is --CH.sub.3, --CH.sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, phenyl, --CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CCl.sub.3 and n' is 2 or 3; ##STR17## where R.sub.12 is --CH.sub.3, --CH.sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, or phenyl; and
provided R has a total number of carbon atoms .ltoreq.13;
when Q is ##STR18## then R is hydrogen; C.sub.1 -C.sub.12 alkyl; (CH.sub.2 CH.sub.2 O).sub.n'" R.sub.12, --CH.sub.2 CH.sub.2 CH.sub.2 OR.sub.12 where R.sub.12 is as defined above and n'" is 1-3; C.sub.3 -C.sub.10 alkenyl;
C.sub.3 -C.sub.6 alkynyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.5 -C.sub.6 cycloalkenyl; C.sub.5 -C.sub.8 cycloalkyl substituted with 1 to 3 substituents selected from 0-2 --OCH.sub.3, 0-3 --CH.sub.3 or --C.sub.2 H.sub.5 ; trifluoromethylcyclohexyl; C.sub.4 -C.sub.10 cycloalkylalkyl; C.sub.4 -C.sub.8 cycloalkylalkyl substituted with 1-2 --CH.sub.3 ; --CH.sub.2 CN; --CH.sub.2 CH.sub.2 CN; ##STR19## where n, R.sub.9, R.sub.10 and R.sub.11 are as defined above; ##STR20## where R' is hydrogen, C.sub.1 -C.sub.4 alkyl, --OCH.sub.3, F, Br, Cl, --CF.sub.3, CN, NO.sub.2, --SO.sub.2 CH.sub.3, --SCH.sub.3, --N(CH.sub.3).sub.2 ;
R" is hydrogen, C.sub.1 -C.sub.4 alkyl, --OCH.sub.3, F, Br, Cl;
R"' is hydrogen, --CH.sub.3, Cl, F or Br;
R.sub.6 is hydrogen, C.sub.1 -C.sub.6 alkyl, allyl, --CH.sub.2 CN; or --CH.sub.2 CH.sub.2 CN; or R.sub.6 and R can be taken together to form --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.6 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --;
or ##STR21## with the proviso that when R is --OCH.sub.3 then R.sub.6 is --CH.sub.3 ; when R.sub.6 is --CH.sub.2 CH.sub.2 CN or --CH.sub.2 CN then R is --CH.sub.2 CH.sub.2 CN or CH.sub.2 CN; and R and R.sub.6 have a total number of carbon atoms .ltoreq.13; ##STR22## R.sub.2 is H, Cl, Br, F, C.sub.1 -C.sub.3 alkyl, --NO.sub.2, --SO.sub.2 CH.sub.3, --OCH.sub.3, --SCH.sub.3, --CF.sub.3, --N(CH.sub.3).sub.2, --NH.sub.2, or --CN;
R.sub.3 is H, Cl, Br, F or CH.sub.3 ;
R.sub.4 is H, or --CH.sub.3 ;
R.sub.5 is H, --CH.sub.3, or --OCH.sub.3 ;
M is an alkali metal;
W is oxygen or sulfur;
X is H, Cl, --CH.sub.3, --OCH.sub.3, --OCH.sub.2 CH.sub.3 or --OCH.sub.2 CH.sub.2 OCH.sub.3 ;
Y is H; F; Cl; Br; C.sub.1 -C.sub.4 alkyl; ##STR23## C.sub.1 -C.sub.4 alkyl substituted with --OCH.sub.3, --OC.sub.2 H.sub.5, --CN, ##STR24## 1 to 3 atoms of F, Cl, Br; C.sub.3 -C.sub.4 alkenyl; --CH.sub.2 C.tbd.CR.sub.13 where R.sub.13 is H, --CH.sub.3, --CH.sub.2 Cl; --A--(CH.sub.2).sub.n' --A.sub.1 --(C.sub.1 -C.sub.3 alkyl), and n', A and A.sub.1 are as previously defined; ##STR25## where L is --NH.sub.2, OH, ##STR26## --NH(C.sub.1 -C.sub.4 alkyl), --N(C.sub.1 -C.sub.4 alkyl).sub.2, C.sub.1 -C.sub.6 alkoxy; SCN; --N.sub.3 ; NR.sub.16 R.sub.17 where R.sub.16 is H or CH.sub.3 and R.sub.17 is H, --OCH.sub.3, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 alkyl substituted with --CN, ##STR27## C.sub.3 -C.sub.4 alkenyl; C.sub.3 -C.sub.6 cycloalkyl; or C.sub.2 -C.sub.3 alkyl substituted with --OCH.sub.3, OC.sub.2 H.sub.5 ; or R.sub.16 and R.sub.17 can be taken together to form --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --; --O--R.sub.14 where R.sub.14 is C.sub.1 -C.sub.4 alkyl; C.sub.2 -C.sub.4 alkyl substituted with 1-3 atoms of F, Cl or Br; C.sub.1 -C.sub.4 alkyl substituted with cyano; C.sub.3 -C.sub.4 alkenyl, --CH.sub.2 C.tbd.CR.sub.13 ; where R.sub.13 is as previously defined; ##STR28## --SR.sub.15 where R.sub.15 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.2 alkyl substituted with CN, allyl, propargyl; with the provision that when Y is .gtoreq.4 carbon atoms, R is .ltoreq.4 carbon atoms, when X is Cl, then Y is Cl, and when X and Y are both H, then R is .ltoreq.4 carbon atoms.
Z is N or CH;
Y.sub.1 is H, --OCH.sub.3, --CH.sub.3 or OCH.sub.2 CH.sub.3 ;
X.sub.1 is H, Cl, --OCH.sub.3, --OCH.sub.2 CH.sub.3, --CH.sub.3 ; providing that X.sub.1 and Y.sub.1 are not both simultaneously hydrogen and when R.sub.1 is ##STR29## then R.sub.4 and R.sub.5 are both H and R is .ltoreq.5 carbon atoms.
More preferred for higher activity and/or ease of synthesis are the following:
More preferred are the following:
1. A compound of the generic scope where R.sub.4 and R.sub.5 are H, W is O, and the carbon of R bonded to Q is also bonded to at least one H.
2. A compound of the preferred 1.--where R.sub.2 is H, Cl, Br, F, C.sub.1 -C.sub.3 alkyl, --NO.sub.2, --OCH.sub.3, --SCH.sub.3, --SO.sub.2 CH.sub.3, --CF.sub.3, --N(CH.sub.3).sub.2, --NH.sub.2, --CN and R.sub.3 is H and is para to the sulfonyl group.
3. A compound of preferred 2. where Q is O or S and R is C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl; C.sub.3 -C.sub.6 alkynyl substituted with one of F, Cl, Br; C.sub.2 -C.sub.4 alkyl substituted with one to four substituents selected from 0-3 F, Cl, 0-2 OCH.sub.3, 0-1 CN; CH.sub.2 CN; C.sub.3 -C.sub.4 alkenyl substituted with 1-3 Cl; C.sub.5 -C.sub.6 cycloalkyl; C.sub.5 -C.sub.6 cycloalkenyl; C.sub.5 -C.sub.6 cycloalkyl substituted with methoxy, C.sub.2 H.sub.5, chloro or up to four methyl groups; C.sub.4 -C.sub.7 cycloalkylalkyl. ##STR30## where R.sub.9 is H, --CH.sub.3 n is 0, 1, R.sub.10 and R.sub.11 are independently H, --CH.sub.3, Cl, --OCH.sub.3 ; ##STR31##
4. Compounds of Preferred 2. where Q is O and R is H, M, --CH.sub.2 CH.sub.2 OR.sub.7, ##STR32## --CH.sub.2 CH.sub.2 CH.sub.2 OR.sub.7 where R.sub.7 is as previously defined, (CH.sub.2 CH.sub.2 O).sub.2 R.sub.8, ##STR33## where R.sub.8 is C.sub.1 -C.sub.3 alkyl, CH.sub.2 CH.sub.2 Cl.
5. Compounds of preferred 2. where Q is --NR.sub.6 -- and R is H; C.sub.1 -C.sub.6 alkyl; --CH.sub.2 CH.sub.2 OR.sub.12 ; --CH.sub.2 CH.sub.2 CH.sub.2 OR.sub.12, where R.sub.12 is defined as above; C.sub.3 -C.sub.6 alkenyl; C.sub.3 -C.sub.6 alkynyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.5 -C.sub.6 cycloalkenyl; C.sub.6 cycloalkyl substituted with any one of 1-2--OCH.sub.3, 1-3 CH.sub.3 or --C.sub.2 H.sub.5 ; trifluoromethylcyclohexyl; C.sub.4 -C.sub.7 cycloalkylalkyl; --CH.sub.2 CN; --CH.sub.2 CH.sub.2 CN; ##STR34## where R' is H, R" is H, C.sub.1 -C.sub.4 alkyl, --OCH.sub.3, F, Br, Cl; R'" is H, --CH.sub.3, Cl, F, Br; ##STR35## where R.sub.9 is H, CH.sub.3 and R.sub.10 and R.sub.11 may independently be H, CH.sub.3, Cl, OCH.sub.3 ; R.sub.6 is H, C.sub.1 -C.sub.3 alkyl, --CH.sub.2 CN, --CH.sub.2 CH.sub.2 CN, --CH.sub.2 CH.dbd.CH.sub.2 and R.sub.6 and R may be taken together to form --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --.
6. Compounds of preferred 2. where X is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 and Y is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.2 alkyl substituted with --OCH.sub.3, --OC.sub.2 H.sub.5, --CN, --CO.sub.2 CH.sub.3, --CO.sub.2 CH.sub.2 H.sub.5, 1 to 3 atoms of F, Cl; C.sub.3 -C.sub.4 alkenyl; --OCH.sub.2 CO.sub.2 (H, C.sub.1 -C.sub.4 alkyl); ##STR36## --OCH.sub.2 CH.sub.2 CO.sub.2 (H, C.sub.1 -C.sub.4 alkyl); --OCH.sub.2 CH.sub.2 O(C.sub.1 -C.sub.3 alkyl); --OCH.sub.2 CH.sub.2 CH.sub.2 O(C.sub.1 -C.sub.3 alkyl); OR.sub.14 where R.sub.14 is C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.3 alkyl substituted with 1-3 F or Cl, C.sub.1 -C.sub.3 alkyl substituted with CN, C.sub.3 -C.sub.4 alkenyl; --SCH.sub.3 ; --SC.sub.2 H.sub.5 ; NR.sub.16 R.sub.17 where R.sub.16 is H, CH.sub.3 and R.sub.17 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkyl substituted with --CN, C.sub.2 -C.sub.3 alkyl substituted with --OCH.sub.3 or --OC.sub.2 H.sub.5, C.sub.3 -C.sub.4 alkenyl; and X.sub.1 and Y.sub.1 are as previously defined.
7. Compounds of preferred 6. where --QR is as defined in preferred 3.
8. Compounds of preferred 6. where --QR is as defined in preferred 4.
9. Compounds of preferred 6. where --QR is as defined in preferred 5.
10. Compounds of preferred 7., 8. or 9. where R.sub.2 is H, Cl, --CH.sub.3.
11. Compounds of preferred 10. where Q is O, S and R is C.sub.1 -C.sub.4 alkyl; C.sub.3 -C.sub.4 alkenyl; C.sub.3 -C.sub.4 alkynyl; C.sub.2 -C.sub.3 alkyl substituted with --OCH.sub.3, Cl, or CN; CH.sub.2 CN; C.sub.3 -alkenyl substituted with 1-3 Cl; CH.sub.2 --C.tbd.C--CH.sub.2 Cl; C.sub.5 -C.sub.6 cycloalkyl; cyclohexenyl, cyclohexyl substituted with 1-3 --CH.sub.3, ##STR37## where R.sub.9 is H, CH.sub.3, n is 0, 1, R.sub.10 and R.sub.11 are independently H, --CH.sub.3, OCH.sub.3, Cl.
12. Compounds of preferred 10. where Q is O and R is H, M, --CH.sub.2 CH.sub.2 OR.sub.7 where R.sub.7 is --C.sub.2 H.sub.5,--CH(CH.sub.3).sub.2, phenyl, --CH.sub.2 CH.sub.2 Cl; and ##STR38##
13. Compounds of preferred 10. where Q is --NR.sub.6 --, R.sub.6 is H, --CH.sub.3, --C.sub.2 H.sub.5, and R is C.sub.1 -C.sub.4 alkyl, --CH.sub.2 CH.sub.2 OCH.sub.3, --CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, C.sub.3 -C.sub.4 alkenyl, C.sub.5 -C.sub.6 cycloalkyl, cyclohexyl substituted with 1-3--CH.sub.3, ##STR39## where R' is H, R" is H, --CH.sub.3, Cl, R'" is H, --CH.sub.3, Cl; ##STR40## and R and R.sub.6 can be taken together to form --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --.
14. Compounds of preferred 10. where R.sub.1 is ##STR41## X is CH.sub.3, --OCH.sub.3, --OC.sub.2 H.sub.5, and Y is H, C.sub.1 -C.sub.3 alkyl, --CH.sub.2 OCH.sub.3, --CH.sub.2 OC.sub.2 H.sub.5, --OCH.sub.2 CO.sub.2 (H, C.sub.1 -C.sub.2 alkyl) ##STR42## --O(C.sub.1 -C.sub.3 alkyl), --O(C.sub.3 -C.sub.4 alkenyl), and NR.sub.16 R.sub.17 where R.sub.16 is H, --CH.sub.3 and R.sub.17 is C.sub.1 -C.sub.3 alkyl and Z is CH or N.
15. Compounds of preferred 14. where QR is as defined in preferred 11.
16. Compounds of preferred 14. where QR is as defined in preferred 12.
17. Compounds of preferred 14. where QR is as defined in preferred 13.
18. Compounds of preferred 15., 16. or 17. where R.sub.2 and R.sub.3 are both hydrogen.
19. Compounds of preferred 18. where Q is O and R is C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.2 -C.sub.3 alkyl substituted with Cl; --CH.sub.2 CH.sub.2 O(CH.sub.3, C.sub.2 H.sub.5) ##STR43## --CH.sub.2 CH.sub.2 CH.sub.2 O(CH.sub.3,C.sub.2 H.sub.5).
20. Compounds of preferred 18. where Q is S and R is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.4 alkenyl.
21. Compounds of preferred 18. where Q is --NR.sub.6 -- and R is C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl, --CH.sub.2 CH.sub.2 O--(CH.sub.3,C.sub.2 H.sub.5) or --CH.sub.2 CH.sub.2 CH.sub.2 O--(CH.sub.3,C.sub.2 H.sub.5) and R.sub.6 is H or CH.sub.3, and R and R.sub.6 taken together are (CH.sub.2).sub.4 or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --.
22. Compounds of preferred 18. where X is CH.sub.3, --OCH.sub.3 or --OC.sub.2 H.sub.5 and Y is C.sub.1 -C.sub.3 alkyl, --OCH.sub.3, --OC.sub.2 H.sub.5, --OCH.sub.2 CO.sub.2 --(CH.sub.3, C.sub.2 H.sub.5), ##STR44## CH.sub.2 OCH.sub.3
23. Compounds of preferred 22. where --QR is as defined in preferred 19.
24. Compounds of preferred 22. where QR is as defined in preferred 20.
25. Compounds of preferred 22. where QR is as defined in preferred 21.
Specifically preferred for higher activity and/or greatest ease of synthesis are:
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide;
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-propoxycarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-phenyl-1-methylethoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-(2-[2-chloroethoxy)ethoxycarbonyl]benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-(2-(2-ethoxyethoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-allyloxycarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-dimethylcarbamoylbenzenesulfonamide;
N-[[[4-methyl-6-(1-methoxycarbonylethoxy)pyrimidin-2-yl]aminocarbonyl]]]-2-methoxycarbonylbenzenesulfonamide;
N-[[[4-methyl-6-(1-methoxycarbonylethoxy)-1,3,5-triazin-2-yl]aminocarbonyl]]-2-methoxycarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methylthiocarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-isopropylthiocarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-isopropylthiocarbonylbenzenesulfonamide;
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-methylpropoxycarbonyl)benzenesulfonamide;
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(4-morpholinylaminocarbonyl)benzenesulfonamide;
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1-pyrrolidinylcarbonyl)benzenesulfonamide;
N[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(allyloxycarbonyl)benzenesulfonamide;
methyl 2-[[[4-(1-carboxyethoxy)-6-methyl-1,3,5-triazin-2-yl]aminocarbonyl]aminosulfonyl]benzoate;
methyl 2-[[(4-ethoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]benzoate;
2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-N,N-dimethylbenzamide.
SYNTHESIS
Many of the compounds of Formula I are prepared as shown in Equation 3 by the reaction of an appropriately substituted o-carbonylbenzenesulfonyl isocyanate or isothiocyanate with an appropriate aminopyrimidine or aminotriazine. These compounds of Formula I can be converted to other compounds of Formula I as will be shown in subsequent equations. Thus, o-carbonylbenzenesulfonyl isocyanates and sulfonyl isothiocyanates are important intermediates for the preparation of the compounds of this invention. Therefore, the synthesis of these is described in Equations 1 and 2.
EQUATION 1 ##STR45##
A mixture of the appropriate sulfonamide, e.g. an o-alkoxycarbonyl benzenesulfonamide IIa such as the methyl ester, which is known in the art, an alkyl isocyanate such as butyl isocyanate and a catalytic amount of 1,4-diaza[2,2,2]bicyclooctane (DABCO) in xylene or other inert solvent of sufficiently high boiling point (e.g. >135.degree.) is heated to approximately 135.degree.. Phosgene is added to the mixture until an excess of phosgene is present as indicated by a drop in the boiling point. (The mixture is heated further to drive off the excess phosgene). After the mixture is cooled and filtered to remove a small amount of insoluble by-products, the solvent and alkyl isocyanate are distilled off in-vacuo leaving a residue which is the crude sulfonyl isocyanate II.
In Equation 1
Q is O
R is C.sub.1 -C.sub.12 alkyl; C.sub.3 -C.sub.10 alkenyl; C.sub.2 -C.sub.6 alkyl substituted with one to four substituents selected from 0-3 atoms of F, Cl, Br, 0-2 methoxy groups; C.sub.3 -C.sub.6 alkenyl substituted with 1-3 atoms of F, Cl, Br; C.sub.5 -C.sub.8 cycloalkyl; C.sub.5 -C.sub.8 cycloalkenyl; C.sub.5 -C.sub.6 cycloalkyl substituted with any of one to four methyl groups, methoxy, alkyl substituents of C.sub.2 -C.sub.4, F, Cl or Br; C.sub.4 -C.sub.10 cycloalkylalkyl; C.sub.4 -C.sub.8 cycloalkylalkyl with 1-2 CH.sub.3 ; --CH.sub.2 CH.sub.2 OR.sub.7 ; CH.sub.2 CH.sub.2 CH.sub.2 OR.sub.7 ; ##STR46## where R.sub.7 is --CH.sub.2 CH.sub.3, CH(CH.sub.3).sub.2, phenyl, --CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CCl.sub.3 ; (CH.sub.2 CH.sub.2 O).sub.n R.sub.8 ; ##STR47## R.sub.8 where R.sub.8 is CH.sub.3, --CH.sub.2 CH.sub.3 --CH(CH.sub.3).sub.2, phenyl, --CH.sub.2 CH.sub.2 Cl, --CH.sub.2 CCl.sub.3 ; and n' is 2 or 3;
R.sub.2 is H, Cl, Br, F, C.sub.1 -C.sub.3 alkyl, --NO.sub.2, --OCH.sub.3, --SCH.sub.3, CF.sub.3, SO.sub.2 CH.sub.3, N(CH.sub.3).sub.2, CN;
R.sub.3 is H, Cl, Br or CH.sub.3
Where W=S in Formula I the useful sulfonylisothiocyanate intermediates are prepared according to Equations 2 and 2'.
EQUATION 2 ##STR48##
The o-carbonyl substituted sulfonamide is dissolved in dimethylformamide (DMF) with an equivalent amount of carbon disulfide and two equivalents of potassium hydroxide are added portionwise at room temperature. The mixture is stirred for 1-8 hours and diluted with ethylacetate, ethyl ether or similar aprotic solvent to cause the dipotassium salt of the dithiocarbamic acid to precipitate. The salt is isolated, dried and suspended in an inert solvent such as xylene, benzene, carbon tetrachloride or methylene chloride. Phosgene is added to the stirred suspension at below room temperature and the mixture stirred for 1-3 hours. In place of phosgene, a chloroformic ester (e.g. methyl chloroformate), phosphoruspentachloride sulfuryl chloride or thionyl chloride can be used.
The sulfonylisothiocyanate which is formed is usually soluble in the solvent and is isolated by filtering off the inorganic potassium chloride and concentrating the filtrate. These isothiocyanates tend to be unstable and dimerize readily, (Equation 2') however, the dimers can be used
EQUATION 2' ##STR49## in the same manner as the parent isothiocyanates for the purposes of this invention.
The synthetic method chosen for the preparation of compounds of Formula I depends largely on the substituents R and R.sub.4. As shown in Equation 3, compounds of Formula I, wherein Q, R, R.sub.2 and R.sub.3 are as defined for Equation 1, are conveniently prepared by reacting an appropriately substituted carbonylbenzenesulfonyl isocyanate or isothiocyanate of Formula IIb with an appropriately substituted aminopyrimidine or aminotriazine of Formula III:
EQUATION 3 ##STR50##
The reaction of Equation 3 is best carried out in inert aprotic organic solvents such as methylene chloride, tetrahydrofuran or acetonitrile, at ambient pressure and temperature. The mode of addition is not critical; however, it is often convenient to add the sulfonyl isocyanate or isothiocyanate to a stirred suspension of amine III. Since such isocyanates and isothiocyanates are liquids, low melting solids or are readily soluble in solvents such as those listed above, their addition can be easily controlled.
The reaction is generally exothermic. In some cases, the desired product is soluble in the warm reaction medium and on cooling crystallizes in pure form. Other products which are soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents such as 1-chlorobutane or ethyl ether, and filtration.
As shown in Equation 3A compounds of Formula Ia, wherein R is not H or M, W is S and R.sub.5 is H, are alternatively prepared by the reaction of an appropriately substituted o-carbonylbenzenesulfonamide with the appropriate triazine or pyrimidine isothiocyanate of formula IIIA.
EQUATION 3A ##STR51##
The reaction of Equation 3A is best carried out by dissolving or suspending the sulfonamide and isothiocyanate in a polar solvent such as acetone, acetonitrile, ethyl acetate or methylethylketone, adding an equivalent of a base such as potassium carbonate and stirring the mixture at ambient temperature up to the reflux temperature for one to twenty-four hours. In some cases, the product precipitates from the reaction mixture and can be removed by filtration. The product is stirred in dilute mineral acid, filtered and washed with cold water. If the product does not precipitate from the reaction mixture it can be isolated by evaporation of the solvent, trituration of the residue with dilute mineral acid and filtering off the insoluble product.
The heterocyclic isothiocyanates which are used in the procedure of Equation 3A are prepared, for example, according to the method of Japan patent Application Pub: Kokai No. 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow Tetrahedron 29, 691-7 (1973).
As shown in Equation 4, compounds of Formula I, wherein Q is O, S or ##STR52## and R is as defined for Equation 1 R.sub.4 is methyl and W is O, can be prepared by methylation of salts IV wherein M is an alkali metal cation such as sodium (derived from compounds of Formula I wherein R.sub.4 is hydrogen):
EQUATION 4 ##STR53## X being an incipient anion and n being an integer corresponding to the valence of X.
The reaction of Equation 4 is best carried out in aprotic organic solvents such as tetrahydrofuran, dimethylformamide, or dimethylacetamide, at ambient pressure and temperature. Methylating agents V, such as dimethyl sulfate or methyl iodide, can be employed. The desired product can be isolated by pouring the reaction mixture into water and filtering off the precipitated solid.
As shown in Equation 5, compounds of Formula Ic, wherein Q is O, S or ##STR54## R and R.sub.4 are as defined for Equation 4, can also be prepared by the reaction of an appropriately substituted sulfonyl-N-methylcarbamyl chloride or sulfonyl-N-methylthiocarbamyl chloride of Formula VI with an appropirate aminopyrimidine or aminotriazine of Formula III:
EQUATION 5 ##STR55##
The preparation of ureas and thioureas, like those of Formula Ic, from amines and carbamyl chlorides and thiocarbamyl chlorides is well known to the art. The reaction can best be carried out by adding equivalent amounts of the chloride VI and amine III to an inert organic solvent, such as tetrahydrofuran, xylene, or methylene chloride, in the presence of an acid acceptor, such as triethylamine, pyridine, or sodium carbonate employing temperatures from 20.degree.-130.degree.. Soluble products can be isolated by filtering off the precipitated salts and concentration of the filtrate. Insoluble products can be filtered off and washed free of salts with water.
The chlorides of Formula VI can be prepared by phosgenation or thiophosgenation of N-alkylsulfonamide salts. The sulfonamide salt is added to an excess of phosgene or thiophosgene in an inert organic solvent, such as tetrahydrofuran, toluene, or xylene, whereupon, after removal of the excess phosgene, the chloride VI can be isolated or reacted in situ with the amine III.
Compounds of Formula Ie, wherein R is --H, can be prepared by hydrolysis of esters of Formula Id wherein R is C.sub.1 -C.sub.12 alkyl. As shown in Equation 6, alkali metal base catalyzed hydrolysis in aqueous methanol produces the alkali metal carboxylate from which the carboxylic acid is obtained by treatment with mineral acids such as HCl:
EQUATION 6 ##STR56##
The reaction of Equation 6 is best carried out in a solution containing the compound being hydrolyzed, 2 to 10 parts of methanol, 10-50 parts of water and 2-10 equivalents of a base such as sodium or potassium hydroxide maintaining the temperature at 30.degree.-90.degree. C. for 3-24 hours. The reaction yields the soluble alkali metal salt of the carboxylic acid, which is suitable for the purposes of this invention. Conversion of these salts to the acid form is easily carried out by addition to the reaction medium of strong mineral acids, such as hydrochloric or sulfuric acid, causing the desired carboxylic acids to precipitate from solution.
Compounds wherein W and Q are O and R is H can be converted to compounds of this invention where R is a higher alkyl or substituted hydrocarbyl group, as already disclosed herein, by the reaction of salts of the parent acid (R=H) with R-Halogen as shown in Equation 6A.
EQUATION 6A ##STR57##
The reaction of Example 6A is of use where the intermediate compound R-Halogen contains a readily replaceable halogen as is the case for substituted or unsubstituted allylic or benzylic halides, .alpha.-halonitriles, or .alpha.-halocarbonyl compounds.
The procedure of Equation 6A is best carried out in inert polar solvents such as tetrahydrofuran, acetonitrile or acetone by combining the appropriately substituted carboxylic acid and base such as triethylamine or 1,4-diaza[2,2,2]bicyclooctane adding the appropriate halide and heating the mixture to reflux with stirring for 1 to 16 hours. The reaction mixture can be evaporated to dryness and the residue triturated with water, filtered and washed with water to separate the desired product from the water soluble salt.
Certain compounds of Formula I, wherein Q is oxygen, are more conveniently prepared by reaction of the silver salt of the carboxylic acid and the appropriate R group containing a suitable leaving group such as iodide. Thus, a substituted iodobenzene is reacted with the silver carboxylate as in Equation 6B.
EQUATION 6B ##STR58## in a suitable solvent such as acetonitrile between 0.degree. and 80.degree. for 1-6 hours.
Esters where R is C.sub.3 -C.sub.9 alkynyl are also conveniently prepared by this method.
The silver salt is prepared by adding an excess of silver nitrate to an aqueous solution of the sodium carboxylate and filtering the precipitate and washing with water.
Compounds of Formula I wherein Y of group R.sub.1 contains ##STR59## and L is OH can be prepared according to the procedure of Equation 6C wherein R, R.sub.2, R.sub.3, Q, R.sub.4, W, X and R.sub.5 are as previously defined.
EQUATION 6C ##STR60##
The reaction of Equation 6C is best carried out by suspending the compound being hydrolyzed in 10 to 100 parts of water with enough of a base such as sodium hydroxide or potassium hydroxide to obtain a pH of 10 to 14, ideally, a pH of 12, heating until a clear solution is obtained and then adjusting the pH to 1-3, preferably 3. The product is thus caused to precipitate in some instances and can be removed by filtration or it can be extracted into a polar organic solvent such as methylene chloride and isolated by evaporation of the solvent.
When Q is NR.sub.6, the compounds can be prepared from the esters of this invention where R is C.sub.1 -C.sub.4 (preferably C.sub.1) by the reaction of the esters with dialkylaluminum-N-alkylamide derivatives according to Equation 7, R, R.sub.1, R.sub.2, R.sub.3 and R.sub.6 being as previously defined.
EQUATION 7 ##STR61##
The intermediate alkylaminoaluminum compounds prepared according to A. Basha, M. Lipton and S. W. Weinreb, Tetrahedron Letters 4171 (1977), are co-mingled with a suspension of the esters in toluene or similar inert solvent and the mixture is refluxed for one to six hours. The product can be isolated by evaporation of the solvent toluene, adding methylene chloride and aqueous hydrochloric acid to decompose the residual reaction mass and extracting the desired product into methylene chloride. Evaporation of the methylene chloride yields the desired product in sufficiently pure form for the purpose of this invention.
Compounds of formula IId, wherein Q is NR.sub.6 and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as previously defined in the general formula, which are useful as intermediates in Equation 3A, are prepared as shown in Equation 7A.
EQUATION 7A ##STR62## The conditions described for Equation 7 are suitable for the conversion of the esters of formula IIc to the amides IId as shown in Equation 7A.
The products of Equation 7A are especially useful for the preparation of compounds of formula Ia wherein Y has an ester substituent CO.sub.2 (C.sub.1 -C.sub.6), by the route described in Equation 3A.
When Q is S, these compounds can be prepared from the esters of this invention wherein QR is C.sub.1 -C.sub.4 alkoxy (preferably C.sub.1) by the reaction of the esters with the appropriate dialkylaluminum alkylthiolate according to Equation 8.
EQUATION 8 ##STR63##
The intermediate aluminum thiolates can be prepared according to R. P. Hatch and S. W. Weinreb, Journal of Organic Chemistry, Vol. 42, 3960 (1977). The reaction of the thiolate with the ester of this invention is best carried out in a neutral solvent such as toluene or xylene at reflux for one to three hours. Best results are obtained when the aluminum thiolate compound is present in excess of the stoichiometric amount required.
Sulfonamides of formula IIb are also converted from carboxylic acid esters to the thiolesters as shown in Equation 8A according to the method of R. P. Hatch and S. W. Weinreb as described for Equation 8 wherein R, R.sub.2, R.sub.3 and R.sub.4 are as previously defined. ##STR64## The conditions described for Equation 8 are suitable for the conversion of the sulfonamides of formula IIb as shown in Equation 8A.
The product of Equation 8A are especially useful for the preparation of compounds of formula Ia, wherein Y has a substituent (CO.sub.2 C.sub.1 -C.sub.6) by the route described for Equation 3A.
An alternate route to prepare compounds where R is bonded to Q (Q=O) at a secondary carbon involves the reaction of the appropriate dialkylaluminum alcoholate and an ester of this invention wherein R is a lower primary alkyl group, preferably methyl, according to Equation 9.
EQUATION 9 ##STR65##
The reaction is carried out in a neutral solvent such as toluene with a boiling point sufficiently high to bring about the desired reaction during reflux. The dialkylaluminum alcoholate being present in greater than an equivalent amount to the ester for best yields. After refluxing for 1-15 hours, the reaction mixture is decomposed with dilute hydrochloric acid and the product extracted into methylene chloride. Evaporation of the methylene chloride yields the desired compound sufficiently pure for the purposes of this invention. The product can be triturated with a solvent, e.g. 1-chlorobutane to remove impurities.
The synthesis of heterocyclic amines has been reviewed in "The Chemistry of Heterocyclic Compounds" a series published by Interscience Publ., New York and London. 2-Aminopyrimidines are described by D. J. Brown in The Pyrimidines, Vol. XVI of this series. The 2-amino-1,3,5-triazines are reviewed by K. R. Huffman and in The Triazines of this same series. The synthesis of triazines are also described by F. C. Schaefer, U.S. Pat. No. 3,154,547 and by K. R. Huffman and F. C. Schaeffer, J. Org. Chem. 28, 1816-1821 (1963).
The preparation of agriculturally suitable salts of the compounds of Formula I, as well as starting materials and intermediates for said compounds, not otherwise described herein, is disclosed in my applications Ser. No. 824,805 filed Aug. 15, 1977 and Ser. No. 840,389 filed Oct. 6, 1977, the contents of which are incorporated herein by reference.
The compounds of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade and parts by weight unless otherwise indicated.

EXAMPLE 1
Methyl-2-(isocyanatosulfonyl)benzoate
A stirred mixture containing 157 g of methyl 2-sulfamoylbenzoate, 73 g of butyl isocyanate 0.3 g of 1,4-diazabicyclo[2,2,2]octane and 1.0 l of xylene was heated to reflux for one half hour. Phosgene gas was then passed into the system under a dry ice reflux condenser allowing the reaction temperature to drop to 120.degree.. This addition was continued until the reflux temperature remained at 120.degree. without further phosgene addition. The temperature of the reaction mixture was then raised to 136.degree. (by removal of the dry ice reflux condenser) after which it was cooled to room temperature and filtered. Evaporation of the filtrate yielded the desired crude sulfonyl isocyanate which could be purified by distillation at 132.degree.-138.degree. C. under 1.0 to 1.1 mm of mercury pressure. The product is extremely reactive with water so contact with moisture should be scrupulously avoided.
EXAMPLE 2
Isopropyl 2-(isocyanatosulfonyl)benzoate
To 60.7 g (0.25 mole) of isopropyl 2-sulfamoylbenzoate in 300 ml dry (molecular sieves) xylenes was added 25.0 g (0.25 mole) N-butyl isocyanate and 0.1 g 1,4-diazabicyclo[2,2,2]octane. The mixture was heated to reflux temperature and phosgene was slowly bubbled through the solution for 2 hours.
An infrared spectrum of the reaction mixture indicated formation of the desired sulfonylisocyanate (2250 cm.sup.-1). The resulting cloudy solution was cooled to room temperature and decanted from a small amount of solid impurity. Evaporation of the resulting clear solution yielded the desired crude sulfonyl isocyanate, which was used in subsequent steps without further purification.
EXAMPLE 3
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
To 37 g. of 2-amino-4,6-dimethylpyrimidine in 500 ml of anhydrous acetonitrile was added 67 g of 2-methoxycarbonylbenzenesulfonylisocyanate with stirring at ambient temperatures. The resulting mixture was thereafter stirred for sixteen hours and then filtered to remove the desired product which had precipitated as a white solid, m.p. 198.degree.-202.degree.. It showed infrared absorption peaks at 1750, 1700, 1600 and 1550 cm.sup.-1, consistent for the desired compound.
EXAMPLE 4
N-[(Pyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
With stirring at ambient temperature, 1.0 g of 2-aminopyrimidine in 25 ml of anhydrous acetonitrile was added to 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate. After stirring that mixture for 24 hours, the resultant precipitate was filtered off to yield 2.2 g of the desired compound which melted at 188.degree.-192.degree.. Its showing infrared absorption peaks at 1700, 1680 and 1580 cm.sup.-1 is consistent for N-[(pyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide.
EXAMPLE 5
N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
To a stirred suspension of 1.4 g of 2-amino-4-methoxy-6-methylpyrimidine in 30 ml of anhydrous methylene chloride was added at ambient temperature 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate. After stirring for 16 hours, the foregoing mixture was filtered to remove unreacted amine, and the filtrate evaporated at temperatures up to 40.degree. and reduced pressure. The resultant residue was stirred in 25 ml of water, the pH adjusted to 10 by the addition of 50% sodium hydroxide and the solution filtered. Acidification of the filtrate to pH 3 with hydrochloric acid caused precipitation of the desired product which was removed by filtration and dried to yield 0.8 g of product melting at 173.degree.-179.degree.. It showed infrared absorption peaks at 1720, 1680, 1630 and 1550 cm.sup.-1, consistent for N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide.
EXAMPLE 6
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
A mixture containing 1.6 g of 2-amino-4,6-dimethoxypyrimidine, 30 ml of anhydrous methylene chloride and 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate was stirred at ambient temperature and pressure for 16 hours. It was then filtered to remove unreacted amine and the filtrate evaporated at temperatures up to 40.degree. and reduced pressure. The residue thus obtained was stirred in 25 ml of water, the pH adjusted to 10 by the addition of 50% aqueous sodium hydroxide and the solution filtered. Acidification of the filtrate to pH 3 caused the formation of a precipitate. Filtration and drying the precipitate yielded 1.7 g of the desired product, melting at 185.degree.-190.degree.. Its infrared absorption peaks at 1700 and 1710 cm.sup.-1 are consistent for the desired structure and the nuclear magnetic resonance absorption peaks at 3.8 and 3.85 are consistent for the two different types of methoxy groups brought together in this product.
EXAMPLE 7
2-(Benzyloxycarbonyl)-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]benzenesulfonamide
To 1.75 g of 2-(4,6-dimethylpyrimidin-2-yl-aminocarbonylsulfamoyl)benzoic acid was added 0.51 g of triethylamine in 10 ml tetrahydrofuran and 0.88 g of benzyl bromide in 10 ml of tetrahydrofuran. The mixture was heated to reflux for 1.5 hours, filtered and the tetrahydrofuran evaporated in-vacuo. The residue was extracted with hot 1-chlorobutane, diluted with ethyl acetate, washed with water and saturated aqueous sodium bicarbonate. The organic phase was dried over magnesium sulfate, filtered and the solvents evaporated in-vacuo. The resultant residue was crystallized from 1-chlorobutane to a melting point of 157.degree.. This product showed absorption peaks in the infrared region at 1720, 1600, 1560 cm.sup.-1 consistent for the desired ester and absorption by nuclear magnetic resonance at 2.45', singlet, for CH.sub.3 ; 5.3.delta. singlet, CH.sub.2 on benzyl; 6.65' singlet CH of pyrimidine and aryl peaks at 7-8.delta..
By using the procedures of Examples 3-6 with equivalent amounts of 2-aminopyrimidines and appropriately substituted sulfonylisocyanates or isothiocyanates, the compounds of Table I can be prepared.
Alternatively, compounds of Table I wherein R is a group which forms an organohalide with a labile halogen can be prepared by the procedure of Example 7 using equivalent amounts of appropriately substituted benzoic acid derivatives and organohalides.
Compounds of this invention can also be used as intermediates for the preparation of other compounds by methods known to those skilled in the art. For example, nitro substituents can be converted to amino groups by catalytic hydrogenation in the presence of palladium on carbon.
TABLE I__________________________________________________________________________ ##STR66##QR R.sub.2 R.sub.3 W R.sub.5 X Y m.p.__________________________________________________________________________ (.degree.C.)OCH.sub.3 H H O H CH.sub.3 HOCH.sub.3 5-F H O H H ClOCH.sub.3 5-Cl H O H OCH.sub.3 OCH.sub.3 196-198.degree.OCH.sub.3 5-Br H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-NO.sub.2 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-OCH.sub.3 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-CH.sub.3 H O H CH.sub.3 CH.sub.3OCH.sub.3 5- .sub.-i-C.sub.3 H.sub.7 H O H CH.sub.3 OC.sub.2 H.sub.5OCH.sub.3 5-SCH.sub.3 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-Cl 3-Cl O H CH.sub.3 OCH.sub.3OCH.sub.3 5-Cl 3-CH.sub.3 O H CH.sub.3 OCH.sub.3OCH.sub.3 5-F 3-Cl O H CH.sub.3 OCH.sub.3OCH.sub.3 5-NO.sub.2 3-Cl O H CH.sub.3 OCH.sub.3OCH.sub.3 5-Br 3-Br O H CH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 6-Cl H S H CH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 108-110.degree.OC.sub.2 H.sub.5 H H O H CH.sub.3 OCH(CH.sub.3)CO.sub.2 CH.sub.3OC.sub.2 H.sub.5 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3OC.sub.2 H.sub.5 H H O H CH.sub.3 OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5OCH.sub.3 H H O CH.sub.3 OCH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 H H O CH.sub.3 OCH.sub.3 OCH.sub.3OCH.sub.3 5-Cl H O CH.sub.3 OCH.sub.3 CH.sub.3 196-198.degree.OCH.sub.3 6-Cl H O CH.sub.3 OCH.sub.3 OC.sub.2 H.sub.5OCH.sub.3 3-CH.sub.3 H O CH.sub.3 OCH.sub.3 OCH.sub.3OCH.sub.3 H H O H CH.sub.3 SCH.sub.2 COOCH.sub.3OCH.sub.3 H H O H CH.sub.3 S(CH.sub.2).sub.2 OC.sub.2 H.sub.5 152.5-160.degree. 3OCH.sub.3 H H O H CH.sub.3 S(CH.sub.2).sub.2 COOC.sub.2 H.sub.5O -n-C.sub.3 H.sub.7 H H O H OCH.sub.3 CH.sub.3 177-179.degree.O -n-C.sub.3 H.sub.7 H H O H OCH.sub.3 OCH.sub.3 160-165.degree.OC.sub.2 H.sub.5 H H O H OCH.sub.3 CH.sub.3 168-170 ##STR67## H H O H OCH.sub.3 CH.sub.3 120-124 ##STR68## H H O H OCH.sub.3 OCH.sub.3 152-155OCH.sub.2 CH.sub.2 Cl H H O H OCH.sub.3 CH.sub.3 150-154OCH.sub.2 CH.sub.2 Cl H H O H OCH.sub.3 OCH.sub.3 157-160O(CH.sub.2).sub.9 CH.sub.3 H H O H OCH.sub.3 CH.sub.3 98-101O(CH.sub.2).sub.9 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3 87-90 ##STR69## H H O H OCH.sub.3 OCH.sub.3 170-172OCH.sub.3 4-Cl H O H OCH.sub.3 CH.sub.3 166-168OCH.sub.3 4-Cl H O H OCH.sub.3 OCH.sub.3 158-160O .sub.-i-C.sub.3 H.sub.7 H H O H OCH.sub.3 CH.sub.3 175-179O .sub.-i-C.sub.3 H.sub.7 H H O H OCH.sub.3 OCH.sub.3 189-190O -n-C.sub.4 H.sub.9 H H O H OCH.sub.3 CH.sub.3 124-126O -n-C.sub.4 H.sub.9 H H O H OCH.sub.3 OCH.sub.3 140-149OC.sub.2 H.sub.5 H H O H OCH.sub.3 OCH.sub.3 149-153O(CH.sub.2).sub.9 CH.sub.3 H H O H CH.sub.3 OCH.sub.2 CF.sub.3 ##STR70## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 Cl H H O H CH.sub.3 OCH.sub.2 CO.sub.2 CH.sub.3OCH.sub.2 CH.sub.2 CH.sub.2 Cl H H O H OCH.sub.3 CH.sub.3 ##STR71## H H O H OCH.sub.3 CH.sub.3 100-104OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Cl H H O H CH.sub.3 CH.sub.3OCH.sub.2 (CH.sub.2).sub.4 CH.sub.2 Cl H H O H CH.sub.3 CH.sub.3 ##STR72## H H O H CH.sub.3 CH.sub.3 ##STR73## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CCl.sub.3 H H O H OCH.sub.3 CH.sub.3OCH.sub.2 CF.sub.3 H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 Br H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H H O H OCH.sub.3 CH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5 H H O H OCH.sub.3 CH.sub.3OCH.sub.2 CHCH.sub.2 H H O H CH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CHCH.sub.2 H H O H OCH.sub.3 CH.sub.3 ##STR74## H H O H CH.sub.3 CH.sub.3OCH.sub.3 4-Cl 5-Cl O H OCH.sub.3 CH.sub.3 193-194.degree.OCH.sub.3 4-Cl 5-Cl O H OCH.sub.3 OCH.sub.3 202-204.degree.OCH.sub.3 4-F H O H OCH.sub.3 CH.sub.3 201-203.degree.OCH.sub.3 4-Br H O H OCH.sub.3 CH.sub.3OCH.sub.2 CH(CH.sub.3).sub.2 H H O H OCH.sub.3 CH.sub.3 108-111.degree.OCH.sub.2 CH(CH.sub.3).sub.2 H H O H OCH.sub.3 OCH.sub.3 166-168.degree.O(CH.sub.2).sub.4 CH.sub.3 H H O H OCH.sub.3 CH.sub.3 87-89.degree. ##STR75## H H O H OCH.sub.3 CH.sub.3 130-132.degree. ##STR76## H H O H CH.sub. 3 OCH.sub.3 153-155.degree. ##STR77## H H O H OCH.sub.3 CH.sub.3 ##STR78## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 H H O H CH.sub.3 CH.sub.3 ##STR79## H H O H CH.sub.3 CH.sub.3OCH.sub.3 H H O H CH.sub.3 ##STR80##OCH.sub.3 H H O H CH.sub.3 ##STR81##OCH.sub.3 H H O H CH.sub.3 ##STR82##OCH.sub.3 H H O H CH.sub.3 ##STR83##OCH.sub.3 H H O H CH.sub.3 ##STR84##OCH.sub.3 H H O H OCH.sub.3 ##STR85##OCH.sub.3 H H O H CH.sub.3 ##STR86## ##STR87## H H O H OCH.sub.3 CH.sub.3 105-110.degree. ##STR88## H H O H OCH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H OCH.sub.3 CH.sub.3 130-134.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3 163-166.degree.O .sub.-i-C.sub.3 H.sub.7 H H O H CH.sub.3 CH.sub.3 194-196.degree.OCH.sub.3 4-F H O H OCH.sub.3 OCH.sub.3 200-202.degree.OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H O H OCH.sub.3 CH.sub.3 121-124.degree.OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H O H OCH.sub.3 OCH.sub.3 151-153.degree.OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H O H CH.sub.3 CH.sub.3 90-93.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H Cl Cl 122-126.degree.o-i-C.sub.3 H.sub.7 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 oilOCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CF.sub.3 156-160.degree.OCH.sub.3 H H O H CH.sub.3 ##STR89## 143-155.degree.OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CO.sub.2 CH.sub.3 174-180.degree.OCH.sub.3 H H O H CH.sub.3 CH.sub.2 OCH.sub.3 154-156.degree.OCH.sub.3 H H O CH.sub.3 CH.sub.3 CH.sub.3 159-174.degree.OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H H O H CH.sub.3 Cl 61-64.degree.OCH.sub.2 (CH.sub.2).sub.3 CH.sub.3 H H O H CH.sub.3 CH.sub.2 OCH.sub.3 oil n .sub.D.sup.251.5 408OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 118-120.degree.O(CH.sub.2).sub.11 CH.sub.3 H H O H CH.sub.3 OCH.sub.3 ##STR90## H H O H CH.sub.3 OCH.sub.3 ##STR91## H H O H CH.sub.3 OCH.sub.3 ##STR92## H H O H CH.sub.3 OCH.sub.3 ##STR93## H H O H CH.sub.3 OCH.sub.3OCH.sub.2 CHCCl.sub.2 H H O H CH.sub.3 OCH.sub.3 ##STR94## H H O H CH.sub.3 OCH.sub.3 ##STR95## H H O H CH.sub.3 OCH.sub.3O(CH.sub.2).sub.4 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3 132-134.degree.O(CH.sub.2).sub.5 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3 134-136.degree. ##STR96## H H O H CH.sub. 3 CH.sub.3 ##STR97## H H O H CH.sub.3 OCH.sub.3 ##STR98## H H O H CH.sub.3 OCH.sub.3 ##STR99## H H O H CH.sub.3 OCH.sub.3 ##STR100## H H O H CH.sub.3 OCH.sub.3Ocyclo C.sub.8 H.sub.15 H H O H CH.sub.3 CH.sub.3 ##STR101## H H O H CH.sub.3 CH.sub.3 ##STR102## H H O H CH.sub.3 CH.sub.3 ##STR103## H H O H CH.sub.3 CH.sub.3 ##STR104## H H O H CH.sub.3 CH.sub.3 O ##STR105## H H O H CH.sub.3 CH.sub.3OCH.sub.3 H H O H CH.sub.3 N.sub.3 173-176.degree. ##STR106## H H O H CH.sub.3 CH.sub.3 O ##STR107## H H O H CH.sub.3 CH.sub.3 ##STR108## H H O H CH.sub.3 CH.sub.3 O ##STR109## H H O H CH.sub.3 OCH.sub.3 ##STR110## H H O H CH.sub.3 CH.sub.3 ##STR111## H H O H OCH.sub.3 OCH.sub.3 ##STR112## H H O H CH.sub.3 OCH.sub.3 ##STR113## H H O H CH.sub.3 OCH.sub.3 ##STR114## H H O H CH.sub.3 OCH.sub.3 ##STR115## H H O H CH.sub.3 OCH.sub.3 ##STR116## H H O H CH.sub.3 OCH.sub.3 ##STR117## H H O H CH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.4 CH.sub.3 H H O H CH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.4 Cl H H O H CH.sub.3 OCH.sub.3 n .sub.D.sup.251.5 458OCH.sub.2 CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2 H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SCH.sub.3 H H O H CH.sub.3 CH.sub.3O(CH.sub.2).sub.3 SC.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SOCH.sub.3 H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3O(CH.sub.2).sub.3 SO.sub.2 C.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3OCH.sub. 2 CH.sub.2 OC.sub.2 H.sub.4 Cl H H O H CH.sub.3 OCH.sub.3 124-127.degree.O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.4 Cl H H O H OCH.sub.3 OCH.sub.3 n .sub.D.sup.251.5 421OCH.sub.2 CHCH.sub.2 H H O H OCH.sub.3 CH.sub.3 129-131.degree.OCH.sub.2 CHCH.sub.2 H H O H OCH.sub.3 OCH.sub.3 142-145.degree. ##STR118## H H O H OCH.sub.3 OCH.sub.3 114-117.degree. ##STR119## H H O H Cl Cl 65-69.degree. ##STR120## H H O H OCH.sub.3 CH.sub.3 153-156.degree.OCH.sub.3 5-CF.sub.3 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-N(CH.sub.3).sub.2 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-SO.sub.2 CH.sub.3 H O H CH.sub.3 OCH.sub.3OCH.sub.3 5-CN H O H CH.sub.3 OCH.sub.3OCH.sub. 3 5-NH.sub.2 H O H CH.sub.3 OCH.sub.3OCH.sub.3 H H O H OCH.sub.2 CH.sub.2 OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 150-152.degree.OCH.sub.3 H H O H OCH.sub.3 -n-C.sub.4 H.sub.9OCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3OCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CH.sub.2 CNOCH.sub.3 H H O H OCH.sub.3 (CH.sub.2).sub.4 CNOCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CO.sub.2 CH.sub.3OCH.sub.3 H H O H OCH.sub.3 CCl.sub.3OCH.sub.3 H H O H OCH.sub.3 ##STR121##OCH.sub.3 H H O H CH.sub.3 (CH.sub.2).sub.3 CH.sub.2 ClOCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CCCH.sub.3OCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CCCH.sub.2 ClOCH.sub.3 H H O H OCH.sub.3 NH -nC.sub.4 H.sub.9OCH.sub.3 H H O H OCH.sub.3 ##STR122##OCH.sub.3 H H O H OCH.sub.3 ##STR123##OCH.sub.3 H H O H OCH.sub.3 NH(CH.sub.2).sub.4 CO.sub.2 C.sub.2 H.sub.5OCH.sub.3 H H O H CH.sub.3 ##STR124##OCH.sub.3 H H O H OCH.sub.3 ##STR125##OCH.sub.3 H H O H CH.sub.3 O(CH.sub.2).sub.3 CH.sub.3OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 BrOCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CCl.sub.3OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 CNOCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CHCH.sub.2OCH.sub.3 H H O H CH.sub.3 ##STR126##OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CO.sub.2 -n-C.sub.6 H.sub.13OCH.sub.3 H H O H CH.sub.3 SCH.sub.2 CH.sub.2 CO.sub.2 -n-C.sub.6 H.sub.13OCH.sub.3 H H O H CH.sub.3 OCH.sub.2 CH.sub.2 OCH(CH.sub.3) .sub.2OCH.sub.3 H H O H CH.sub.3 SCH.sub.2 CH.sub.2 SCH.sub.3OCH.sub.3 H H O H CH.sub.3 ##STR127##OCH.sub.3 H H O H CH.sub.3 SCH.sub.2 CH.sub.3OCH.sub.3 H H O H CH.sub.3 SCH.sub.2 CCH ##STR128## H H O H OCH.sub.3 CH.sub.3 158-160.degree. ##STR129## H H O H OCH.sub.3 CH.sub.3 ##STR130## H H O H OCH.sub.3 CH.sub.3 ##STR131## H H O H OCH.sub.3 CH.sub.3 ##STR132## H H O H OCH.sub.3 CH.sub.3 ##STR133## H H O H OCH.sub.3 CH.sub.3 ##STR134## H H O H OCH.sub.3 OCH.sub.3 ##STR135## H H O H OCH.sub.3 CH.sub.3 ##STR136## H H O H OCH.sub.3 CH.sub.3 ##STR137## H H O H OCH.sub.3 OCH.sub.3 ##STR138## H H O H OCH.sub.3 CH.sub.3 ##STR139## H H O H OCH.sub.3 CH.sub.3 ##STR140## H H O H OCH.sub.3 CH.sub.3 ##STR141## H H O H OCH.sub.3 CH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 CH(CH.sub.3).sub.2 H H O H OCH.sub.3 CH.sub.3 ##STR142## H H O H OCH.sub.3 CH.sub.3 ##STR143## H H O H OCH.sub.3 CH.sub.3 ##STR144## H H O H OCH.sub.3 CH.sub.3 ##STR145## H H O H OCH.sub.3 CH.sub.3 ##STR146## H H O H OCH.sub.3 CH.sub.3 ##STR147## H H O H OCH.sub.3 CH.sub.3 ##STR148## H H O H OCH.sub.3 CH.sub.3OCH.sub.3 H H O H CH.sub.3 CO.sub.2 CH.sub.3OCH.sub.3 H H O H CH.sub.3 CO.sub.2 HOCH.sub.3 5-NO.sub.2 H O H CH.sub.3 CH.sub.3 105-110.degree.OCH.sub.3 5-NO.sub.2 H O H CH.sub.3 OCH.sub.3 80-90.degree.OCH.sub.3 5-NO.sub.2 H O H OCH.sub.3 OCH.sub.3 210-212.degree.OCH.sub.3 5-NH.sub.2 H O H CH.sub.3 OCH.sub.3 130.degree.OCH.sub.3 5-NH.sub.2 H O H OCH.sub.3 OCH.sub.3 135.degree.OCH.sub.2 CHCH.sub.2 H H O H CH.sub.3 CH.sub.3 178-180.degree.OCH.sub.3 5-Cl H O H CH.sub.3 CH.sub.3 193-196.degree.OCH.sub.3 H H O H CH.sub.3 SCN 101-112.degree.OCH.sub.2 CHCH.sub.2 5-Cl H O H OCH.sub.3 OCH.sub.3 155-157.degree.OCH.sub.2 CHCH.sub.2 5-Cl H O H OCH.sub.3 CH.sub.3 151-153.degree.OCH.sub.2 CHCH.sub.2 5-Cl H O H CH.sub.3 CH.sub.3 155-157.degree. ##STR149## H H O H CH.sub.3 OCH.sub.3 137-140.degree.OCH.sub.2 CCCH.sub.2 Cl H H O H CH.sub.3 OCH.sub.3 183-185.degree.O .sub.-i-C.sub.3 H.sub.7 5-Cl H O H OCH.sub.3 OCH.sub.3 194-195.degree.O .sub.- i-C.sub.3 H.sub.7 5-Cl H O H CH.sub.3 OCH.sub.3 176-178.degree.O .sub.-i-C.sub.3 H.sub.7 5-Cl H O H CH.sub.3 CH.sub.3 190-192.degree. ##STR150## H H O H OCH.sub.3 OCH.sub.3 150-155.degree. ##STR151## H H O H CH.sub.3 CH.sub.3 140-144.degree. ##STR152## H H O H CH.sub.3 OCH.sub.3 139-142.degree.OCH.sub.3 H H O H OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 138-141.degree. ##STR153## H H O H OCH.sub.3 OCH.sub.3 151-153.degree. ##STR154## H H O H OCH.sub.3 OCH.sub.3 153-155.degree. ##STR155## H H O H OCH.sub.3 OCH.sub.3 142-145.degree.OCH.sub.2 CN H H O H OCH.sub.3 OCH.sub.3 184-187.degree.OCH.sub.2CCC.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3OCH.sub.2CC(CH.sub.2).sub.5 H H H O H CH.sub.3 CH.sub.3OCH.sub.2CC(CH.sub.2).sub.7 H H H O H OCH.sub.3 CH.sub.3 ##STR156## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3OCH.sub.2 CN H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 CH.sub.2 CN H H O H CH.sub.3 CH.sub.3O(CH.sub.2).sub.5 CN H H O H CH.sub.3 CH.sub.3OCHCCCH.sub.2 Cl H H O H CH.sub.3 CH.sub.3OCHCC(CH.sub.2).sub.2 Cl H H O H CH.sub.3 CH.sub.3 ##STR157## H H O H CH.sub.3 CH.sub.3 ##STR158## H H O H CH.sub.3 CH.sub.3 ##STR159## H H O H CH.sub.3 CH.sub.3 ##STR160## H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH.sub.3 H H O H CH.sub.3 CH.sub.3OCH.sub.2 OC.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH(CH.sub.3).sub.2 H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH.sub.2 CH.sub.2 Cl H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH.sub.2 CCl.sub.3 H H O H CH.sub.3 CH.sub.3 ##STR161## H H O H CH.sub.3 CH.sub.3 ##STR162## H H O H CH.sub.3 CH.sub.3 ##STR163## H H O H CH.sub.3 CH.sub.3 ##STR164## H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 H H O H CH.sub.3 CH.sub.3OCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H CH.sub.3 CH.sub.3OCH.sub.3 H H O H CH.sub.3 FOCH.sub.3 H H O H CH.sub.3 BrOCH.sub.3 H H O H CH.sub.3 CO.sub.2 CH.sub.3OCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CO.sub.2 CH.sub.3OCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CO.sub.2 HOCH.sub.3 H H O H OCH.sub.3 CH.sub.2 CO.sub.2 -n-C.sub.4 H.sub.9OCH.sub.3 H H O H OCH.sub.3 (CH.sub.2).sub.3 CO.sub.2 .sub.--C.sub.3 H.sub.7OCH.sub.3 H H O H OCH.sub. 3 CH.sub.2 CO.sub.2 -n-C.sub.6 H.sub.13OCH.sub.3 H H O H OCH.sub.3 ##STR165##OCH.sub.3 H H O H CH.sub.3 ##STR166##OCH.sub.3 H H O H CH.sub.3 NH(CH.sub.2).sub.2 CO.sub.2 .sub.-i-C.sub.3 H.sub.7OCH.sub.3 H H O H CH.sub.3 ##STR167##OCH.sub.3 H H O H CH.sub.3 ##STR168##OCH.sub.3 H H O H CH.sub.3 ##STR169##OCH.sub.3 H H O H CH.sub.3 ##STR170##OCH.sub.3 H H O H CH.sub.3 ##STR171##OCH.sub.3 H H O H CH.sub.3 ##STR172##__________________________________________________________________________
EXAMPLE 8
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide
To 0.7 g of 2-amino-4,6-dimethoxy-1,3,5-triazine in 10 ml anhydrous methylene chloride solvent was added 1.45 g 2-(.beta.-chloroethoxycarbonyl)benzenesulfonyl isocyanate. After stirring at ambient temperature for sixteen hours the solvent was removed under reduced pressure, the residue triturated with ether and the solid product filtered off, yield 1.21 g m.p. 171.degree.-174.degree. C. The solid showed infrared absorption peaks at 1705 and 1715 cm.sup.-1, consistent for N-[(4,6-dimethoxy-1,3,5-triazine-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide.
EXAMPLE 9
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide
To 0.7 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 10 ml anhydrous methylene chloride solvent was added 1.45 g 2-(.beta.-chloroethoxycarbonyl)benzenesulfonyl isocyanate with stirring at ambient temperature. The mixture was thereafter stirred for sixteen hours. The solvent was evaporated under reduced pressure and the residue triturated with hexane and filtered to yield 1.72 g of compound which melted at 167.degree.-170.degree. C. The solid showed infrared absorption peaks at 1700 and 1705 cm.sup.-1, consistent for N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(2-chloroethoxycarbonyl)benzenesulfonamide.
EXAMPLE 10
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide
To 0.7 g of 2-amino-4,6-dimethoxy-1,3,5-triazine suspended in 5.0 ml anhydrous methylene chloride was added 1.6 g of 2-isopropoxycarbonylbenzenesulfonyl isocyanate in 5.0 ml anhydrous methylene chloride. The resulting mixture was filtered to remove some unreacted 2-amino-4,6-dimethoxytriazine, the methylene chloride filtrate was evaporated at reduced pressure and the residue triturated with chlorobutane to yield 0.5 g of desired product melting at 192.degree.-195.degree. C. The solid showed infrared absorption peaks at 1705 and 1715 cm.sup.-1 consistent for N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide.
EXAMPLE 11
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide
To 26.8 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 300 ml anhydrous methylene chloride was added 67.0 g of 2-isopropoxycarbonylbenzenesulfonyl isocyanate in 100 ml anhydrous methylene chloride. The resultant suspension was stirred at ambient temperature for 72 hours, and filtered to yield 40.0 g of the desired product as a white solid, m.p. 193.degree.-196.degree. C. The solid showed infrared absorption peaks at 1700 and 1710 cm.sup.-1 consistent for N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(isopropoxycarbonyl)benzenesulfonamide.
EXAMPLE 12
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
A mixture of 1.6 g of 2-amino-4,6-dimethoxy-1,3,5-triazine, 25 ml of anhydrous methylene chloride and 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate was stirred at ambient temperature for 16 hours. It was then filtered to remove unreacted amine and the filtrate evaporated at temperatures up to 40.degree. under reduced pressure. The residue was triturated with butyl chloride and filtered to yield the desired compound which melted above 170.degree. with decomposition.
EXAMPLE 13
N-[(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
To an anhydrous suspension of 1.4 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 25 ml of methylene chloride was added with stirring at ambient temperature and pressure 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate. The mixture was thereafter stirred for 16 hours and filtered. The filtrate was evaporated to dryness, the residue was triturated with butyl chloride and the product removed by filtration. The product thus obtained melted at 165.degree., and had absorption peaks in the infrared at 1550, 1600, 1680 and 1700 cm.sup.-1 and in the NMR spectrum at 2.5, 3.65, 4.0 and an aromatic multiplet at 7.2-8 ppm.
By using the procedures of Examples 8 to 13 with equivalent amounts of appropriate 2-amino-1,3,5-triazines and appropriately substituted sulfonylisocyanates or isothiocyanates, the compounds of Table II can be prepared:
EXAMPLE 14
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1-methylpentyloxycarbonyl)benzenesulfonamide
2-Hexanol (0.61 g) in 2 ml dry toluene was slowly added at room temperature to a solution of 1.5 ml (2M) trimethylaluminum diluted with 5.0 ml dry toluene under nitrogen. The mixture was stirred at room temperature for 15 minutes and 0.95 g of N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide was added. The mixture was warmed under N.sub.2 to reflux temperature for 2.5 hr. cooled to room temperature and carefully quenched with 20 ml 10% HCl. The organic phase was taken up in methylene chloride, separated, washed with water, dried over magnesium sulfate, filtered and the solvent evaporated under reduced pressure to give 0.65 g of the desired compound which melted at 125.degree.-130.degree. C. The infrared spectrum exhibited characteristic absorption for the product at 3300, 1725, 1730, 1585, 1555 cm.sup.-1.
Alternatively, compounds of Tables I and II wherein the desired ester group R is a higher alkane (C.sub.5 -C.sub.12) are also prepared by the procedure of Example 14 with an equivalent amount of the appropriate dialkylaluminum alcoholate and an appropriately substituted lower alkyl ester of this invention.
EXAMPLE 15
N-[(4,6-dimethoxy-1,3,5-traizin-2-yl)aminothioxomethyl]-2-methoxycarbonylbenzenesulfonamide
A mixture of 4.2 g of methyl 2-sulfamoyl benzoate, 4.0 g of 4,6-dimethoxy-2-isothiocyanato-1,3,5-triazine and 2.7 g of anhydrous potassium carbonate in 70 ml of acetone was warmed to 40.degree. with stirring. After 2 hours a thick precipitate formed and stirring was continued for three more hours at ambient temperature. The precipitate was removed by filtration, suspended in 150 ml of water, stirred and the pH adjusted to 2 by the addition of hydrochloric acid.
The desired product was removed by filtration washed with cold water and dried to yield 4.8 g of product melting at 165.degree.-170.degree.. It showed infrared absorption peaks at 1760, 1650 and 1600 cm.sup.-1 and nuclear magnetic resonance peaks for the methoxy groups at 4.0 and 3.8 (singlets) and 8.0-8.7 (multiplet) consistent for the desired product.
Example 15 demonstrates a method whereby compounds of this invention can be prepared wherein W is S by using equivalent amounts of the appropriate isothiocyanato pyrimidine or triazine and an appropriately substituted benzenesulfonamide.
TABLE II__________________________________________________________________________ ##STR173##QR R.sub.2 R.sub.3 W R.sub.4 R.sub.5 X Y m.p. .degree.C.__________________________________________________________________________OCH.sub.3 H H O H H CH.sub.3 CH.sub.3 187-189.degree.OCH.sub.3 H H O H CH.sub.3 OCH.sub.3 OCH.sub.3OCH.sub.3 H H O H H H HOCH.sub.3 H H S H H CH.sub.3 OCH.sub.3OCH.sub.3 3-Cl H O H H CH.sub.3 OCH.sub.3OCH.sub.3 3-CH.sub.3 H O H H OCH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 3-Cl 5-Cl O H H OC.sub.2 H.sub.5 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 5-NO.sub.2 H O H H OC.sub.2 H.sub.5 OCH.sub.3 CH.sub.2 OCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3O -n-C.sub.3 H.sub.7 3-Cl 6-Cl O H H CH.sub.3 CH.sub.2 O CH.sub.3 OO -n-C.sub.4 H.sub.9 H H O H H CH.sub.3 O CF.sub.3OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 3-OCH.sub.3 H S H H CH.sub.3 OC.sub.2 H.sub.5OC.sub.2 H.sub.5 5-SCH.sub.3 H O H H CH.sub.3 O(CH.sub.2).sub.2 OC.sub.2 H.sub.5OCH.sub.3 5-F H O H H OCH.sub.3 O(CH.sub.2).sub.2 COOC.sub.2 H.sub.5OCH.sub.3 5-CH.sub.3 H O H CH.sub.3 OCH.sub.3 OCH.sub.3OCH.sub.3 5-F H O H CH.sub.3 CH.sub.3 OCH.sub.3OCH.sub.3 3-Cl H O H CH.sub.3 OCH.sub.3 N(CH.sub.3).sub.2OCH.sub.3 5-CH.sub.3 H O H H CH.sub.3 OCH.sub.3 ##STR174## H H O H H CH.sub.3 OCH.sub.3 160-162.degree.OCH.sub.2 CH(CH.sub.3).sub.2 H H O H H OCH.sub.3 OCH.sub.3 167-170.degree.O(CH.sub.2).sub.5 CH.sub.3 H H O H H OCH.sub.3 OCH.sub.3 133-135.degree.OCH.sub.3 5-CN H O H H OCH.sub.3 OCH.sub.3OCH.sub.3 5-CF.sub.3 H O H H OCH.sub.3 OCH.sub.3OCH.sub.3 5-SO.sub.2 CH.sub.3 H O H H OCH.sub.3 OCH.sub.3OCH.sub.3 5-N(CH.sub.3).sub.2 H O H H OCH.sub.3 OCH.sub.3OCH.sub.3 5-NH.sub.2 H O H H OCH.sub.3 OCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 SCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 SCH.sub.2 COOCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 S(CH.sub.2).sub.2 OC.sub.2 H.sub.5O -n-C.sub.3 H.sub.7 H H O H H OCH.sub.3 CH.sub.3 157-160.degree.O -n-C.sub.3 H.sub.7 H H O H H OCH.sub.3 OCH.sub.3 162-166.degree.O -n-C.sub. 4 H.sub.9 H H O H H OCH.sub.3 OCH.sub.3 147-150.degree.O -n-C.sub.4 H.sub.9 H H O H H OCH.sub.3 CH.sub.3 144-145.degree.OC.sub.2 H.sub.5 H H O H H OCH.sub.3 OCH.sub.3 163-165.degree.OC.sub.2 H.sub.5 H H O H H OCH.sub.3 CH.sub.3 164-167.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl H H O H H OCH.sub.3 CH.sub.3 143-144.degree.OCH.sub.2 CH.sub.2 Cl H H O H H OCH.sub.3 OCH.sub.3 171-174.degree.O(CH.sub.2).sub.9 CH.sub.3 H H O H H OCH.sub.3 CH.sub.3 129-130.degree.O(CH.sub.2).sub.9 CH.sub.3 H H O H H OCH.sub.3 OCH.sub.3 94-97.degree. ##STR175## H H O H H OCH.sub.3 OCH.sub.3 139-143.degree.OCH.sub.3 4-Cl H O H H OCH.sub.3 OCH.sub.3 142-145.degree.OCH.sub.2 CHCH.sub.2 H H O H H OCH.sub.3 OCH.sub.3 155-158.degree.O .sub.-i-C.sub.3 H.sub.7 H H O H H CH.sub.3 CH.sub.3 187-189.degree. ##STR176## H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 (CH.sub.2).sub.4 CH.sub.2 Cl H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 Br H H O H H OCH.sub.3 CH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5 H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 CHCH.sub.2 H H O H H OCH.sub.3 CH.sub.3 153-155.degree.O(CH.sub.2).sub.4 CHCH.sub.2 H H O H H OCH.sub.3 CH.sub.3OCH.sub.3 4-Cl 5-Cl O H H OCH.sub.3 OCH.sub.3 172-175.degree.OCH.sub.3 4-F H O H H OCH.sub.3 OCH.sub.3 192-194.degree.OCH.sub.3 4-Cl 5-Cl O H H OCH.sub.3 CH.sub.3 159-161.degree.OCH.sub.3 4-F H O H H OCH.sub.3 CH.sub.3 169-172.degree.OCH.sub.3 4-Br H O H H OCH.sub.3 CH.sub.3O(CH.sub.2).sub.3 F H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 Cl H H O H H CH.sub.3 CH.sub.3 ##STR177## H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 CCl.sub.3 H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CF.sub.3 H H O H H OCH.sub.3 CH.sub.3 ##STR178## H H O H H OCH.sub.3 CH.sub.3 oilO(CH.sub.2).sub.4 CH.sub.3 H H O H H OCH.sub.3 CH.sub.3 ##STR179## H H O H H OCH.sub.3 CH.sub.3 136-138.degree.OCH(CH.sub.2 CH.sub.3).sub.2 H H O H H CH.sub.3 OCH.sub.3 120-123.degree. ##STR180## H H O H H OCH.sub.3 CH.sub.3 ##STR181## H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 H H O H H CH.sub.3 CH.sub.3 ##STR182## H H O H H OCH.sub.3 CH.sub.3 ##STR183## H H O H H OCH.sub.3 CH.sub.3 192-194.degree. ##STR184## H H O H H OCH.sub.3 CH.sub.3 179-181.degree. ##STR185## H H O H H OCH.sub.3 CH.sub.3 125-130.degree.O(CH.sub.2).sub.4 CH.sub.3 H H O H H OCH.sub.3 OCH.sub.3 122-125.degree.OCH.sub.3 H H O H H CH.sub.3 N(CH.sub.3).sub.2 190-191.degree.OCH.sub.3 H H O H H OCH.sub.3 OCH.sub.2 CF.sub.3 glassOCH.sub.3 H H O H H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 glassOCH.sub.3 H H O H H OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 glassOCH.sub.3 H H O H H Cl ClOCH.sub.3 H H O H H CH.sub.3 ##STR186##OCH.sub.3 H H O H H CH.sub.3 ##STR187##OCH.sub.3 H H O H H CH.sub.3 ##STR188##OCH.sub.3 H H O H H CH.sub.3 ##STR189##OCH.sub.3 H H O H H CH.sub.3 ##STR190## ##STR191## H H O H H OCH.sub.3 CH.sub.3 170-172.degree. ##STR192## H H O H H OCH.sub.3 CH.sub.3 120-126.degree. ##STR193## H H O H H OCH.sub.3 CH.sub.3 120-124.degree. ##STR194## H H O H H OCH.sub.3 CH.sub.3 132-136.degree. ##STR195## H H O H H OCH.sub.3 CH.sub.3 144-146.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H H OCH.sub.3 CH.sub.3 123-127.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H H OCH.sub.3 OCH.sub.3 168-170.degree.OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H O H H OCH.sub.3 OCH.sub.3 137-139.degree.OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H O H H OCH.sub.3 CH.sub.3 125-128.degree. ##STR196## H H O H H OCH.sub.3 CH.sub.3 125-130.degree. ##STR197## H H O H H OCH.sub.3 CH.sub.3 130-134.degree.O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.4 Cl H H O H H OCH.sub.3 CH.sub.3 n.sub. D.sup.25 -1.5311 ##STR198## H H O H H OCH.sub.3 CH.sub.3 80-84.degree.O(CH.sub.2).sub.11 CH.sub.3 H H O H H CH.sub.3 CH.sub.3 O ##STR199## H H O H H CH.sub.3 CH.sub.3 OOCH.sub.2 CHCH(CH.sub.2).sub.4 CH.sub.3 H H O H H CH.sub.3 CH.sub.3 O ##STR200## H H O H H CH.sub.3 CH.sub.3 O ##STR201## H H O H H CH.sub.3 CH.sub.3 O ##STR202## H H O H H CH.sub.3 CH.sub.3 O ##STR203## H H O H H CH.sub.3 CH.sub.3 O ##STR204## H H O H H CH.sub.3 CH.sub.3 O ##STR205## H H O H H CH.sub.3 CH.sub.3 O ##STR206## H H O H H CH.sub.3 CH.sub.3 ##STR207## H H O H H CH.sub.3 OCH.sub.3 ##STR208## H H O H H CH.sub.3 OCH.sub.3 ##STR209## H H O H H CH.sub.3 OCH.sub.3 ##STR210## H H O H H CH.sub.3 OCH.sub.3Ocyclo C.sub.8 H.sub.15 H H O H H CH.sub.3 CH.sub.3 ##STR211## H H O H H CH.sub.3 CH.sub.3 ##STR212## H H O H H CH.sub.3 CH.sub.3 ##STR213## H H O H H CH.sub.3 CH.sub.3 ##STR214## H H O H H CH.sub.3 CH.sub.3 O ##STR215## H H O H H CH.sub.3 CH.sub.3 ##STR216## H H O H H CH.sub.3 CH.sub.3 ##STR217## H H O H H CH.sub.3 CH.sub.3 O ##STR218## H H O H H CH.sub.3 OCH.sub.3 ##STR219## H H O H H CH.sub.3 CH.sub.3 ##STR220## H H O H H CH.sub.3 CH.sub.3 ##STR221## H H O H H CH.sub.3 OCH.sub.3 ##STR222## H H O H H CH.sub.3 OCH.sub.3 155-158.degree. ##STR223## H H O H H CH.sub.3 OCH.sub.3 ##STR224## H H O H H CH.sub.3 OCH.sub.3 ##STR225## H H O H H CH.sub.3 OCH.sub.3 ##STR226## H H O H H CH.sub.3 OCH.sub.3 ##STR227## H H O H H CH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.4 CH.sub.3 H H O H H CH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.3 C.sub.2 H.sub.5 H H O H H CH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.4 Cl H H O H H CH.sub.3 OCH.sub.3OCH.sub.2 CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2 H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SC.sub.2 H.sub.5 H H O H H CH.sub.3 CH.sub.3O(CH.sub.2).sub.3 SC.sub.2 H.sub.5 H H O H H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SO.sub.2 C.sub.2 H.sub.5 H H O H H CH.sub.3 CH.sub.3O(CH.sub.3).sub.2 SOCH.sub.3 H H O H H CH.sub.3 CH.sub.3OCH.sub.3 H H O H H CH.sub.3 CO.sub.2 CH.sub.3OCH.sub.3 H H O H H CH.sub.3 CO.sub.2 HOi-C.sub.3 H.sub.7 H H O H H CH.sub.3 N(CH.sub.3).sub.2 151-157.degree.OCH.sub.3 H H O H H OCH.sub.2 CH.sub.2 OCH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 142-145.degree.OCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 100-105.degree.OCH.sub.3 H H O H H CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 glassOCH.sub.3 H H O H H CH.sub.3 CH.sub.2 CH.sub.2 CH.sub. 2 OCH.sub.3 126-128.degree.OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CO.sub.2 CH.sub.3 176-178.degree.OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 105-110.degree.OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CF.sub.3 165-168.degree.OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 125-135.degree.OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.3 170-172.degree.OCH.sub.3 H H O H H CH.sub.3 ##STR228## glassOCH(CH.sub.3).sub.2 H H O H H CH.sub.3 ##STR229## glassOCH.sub.3 H H O H H H OCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 -n-C.sub.4 H.sub.9OCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub. 2 OCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CNOCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CH.sub.2 CNOCH.sub.3 H H O H H OCH.sub.3 (CH.sub.2).sub.3 CNOCH.sub.3 H H O H H OCH.sub.3 (CH.sub.2).sub.4 CO.sub.2 CH.sub.3OCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CH.sub.2 ClOCH.sub.3 H H O H H OCH.sub.3 (CH.sub.2).sub.3 BrOCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 CHCHCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 CH.sub.2 C CCH.sub.3OCH.sub.3 H H O H H OCH.sub.3 NHnC.sub.4 H.sub.9OCH.sub.3 H H O H H OCH.sub.3 ##STR230##OCH.sub.3 H H O H H OCH.sub.3 ##STR231##OCH.sub.3 H H O H H OCH.sub.3 ##STR232##OCH.sub.3 H H O H H OCH.sub.3 ##STR233##OCH.sub.3 H H O H H CH.sub.3 OCH(CH.sub.3).sub.2OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 ClOCH.sub.3 H H O H H CH.sub.3 CH.sub.2 CCl.sub.3OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 CNOCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CHCH.sub.2OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CCCH.sub.3OCH.sub.3 H H O H H CH.sub.3 ##STR234##OCH.sub.3 H H O H H CH.sub.3 ##STR235##OCH.sub.3 H H O H H CH.sub.3 O(CH.sub.2).sub.2 OCH(CH.sub.3) .sub.2OCH.sub.3 H H O H H CH.sub.3 SCH.sub.2 CH.sub.2 SCH.sub.3OCH.sub.3 H H O H H CH.sub.3 ##STR236##OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 SCH(CH.sub.3 ).sub.2OCH.sub.3 H H O H H CH.sub.3 OCH.sub.2 CH.sub.2 SCH.sub.3OCH.sub.3 H H O H H CH.sub.3 SCH.sub.2 CH.sub.3OCH.sub.3 H H O H H CH.sub.3 SCH.sub.2 CH.sub.2 CNOCH.sub.3 H H O H H CH.sub.3 SCH.sub.2 CHCH.sub.2 ##STR237## H H O H H CH.sub.3 CH.sub.3 ##STR238## H H O H H OCH.sub.3 OCH.sub.3 ##STR239## H H O H H OCH.sub.3 CH.sub.3 ##STR240## H H O H H OCH.sub.3 OCH.sub.3 ##STR241## H H O H H CH.sub.3 CH.sub.3 ##STR242## H H O H H OCH.sub.3 OCH.sub.3 ##STR243## H H O H H OCH.sub.3 OCH.sub.3 ##STR244## H H O H H OCH.sub.3 CH.sub.3 ##STR245## H H O H H OCH.sub.3 CH.sub.3 ##STR246## H H O H H OCH.sub.3 OCH.sub.3 ##STR247## H H O H H OCH.sub.3 CH.sub.3 ##STR248## H H O H H OCH.sub.3 CH.sub.3 ##STR249## H H O H H OCH.sub.3 CH.sub.3 ##STR250## H H O H H OCH.sub.3 CH.sub.3 ##STR251## H H O H H OCH.sub.3 CH.sub.3 ##STR252## H H O H H OCH.sub.3 CH.sub.3 ##STR253## H H O H CH.sub.3 OCH.sub.3 CH.sub.3 ##STR254## H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 SCH(CH.sub.3).sub.2 H H O H H OCH.sub.3 CH.sub.3 ##STR255## H H O H H OCH.sub.3 CH.sub.3OCH.sub.2 CN H H O H H OCH.sub.3 CH.sub.3 ##STR256## H H O H H OCH.sub.3 OCH.sub.3 ##STR257## H H O H H OCH.sub.3 CH.sub.3 ##STR258## H H O H H OCH.sub.3 CH.sub.3__________________________________________________________________________
EXAMPLE 16
N-[(5,6-dimethyl-1,2,4-triazin-3-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide
To a stirred suspension of 1.2 g of 3-amino-5,6-dimethyl-1,2,4-triazine in 25 ml of anhydrous acetonitrile was added at ambient temperature 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate. After stirring for 24 hours at ambient temperature, the resultant precipitate was filtered off to yield 2.5 g of the desired compound melting at 150.degree.-151.degree.. It showed infrared absorption peaks at 1700, 1680 and 1550 cm.sup.-1, consistent for N-[(5,6-dimethyl-1,2,4-triazin-3-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide.
By using the procedure of Example 16 with an equivalent amount of a 3-amino-1,2,4-triazine and an appropriately substituted benzenesulfonyl isocyanate or isothiocyanate the compounds of Table III can be prepared.
TABLE III______________________________________ ##STR259## m.p.QR R.sub.2 R.sub.3 W X.sub.1 Y.sub.1 .degree.C.______________________________________OCH.sub.3 5-Cl HO CH.sub.3 CH.sub.3OCH.sub.3 5-NO.sub.2 HO CH.sub.3 CH.sub.3OC.sub.2 H.sub.5 5-CH.sub.3 HO CH.sub.3 CH.sub.3O .sub.-i-C.sub.3 H.sub.7 5-F HO CH.sub.3 CH.sub.3O -n-C.sub.4 H.sub.9 H HO CH.sub.3 CH.sub.3 ##STR260## H HO CH.sub.3 CH.sub.3 ##STR261## 6-Cl HO CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H HO H CH.sub.3OCH.sub.3 H HSCH.sub.3 CH.sub.3OCH.sub.3 3-Cl 5-Cl O OCH.sub.3 OCH.sub.3OCH.sub.2 CH.sub.2 Cl H HO OCH.sub.3 OCH.sub.3 ##STR262## H HO CH.sub.3 CH.sub.3OCH.sub.2 CCl.sub.3 H HO CH.sub.3 CH.sub.3OCH.sub.2 CF.sub.3 H HO CH.sub.3 CH.sub.3 ##STR263## H HO CH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CH.sub.3 H HO CH.sub.3 CH.sub.3OCH.sub.3 H HO CH.sub.3 OC.sub.2 H.sub.5OCH(CH.sub.3).sub.2 H HO CH.sub.3 OC.sub.2 H.sub.5OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H HO CH.sub.3 CH.sub.3 124- 127 ##STR264## H HO CH.sub.3 CH.sub.3 ##STR265## H HO CH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 H HO CH.sub.3 CH.sub.3 ##STR266## H HO CH.sub.3 CH.sub.3OCH.sub.3 5-CN HO CH.sub.3 OCH.sub.3OCH.sub.3 5-CF.sub.3 HO CH.sub.3 OCH.sub.3OCH.sub.3 5-SO.sub.2 CH.sub.3 HO CH.sub.3 OCH.sub.3OCH.sub.3 5-OCH.sub.3 HO CH.sub.3 OCH.sub.3______________________________________
EXAMPLE 17
N-[(2,6-dimethylpyrimidin-4-yl)aminocarbonyl]2-methoxycarbonylbenzenesulfonamide
To a suspension of 1.2 g of 4-amino-2,6-dimethylpyrimidine in 30 ml of dry acetonitrile with stirring was added 2.4 g of 2-methoxycarbonylbenzenesulfonylisocyanate. The mixture was stirred for two hours at ambient temperature, allowed to stand for sixteen hours and the desired product, which had precipitated, was removed by filtration and washed with butyl chloride to yield 2.4 g, m.p. 125.degree.-127.degree.. The product showed absorption peaks by Nuclear Magnetic Resource at 4.0, 2.62 and 2.9 ppm; consistent for the product.
By using the procedure of Example 17 with equivalent amounts of appropriate 4-aminopyrimidines and appropriately substituted sulfonylisocyanates or isothiocyanates, the compounds of Table IV can be prepared.
TABLE IV______________________________________ ##STR267## m.p.QR R.sub.2 R.sub.3 WX.sub.1 Y.sub.1 .degree.C.______________________________________OCH.sub.3 HHOOCH.sub.3 CH.sub.3OCH.sub.3 HHOCH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 6-ClHOOCH.sub.3 OCH.sub.3OCH.sub.3 3-Cl5-ClOOCH.sub.3 C.sub.2 H.sub.5OCH.sub.3 5-OCH.sub.3 HOOCH.sub.3 OCH.sub.3OCH.sub.3 5-NO.sub.2 3-ClOOCH.sub.3 CH.sub.2 OCH.sub.3OC.sub.2 H.sub.5 5-ClHOOCH.sub.3 OCH.sub.3OCH.sub.2 CH.sub.2 Cl HHOOCH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3 HHOOCH.sub.3 OCH.sub.3 ##STR268## HHOOCH.sub.3 OCH.sub.3OCH.sub.2 CH.sub.2 Br HHOClOCH.sub.3OCH.sub.2 CF.sub.3 HHOOCH.sub.3 OCH.sub.3 ##STR269## HHOOCH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CH.sub.3 HHOOCH.sub.3 OCH.sub.3OCH(CH.sub.3).sub.2 HHOCH.sub.3 OC.sub.2 H.sub.5OCH.sub.3 HHOCH.sub.3 OC.sub.2 H.sub.5OCH.sub.3 5-CNHOCH.sub.3 OCH.sub.3OCH.sub.3 5-CF.sub.3 HOCH.sub.3 OCH.sub.3OCH.sub.3 5-SO.sub.2 CH.sub.3 HOCH.sub.3 OCH.sub.3 ##STR270## HHOOCH.sub.3 OCH.sub.3 ##STR271## HHOOCH.sub.3 OCH.sub.3 ##STR272## HHOOCH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 HHOOCH.sub.3 OCH.sub.3 ##STR273## HHOOCH.sub.3 OCH.sub.3______________________________________
By using an appropriate N-[(triazinyl)aminocarbonyl]-2-carbonylbenzenesulfonamide or N[(pyrimidinyl)aminocarbonyl]-2-carbonylbenzenesulfonamide, the compounds of Formula I set forth in Table V can be prepared. For example, the compound of Example 12 can be converted to N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonyl-N-methylbenzenesulfonamide by the methylation reaction set forth in Equation 2 as follows: An equivalent amount of sodium hydride (50% mineral oil dispersion) can be added to a solution of the compound of Example 12 in dimethylformamide under a nitrogen atmosphere. After hydrogen evolution has ceased, an equivalent amount of dimethylsulfate can be added. The resulting reaction mixture can be stirred for 2-18 hours and the reaction mixture can then be poured into a large volume of water to form a precipitate which can be filtered to yield the above-identified product.
TABLE V-a______________________________________ ##STR274## m.p.QR R.sub.2 R.sub.3 R.sub.5 X Y (.degree.C.)______________________________________OCH.sub.3 HH HCH.sub.3 CH.sub.3OCH.sub.3 HH CH.sub.3 OCH.sub.3 CH.sub.3O -n-C.sub.3 H.sub.7 HH HCH.sub.3 CH.sub.3O .sub.-i-C.sub.3 H.sub.7 HH HOCH.sub.3 OCH.sub.3OCH.sub.3 5-ClH CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3OCH.sub.3 3-Cl6-Cl HCH.sub.3 OCH.sub.2 CH.sub.2O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3 HH HOCH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CHCH.sub.2 H H HOCH.sub.3 CH.sub.3OCH.sub.2 CF.sub.3 HH HOCH.sub.3 CH.sub.3(OCH.sub.2).sub.4 CH.sub.3 HH HCH.sub.3 CH.sub.3 ##STR275## HH HOCH.sub.3 OCH.sub.3 ##STR276## HH HOCH.sub.3 CH.sub.3______________________________________
TABLE V-b______________________________________ ##STR277##QR R.sub.2 R.sub.3 R.sub.3 X Y______________________________________OCH.sub.3 HH HCH.sub.3 OCH.sub.3OCH.sub.3 HH CH.sub.3 CH.sub.3 OCH.sub.3OC.sub.2 H.sub.5 5-NO.sub.2 H CH.sub.3 H OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3O -n-C.sub.4 H.sub.9 6-ClH HCH.sub.3 ##STR278##N(C.sub.2 H.sub.5).sub.2 HH CH.sub.3 OCH.sub.3 N(CH.sub.3).sub.2 ##STR279## HH HOCH.sub.3 NH(CH.sub.3)O(CH.sub.2).sub.9 CH.sub.3 HH HOCH.sub.3 CH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5 HH HOCH.sub.3 CH.sub.3 ##STR280## HH HOCH.sub.3 CH.sub.3 ##STR281## HH HCH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CH.sub.3 HH HOCH.sub.3 OCH.sub.3 ##STR282## HH HCH.sub.3 CH.sub.3 ##STR283## HH HOCH.sub.3 OCH.sub.3 ##STR284## HH HCH.sub.3 CH.sub.3 ##STR285## HH HCH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 HH HCH.sub.3 CH.sub.3 ##STR286## HH HOCH.sub.3 CH.sub.3______________________________________
By using an appropriately substituted benzenesulfonyl-N-methylcarbamyl chloride or thiocarbamylchloride and an appropriate aminopyrimidine or amino-traizine, the compounds of Formula I set forth in Table VI can be prepared by the procedure of Equation 5. For example, N-[N-(4-methoxy-6-methylpyrimidin-2-yl)-N-methylaminocarbonyl]-2-methoxycarbonyl-N-methylbenzenesulfonamide can be prepared by adding 3.0 g of N-[(2-methoxycarbonylphenyl)sulfonyl]-N-methylcarbamylchloride in 50 ml of tetrahydrofuran containing 1.0 g of triethyl amine to 1.5 g of 2-methylamino-4-methoxy-6-methylpyridine. That mixture can be stirred at reflux for several hours, the precipitated salts can be filtered off and the filtrate can be concentrated to yield the foregoing product.
TABLE VI-a__________________________________________________________________________ ##STR287##QR R.sub.2 R.sub.3 W R.sub.5 X Y__________________________________________________________________________OCH.sub.3 H H S CH.sub.3 OCH.sub.3 OCH.sub.3OCH.sub.3 H H S H CH.sub.3 CH.sub.3OCH.sub.3 6-CH.sub.3 H O CH.sub.3 OCH.sub.3 OCH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3O(CH.sub.2).sub.9 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3O(CH.sub.2).sub.4 CHCH.sub.2 H H O H OCH.sub.3 OCH.sub.3OCH.sub.2 CH.sub.2 Cl H H O H OCH.sub.3 OCH.sub.3 ##STR288## H H O H CH.sub.3 CH.sub.3O(CH.sub.2).sub.4 CH.sub.3 H H O H CH.sub.3 CH.sub.3 ##STR289## H H O H CH.sub.3 CH.sub.3 ##STR290## H H O H CH.sub.3 CH.sub.3 ##STR291## H H O H CH.sub.3 CH.sub.3 ##STR292## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CBr.sub.3 H H O H CH.sub.3 CH.sub.3 ##STR293## H H O H CH.sub.3 CH.sub.3OCH.sub.2 CH.sub.2 F H H O H OCH.sub.3 OCH.sub.3OCH.sub.2 CCl.sub.3 H H O H OCH.sub.3 OCH.sub.3__________________________________________________________________________
TABLE VI-b______________________________________ ##STR294##QR R.sub.2 R.sub.3 W R.sub.5 X Y______________________________________OCH.sub.3 H H S CH.sub.3 OCH.sub.3 OCH.sub.3O .sub.-i-C.sub.3 H.sub.7 5-F H S CH.sub.3 OCH.sub.3 OC.sub.2 H.sub.5O(CH.sub.2).sub.9 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3O(CH.sub.2).sub.4 CHCH.sub.2 H H O H OCH.sub.3 OCH.sub.3 ##STR295## H H O H OCH.sub.3 OCH.sub.3O(CH.sub. 2).sub.4 CH.sub.3 H H O H OCH.sub.3 OCH.sub.3 ##STR296## H H O H CH.sub.3 CH.sub.3 ##STR297## H H O H OCH.sub.3 OCH.sub.3 ##STR298## H H O H OCH.sub.3 OCH.sub.3OCH.sub.2 CBr.sub.3 H H O H OCH.sub.3 OCH.sub.3 ##STR299## H H O H OCH.sub.3 OCH.sub.3OCH.sub.2 CF.sub.3 H H O H OCH.sub.3 OCH.sub.3______________________________________
EXAMPLE 18
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-carboxybenzenesulfonamide
A mixture of 2.0 g of N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide and 11 ml. of 50% aqueous sodium hydroxide was warmed on a steam bath with shaking; 40 ml. of water was added and heating and shaking continued during the next half hour. The resulting solution was then filtered and the filtrate acidified with hydrochloric acid to pH 2 to yield a precipitate which was isolated by filtration to yield the title compound, 0.7 g melting at 160.degree. with decomposition. The nuclear magnetic resonance spectrum showed resonance peaks for the methyl substituents on the pyrimidine ring at 2.66 ppm and the ring hydrogens at 7.2 to 8.4 ppm. The disappearance of the resonance peak at 4.0 ppm confirmed the conversion of the methyl ester to the carboxy group.
EXAMPLE 18-A
N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-carboxybenzenesulfonamide
4.0 g of N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide was dissolved in a mixture of 20 ml of absolute ethanol, 2.5 ml of water and 2.5 g of potassium hydroxide. After stirring at 25.degree. for 24 hours the mixture had become a semi-solid mass. Enough cold water was added to dissolve the solid and the solution was acidified to pH 3 with concentrated hydrochloric acid. The resultant precipitate was isolated by filtration and washed with cold water. The precipitate was dried to afford 3.7 g of the title compound, melting at 195.degree.-200.degree.. The nuclear magnetic resonance spectrum exhibited resonances for the methyl and methoxy substituents on the pyrimidine ring at 2.67 ppm and 4.20 ppm respectively.
Peaks for the pyrimidine ring proton and phenyl ring protons were observed at 6.73 ppm and 7.9 to 8.6 ppm respectively. The disappearance of the resonance peak at 4.10 confirmed the conversion of the methyl ester to the carboxy group.
By using an appropriate N-[(triazinyl)aminocarbonyl]-2-alkoxycarbonylbenzenesulfonamide or a N-[(pyrimidinyl)aminocarbonyl]-2-alkoxycarbonylbenzenesulfonamide or their aminothioxomethyl analogs (W=S), the compounds of Formula I set forth in Table VII-a-VII-d can be prepared by the procedure of Example 18 or 18-A.
TABLE VII-a______________________________________ ##STR300##R.sub.2 R.sub.3 R.sub.4 R.sub.5 W X Y______________________________________H H H H O CH.sub.3 OCH.sub.36-Cl H CH.sub.3 H O OCH.sub.3 CH.sub.2 OCH.sub.36-Cl H H H S OCH.sub.3 CH.sub.33-Cl 5-Cl H H S OCH.sub.3 N(CH.sub.3).sub.2______________________________________
TABLE VII-b______________________________________ ##STR301##R.sub.2 R.sub.3 R.sub.4 R.sub.5 W X Y______________________________________H H H H O CH.sub.3 OCH.sub.3H H H H S OCH.sub.3 OCH.sub.34-Cl 6-Cl H H O OCH.sub.3 OCH.sub.2 CH.sub.3______________________________________
TABLE VII-c______________________________________ ##STR302##R.sub.2 R.sub.3 W X Y______________________________________H H O CH.sub.3 CH.sub.3H H S CH.sub.3 CH.sub.3______________________________________
TABLE VII-d______________________________________ ##STR303##R.sub.2 R.sub.3 W X Y______________________________________H H O OCH.sub.3 OCH.sub.3H H S OCH.sub.3 OCH.sub.33-Cl H O OCH.sub.3 CH.sub.3______________________________________
EXAMPLE 18-B
Methyl 2-[[[4-(1-carboxyethoxy)-6-methyl-1,3,5-triazin-2-yl]aminocarbonyl]aminosulfonyl]benzoate
Methyl 2-(isocyanatosulfonyl)benzoate (10.1 g) and 8.0 g of ethyl 2-[(4-amino-6-methyl-1,3,5-triazin-2-yl)oxy]propanoate were stirred in 80 ml of methylene chloride at ambient temperature for 18 hours. An additional 2 g of the sulfonylisocyanate was added and the reaction mixture was stirred for four more hours and then 2 g more of the sulfonylisocyanate was added. After stirring for four more hours at ambient temperature, 400 ml of water was added and the pH of this mixture was adjusted to pH 8 by the addition of 10% aqueous sodium hydroxide. The aqueous phase was separated and acidified to pH 1 with hydrochloric acid to precipitate a thick white gum. Sufficient 50% aqueous sodium hydroxide was added to achieve pH 12 and the mixture was heated on a steam bath until a clear solution resulted. The solution was again acidified with hydrochloric acid to pH 3 and the resultant cloudy solution was extracted with dichloromethane. The organic phase was dried and the solvent was removed to afford 3.7 g of the title compound as a glass.
By using an appropriate N-[(triazinyl)aminocarbonyl]-2-carbonylbenzenesulfonamide or a N-[(pyridinyl)aminocarbonyl]-2-carbonylbenzenesulfonamide or their aminothioxomethyl analogs, the compounds of Formula I wherein L=OH as shown in Table VII-e and VII-f can be prepared by the procedure of Example 18-B.
TABLE VII-e______________________________________ ##STR304##QR R.sub.2 R.sub.3 R.sub.4 R.sub.5 W X Y______________________________________OCH.sub.3 H H H H O OCH.sub.3 ##STR305##OCH.sub.3 H H H H O OCH.sub.3 ##STR306##OCH.sub.3 H H H H O OCH.sub.3 ##STR307##OCH.sub.3 H H H H O OCH.sub.3 ##STR308##OCH.sub.3 H H H H O CH.sub.3 ##STR309##OCH.sub.3 H H H H O CH.sub.3 ##STR310##OCH.sub.3 H H H H O CH.sub.3 ##STR311##OCH.sub.3 H H H H O CH.sub.3 ##STR312##OCH.sub.3 H H H H O CH.sub.3 ##STR313##OCH.sub.3 H H H H O CH.sub.3 ##STR314##______________________________________
TABLE VII-f______________________________________ ##STR315##QR R.sub.2 R.sub.3 R.sub.4 R.sub.5 W X Y______________________________________OCH.sub.3 H H H H O OCH.sub.3 ##STR316##OCH.sub.3 H H H H O OCH.sub.3 ##STR317##OCH.sub.3 H H H H O OCH.sub.3 ##STR318##OCH.sub.3 H H H H O OCH.sub.3 ##STR319##OCH.sub.3 H H H H O CH.sub.3 ##STR320##OCH.sub.3 H H H H O CH.sub.3 ##STR321##OCH.sub.3 H H H H O CH.sub.3 ##STR322##OCH.sub.3 H H H H O CH.sub.3 ##STR323##OCH.sub.3 H H H H O CH.sub.3 ##STR324##OCH.sub.3 H H H H O CH.sub.3 ##STR325##______________________________________
EXAMPLE 19
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-dimethylaminocarbonylbenzenesulfonamide
To 4.1 g of N[(4,6-dimethylpyrimidin-2-yl)-2-methoxycarbonylbenzenesulfonamide in 75 ml of toluene was added 37 ml of a methylene chloride and toluene solution (3:5) containing 1.25 g of dimethylaluminum dimethylamide with stirring at ambient temperature. The mixture was heated to reflux (82.degree. C.) for two hours, cooled, 10 ml of methanol added and the solvents evaporated in vacuo. The residue was treated with a mixture of methanol, water and dilute hydrochloric acid and the precipitated product filtered off to yield 1.25 g of the desired product. Extraction of the aqueous filtrate with methylene chloride gave 1.12 g more product, m.p. 166.degree.-8.degree. C. The product showed NMR absorption peaks at 2.5 ppm, pyrimidinmethyl; 2.85 and 3.1 ppm, nonequivalent methyl groups of the dimethylamide; 6.8 ppm, pyrimidin H; and 7.2-8.4 ppm, aromatic hydrogens.
EXAMPLE 20
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-isopropylaminocarbonylbenzenesulfonamide
To 4.5 g of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide in 75 ml methylene chloride was added with stirring at ambient temperature, 37 ml of a methylene chloride solution containing 1.44 g of dimethyaluminum isopropylamide. The mixture was heated to reflux and the methylene chloride removed by distillation while adding dry toluene until a temperature of 100.degree. C. was reached. Refluxing was continued for two hours at 100.degree. C. after which the mixture was cooled and 10 ml of methanol was added and the solvents evaporated in vacuo. The residue was then triturated with a mixture of methanol, water and dilute HCl and the product extracted from this aqueous slurry with methylene chloride. Evaporation of the methylene chloride extract yielded the product as a solid (4.28 g). Trituration of the product with 1-chlorobutane gave 2.0 g of pure product m.p. 148.degree.-150.degree. C. which showed a single spot on TLC (Silica gel, Acetone/Hexane 1:1, R.sub.f =0.34) and gave absorption peaks in the NMR spectrum at 1.15, 4.0, 3.8-4.3 and 7.5-8.2 ppm.
Elem. Anal. Calcd. for C.sub.17 H.sub.21 N.sub.5 O.sub.6 S; Calc.: C, 48.2; H, 4.96; N, 16.5. Found: C, 48.1; H, 5.20; N, 16.0.
By using the procedure of Examples 19 and 20 with equivalent amounts of appropriately substituted dialkylaluminum-N-alkylamide and appropriately substituted esters of this invention, the compounds of Table VIII can be prepared.
TABLE VIII-a__________________________________________________________________________ ##STR326##R R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6 W X Y m.p. (.degree.C.)__________________________________________________________________________CH.sub.3 H H H H H O OCH.sub.3 CH.sub.3 184-185.degree.CH.sub.3 H H H H H O OCH.sub.3 OCH.sub.3 168-170.degree. -n-C.sub.3 H.sub.7 H H H H H O OCH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 5-Cl H H H H O CH.sub.3 CH.sub.2 OCH.sub.3CH.sub.2C.sub.6 H.sub.5 H H H H H O OCH.sub.3 CH.sub.3 95- 102.degree.H H H H H H O CH.sub.3 SCNCH.sub.3 H H H H CH.sub.3 O CH.sub.3 CH.sub.3 166-168.degree. .sub.-i-C.sub.3 H.sub.7 H H H H H O OCH.sub.3 OCH.sub.3 148-150.degree. -n-C.sub.3 H.sub.7 H H H H C.sub.2 H.sub.5 O CH.sub.3 ##STR327##(CH.sub.2).sub.7 CH.sub.3 H H H H H O CH.sub.3 CH.sub.3 O(CH.sub.2).sub.11 CH.sub.3 H H H H H O CH.sub.3 CH.sub.3 O 65-70.degree. .sub.-i-C.sub.3 H.sub.7 H H H H H O OCH.sub.3 CH.sub.3 157-158.degree.CH.sub.2 C.sub.6 H.sub.5 H H H H CH.sub.3 S OCH.sub.3 CH.sub.3CH.sub.2 C.sub.6 H.sub.5 H H H H C.sub.2 H.sub.5 O CH.sub.3 CH.sub.3H H H H H H O OCH.sub.3 CH.sub.3 148-150.degree.CH.sub.2 CHCH.sub.2 H H H H H S OCH.sub.3 CH.sub.3 ##STR328## H H H H CH.sub.3 O OCH.sub.3 CH.sub.3 127-130.degree.CH.sub.3 H H H H CH.sub.3 O CH.sub.3 OCH.sub.3 162-165.degree.C.sub.2 H.sub.5 H H H H C.sub.2 H.sub.5 S CH.sub.3 OCH.sub.3C.sub.2 H.sub.5 H H H H CH.sub.3 O CH.sub.3 CH.sub.3C.sub.2 H.sub.5 H H H H CH(CH.sub.3).sub.2 O CH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 H H H H H S CH.sub.3 OCH.sub.3 ##STR329## H H H H H O CH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 H H H H H O CH.sub.3 CH.sub.3 179.degree. ##STR330## H H H H H O CH.sub.3 OCH.sub.3 122-124.degree. ##STR331## H H H H H O CH.sub.3 CH.sub.3(CH.sub.2).sub.3 OCH.sub.3 H H H H H O OCH.sub.3 OCH.sub.3(CH.sub.2).sub.2 OC.sub.2 H.sub.5 H H H H H S OCH.sub.3 CH.sub.3CH.sub.2CH.sub.2CHCH.sub.2 H H H H H O CH.sub.3 OCH.sub.3 ##STR332## H H H H H O CH.sub.3 OCH.sub.3 ##STR333## H H H H H S CH.sub.3 OCH.sub.3(CH.sub.2).sub.4 C.sub.6 H.sub.5 H H H H H O CH.sub.3 OCH.sub.3 ##STR334## H H H H H O CH.sub.3 OCH.sub.3 ##STR335## H H H H H S CH.sub.3 OCH.sub.3 ##STR336## H H H H H O CH.sub.3 OCH.sub.3(CH.sub.2).sub.4* H H H H * O CH.sub.3 OCH.sub.3 175-177.degree.(CH.sub.2).sub.4* H H H H * O OCH.sub.3 OCH.sub.3 189-191.degree.(CH.sub.2).sub.4* H H H H * O CH.sub.3 CH.sub.3 180-181.degree.(CH.sub.2).sub.5* H H H H * O CH.sub.3 CH.sub.3 178-181.degree.(CH.sub.2).sub.5* H H H H * O OCH.sub.3 CH.sub.3 180-183.degree.(CH.sub.2).sub.2 O(CH.sub.2).sub.2* H H H H * O OCH.sub.3 CH.sub.3 162-164.degree. ##STR337## H H H H * O OCH.sub.3 CH.sub.3CH.sub.2 C.sub.6 H.sub.5 H H H H H O OCH.sub.3 OCH.sub.3 112-117.degree.CH.sub.2 C.sub.6 H.sub.5 H H H H H O CH.sub.3 CH.sub.3 75-85.degree.CH.sub.3 O H H H H CH.sub.3 O CH.sub.3 CH.sub.3 183-184.degree. .sub.-t-C.sub.4 H.sub.9 H H H H H O OCH.sub.3 CH.sub.3 122-125.degree.(CH.sub.2).sub.5 * H H H H * O OCH.sub.3 OCH.sub.3 193-195.degree.(CH.sub.2).sub.5 * H H H H * O Cl Cl 156-157.degree. -n-C.sub.3 H.sub.7 H H H H H O OCH.sub.3 OCH.sub.3 184-185.degree.CH.sub.3 H H H H CH.sub.3 O OCH.sub.3 OCH.sub.3 184-186.degree.C(CH.sub.3).sub.3 H H H H H O CH.sub.3 OCH.sub.3 122-125.degree. ##STR338## H H H H H O OCH.sub.3 OCH.sub.3 194-195.degree. ##STR339## H H H H H O OCH.sub.3 OCH.sub.3 199-200.degree.CH.sub.2 CHCH.sub.2 H H H H H O OCH.sub.3 OCH.sub.3 147-150.degree. ##STR340## H H H H H O OCH.sub.3 OCH.sub.3 164-166.degree. ##STR341## H H H H H O OCH.sub.3 OCH.sub.3 122-127.degree.C.sub.2 H.sub.5 H H H H C.sub.2 H.sub.5 O OCH.sub.3 OCH.sub.3 188-190.degree.CH.sub.2CH H H H H H O CH.sub.3 OCH.sub.3C(CH.sub.3).sub.2 CCH H H H H H O CH.sub.3 CH.sub.3CH.sub.2CCCH.sub.3 H H H H H O CH.sub.3 OCH.sub.3 ##STR342## H H H H H O CH.sub.3 CH.sub.3__________________________________________________________________________ *R and R.sub.6 are taken together.
TABLE VIII-b__________________________________________________________________________ ##STR343##R R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6 W X Y m.p. (.degree.C.)__________________________________________________________________________CH.sub.3 H H H H H O OCH.sub.3 OCH.sub.3 166-168.degree.CH.sub.3 H H H H H O CH.sub.3 OCH.sub.3 172.degree.C.sub.2 H.sub.5 5-Cl H CH.sub.3 H H O CH.sub.3 CH.sub.2 OCH.sub.3CH.sub.3 4-Cl 6-Cl CH.sub.3 CH.sub.3 H O OCH.sub.3 OC.sub.2 H.sub.5CH.sub.3 H H H H H S CH.sub.3 OCH.sub.3(CH.sub.2).sub.4 CH.sub.3 H H H H H S OCH.sub.3 CH.sub.3(CH.sub.2).sub.11 CH.sub.3 H H H H H O OCH.sub.3 CH.sub.3 107-109.degree. ##STR344## H H H H H O CH.sub.3 CH.sub.3 O ##STR345## H H H H H O CH.sub.3 O CH.sub.3 O 212-217.degree. ##STR346## H H H H H O CH.sub.3 CH.sub.3 O .sub.-i-C.sub.3 H.sub.7 H H H H H O OCH.sub.3 OCH.sub.3 102.degree. ##STR347## H H H H H O OCH.sub.3 CH.sub.3C.sub.2 H.sub.5 H H H H CH.sub.3 S OCH.sub.3 CH.sub.3 ##STR348## H H H H .sub.-i-C.sub.3 H.sub.7 S OCH.sub.3 CH.sub.3 ##STR349## H H H H H O OCH.sub.3 CH.sub.3 ##STR350## H H H H H O CH.sub.3 OCH.sub.3 127-130.degree.CH.sub.2CHCH.sub.2 H H H H H O CH.sub.3 OCH.sub.3 118-120.degree.(CH.sub.2).sub.2 OCH.sub.3 H H H H CH.sub.3 S CH.sub.3 OC.sub.2 H.sub.5CH.sub.2C.sub.6 H.sub.5 H H H H H O OCH.sub.3 OCH.sub.3(CH.sub.2).sub.4* H H H H * O CH.sub.3 OCH.sub.3(CH.sub.2).sub.5* H H H H * O CH.sub.3 OCH.sub.3 115-118.degree.(CH.sub.2).sub.6* H H H H * O CH.sub.3 OCH.sub.3 -n-C.sub.4 H.sub.9 H H H H -n-C.sub.3 H.sub.7 S CH.sub.3 OCH.sub.3(CH.sub.2).sub.6 CH.sub.3 H H H H -n-C.sub.3 H.sub.7 O CH.sub.3 OCH.sub.3 ##STR351## H H H H H O CH.sub.3 OCH.sub.3cyclo-C.sub.8 H.sub.15 H H H H H O CH.sub.3 OCH.sub.3 ##STR352## H H H H H O CH.sub.3 OCH.sub.3 ##STR353## H H H H H O CH.sub.3 OCH.sub.3 ##STR354## H H H H H O CH.sub.3 OCH.sub.3 ##STR355## H H H H H O CH.sub.3 OCH.sub.3 ##STR356## H H H H H O CH.sub.3 OCH.sub.3 ##STR357## H H H H H O CH.sub.3 OCH.sub.3 ##STR358## H H H H H O CH.sub.3 OCH.sub.3 ##STR359## H H H H H O CH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 H H H H H O CH.sub.3 ##STR360## 125-130.degree.(CH.sub.2).sub.5 * H H H H * O Cl Cl 181-183.degree.(CH.sub.2).sub.5* H H H H * O OCH.sub.3 OCH.sub.3 158-161.degree.C(CH.sub.3).sub.3 H H H H H O CH.sub.3 OCH.sub.3 118-121.degree.CH.sub.2 CCH H H H H H O CH.sub.3 CH.sub.3C(CH.sub.3).sub.2 CCH H H H H H O CH.sub.3 CH.sub.3CH.sub.2CCCH.sub.3 H H H H H O CH.sub.3 OCH.sub.3 ##STR361## H H H H H O CH.sub.3 OCH.sub.3__________________________________________________________________________ * R and R.sub.6 are taken together.
TABLE VIII-c______________________________________ ##STR362##R R.sub.2 R.sub.3 W R.sub.6 X.sub.1 Y.sub.1______________________________________H H H O H CH.sub.3 CH.sub.3CH.sub.3 H H O H CH.sub.3 OCH.sub.3CH.sub.3 5-Cl H S H OCH.sub.3 OCH.sub.3CH.sub.3 6-Cl H S H CH.sub.3 CH.sub.3C.sub.2 H.sub.5 H H O H CH.sub.3 CH.sub.3 ##STR363## H H O H CH.sub.3 CH.sub.3______________________________________
TABLE VIII-d______________________________________ ##STR364##R R.sub.2 R.sub.3 W R.sub.6 X.sub.1 Y.sub.1______________________________________CH.sub.3 H H O H OCH.sub.3 CH.sub.3C.sub.2 H.sub.5 5-Cl H O H CH.sub.3 OCH.sub.3 .sub.-i-C.sub.3 H.sub.7 H H O H CH.sub.3 CH.sub.3______________________________________
EXAMPLE 21
N-[(4-methoxy-6-methyltriazin-2-yl)aminocarbonyl]-2-(methylthio)carbonylbenzenesulfonamide
Trimethylaluminum (6.0 ml, 2M) was charged via syringe to 15 ml dry toluene under nitrogen atmosphere and 3.8 g N-[(4-methoxy-6-methyltriazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide was added portionwise. After stirring at room temperature for one hour, methyl mercaptan (gas) was passed through the reaction mixture until the initial temperature rise subsided, whereupon the addition was discontinued. The reaction mixture was allowed to stir at room temperature for 1 hour, and quenched with 25 ml of 10% HCl. The resultant white suspension was filtered to give 2.9 g white solid which showed infrared absorption peaks at 1740, 1690 cm.sup.-1, consistent for N-[(4-methoxy-6-methyltriazin-2-yl)aminocarbonyl]-2-(methylthio)carbonylbenzenesulfonamide.
EXAMPLE 23
N-[(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-isopropylthiocarbonylbenzenesulfonamide
To 1.5 ml (2N) trimethylaluminum in 5 ml dry toluene under N.sub.2 was added dropwise 0.48 g (6.0 mmole) 2-propanethiol in 2 ml toluene. The resultant aluminum reagent was stirred at room temperature for 15 minutes, and 0.95 g (2.5 mmole) N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methoxycarbonylbenzenesulfonamide was added in one portion. The suspension was heated to 80.degree. C. for 3 hours, cooled to room temperature and 10% HCl (15 ml) was added. The mixture was stirred until a fine solid precipitated which was filtered off, washed with hexanes and air dried to yield 0.4 g of product melting at 155.degree.-158.degree. C. It showed infrared absorption peaks consistent for N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-isopropylthiocarbonylbenzenesulfonamide.
By using the procedures of Examples 21-23 with equivalent amounts of an appropriately substituted dialkyl-aluminum alkylthiolate and appropriately substituted esters of this invention, the compounds of Table IX can be prepared.
TABLE IX-a______________________________________ ##STR365## m.p.QR R.sub.2 R.sub.3 W R.sub.5 X Y (.degree.C.)______________________________________SCH.sub.3 H H O H CH.sub.3 OCH.sub.3SCH.sub.3 H H O H CH.sub.3 CH.sub.3SC.sub.2 H.sub.5 H H O H OCH.sub.3 OCH.sub.3S -n(C.sub.7 H.sub.15) H H O H OCH.sub.3 OCH.sub.3 ##STR366## H H O H OCH.sub.3 CH.sub.3 143- 146.degree. ##STR367## H H O H CH.sub.3 CH.sub.3 ##STR368## H H O H OCH.sub.3 OCH.sub.3 ##STR369## H H O H OCH.sub.3 CH.sub.3 ##STR370## H H O H OCH.sub.3 CH.sub.3 ##STR371## H H O H CH.sub.3 CH.sub.3 ##STR372## H H O H OCH.sub.3 CH.sub.3 133- 136.degree. ##STR373## H H O H CH.sub.3 CH.sub.3 ##STR374## H H O H CH.sub.3 CH.sub.3Scyclo-C.sub.8 H.sub.15 H H O H CH.sub.3 OCH.sub.3 ##STR375## H H O H OCH.sub.3 CH.sub.3 ##STR376## H H O H CH.sub.3 CH.sub.3 ##STR377## H H O H CH.sub.3 CH.sub.3 ##STR378## H H O H OCH.sub.3 OCH.sub.3 ##STR379## H H O H OCH.sub.3 CH.sub.3 148- 150.degree. ##STR380## H H O H OCH.sub.3 CH.sub.3 ##STR381## H H O H CH.sub.3 CH.sub.3 ##STR382## H H O H CH.sub.3 CH.sub.3______________________________________
TABLE IX-b______________________________________ m.p.QR R.sub.2 R.sub.3 W R.sub.5 X Y .degree.C.______________________________________ ##STR383##SCH.sub.3 HHO H CH.sub.3 OCH.sub.3 144- 146.degree.SC.sub.2 H.sub.5 HHO H OCH.sub.3 OCH.sub.3S -n(C.sub.2 H.sub.11) HHO H OCH.sub.3 OCH.sub.3S -n(C.sub.8 H.sub.17) HHO H OCH.sub.3 OCH.sub.3S -n(C.sub.4 H.sub.9) HHO H OCH.sub.3 CH.sub.3 115- 120.degree. ##STR384## HHO H OCH.sub.3 CH.sub.3 ##STR385## HHO H OCH.sub.3 CH.sub.3 ##STR386## HHO H OCH.sub.3 CH.sub.3 ##STR387## HHO H OCH.sub.3 CH.sub.3 ##STR388## HHO H OCH.sub.3 CH.sub.3 ##STR389## HHO H OCH.sub.3 CH.sub.3 ##STR390## HHO H OCH.sub.3 CH.sub.3S(CH.sub.2).sub.8 CHCH.sub.2 HHO H OCH.sub.3 CH.sub.3______________________________________ ##STR391## ##STR392## HHO H OCH.sub.3 CH.sub.3 177- 178 ##STR393## HHO H OCH.sub.3 CH.sub.3 ##STR394## HHO H OCH.sub.3 OCH.sub.3 ##STR395## HHO H CH.sub.3 CH.sub.3 ##STR396## HHO H OCH.sub.3 CH.sub.3 ##STR397## HHO H CH.sub.3 CH.sub.3 ##STR398## HHO H CH.sub.3 CH.sub.3 ##STR399## HHO H CH.sub.3 CH.sub.3 ##STR400## H HO H CH.sub.3 CH.sub.3 ##STR401## HHO H CH.sub.3 CH.sub.3 ##STR402## HHO H CH.sub.3 CH.sub.3 ##STR403## HHO H OCH.sub.3 CH.sub.3 125- 130 ##STR404## HHO H CH.sub.3 CH.sub.3 ##STR405## HHO H CH.sub.3 CH.sub.3 ##STR406## HHO H CH.sub.3 CH.sub.3______________________________________
TABLE IX-c______________________________________ ##STR407##QR R.sub.2 R.sub.3 W X.sub.1 Y.sub.1 m.p. (.degree.C.)______________________________________ ##STR408## H H O CH.sub.3 CH.sub.3 ##STR409## H H O OCH.sub.3 CH.sub.3SCH.sub.2 CH.sub.3 H H O OCH.sub.3 CH.sub.3 ##STR410## H H O CH.sub.3 CH.sub.3 ##STR411## H H O CH.sub.3 CH.sub.3S -n(C.sub.3 H.sub.7) H H O OCH.sub.3 OCH.sub.3SCH.sub.3 H H O CH.sub.3 CH.sub.3______________________________________
TABLE IX-d______________________________________ ##STR412##QR R.sub.2 R.sub.3 W X.sub.1 Y.sub.1 m.p. (.degree.C.)______________________________________ ##STR413## H H O OCH.sub.3 CH.sub.3 ##STR414## H H O OCH.sub.3 CH.sub.3 ##STR415## H H O OCH.sub.3 OCH.sub.3 ##STR416## H H O CH.sub.3 CH.sub.3SCH.sub.3 H H O CH.sub.3 OCH.sub.3S -n(C.sub.5 H.sub.11) H H O OCH.sub.3 OCH.sub.3______________________________________
FORMULATIONS
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of them can 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. 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 diluent(s). More specifically, they will contain these ingredients in the approximate proportions set forth in Table X.
TABLE X______________________________________ Weight Percent* Active Ingredient Diluent(s) Surfactant(s)______________________________________Wettable Powders 20-90 0-74 1-10Oil Suspensions, 3-50 40-95 0-15Emulsions(includingEmulsifiableConcentrates)Aqueous Suspensions 10-50 40-84 1-20Dusts 1-25 70-99 0-5Granules and Pellets 0.1-95 5-99.9 0-15______________________________________ *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.
Some typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 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, "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.degree. C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Enclopedia 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. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material on preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, 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, 169-182.
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
Unless indicated otherwise, all parts are by weight in the following examples.
EXAMPLE 24
Wettable Powder:
______________________________________N--[(4,6-dimethoxy-pyrimidin-2-yl)amino- 95%carbonyl]-2-methoxycarbonylbenzene-sulfonamidedioctyl sodium sulfosuccinate 0.1%sodium ligninsulfonate 1%synthetic fine silica 4%______________________________________
The ingredients ae blended and ground in a hammer-mill to produce particles almost all of which are below 100 microns in size. That material is sifted through a U.S.S. No. 50 screen and packaged.
EXAMPLE 25
Granule
______________________________________wettable powder of Example 24 10%attapulgite granules 90%(U.S.S. #20-40; 0.84-0.42 mm)______________________________________
A slurry of wettable powder containing 50% solids is sprayed onto the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
EXAMPLE 26
Wettable Powder
______________________________________N[(4-methoxy-6-methyl-1,3,5-triazin- 40%2-yl)aminocarbonyl]-2-methoxy-carbonylbenzenesulfonamidedioctyl sodium sulfosuccinate 1.5%sodium ligninsulfonate 3%low viscosity methyl cellulose 1.5%attapulgite 54%______________________________________
The ingredients are thoroughly blended and 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.
EXAMPLE 27
Granule
______________________________________wettable powder of Example 26 25%gypsum 64%potassium sulfate 11%______________________________________
The ingredients are blended in a rotating mixer, and water is sprayed onto that blend so as to effect granulation. When most of the granules have reached 1.0 to 0.42 mm (U.S.S. #18 to 40 sieves) in size, they are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. The resulting granules contain 10% of the active ingredient.
EXAMPLE 28
Wettable Powder
______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl) 65%aminocarbonyl]-2-methoxycarbonyl-benzenesulfonamidedodecylphenol 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 on the solid ingredients in a blender. After grinding in a hammer mill to produce particles almost all of which are below 100 microns in size, the material is reblended, sifted through a U.S.S. #50 sieve (0.3 mm opening) and packaged.
EXAMPLE 29
Oil Suspension
______________________________________N--[(4-methoxy-6-methylpyrimidin-2-yl) 25%aminocarbonyl]-2-methoxycarbonyl-benzenesulfonamidepolyoxyethylene 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 suspension may be applied directly, but preferably after being extended further with coils or emulsified in water.
EXAMPLE 30
Aqueous Suspension
______________________________________N--(4,6-dimethyl-1,3,5-triazin-2-yl)- 25%aminocarbonyl]-2-methoxycarbonyl-benzenesulfonamidehydrated 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 sizes under 10 microns, and then packaged.
EXAMPLE 31
Extruded Pellet
______________________________________N--[(4,6-dimethylpyrimidin-2-yl)- 25%aminocarbonyl]-2-methoxycarbonyl-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 in the form of cylinders about 3 mm in diameter which are cut to produce pellets about 3 mm long. The pellets may be used directly, after drying, or 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 32
Solution
______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl) 5%aminocarbonyl]-2-methoxycarbonyl-benzenesulfonamidedimethylformamide 95%______________________________________
The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.
EXAMPLE 33
Wettable Powder
______________________________________N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)- 80%aminocarbonyl]-2-isopropoxycarbonylbenzenesulfonamidesodium alkylnaphthalenesulfonate 2%sodium ligninsulfonate 2%synthetic amorphous silica 3%kaolinite 13%______________________________________
The ingredients are thoroughly blended after grinding in a hammer mill to produce particles essentially all of which are under 100 microns in size; the material is reblended, sifted through a U.S.S. No. 50 sieve and packaged.
EXAMPLE 34
Tank Mix
______________________________________Wettable Powder of Example 33 2.5 gmAn alkylarylpolyglycol ether type 0.6 literspreader/sticker adjuvant______________________________________
A tank mix of these materials may be made by adding these ingredients (in the amounts given) to 300 liters of water in a spray tank. After agitation, this suspension is applied to 1 hectare of land. Larger spray tanks and land areas may be used if the materials are used in the same proportions.
For good spraying properties, the wettable powder should be added first and be properly dispersed before adding the adjuvant. Then the mixture may be sprayed using conventional spraying techniques.
EXAMPLE 35
Tank Mix
______________________________________Wettable Powder of Example 33 2.5 gmCitowett .RTM. Plus (Spreader/Sticker 0.3 literAdjuvant by BASF)______________________________________
Specifically, a tank mix of these materials may be made by adding these ingredients (in the amounts given) to 300 liters of water in a spray tank. After agitation, this suspension is applied to 1 hectare of land. Larger spray tanks may be used and larger land areas sprayed if the materials are used in the same proportions.
For good spraying properties, the wettable powder should be added first and be properly dispersed before adding the adjuvant. Then, the mixture may be sprayed using conventional spraying techniques.
The compounds of this invention may be used in combination with other commercial herbicides. They are particularly useful in combination with the following herbicides:
______________________________________Common Name Chemical Name______________________________________acifluorfen 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitrobenzoic acidacrolein acroleinalachlor 2-chloro-2',6'-diethyl-N--(methoxymethyl)- acetanilideametryn 2-(ethylamino)-4-(isopropylamino)-6- methylthio)- .sub.-s-triazineamitrole 3-amino- .sub.-s-triazoleAMS ammonium sulfamateasulam methyl sulfanilylcarbamateatrazine 2-chloro-4-(ethylamino)-6-(isopropylamino)- .sub.-s-triazinebarban 4-chloro-2-butynyl .sub.--m-chlorocarbanilatebenefin N--butyl-N--ethyl-.alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro- -p-toluidinebensulide O,O--diisopropyl phosphorodithioate S--ester with N--(2-mercaptoethyl)benzenesulfonamidebenzipram 3,5-dimethyl-N--(1-methylethyl)-N--(phenyl- methyl)benzamidebenzoylprop N--benzoyl-N--(3,4-dichlorophenyl)-DL-alainebifenox methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoatebromacil 5-bromo-3-sec-butyl-6-methyluracilbromoxynil 3,5-dibromo-4-hydroxybenzonitrilebutachlor N--(butoxymethyl)-2-chloro-2',6'-diethyl- acetanilidebutam 2,2-dimethyl-N--(1-methylethyl)-N--(phenyl- methyl)propanamidebuthidazole 3-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol- 2-yl]-4-hydroxy-1-methyl-2-imidazolidinonebutralin 4-(1,1-dimethylethyl)-N--(1-methylpropyl)-2,6- dinitrobenzenaminecacodylic acid hydroxydimethylarsine oxidecarbetamide D-N--ethyllactamide carbanilate (ester)CDAA N--N--diallyl-2-chloroacetamideCDEC 2-chloroallyl diethyldithiocarbamatechloramben 3-amino-2,5-dichlorobenzoic acidchlorbromuron 3-(4-bromo-3-chlorophenyl)-1-methoxy-1- methylureachloroxuron 3-[ -p-( -p-chlorophenoxy)phenyl]-1,1- dimethylureachlorpropham isopropyl .sub.--m-chlorocarbanilatecisanilide cis-2,5-dimethyl-N--phenyl-1-pyrrolidine- carboxamideCMA calcium methanearsonatecyanazine 2-[[4-chloro-6-(ethylamino)- .sub.-s-triazin- 2-yl]amino]-2-methylpropionitrilecycloate S--ethyl N--ethylthiocyclohexanecarbamatecycluron 3-cyclooctyl-1,1-dimethylureacyperquat 1-methyl-4-phenylpyridiniumcyprazine 2-chloro-4-(cyclopropylamino)-6-(iso- propylamino)- .sub.-s-triazinecyprazole N--[5-(2-chloro-1,1-dimethylethyl)-1,3,4- thiadiazol-2-yl] cyclopropanecarboxamidecypromid 3',4'-dichlorocyclopropanecarboxanilidedalapon 2,2-dichloropropionic aciddazomet tetrahydro-3,5-dimethyl-2H--1,3,5-thia- diazine-2-thioneDCPA dimethyl tetrachloroterephthalatedesmetryn 2-(isopropylamino)-4-(methylamino)-6- methylthio)- .sub.-s-triazinediallate S--(2,3-dichloroallyl)diisopropylthiocarbamatedicamba 3,6-dichloro- -o-anisic aciddichlobenil 2,6-dichlorobenzonitriledichlorprop 2-(2,4-dichlorophenoxy)propionic aciddiclofop 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoic aciddiethatyl N--(chloroacetyl)-N--(2,6-diethylphenyl)glycinedifenzoquat 1,2-dimethyl-3,5-diphenyl-1H--pyrazoliumdinitramine N.sup.4,N.sup.4 --diethyl-.alpha.,.alpha.,.alpha.-trifluoro-3,5- dinitro- toluene-2,4-diaminedinoseb 2-sec-butyl-4,6-dinitrophenoldiphenamid N,N--dimethyl-2,2-diphenylacetamidedipropetryn 2-(ethylthio)-4,6-bis(isopropylamino)- .sub.-s- triazinediquat 6,7-dihydrodipyrido[1,2-.alpha.:2',1'-c]pyra- zinediium iondiuron 3-(3,4-dichlorophenyl)-1,1-dimethylureaDSMA disodium methanearsonateendothall 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic aciderbon 2-(2,4,5-trichlorophenoxy)ethyl 2,2-dichloro- propionateethafluralin N--ethyl-N--(2-methyl-2-propenyl)-2,6-dinitro- 4-(trifluoromethyl)benzenamineethofumesate (.+-.)-2-ethoxy-2,3-dihydro-3,3-dimethyl-5- benzofuranyl methanesulfonatefenac (2,3,6-trichlorophenyl)acetic acidfenuron 1,1-dimethyl-3-phenylureafenuron TCA 1,1-dimethyl-3-phenylurea mono(trichloro- acetate)flamprop N--benzoyl-N--(3-chloro-4-fluorophenyl)-DL- alaninefluchloralin N--(2-chloroethyl)-2,6-dinitro-N--propyl-4- (trifluoromethyl)anilinefluometuron 1,1-dimethyl-3-(.alpha.,.alpha.,.alpha.-trifluoro- .sub.--m-toly l)ureafluorodifen -p-nitrophenyl .alpha.,.alpha.,.alpha.-trifluoro-2-nitro- -p-tolyl etherfluridone 1-methyl-3-phenyl-5-[3-(trifluoromethyl)- phenyl]-4(1H)--pyridinonefosamine ethyl hydrogen (aminocarbonyl)phosphonateglyphosate N--(phosphonomethyl)glycinehexaflurate potassium hexafluoroarsenatehexazinone 3-cyclohexyl-6-(dimethylamino)-1- methyl-1,3,5-triazin-2,4(1H,3H)--dioneioxynil 4-hydroxy-3,5-diiodobenzonitrileisopropalin 2,6-dinitro-N,N--dipropylcumidinekarbutilate tert-butylcarbamic acid ester with 3( .sub.--m- hydroxyphenyl)-1,1-dimethylurealenacil 3-cyclohexyl-6,7-dihydro-1H--cyclopenta- pyrimidine-2,4(3H,5H)--dionelinuron 3-(3,4-dichlorophenyl)-1-methoxy-1- methylureaMAA methanearsonic acidMAMA monoammonium methanearsonateMCPA [(4-chloro- -o-tolyl)oxy]acetic acidMCPB 4-[(4-chloro- -o-tolyl)oxy]butyric acidmecoprop 2-[(4-chloro- -o-tolyl)oxy]propionic acidmefluidide N--[(2,4-dimethyl-5-[[(trifluoromethyl)sul- fonyl]amino]phenyl]acetamidemethalpropalin N--(2-methyl-2-propenyl)-2,6-dinitro-N-- propyl-4-(trifluoro-methyl)benzenamidemetham sodium methyldithiocarbamatemethazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4- oxadiazolidine-3,5-dionemetolachlor 2-chloro-N--(2-ethyl-6-methylphenyl)-N-- (2-methoxy-1-methylethyl)acetamidemetribuzin 4-amino-6-tert-butyl-3-(methylthio)-as- triazin-5(4H)--onemolinate S--ethyl hexahydro-1H--azepine-1-carbothioatemonolinuron 3-( -p-chlorophenyl)-1-methoxy-1-methylureamonuron 3-( -p-chlorophenyl)-1,1-dimethylureamonuron TCA 3-( -p-chlorophenyl)-1,1-dimethylurea mono- (trichloroacetate)MSMA monosodium methanearsonatenapropamide 2-(.alpha.-naphthoxy)-N,N--diethylpropionamidenaptalam N--1-naphthylphthalamic acidneburon 1-butyl-3-(3,4-dichlorophenyl)-1-methylureanitralin 4-(methylsulfonyl)-2,6-dinitro-N,N--dipropyl- anilinenitrofen 2,4-dichlorophenyl -p-nitrophenyl ethernitrofluorfen 2-chloro-1-(4-nitrophenoxy)-4-(trifluoro- methyl)benzenenorea 3-(hexahydro-4,7-methanoindan-5-yl)-1,1- dimethylureanorflurazon 4-chloro-5-(methylamino)-2-(.alpha.,.alpha.,.alpha.-trifluoro- .sub.--m-tolyl)-3(2H)--pyridazinoneoryzalin 3,5-dinitro-N.sup.4,N.sup.4 --dipropylsulfanilamideoxadiazon 2-tert-butyl-4-(2,4-dichloro-5-isopropoxy- phenyl).DELTA..sup.2 -1,3,4-oxadiazolin-5-oneoxyfluorfen 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4- (trifluoromethyl)benzeneparaquat 1,1'-dimethyl-4,4'-bipyridinium ionPBA chlorinated benzoic acidpendimethalin N--(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro- benzenamineperfluidone 1,1,1-trifluoro-N--[2-methyl-4-(phenylsul- fonyl)phenyl]methanesulfonamidepicloram 4-amino-3,5,6-trichloropicolinic acidprocyazine 2-[[4-chloro-6-(cyclopropylamino)-1,3,5- traizine-2-yl]amino]-2-methylpropanenitrileprofluralin N--(cyclopropylmethyl)-.alpha.,.alpha.,.alpha.-trifluoro-2,6- dinitro-N--propyl- -p-toluidineprometon 2,4-bis(isopropylamino)-6-methoxy- .sub.-s-triazineprometryn 2,4-bis(isopropylamino)-6-(methylthio)- .sub.-s- traizinepronamide 3,5-dichloro(N-- 1,1-dimethyl-2-propynyl)- benzamidepropachlor 2-chloro-N--isopropylacetanilidepropanil 3',4'-dichloropropionalidepropazine 2-chloro-4,6-bis(isopropylamino)- .sub.-s-triazinepropham isopropyl carbanilateprosulfalin N--[[4-(dipropylamino)-3,5-dinitrophenyl]- sulfonyl]-S,S--dimethylsulfilimineprynachlor 2-chloro-N--(1-methyl-2-propynyl)acetanilidesecbumeton N--ethyl-6-methoxy-N'(1-methylpropyl)-1,3,5- triazine-2,4-diaminesiduron 1-(2-methylcyclohexyl)-3-phenylureasimazine 2-chloro-4,6-bis(ethylamino)- .sub.-s-triazinesimetryn 2,4-bis(ethylamino)-6-(methylthio)- .sub.-s- triazineTCA trichloroacetic acidtebuthiuron N--[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2- yl]-N,N'--dimethylureaterbacil 3-tert-butyl-5-chloro-6-methyluracilterbuchlor N--(butoxymethyl)-2-chloro-N--[2-(1,1- dimethylethyl)-6-methylphenyl]acetamideterbuthylazine 2-(tert-butylamino)-4-chloro-6-(ethylamino)- .sub.-s-triazineterbutol 2,6-di-tert-butyl- .sub.-p-tolyl methylcarbamateterbutryn 2-(tert-butylamino)-4-(ethylamino)-6-(methyl- thio)- .sub.-s-triazinetetrafluron N,N--dimethyl-N'--[3-(1,1,2,2-tetrafluoroethoxy)- phenyl]ureathiobencarb S--[(4-chlorophenyl)methyl] diethyl- carbamothioatetriallate S--(2,3,3-trichloroallyl)diisopropylthiocarbamatetrifluralin .alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro-N,N--dipropyl- -p- toluidinetrimeturon 1- -p-chlorophenyl)-2,3,3-trimethylpseudourea2,3,6-TBA.sup.b 2,3,6-trichlorobenzoic acid2,4-D (2,4-dichlorophenoxy)acetic acid2,4-DB 4-(2,4-dichlorophenoxy)butyric scid2,4-DEP tris[2-(2,4-dichlorophenoxy)ethyl] phosphitemethabenz- 1,3-dimethyl-3-(2-benzothiazolyl)ureathiazuronchlortoluran N'--(3-chloro-4-methylphenyl)-N' N--dimethyl- ureaisoproturan N--(4-isopropylphenyl)-N'N'--dimethylureametoxuran N'--(3-chloro-4-methoxyphenyl)-N,N-- dimethylurea______________________________________
UTILITY
The compounds of the present invention are highly active herbicides. They 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, oil well sites, drive-in theatres, around billboards, highway and railroad structures. By properly selecting rate and time of application, compounds of this invention may be used also to modify plant growth beneficially and for the selective control of weeds in crops such as wheat and barley.
The precise amount of the compound of Formula I to be used in any given situation will vary according to the particular end result desired, the amount of foliage present, the weeds to be controlled, the crop species, the soil type, the formulation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.005 to 20 kg/ha with a preferred range of 0.125 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistance in soil is desired and the lower rates for selective weed control in crops.
The activity of these compounds was discovered in a number of greenhouse and field tests. The tests are described and the data resulting from them are shown below. The ratings are based on a numerical scale extending from 0=no effect, to 10 =maximum effect. The accompanying descriptive symbols have the following meanings:
C=chlorosis or necrosis
D=defoliation
E=emergence inhibition
G=growth retardation
H=formative effects
U=unusual pigmentation
6Y=abscised buds or flowers
TEST A
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated preemergence with a nonphytotoxic solvent solution of the compounds of Table XII. Other batches of seeds and tubers for all of the foregoing weed and crop plants were planted at the same time as controls. The control plantings were untreated; i.e., neither any compound nor any solvent was applied. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass with two leaves, barnyardgrass with two leaves, wild oats with two leaves, cassia with three leaves (including cotyledonary ones), morningglory with four leaves (including the cotyledonary ones), cocklebur with four leaves (including the cotyledonary ones), sorghum with four leaves, corn with four leaves, soybean with two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three-five leaves were sprayed with a nonphytotoxic solvent solution of the compounds of Table XII. Other groups of all the same weed and crop plants were sprayed with the same nonphytotoxic solvent so as to provide control plants. Preemergence and postemergence treated plants and controls were maintained in a greenhouse for sixteen days, then all treated plants were compared with their respective controls and rated visually for response to treatment. The data in Table XII shows that the compounds of this invention are very effective as herbicides.
TABLE XII BARN- kg/ BUSH COT- MORNING COCK- CAS- NUT- CRAB- YARD WILD SOY- SOR- ha BEAN TON GLORY LEBUR SIA SEDGE GRASS GRASS OATS WHEAT CORN BEAN RICE GHUM POST EMERGENCE ##STR417## 0.42.0 9C9C 9C9C 10C10C 10C9C 9C9C 9C9C 9C9C 10C10C 9C9C 9C9C 9C9C 9C6C 9G 10C10C 9C10C ##STR418## 0.4 9C 9C 10C 9C 9C 9C 5C 9G 9C 9C 9C 10C 9C 5C 9G 9C ##STR419## 0.4 9C 9C 10C 9C 9C 10C 5C 8G 9C 9C 9C 9C 9C 8C 9C ##STR420## 0.4 9C 9C 10C 9C -- 9C 10C 10C 10C 10C 10C 9C 10C 10C ##STR421## 0.4 9C 5U 5C9G 10C 9C 9C 9C 9C 10C 4C 7G 3C 7G 10C 9C 10C 9C ##STR422## 2 5C10D 5C 9G 5C 9G 9C 9C 9C 9C 9C 9C 10C 5U 9C 9C 9C 9C ##STR423## 2 6C 9G 3C 9G 5C 8G 5C 9G 3C 6G 1C 8G 5C 8G 9C 2G 5G 1C 8G 2C 8G 3C 8G 2C 8G ##STR424## 0.4 3C,8G,6Y 3C,9G 3C,9G 2C,7G 2C 7G 7G 9C 6C 2C,6G 1C,8G 3C 3C,8G 2C,8G ##STR425## 0.4 9C 9C 10C 10C 9C 9C 2C,6G 10C 2C,6G 3C,6G 2U,9G 10C 3C,8G 10C ##STR426## 0.4 9C 9C 10C 10C 10C 10C 3C,7G 10C 2C,8G 3C,7G 10C 5C,9G 3C,8G 9C ##STR427## 0.4 9C 9C 10C 10C 10C 10C 2C 2C,9H 2C,5G 1C 3C,9G 3C,9G 6G 2H,8G ##STR428## 0.4 9D,9G 6C,9G 9C 6C,9G 5C,8G 7G 2A 9C 2C 1C 9H 9C 4C,8G 2C,9G ##STR429## 0.4 9D,9G 7C,9G 10C 9C 5C,8G 8G 0 5C,9H 8G 5C,8G 5C,9H 3C,9G 5C,9G 3C,9G ##STR430## 0.4 9C 9C 10C 10C 10C 10C 5C,8G 6C,9H 2C,6G 2C 10C 5C,9G 5C,8G 5C,9G ##STR431## 0.4 9C 9C 10C 10C 9C 9C 2C,5G 2C,8H 4G 1C 9C 6C,9G 1C,7G 2U,9G ##STR432## 0.4 5C,8G,6Y 2C,2H,7G 1C 3C,9G 5G 2G 2G 3C,9H 1C 1C 3U,9G 1H 8G 9G ##STR433## 0.4 6C,6G,6Y 2C,2H,7G 2C,8G 4C,9G 5G 7G 0 3C,9H 5G 3C 2C,9G 2H,5G 2C,9G 2U,9G ##STR434## 0.4 6C,8G,6Y 2C,2H,8G 1C,8G 2C,9G 5G 3G 3G 1C 0 0 6H 7G 2G 7H ##STR435## 0.4 8C,5G,6Y 2C,2H,8G 3C,7G 5C,9G 2C,5G 2G 0 2H 0 0 7H 6H 6G 2C,9G ##STR436## 0.4 5S,8G,6Y 3C,3H,9G 9C 9C 1C 1C,5G 1C,5G 5C,9H 2C,5G 1C 7H 2H,9G 0 8H ##STR437## 0.4 6C,8G,6Y 2H,3C,8G 6C,9G 3C,9G 5C 2G 0 3C,8H 0 0 6H 2H,8G 2G 3G ##STR438## 0.4 9C 9C 10C 10C 9C 10C 2C,6G 3C,9H 9G 1C,2G 6H 5C,9G 5C,9G 3C,9G ##STR439## 0.4 9C,9G 9C,9G 10C 10C 9C 6C,9G 3G 6C,9H 3C,9G 3C,5G 9H 4C,9G 9C 4C,9G ##STR440## 0.4 9C,9G 7C,9G 10C 10C 6C,9G 10C 1C 3G 0 0 9H 5C,9G 2C,9G 8H ##STR441## 0.4 5H,8C 9C 10C 10C 9C 9C 6C 9C 6C 3G,4G 5U,8G 6H,8G 7C 9C ##STR442## 0.4 5C,9H 10C 9C 10C 9C 9C 3U,5G 10C 3C,7G 3C,8G 9C 5H,9G 8C 10C ##STR443## 0.4 8H,9G 9C 10C 10C 9C 9C 6G 8C 2C 2C 5H,7G 5H,8G 8C 2H,7G ##STR444## 20.4 3C,9G,9D3C,9G,9D 9C4C,9G 10C9C 9C9C 9C3C,7G 9C2C,6G 4C,7G2C,6G 10C9C 9C2C,5G 9C1C,4G 9C2U,8H 6C,9G6C,9G 9C6C,8G 9C3C,8G ##STR445## 20.4 3C,9G,10D3C,9G,9D 5C,9G5C,9G 10C9C 10C9C 9C3C,7G 9C2C,7G 5C,8G3G 10C10C 4C,8G8G 8C 4C,8G 9C5C,9G 9C4C,8G 8C5C,8G 9C2C,8G ##STR446## 2 9G,10D 9C 10C 9C 9C 9C 9C 10C 9C 9C 9C 6C,9G 9C 10C ##STR447## 0.4 3C,9G,9D 9C 10C 9C 9C 9C 4C,7G 10C 9C 9C 9C 6C,9G 9C 9C ##STR448## 22 5H,8G,6F1C 4C,7G 4G0 8C0 3C,8G0 8C0 5G0 8C1H 4C0 4C0 3H,8G0 6H,9G1C 9 C3G 3H,8G1C,5G ##STR449## 10220.4 2C,2H1C00 00 0000 0000 01C00 0000 0002G 2G001C,2H 0000 0000 0000 1C000 5G000 3G000 ##STR450## 0.4 8C 6C,9G 10C 9C 5C,7G 7G 1C 1C,7G 1C 1C 3U,8G 9C 3C,7G 8G ##STR451## 0.4 9C 5C,9G 9C 5C,9G 5C,9G 3C,8G 2C,8G 9C 7C 7C 5U,9C 9C 5C,8G 9C ##STR452## 0.4 9C 5C,9G 5C,9G 6G 9C 4G 3G 2G 0 2G 8G 9C 2C,5G 1C,9G ##STR453## 0.4 9C 9C 10C 9C 9C 2C,6G 3C,8G 10C 9C 9C 5U,8G 8C 8C 5C,9G ##STR454## 0.4 10D 3C,9G 10C 5C,9G 3C,8G 2C,9G 5C,8G 9C 5C,7G 3C,8G 9H 2C,9G 5C,9G 3U,9G ##STR455## 0.4 9C 5C,9G 9C 3H,9G 9C 6C,9G 9C 5C,8H 0 0 9C 5C,9G 9C 2C,9G ##STR456## 0.4 9C 5C,9G 10C 10C 9C 6C,9G 2C,6G 9C 9C 9C 9C 9C 9C 9C ##STR457## 0.4 4C,9G,6Y 2C,3H 5C,8G 3C,8G 2C 6G 2G 7H 0 0 2G 5C,7G 2C 5G ##STR458## 0.4 3C,5G,6Y 1C 0 5C 0 0 2C 2C,6G 1C 2G 1C,7G 1C,5G 2C,4G 2C,7G ##STR459## 0.4 9C 9C 10C 9C 9C 2C,8G 2C,8G 5C,9H 1C,8G 1C,7G 10C 2C,8G 3C,8G 2C,8G ##STR460## 0.4 9C 9C 10C 10C 9C 7G 9C 6C,9H 2C,7G 2C,6G 9C 9C 5C,8G 2C,8G ##STR461## 0.4 9C 9C 10C 9C 9C 4G 1C,5G 6C,9H 4G 2G 9C 5C,9G 5C,9G 1C,8G ##STR462## 0.4 9C 5C,9G 10C 9C 10C 7G 9C 9C 3C,7G 3C,6G 9C -- -- 5C,9G ##STR463## 0.4 9C 6C,9G 10C 10C 9C 1C,8G 3C 9C 1C,2G 1C,4G 9C 9C -- 5C,9G ##STR464## 0.4 9C 4C,9G 10C 9C 5C,9G 2C,8G 2C,6G 3C,9H 3G 2G 3U,8G 5C,9G 3C,7G 2C,8G ##STR465## 0.4 5C,8G,6Y 5C,9G 9C 5C,9G 5C,9G 0 5C,8G 3C,7H 2C 0 8U,9G 5C,8G 3C,8G 2C,9G ##STR466## 0.4 9C 9C 9C 10C 5C,9G 8G 4G 9C 1C,2G 1C,2G 5U,9H 9C 3C,8G 8G ##STR467## 0.4 9C 2C,2H,5G 9C 9C 9C 9G 5C,8H 6C,9H 4C,8G 2C,8G 2C,9H 2C,8G 3C,8G 2U,9G ##STR468## 0.4 6C,9G 4C,9G 10C 9C 9C 9C 10C 9C 9C 6C,8G 5U,9C 9C 5C,9G 9C ##STR469## 0.4 9C 9C 10C 9C 6C,9G 6C,9G 4C,8G 9C 9C 9C 10C 9C 6C,8G 9C ##STR470## 0.4 10D,9G 6C,9G 10C 5C,9G 9C 7C,9G 5C,8G 10C 9C 9C 9C 9C 9C 9C ##STR471## 0.4 9C 10C 10C 9C 9C 10C 9C 9C 9C 9C 10C 9C 5C,9G 10C ##STR472## 0.4 8C,9G 6C,9G 9C 2H,8G 5C,9G 9G 2C,6G 4C,9H 2C,6G 3C,5G 5U,9G 9C 5C,9G 3C,9H ##STR473## 0.4 9C 6C,9G 9C 5C,9G 9C 9C 9C 9C 9C 9C 9C 9C 9C 9C ##STR474## 0.4 9C 2C,3H,8G 2C,8G 2C 1C,6H 8G 1C,5G 5C,9H 1C,7G 6G 9H 1C,5H 8G 9G ##STR475## 0.4 9C 2C,3H,9G 5C,9G 3C,8G 9C 9C 9C 9C 6C,9G 5C,8G 9C 8C 8C 9C ##STR476## 0.4 4C,7G,6G 2C 2C 2C,5G 1C 1C,5G 0 3C 0 0 1C,7H 2C 2C,7G 1C,5G ##STR477## 0.4 9C 9C 10C 9C 9C 8G 3C,9G 10C 9C 9C 9C 9C 10C 10C ##STR478## 0.4 9C 9C 10C 10C 10C 5C,9G 3G 6C,9H 3C,7G 2C,6G 10C 6C,9G -- 2C,9G ##STR479## 0.4 9C 9C 10C 2C,8G 3C,8G 1C,8G 9C 5C,8H 1C,3G 1C 9C 9C 5C,9G 3C,9G ##STR480## 0.4 9C 9C 10C 9C 9C 2C,9G 1C,8G 9C 4C,7G 4C,6G 9C 8C 5C,9G 3C,9G ##STR481## 0.4 9C 9C 10C 9C 9C 10C 5C,8G 9C 9C 5C,8G 7U,9C 6C,9G 9C 9C ##STR482## 0.4 9C 9C 9C 9C 9C 2C,8G 2C,7G 9C 3C,7H 1C,5H 9C 9C 5C,8G 9C ##STR483## 0.4 6C,9G 9C 10C 9C 10C 9C 9C 10C 8C 8C 9C 5C,9G 6C,9G 9C PRE EMERGENCE ##STR484## 0.42.0 9G9G 9G9G 8G9G 10E10E 9G9G 9H9H 3C 9H3C 9H 9H9H 10E10E 9H9H 1 10E0E 10E10E ##STR485## 0.4 9G 9G 9G 10E 9H 9H 9H 9H 10H 9H 10E 9H ##STR486## 0.4 9G 9G 9G 10E 9H 9H 9H 9H 9H 10E 10E 9H ##STR487## 0.4 9H 9G 9G 10E 10E 9H 9H 9H 10E 9H 10E 9H ##STR488## 0.4 9G 9G 9G 9G 9H 9H 9G 9G 9G 9H 10E 9G ##STR489## 2 9C 9G 9C 10E 4C 9G 9H 9H 9H 9G 9H 10E 9H ##STR490## 2 5C 9G 9G 9G 10E 2C 8G 2C 9H 8G 8G 9G 2C 8H 10E 9G ##STR491## 0.4 0 -- 0 0 3G 2G 0 4H 3G 0 8H 4G ##STR492## 0.4 9G 9G 4C,8G 10E 2C,5G 9H 9G 9G 2U,9G 9H 10E 9H ##STR493## 0.4 9C 9G 9C 10E 2C,6G 10H 5C,9H 9H 10H 9H 10E 10H ##STR494## 0.4 9C 9G 5C,9G 10E 4G 2C,9G 8G 5G 9G 9H 9H 9G ##STR495## 0.4 9G 9G 8G 10E 0 9H 8G 2G 2C,8G 8H 10E 9G ##STR496## 0.4 9G 10E 9G 10E 6G 9H 2C,9H 9G 2U,9H 9H 10E 9H ##STR497## 0.4 9G 9G 6C,9G 10E 2C,6G 2C,9H 9G 5G 9G 9H 10E 2C,9G ##STR498## 0.4 9C 9G 6C,9G 9G 1C,3G 4C,9G 8H 1C,2G 3C,9G 9H 9H 2C,9G ##STR499## 0.4 5G 9G 5G 5G 0 2C,8G 6G 2G 2C,7G 3G 8G 8G ##STR500## 0.4 8G 9G 7G 7G 0 2C,9G 2C,8G 8G 2C,8G 1C,3G 9H 2H,8G ##STR501## 0.4 4G 5C,9G 2C,5G 0 0 0 0 0 2G 1C 0 2H ##STR502## 0.4 05C,9G3C,7G 2G2G0 0 0 4G 0 0 3G ##STR503## 0.4 8G 8G 3G 5G 0 9H 5G 3G 1C,7G 2C,4H 9H 8G ##STR504## 0.4 9G 9C 2C 0 0 9H 2G 2G 1C,7G 2C 5G 8G ##STR505## 0.4 9G 9G 2C,9G 10E 5G 9H 9G 3G 9H 9H 10E 9H ##STR506## 0.4 9G 9H 3C,9G 10E 2C,5G 9H 9G 8H 2U,9G 9H 10E 9H ##STR507## 0.4 9G 9G 5C,9G 10E 1C 2C,8H 8G 1C 2C,9H 9H 10E 9H ##STR508## 0.4 9G 5H,9G 5H,8G 10E 8G 5H,9G 7G 7G 5H,9G 6H,8G 10E 5H,9G ##STR509## 0.4 9H 8H,9G 8H,9G 10E 8G 5H,9G 8G 9G 7H,9G 8H,9G 10E 8H,9G ##STR510## 0.4 8H,9G 8H,9G 8H,8G 9E,9G 7G 5H,9G 8G 7G 7H,9G 7H,8G 7E,8G 7H,9G ##STR511## 20.4 5C,9G9G 9G9G 9C9G 10E10E 7G8G 9H9H 8G7G 9G9G 9G2C,9G 9H7H 10E10E 9 H9H ##STR512## 20.4 5C,9H9G 9G9G 3C,9G9G 10E10E 3C,9G7G 9H9H 3C,9G2C,8G 9H9H 9G9G 9H9H 10E10E 9H9H ##STR513## 2 10E 9G 9G 10E 9H 9H 2C,9G 9H 10E 9H 10E 10H ##STR514## 0.4 10E 9G 9G 10E 3C,9G 9H 9G 9H 10E 9H 10E 9H ##STR515## 22 7G1C 5H,8G1C 5H,8G1C 10E0 2G0 5H,8G0 5H,7G0 5H,8G 0 5H,9G3G 5H,8G1C 8H,9G0 5H,8G0 ##STR516## 10220.4 7G1C00 9G000 1C,5G1C00 9G9G00 1C000 1C,3G000 1C,5G000 0 2C,7G3G0 8G3G00 4G000 2C,7G000 5G000 ##STR517## 0.4 9G 9G 8G 9G 6G 9H 4G 4G 2C,7G 9H 9H 1C,9G ##STR518## 0.4 9G 9G 9G 10E 4C,9G 9H 2C,8G 9H 10E 9H 10E 10E ##STR519## 0.4 8G 9G 9G 2G 5G 5G 2G 0 2C,7G 2C,4H 2C,5G 8G ##STR520## 0.4 9G 9G 9C 10E 2C,9G 9H 1C,8G 1C,9H 2C,9H 9H 10E 2C,9H ##STR521## 0.4 9G 9G 9G 9G 2C,9G 5C,9H 2C,8H 9G 9G 8H 10E 9H ##STR522## 0.4 9G 10E 9G 10E 5G 2C,8G 2G 0 -- 9H 9H 9G ##STR523## 0.4 9G 9G 9G 10E 9H 9H 3C,9G 9H 10E 9H 10E 10H ##STR524## 0.4 8G 8G 0 10E 2G 9G 4G 5G 2C,7G 1C,5H 9H 2C,9G ##STR525## 0.4 3G -- 0 10E 2G 1C,8H 0 0 1C 0 8H 8G ##STR526## 0.4 9G 9G 9G 8G 2C,9G 9H 1C,7G 1C,5G 1C,9G 9H 10E 2C,9G ##STR527## 0.4 9G 9G 9G 9G 1C,8G 2C,9H 1C,8G 7G 2C,9G 9H 10E 9H ##STR528## 0.4 3C,9C 9G 8G 7G 5G 9H 7G 5G 1U,9G 9H 9H 1C,9G ##STR529## 0.4 9G 9G 10E 10E 2C,9G 9H 9H 9H 9H 9H 10E 9H ##STR530## 0.4 9G 8G 8G 5G 0 9H 5G 3G 8G 9H 9H 2C,9G ##STR531## 0.4 9G 9G 8G 2C,9G 2C,8G 2C,9H 2C,8G 4G 9G 9H 9H 9H ##STR532## 0.4 9G 8G 8G 9G 2C,8H 2C,9H 4G 0 2C,8G 7H 9H 1C,9G ##STR533## 0.4 9C 9G 3C,8G 10E 2C,8G 5C,9H 1C,8G 9H 9G 9H 10E 5C,9H ##STR534## 0.4 9G 9G 9G 1C,9G 2C,9G 6C,9H 2C,8G 9G 2C,8G 9H 9H 4C,9H ##STR535## 0.4 9G 8G 9G 10E 9H 9H 2C,8G 9H 9H 9H 10E 9H ##STR536## 0.4 9G 8G 9G 10E 3C,9G 9H 3C 9H 1C,9G 9H 10E 5C,9H ##STR537## 0.4 9G 9G 9G 10E 2C,9G 9H 2C,9G 9H 9H 9H 10E 9H ##STR538## 0.4 10E 9G 9G 10E 1C,9G 1C,9H 2C,9H 9H 10E 9H 10E 10E ##STR539## 0.4 9G 8G 8G 10E 2C,5H 9H 6G 6G 8G 2C,5H 9H 1C,9G ##STR540## 0.4 10E 10E 3C,9G 10E 5C,9G 5C,9H 5C,9H 10E 10H 9H 10E 10H ##STR541## 0.4 9G 10E 2C,8G 10E 2C,8G 3C,9H 1C,5G 2C,9H 9G 9H 10E 9H ##STR542## 0.4 10E 9G 8G 10E 5C,9G 7C,9H 4C,6G 9H 9H 9H 10E 9H ##STR543## 0.4 0 0 0 10E 0 2G 0 0 1C,4G 0 8H 3G ##STR544## 0.4 9G 9G 8G 10E 2C,9G 2C,9H 2C,7G 9H 9G 9H 10E 9H ##STR545## 0.4 9G 9G 9G 10E 2G 2C,9H 1C,7G 6G 2U,9G 9H 10E 2C,9G ##STR546## 0.4 9G 9G 2C,8G 1C,9G 1C,5G 2C,9H 2C,8G 6G 10H 9H 10E 9H ##STR547## 0.4 9G 8G 9G 10E 2C,9G 4C,9H 2C,7G 9H 9G 9H 10E 9H ##STR548## 0.4 9H 9G 9G 10E 5C,9G 9H 4C,9G 9H 9G 9H 10E 9H ##STR549## 0.4 9G 9G 9G 2C,8G 2C,9G 2C,9H 2C,8G 1C,6G 1U,9G 9H 10E 9H ##STR550## 0.4 9G 9G 9G 10E 1C,9G 6C,9H 5C,8G 9H 9H 9H 10E 5C,9H
TEST B
Two bulb pans were filled with fertilized and limed Fallsington silt loam soil. One pan was planted with seeds of corn, sorghum, Kentucky bluegrass and several grassy weeds. The other pan was planted with seeds of soybeans, purple nutsedge tubers (Cyperus rotundus), and seeds of several broadleaf wees. Seeds of the following grassy and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), giant foxtail (Setaria faberii), dallisgrass (Paspalum dilatatum), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus), morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A smaller pot was also filled with prepared soil and planted with rice and wheat seeds. Another small pot was planted with seeds of sugarbeets. The above four containers were treated preemergence with nonphytotoxic solvent solutions of the compounds of this invention (i.e., solutions of said compound were sprayed on the soil surface before seed germination). Duplicates of the above-described seeded containers were prepared without treatment and used as controls.
Twenty-eight days after treatment, the treated and control plants were evaluated and the data recorded as set forth in Table XIII.
TABLE XIII______________________________________Preemergence on Fallsington Silt Loam______________________________________ ##STR551##Rate kg/ha 1/128 1/64 1/32______________________________________CRABGRASS 9G 9C 10C 10CBARNYARDGRASS 10C 10C 10CSORGHUM 10C 10C 10CWILD OATS 8G 8C 10C 10CJOHNSONGRASS 10C 10C 10CDALLISGRASS 8G 8C 10C 10CGIANT FOXTAIL 9G 9C 10C 10CKY. BLUEGRASS 10C 10E 10ECHEATGRASS 10C 10C 10CSUGARBEETS 8G 5H 10C 10CCORN 10C 10C 10CMUSTARD 10C 10C 10CCOCKLEBUR 7G 5C 7G 8GPIGWEED -- -- --NUTSEDGE 10E 10E 10ECOTTON 7G 8G 8G 5CMORNINGGLORY 7G 7G 8G 6CCASSIA 8G 8C 10C 10CTEAWEED -- -- --VELVETLEAF 10C 10C 10CJIMSONWEED 9G 9C 9G 9C 9G 9CSOYBEAN 8G 8G 5C 10CRICE 10C 10C 10EWHEAT 10C 10C 10C______________________________________ ##STR552##Rate kg/ha 1/16 1/4______________________________________CRABGRASS 10C 10CBARNYARDGRASS 10C 10CSORGHUM 10E 10EWILD OATS 7G 5C 8G 8CJOHNSONGRASS 10C 10CDALLISGRASS 10C 10CGIANT FOXTAIL 10C 10CKY. BLUEGRASS 10C 10CCHEATGRASS 10C 10CSUGARBEETS 10C 10CCORN 10E 10EMUSTARD 10C 10CCOCKLEBUR 8G 5H 8G 8HPIGWEED 10E 10ENUTSEDGE 10E 10ECOTTON 10E 10EMORNINGGLORY 8G 8G 8CCASSIA 8G 5C 8G 8CTEAWEED 10C 10CVELVETLEAF 10C 10CJIMSONWEED 8G 8GSOYBEAN 8G 8C 8G 8CRICE 10E 10EWHEAT 9G 9H 10H______________________________________ ##STR553##Rate kg/ha 1/64 1/32 1/16______________________________________CRABGRASS 8G 3C 9G 9C 10CBARNYARDGRASS 10C 10C 10CSORGHUM 10C 10C 10CWILD OATS 8G 8C 10C 9G 9CJOHNSONGRASS 10C 10C 10CDALLISGRASS 10C 10C 10CGIANT FOXTAIL 10C 10C 10CKY. BLUEGRASS 10C 10E 10ECHEATGRASS 10C 10C 10CSUGARBEETS 10C 10C 10CCORN 10C 10C 10CMUSTARD 10C 10C 10CCOCKLEBUR 8G 8G 5C 8G 7CPIGWEED -- -- --NUTSEDGE 10E 10E 10ECOTTON 9G 9C 10C 9G 9CMORNINGGLORY 8G 8C 10C 10CCASSIA 10C 10C 10CTEAWEED -- -- --VELVETLEAF 10C 10C 10CJIMSONWEED 9G 9C 10C 10CSOYBEAN 10C 9G 9C 8G 5CRICE 10E 10E 10EWHEAT 8G 8C 10C 10C______________________________________ ##STR554##Rate kg/ha 1/64 1/32 1/16______________________________________CRABGRASS 8G 5C 8G 5C 10CBARNYARDGRASS 10C 10C 10CSORGHUM 9G 9C 10C 10CWILD OATS 5G 7G 5C 6G 5CJOHNSONGRASS 9G 9C 10C 10CDALLISGRASS 5G 7G 8G 8CGIANT FOXTAIL 8G 9G 9C 10CKY. BLUEGRASS 10C 10E 10ECHEATGRASS 10C 10C 10CSUGARBEETS 10C 10C 10CCORN 7G 3C 7G 5C 10CMUSTARD 10C 10C 10CCOCKLEBUR 7G 8G 5C 8G 7CPIGWEED -- -- --NUTSEDGE 10E 10E 10ECOTTON 7G 7G 7GMORNINGGLORY 8G 8C 10C 9G 9CCASSIA 10C 10C 10CTEAWEED -- -- --VELVETLEAF 10C 10C 10CJIMSONWEED 10C 8G 8C 10CSOYBEAN 8G 5C 8G 5C 8G 5CRICE 10C 10C 10EWHEAT 10C 8G 8C 10C______________________________________ ##STR555##Rate kg/ha 1/64 1/32 1/16______________________________________CRABGRASS 7G 3C 9G 9C 10CBARNYARDGRASS 9G 9C 10C 10CSORGHUM 10C 10C 10CWILD OATS 4G 5G 3C 10CJOHNSONGRASS 7G 7C 8G 8C 10CDALLISGRASS 0 4G 3C 6GGIANT FOXTAIL 7G 3C 8G 5C 10CKY. BLUEGRASS 10C 10E 10ECHEATGRASS 7G 8G 8C 10CSUGARBEETS 10C 10C 10CCORN 7G 5C 10C 10CMUSTARD 10C 10C 10CCOCKLEBUR 8G 9C 8G 5C 8G 5CPIGWEED -- -- --NUTSEDGE 7G 7G 8GCOTTON 10C 8G 5C 10CMORNINGGLORY 8G 8C 9G 9C 10CCASSIA 10C 10C 10CTEAWEED -- -- --VELVETLEAF 10C 10C 10CJIMSONWEED 8G 5C 9G 8C 9G 9CSOYBEAN 10C 8G 5C 8G 8CRICE 8G 8C 10C 10CWHEAT 3G 4G 5G______________________________________ ##STR556##Rate kg/ha 1/64 1/32 1/16______________________________________CRABGRASS 7G 8G 5C 10CBARNYARDGRASS 3G 7G 7C 9G 9CSORGHUM 7G 9G 8C 10CWILD OATS 0 10C 5G 3CJOHNSONGRASS 6G 7G 7C 8G 8CDALLISGRASS 0 0 3GGIANT FOXTAIL 6G 3C 5G 3C 8G 8CKY. BLUEGRASS 7G 3C 8G 5C 10CCHEATGRASS 3G 3G 6G 3CSUGARBEETS 10C 10C 10CCORN 6G 5H 7G 5C 10CMUSTARD 10C 10C 10CCOCKLEBUR 8G 3C 10C 8G 5CPIGWEED -- -- --NUTSEDGE 7G 7G 3C 8GCOTTON 10C 8G 9G 5CMORNINGGLORY 8G 8C 10C 10CCASSIA 10C 10C 10CTEAWEED -- -- --VELVETLEAF 7G 8C 8G 9C 10CJIMSONWEED 9G 9C 10C 10CSOYBEAN 8G 7C 9G 8C 8G 5CRICE 6G 5C 8G 8C 10CWHEAT 0 2G 4G 3C______________________________________ ##STR557##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 5GBarnyardgrass 10C 10CSorghum 10C 10CWild Oats 0 5GJohnsongrass 10C 10CDallisgrass 5G 8G,3CGiant Foxtail 3G 6GKy. Bluegrass 8G 10ECheatgrass 10E 10ESugarbeets 7G 10CCorn 4G 8G,8CMustard 10E 10ECocklebur 7G 8GPigweed 10E 10ENutsedge 6G 10ECotton 4G 7GMorningglory 4G 10ECassia 5G 7G,2CTeaweed 0 8G,5CVelvetleaf 5G 7GJimsonweed 2G 6GSoybean 7G,7H 8G,8HRice 10E 10EWheat 2G 8G,5C______________________________________ ##STR558##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 4G 7GBarnyardgrass 10C 10C 10CSorghum 10C 10C 10CWild Oats 8G,7C 8G,8C 10CJohnsongrass 9G,9C 10C 10CDallisgrass 0 0 6GGiant Foxtail 4G,3H 5G,5H 9G,9CKy. Bluegrass 10E 10E 10ECheatgrass 8G,9C 10E 10ESugarbeets 10C 10C 10CCorn 8G,8C 10C 10CMustard 10C 10C 10CCocklebur 7G,2C 7G,5H 7G,5HPigweed 10E 10E 10ENutsedge 10E 10E 10ECotton 7G 8G 8GMorningglory 5G 7G 8GCassia 7G 8G,3C 8G,8CTeaweed 7G 7G 10CVelvetleaf 8G,7C 10C 10CJimsonweed 7G 7G 8G,5CSoybean 8G,3H 7G,5H 9G,9CRice 10E 10E 10EWheat 4G,2C 6G,4C 7G,4C______________________________________ ##STR559##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 0 0Barnyardgrass 0 0 0Sorghum 0 0 0Wild Oats 0 0 0Johnsongrass 0 0 0Dallisgrass 0 0 0Giant Foxtail 0 0 0Ky. Bluegrass 0 0 0Cheatgrass 0 0 6GSugarbeets 6G,3H 10C 7G,5HCorn 0 0 0Mustard 0 0 5GCocklebur 0 0 0Pigweed 0 0 5GNutsedge 0 0 5GCotton 0 0 0Morningglory 0 0 0Cassia 0 0 0Teaweed 0 0 0Velvetleaf 0 0 0Jimsonweed 0 0 0Soybean 0 0 0Rice 0 0 6G,5CWheat 0 0 0______________________________________ ##STR560##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 0 4GBarnyardgrass 7G,3C 8G,3C 10CSorghum 6G,3H 5G 10CWild Oats 0 0 6G,3CJohnsongrass 0 0 5G,5HDallisgrass 4G 5G 10EGiant Foxtail 3H 3H 10HKy. Bluegrass 9G 10E 10ECheatgrass 0 2G 8G,8CSugarbeets 4G 4G 7G,7CCorn 0 4G 5G,5HMustard 9G 9G,5C 10CCocklebur 3H 2H 5G,5HPigweed 10E 10E 10ENutsedge 5G 5G 8GCotton 0 0 3G,3HMorningglory 3G 6G 4GCassia 0 0 3GTeaweed -- -- 5G,5HVelvetleaf 7G,7C 10C 10CJimsonweed 0 2G 4GSoybean 0 0 6G,6HRice 9G,9C 7G,5C 10EWheat 3G 4G 6G______________________________________ ##STR561##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 0 6GBarnyardgrass 10C 10C 10CSorghum 9G,9C 10C 10CWild Oats 2G 6G 7G,5CJohnsongrass 8G,8C 10C 10CDallisgrass 0 0 5G,3HGiant Foxtail 3H 4G,3H 10CKy. Bluegrass 10C 10C 10CCheatgrass 5G 8G,8C 10ESugarbeets 10C 10C 10CCorn 6G,3H 7G,7H 10CMustard 10C 10C 10CCocklebur 7G,5H 8G,5H 8G,5HPigweed 10E 10E 10ENutsedge 10E 10E 10ECotton 6G 7G 9GMorningglory 8G 8G 10CCassia 8G 8G,5H 10CTeaweed 0 6G,5C 10CVelvetleaf 10C 10C 10CJimsonweed 8G,3C 8G,5C 8G,5CSoybean 7G,5H 7G,5H 9G,5HRice 8G,8C 10C 10EWheat 2G 4G 6G______________________________________ ##STR562##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 2G 7GBarnyardgrass 10C 10C 10ESorghum 10C 10E 10EWild Oats 4G 7G,3C 10CJohnsongrass 10C 10C 10CDallisgrass 5G 7G 10CGiant Foxtail 6G,3H 9G,9C 10CKy. Bluegrass 10C 10E 10ECheatgrass 10E 10E 10ESugarbeets 10C 10C 10CCorn 10C 10C 10CMustard 10C 10C 10CCocklebur 8G,5H 8G,5H 8G,8HPigweed 10E 10E 10ENutsedge 10E 10E 10ECotton 6G,3H 8G,6C 8G,6CMorningglory 9G 9G 10CCassia 8G,8C 8G,5C 8G,9CTeaweed 10C 10C 10CVelvetleaf 10C 10C 10CJimsonweed 8G,5C 8G,7C 8G,8CSoybean 8G,5H 9G,5H 9G,5HRice 8G,9C 10C 10EWheat 6G 6G,5C 10C______________________________________ ##STR563##Rate kg/ha 1/32 1/16 1/4______________________________________Crabgrass 0 4G 8GBarnyardgrass 0 6G,3H 8C,5HSorghum 6G,3H 7G,3H 10CWild Oats 0 0 5G,3CJohnsongrass 2H 2H 6G,5HDallisgrass 0 0 4GGiant Foxtail 0 0 7GKy. Bluegrass 5G,6C 7G,8C 10ECheatgrass 0 6G,3C 7G,8CSugarbeets 10C 10C 10CCorn 7G,7H 10C 10CMustard 10C 10C 10CCocklebur 8G,8H 8G,8H 8G,8HPigweed 10E 10E 10ENutsedge 10E 10E 10ECotton 8G 8G 10CMorningglory 10C 10C 10CCassia 8G,9C 10C 10CTeaweed 10C 10C 10CVelvetleaf 10C 10C 10CJimsonweed 8G,8C 10C 8G,9CSoybean 9G,5H 9G,5H 9G,5HRice 5G,3C 5G,3C 7G,4CWheat 0 0 2G______________________________________ ##STR564##Rate kg/ha 1/16 1/4______________________________________Crabgrass 3H 6GBarnyardgrass 6G,4C 10CSorghum 10C 10CWild Oats 6G 8G,5CJohnsongrass 6G,3H 8G,8CDallisgrass 0 4GGiant Foxtail 3H 6G,2CKy. Bluegrass 8G 10ECheatgrass 10E 10ESugarbeets 8G,8C 10CCorn 5G,5H 9G,9CMustard 10C 10CCocklebur 8G,5H 8G,3HPigweed 10C 10CNutsedge 10E 10ECotton 5G 5GMorningglory 6G 8G,8CCassia 4G 8G,8CTeaweed 6G,5C 10CVelvetleaf 8G,8C 10CJimsonweed 5G,3H 10CSoybean 8G,8C 8G,8CRice 10E 10EWheat 0 3G______________________________________ ##STR565##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 6GBarnyardgrass 6G,3H 10CSorghum 10C 10CWild Oats 6G 10CJohnsongrass 6G,3H 10CDallisgrass 0 5GGiant Foxtail 2H 5G,2CKy. Bluegrass 9G 10ECheatgrass 10E 10ESugarbeets 7G,8C 10CCorn 6G,5H 9G,9CMustard 10C 10CCocklebur 6G,2C 8G,3CPigweed 10C 10CNutsedge 10E 10ECotton 3G 8GMorningglory 4G 10CCassia 3G 6GTeaweed 10C 10CVelvetleaf 8G 10CJimsonweed 8G,8C 10CSoybean 7G,5H 9G,9CRice 8G,8C 10EWheat 3G 5G,2C______________________________________ ##STR566##Rate kg/ha 1/16 1/4______________________________________Crabgrass 6G 7GBarnyardgrass 8G,4C 8G,6HSorghum 9G,8C 10CWild Oats 6G,2C 8G,5CJohnsongrass 8G,2C 10CDallisgrass 3G 5GGiant Foxtail 6G 8G,4CKy. Bluegrass 9G 10ECheatgrass 7G 10CSugarbeets 10C 10CCorn 9G,9C 10CMustard 10C 10CCocklebur 8G,8C 8G,8CPigweed 10E 10ENutsedge 7G 9GCotton 9G,5H 9G,5HMorningglory 9G,9C 9G,9CCassia 8G,9C 10CTeaweed 10C 10CVelvetleaf 10C 10CJimsonweed 5G 8G,7CSoybean 9G,9C 9G,9CRice 6G,3C 8G,8CWheat 0 0______________________________________ ##STR567##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 6GBarnyardgrass 10C 10CSorghum 10C 10CWild Oats 8G,3C 8G,3CJohnsongrass 9G,3C 10CDallisgrass 4G 8G,5CGiant Foxtail 10C 10CKy. Bluegrass 10E 10ECheatgrass 10C 10ESugarbeets 9G,9C 9G,9CCorn 5G,3H 7G,7HMustard 10C 10CCocklebur 7G,5H 8G,5CPigweed 10E 10ENutsedge 10E 10ECotton 3G 8GMorningglory 5G 10CCassia 7G,5C 8G,7CTeaweed 3H 7G,5HVelvetleaf 10C 10CJimsonweed 5G 7GSoybean 8G,8H 9G,9HRice 10C 10EWheat 5G 6G______________________________________ ##STR568##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 4GBarnyardgrass 10C 10CSorghum 10C 10CWild Oats 8G,2C 8G,6CJohnsongrass 9G,9C 10CDallisgrass 5G 8G,9CGiant Foxtail 6G,4H 10CKy. Bluegrass 10E 10ECheatgrass 10E 10ESugarbeets 9G,9C 9G,9CCorn 9G,9C 9G,9CMustard 10C 10CCocklebur 8G,5H 7G,5HPigweed 10E 10ENutsedge 10E 10ECotton 6G,2H 8G,5HMorningglory 10C 8G,5CCassia 7G,3C 8G,7CTeaweed 9G,9C 10CVelvetleaf 10C 10CJimsonweed 6G 8G,7CSoybean 8G,8H 8G,9HRice 10E 10EWheat 7G 10C______________________________________ ##STR569##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 0Barnyardgrass 4G 4GSorghum 5G 7GWild Oats 3G 0Johnsongrass 0 6G,6EDallisgrass 0 0Giant Foxtail 0 3HKy. Bluegrass 6G 8GCheatgrass 0 3GSugarbeets 10C 10CCorn 4G,2H 7G,5HMustard 9G 10CCocklebur 8G,5H 8G,5CPigweed 10E 10ENutsedge 8G 8GCotton 7G,5H 8G,5HMorningglory 8G 8G,5CCassia 7G,3C 8G,9CTeaweed 5G,6H 10CVelvetleaf 7G,7C 10CJimsonweed 3G 5GSoybean 3G 6G,5HRice 6G,3C 5G,3CWheat 0 0______________________________________ ##STR570##Rate kg/ha 1/16 1/4______________________________________Crabgrass 0 5GBarnyardgrass 0 7G,4CSorghum 8G 10CWild Oats 3G 6GJohnsongrass 0 6GDallisgrass 0 0Giant Foxtail 0 6GKy. Bluegrass 8G 10ECheatgrass 3G 6GSugarbeets 9G,9C 10CCorn 5G,3H 7G,8HMustard 10C 10CCocklebur 8G,5H 8G,8CPigweed 10E 10ENutsedge 7G 7GCotton 7G 8GMorningglory 8G 8G,5CCassia 7G,3C 8G,9CTeaweed 5G,5H 10CVelvetleaf 10C 10CJimsonweed 3G 5GSoybean 2G,2H 7G,7HRice 6G,3C 6G,3CWheat 0 0______________________________________
TEST C
Pots filled with Fallsington silt loam were planted to soybeans, cotton, corn, rice, wheat, sorghum, alfalfa, velvet leaf (Abutulon theophrasti), sesbania (Sesbania exaltata), cassia (Cassia tora), morningglory (Ipomoea spp.), jimsonweed (Datura stramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitaria spp.),nutsedge (Cyperus rotunda), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii), and wild oats (Avena fatua). Approximately 21/2 weeks after planting, the young plants and the soil around them were sprayed overall with the compound of Example 1 dissolved in a nonphytotoxic solvent. Other groups of all the same weed and crop plants were sprayed with the same nonphytotoxic solvent so as to protrude control plants. Fourteen days after treatment, all treated plants were compared with the nonphytotoxic solvent controls and visually rated for response to treatment to give the data presented in Table XIV. It will be noted that wheat shows tolerance for several of the compounds included in this table.
TABLE XIV______________________________________Over-the-Top Soil/Foliage Treatment______________________________________ ##STR571##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G 8C 10G 7CVelvetleaf 10C 10CSesbania 10G 9C 10CCassia 10G 6C 10G 7CCotton 10G 7C 10G 6CMorningglory 10G 7C 10CJimsonweed 10G 9C 10G 9CCocklebur 10G 8C 10G 8CCorn 10G 9C 10CCrabgrass 10G 4C 10G 8CRice 10G 4C 10G 6CNutsedge 10G 6C 10G 7CBarnyardgrass 10G 8C 10G 9CWheat 10G 7C 10G 7CGiant Foxtail 10G 7C 10G 8CWild Oats 10G 8C 10G 9CSorghum 10G 9C 10G 8C______________________________________ ##STR572##Rate kg/ha 1/500 1/250 1/128______________________________________Soybeans 10G,8C 10G,9C 10G,9CVelvetleaf 10C 10C 10CSesbania 8G,7C 10G,8C 10G,9CCassia 8G,3C 10G,8C 10G,6CCotton 10G,7C 10C 10G,9CMorningglory 2G 6G 7G,3CAlfalfa 5G 10G,6C 10G,5CJimsonweed 3G 8G,3C 10CCocklebur 10G 8G,2C 10G,8CCorn 10G,7C 8G,3U 10G,9CCrabgrass 5G 5G 6GRice 10G,4C 8G,2C 10G,5CNutsedge 10G,3C 10G,4C 10CBarnyardgrass 10C 10G,3C 10G,8CWheat 10G,9C 8G 10G,4CGiant Foxtail 10G,8C 8G 10G,7CWild Oats 8G,3C 8G 10G,5CSorghum 10G,3C 10G,4C 10G,7C______________________________________ ##STR573##Rate kg/ha 1/64 1/32______________________________________Soybeans 10G,8C 10G,8CVelvetleaf 10G,8C 10CSesbania 10G,9C 10G,9CCassia 10G,8C 10G,8CCotton 10G,8C 10G,8CMorningglory 10G,9C 10G,9CAlfalfa 10G,8C 10G,8CJimsonweed 10G,9C 10CCocklebur 10G,7C 10CCorn 10G,9C 10G,8CCrabgrass 6G 10G,4CRice 10G,6C 10G,6CNutsedge 10G,8C 10G,9CBarnyardgrass 10G,9C 10G,9CWheat 10G,9C 10G,7CGiant Foxtail 10G,9C 10G,9CWild Oats 10G,7C 10G,7CSorghum 10G,8C 10G,8C______________________________________ ##STR574##Rate kg/ha 1/64 1/32 1/16______________________________________Soybeans 10G,9C 10G,9C 10G,8CVelvetleaf 10C 10C --Sesbania 10G,9C 10G,9C 10G,9CCassia 10G,9C 10G,8C 10G,9CCotton 10G,7C 10G,7C 10G,7CMorningglory 10G,9C 10C 10CAlfalfa 10G,9C 10C 10G,9CJimsonweed 10C 10C 10CCocklebur 10G,9C 10G,9C 10CCorn 10G,8C 10G,7C 10G,9CCrabgrass 3G 7G,3C 10G,5CRice 10G,3C 10G,4C 10G,6CNutsedge 10G,6C 10G,6C 10G,8CBarnyardgrass 10G,9C 10G,7C 10G,9CWheat 10G,8C 10G,7C 10G,9CGiant Foxtail 10G,7C 10G,7C 10CWild Oats 10G,7C 10G,9C 10G,8CSorghum 10G,7C 10G,7C 10G,9C______________________________________ ##STR575##Rate kg/ha 1/64 1/32 1/16______________________________________Soybeans 10G,9C 10G,9C 10G,8CVelvetleaf 10C 10C 10CSesbania 10G,9C 10G,9C 10G,9CCassia 10G,8C 10C 10G,9CCotton 10G,6C 10G,6C 10G,8CMorningglory 10C 10C 10G,9CAlfalfa 10G,9C 10G,9C 10G,9CJimsonweed 10C 10C 10CCocklebur 10C 10C 10CCorn 10G,7C 10G,8C 10G,8CCrabgrass 4G 5G,2C 3G,2CRice 10G,4C 10G,4C 10G,4CNutsedge 10G,9C 10G,9C 10G,9CBarnyardgrass 10G,7C 10G,9C 10G,8CWheat 8G,3C 10G,7C 10G,8CGiant Foxtail 10G,9C 10G,9C 10CWild Oats 10G,6C 10G,5C 8G,4CSorghum 10G,8C 10G,9C 10G,9C______________________________________ ##STR576##Rate kg/ha 1/64 1/32 1/16______________________________________Soybeans 10G,8C 10G,8C 10G,9CVelvetleaf -- 10C 10CSesbania 10G,9C 10G,9C 10G,9CCassia 10G,7C 10G,9C 10G,8CCotton 10G,5C 10G,8C 10G,8CMorningglory 10C 10C 10CAlfalfa 10G,8C 10G,9C 10G,9CJimsonweed 10C 10C 10CCocklebur 10G,8C 10C 10CCorn 9G,3C 10G,8C 10G,9CCrabgrass 0 3G,2H 5G,2CRice 7G 10G,2C 10G,4CNutsedge 0 4G 2GBarnyardgrass 8G,5H 10G,6C 10G,7CWheat 7G,3H 5G 5GGiant Foxtail 10G,2C 10G,7C 10G,4CWild Oats 6G 10G,2C 10G,3CSorghum 10G,2C 10G,5C 10G,5C______________________________________ ##STR577##Rate kg/ha 1/64 1/32 1/16______________________________________Soybeans 10G,8C 10G,8C 10G,8CVelvetleaf -- -- 10CSesbania 10G,9C 10G,9C 10G,9CCassia 10G,8C 10G,8C 10G,8CCotton 10G,5C 10G,9C 10G,8CMorningglory 10G,9C 10C 10CAlfalfa -- 8G,6C 10G,6CJimsonweed 10G,9C 10C 10CCocklebur 10G,2C 10G,7C 10G,9CCorn 8G,4H 8G,2C 9G,4CCrabgrass 0 0 2GRice 6G 10G,2C 10G,3CNutsedge 0 0 5G,2CBarnyardgrass 6G,2H 9G,3H 10G,5HWheat 3G,2H 3G 3GGiant Foxtail 3G 7G 10G,3CWild Oats 0 2G 3G,2CSorghum 5G,2H 10G,4H 10G,4H______________________________________ ##STR578##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,8C 10G,9CVelvetleaf 5G 10CSesbania 10C 10CCassia 10G,8C 10G,8CCotton 5G,2C 7G,3HMorningglory 4G 9G,3CAlfalfa 2C 10G,6CJimsonweed 4G,2C 6G,2CCocklebur 3G,3C 9G,6CCorn 6G,3H 10G,7CCrabgrass 0 2GRice 10G,8C 10G,7CNutsedge 10G,3C 10G,3CBarnyardgrass 10G,4C 10G,5CWheat 8G 10GGiant Foxtail 5G 8GWild Oats 5G 8GSorghum 10G,6C 10G,6C______________________________________ ##STR579##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 0 0 5G,2CVelvetleaf 0 0 5GSesbania 0 3G 7GCassia 0 0 5G,3CCotton 0 0 5GMorningglory 0 0 5GAlfalfa 0 0 3GJimsonweed 0 0 2GCocklebur 0 0 3GCorn 0 0 8G,5HCrabgrass 0 0 0Rice 0 3G 8GNutsedge 0 3G 8GBarnyardgrass 0 0 4GWheat 0 0 4GGiant Foxtail 0 0 2GWild Oats 0 0 3GSorghum 0 4G 8G,3H______________________________________ ##STR580##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 10G,8C 10G,8C 10CVelvetleaf 10C 10C 10CSesbania 10G,9C 10C 10CCassia 10G,8C 10G,8C 10G,9CCotton 10C 10C 10CMorningglory 10C 10C 10CAlfalfa 10C 10C 10CJimsonweed 10C 10C 10CCocklebur 10C 10C 10CCorn 8G,3H 10G,3C 10G,8CCrabgrass 5G 5G 9G,3CRice 10G,6C 10G,5C 10G,6CNutsedge 10G,8C 10G,9C 10G,8CBarnyardgrass 10G,8C 10G,9C 10G,9CWheat 8G 10G 10G,3HGiant Foxtail 10G 10G 10G,3CWild Oats 10G 10G 10G,3CSorghum 10G,5C 10C 10G,8C______________________________________ ##STR581##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 10G,8C 10G,8C 10G,8CVelvetleaf 10C 10C --Sesbania 10G,9C 10C 10CCassia 10G,8C 10G,8C 10G,8CCotton 10C 10C 10CMorningglory 10C 10C 10CAlfalfa 10C 10C 10CJimsonweed 10C 10C 10CCocklebur 10G,9C 10C 10CCorn 8G,3C 7G,3C 10G,9CCrabgrass 8G 8G 10G,3CRice 10G,5C 10G,4C 10G,6CNutsedge 10G,8C 8G,3C 10G,8CBarnyardgrass 10G,8C 10G,6C 10G,8CWheat 9G 10G,3C 10G,5CGiant Foxtail 10G 10G 10G,6CWild Oats 10G 10G,3C 10G,5CSorghum 10G,4C 10G,3C 10G,8C______________________________________ ##STR582##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 10G,8C 10G,9C 10G,8CVelvetleaf 10C 10C 10CSesbania 10C 10C 10CCassia 10G,9C 10G,9C 10G,9CCotton 10G,7C 10C 10CMorningglory 10C 10C 10CAlfalfa 10G,9C 10C 10CJimsonweed 10C 10C 10CCocklebur 10C -- 10CCorn -- 8G,5H 10G,4CCrabgrass 0 3G 7GRice 6G 8G 10G,4CNutsedge 10G,8C 10G,9C 10CBarnyardgrass 7G,3H 8G,3H 8G,3HWheat 0 0 0Giant Foxtail 2G 0 5GWild Oats 5G 5G 8GSorghum 8G,3H 10G,3H 10G,3H______________________________________ ##STR583##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 10G,8C 10C 10G,9CVelvetleaf 10C 10C 10CSesbania 10C 10C 10G,9CCassia 10G,9C 10G,9C 10G,9CCotton 10G,9C 10C 10CMorningglory 10C 10C 10CAlfalfa 10C 10C 10CJimsonweed 10G,9C 10C 10CCocklebur 10C 10C 10CCorn 10G,9C 10G,9C 10CCrabgrass 5G 7G 10G,3CRice 10G,7C 10G,7C 10G,7CNutsedge 10C 10C 10CBarnyardgrass 10G,8C 10G,7C 10G,9CWheat 8G 10G,3C 10G,4CGiant Foxtail 7G 10G 10G,3CWild Oats 10G,6C 10G,5C 10G,7CSorghum 10C 10G,8C 10C______________________________________ ##STR584##Rate kg/ha 1/32 1/16 1/4______________________________________Soybeans 10G,3C 10G,6C 10G,6CVelvetleaf 10G,7C 10C 10CSesbania 10G,5C 10G,7C 10G,8CCassia 3G 4G 8G,3CCotton 10G,4C -- 10G,8CMorningglory 10G,3B 10G,5B 10BAlfalfa 10G,6C 10G,6C 10G,9CJimsonweed 8G,3C 8G,3C 10G,6CCocklebur 10G,4C 10G,6C 10G,6CCorn 5G,2H 8G,3H 10G,3HCrabgrass 0 0 0Rice 8G 10G,2C 10G,4CNutsedge 3G 8G 9GBarnyardgrass 8G,2C 10G,3C 10G,3CWheat 0 3G 5GGiant Foxtail 7G 7G 10G,3HWild Oats 6G 7G 9GSorghum 5G 10G,3H 10G,3H______________________________________ ##STR585##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,9C 10G,9CVelvetleaf 10C --Sesbania 10C 10CCassia 10C 10G,9CCotton 10C 10CMorningglory 10C 10CAlfalfa 10C 10CJimsonweed 10G,6C 10G,7CCocklebur 10C 10CCorn 10G,2C 10G,8CCrabgrass 4G 7GRice 7G 10G,2CNutsedge 8G,3C 10CBarnyardgrass 7G 10G,3CWheat 0 3GGiant Foxtail 0 7GWild Oats 3G 8GSorghum 8G,5H 8G,2C______________________________________ ##STR586##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,9C 10G,9CVelvetleaf 10C --Sesbania 10G,9C 10CCassia 10G,8C 10CCotton 10G,8C 10G,9CMorningglory 10C 10CAlfalfa 10G,9C 10CJimsonweed 8G,3C 10G,5CCocklebur 10C 10CCorn 8G,2C 9G,2CCrabgrass 5G 8G,2CRice 10G,4C 10G,5CNutsedge 10G,6C 10G,6CBarnyardgrass 10G,7C 10G,8CWheat 6G 10GGiant Foxtail 10G,7C 10G,9CWild Oats 8G 10G,3CSorghum 10G 10G______________________________________ ##STR587##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,9C 10G,9CVelvetleaf -- --Sesbania 10C 10CCassia 10C 10CCotton 10C 10G,8CMorningglory 10G,9C 10G,9CAlfalfa 10C 10CJimsonweed 10G,7C 10G,8CCocklebur -- 10CCorn 10G,5C 10G,3CCrabgrass 4G 7GRice 10G,4C 10G,5CNutsedge 10G,8C 10G,5CBarnyardgrass 10G,8C 10G,8CWheat 10G 10G,4CGiant Foxtail 10G,3C 10G,9CWild Oats 10G,2C 10G,2CSorghum 10G 10G,2C______________________________________ ##STR588##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,9C 10G,9CVelvetleaf -- 10CSesbania 10C 10CCassia 10G,9C 10CCotton 10G,9C 10G,8CMorningglory 10C 10CAlfalfa 5G 10G,9CJimsonweed 8G,4C 10G,4CCocklebur 10C --Corn 5G 8G,2CCrabgrass 3G 4GRice 4G 6GNutsedge 10G,4C 10G,4CBarnyardgrass 7G 8GWheat 0 0Giant Foxtail 0 0Wild Oats 0 5GSorghum 6G 8G______________________________________ ##STR589##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,9C 10G,9CVelvetleaf 10C --Sesbania 10C 10CCassia 10G,9C 10CCotton 10G,8C 10G,9CMorningglory 10C 10CAlfalfa 10C 10CJimsonweed 10G,5C 10G,8CCocklebur 10C 10CCorn 10G,3H 10G,3CCrabgrass 0 3GRice 4G 7GNutsedge 5G 9G,4CBarnyardgrass 6G 8GWheat 0 0Giant Foxtail 0 3GWild Oats 3G 5GSorghum 10G,3H 10G______________________________________ ##STR590##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,7C 10G,8CVelvetleaf 10C 10CSesbania 10C 10CCassia 10G,7C 10G,7CCotton 10G,7C 10G,9CMorningglory 10G,9C 10CAlfalfa 10G,9C 10G,9CJimsonweed 10G,3C 10G,6CCocklebur 10C 10CCorn 4G 7G,3HCrabgrass 0 4GRice 10G,3C 10G,3CNutsedge 10G,5C 10G,8CBarnyardgrass 10G,3H 10G,4CWheat 2G 7GGiant Foxtail 0 5G,2CWild Oats 5G 8G,3HSorghum 10G 10G,2C______________________________________ ##STR591##Rate kg/ha 1/16 1/4______________________________________Soybeans 10G,7C 10G,7CVelvetleaf 10C 10CSesbania 10G,7C 10G,9CCassia 10G,7C 10G,7CCotton 10G,6C 10G,9CMorningglory 10C 10CAlfalfa 10G,9C 10G,9CJimsonweed 10G,8C 10G,8CCocklebur 10C 10G,9CCorn 10G,5H 8GCrabgrass 0 5GRice 8G,2C 10G,6CNutsedge 7G,2C 7G,3CBarnyardgrass 8G,3C 10G,6CWheat 4G 8GGiant Foxtail 2G 6GWild Oats 10G 8G,3CSorghum 10G 10G______________________________________
TEST D
The high herbicidal activity of one of the compounds from within the scope of the invention is evident from the results obtained in this test. The experiment concerned pre-emergence applications on soil. The containers used were 25 cm diameter plastic pots filled with Fallsington silt loam. One set of pots was planted to weeds the seeds of which were uniformly mixed with the top 1.2 cm layer of soil. The species selected were: johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), velvetleaf (Abutilon theophrasti), jimsonweed (Datura stramonium), mustard (Brassica arvensis) and pigweed (Amaranthus retroflexus). Another set of pots was planted to the following crops with from one to four species per pot: corn (planting depth 3.7 cm), cotton, soybeans, sunflower, Clinton oats, wheat, Black Valentine beans, rice, sorghum, peas, flax and peanuts (all at 2.5 cm depth), cucumbers, cabbage, alfalfa, safflower, sugarbeets, tomato, spinach, barley and Kentucky bluegrass (all at 1.2 cm depth). Immediately after planting, the test chemical was applied to the soil surfaces dissolved in a non-phytotoxic solvent. One pot from the weed phase and one of each of the crop species were left untreated for the purpose of comparison. The treated and untreated pots were promptly watered with approximately 4 mm of simulated rainfall and then held in a greenhouse for several wees. Visual weed and crop response ratings were made 28 days after treatment utilizing the rating system as described above for test procedure A. The data are given in Table XV.
TABLE XV______________________________________PRE-EMERGENCE ON SOIL ##STR592##Rate kg/ha 1/64 1/32 1/16 1/8______________________________________Corn -- -- -- 10CCotton -- -- -- 9G,9CSoybean -- -- -- 9G,9HPeanut -- -- -- 10ESunflower -- -- -- 8G,7COats -- -- -- 8G,9CWheat -- -- -- 10CSorghum -- -- -- 10CSugarbeet -- -- -- 10CPea -- -- -- 10CFlax -- -- -- 10EAlfalfa -- -- -- 10CBean -- -- -- 7G,8HSpinach -- -- -- 10CCabbage -- -- -- 10CTomato -- -- -- 8G,8CRice -- -- -- 10ESafflower -- -- -- 9G,9CCucumber -- -- -- 8G,7CKy. blue- -- -- -- 10CgrassBarley -- -- -- 9G,8CTobacco -- -- -- 5G,2CBroad- 7G,5C 8G,8C 9G,8C --leavesGrasses 6G 8G,6C 8G,8C --______________________________________
TEST E
This greenhouse test demonstrates the utility of certain compounds from within the scope of the invention for the pre- and post-emergence control of broadleaved weeds and nutsedge in young wheat and barley plantings. The containers used were 25 cm diameter plastic pots filled with fertilized and limed Fallsington silt loam. Plantings of the following weed species were made twice, at a 10-day interval: mustard (Brassica arvensis), cocklebur (Xanthium spp.), morningglory (Ipomoea hederacea), cassia (Cassia tora), velvetleaf (Abutilon theophrasti), alfalfa (used as an indicator species), kochia (Kochia scoparia), sesbania (Sesbania exaltata), Russian thistle (Salsola kali), jimsonweed (Datura stramonium), and nutsedge (Cyperus rotundus). In addition, wheat and barley were planted in separate 15 cm diameter plastic pots filled with the same soil at the time of the early planting only. All plantings were treated with the test chemicals dissolved in a non-phytotoxic solvent immediately following completion of the second planting operation. At this time, the wheat was around 15-17.5 cm tall and the barley 12.5 to 15 cm tall, both in the 2-leaf stage of growth. The weed species of the earliest planting date were from 2.5 to 12.5 cm tall. The rates of application selected were 0.004, 0.007, 0.015 and 0.030 kg/ha for the weed phase and 0.12, 0.25 and 0.50 kg/ha for wheat and barley. The post-emergence part of this test was visually rated for plant response 21 days after treatment, and the pre-emergence part 28 days after treatment. The rating system used was as described for test procedure A. The data are summarized in Table XVI.
TABLE XVI PRE-EMERGENCE ON FALLSINGTON SILT LOAM Morning- Jimson- Rate kg/ha Mustard Cocklebur glory Cassia Velvetleaf Alfalfa Sesbania Kochia R. Thistle weed Nutsedge Wheat Barley ##STR593## 1/2561/1281/641/321/81/41/2 9G,9C10C10C10C 7G,7H8G,8H8G,8H8G,9H 8G,7C8G,7C8G,7C8G,9C 8G,5C8G,5C8G,5C8G,8C 8G,3H8G,3H8G,5H9G,5H 5G5G,2C5G8 G,7C 7G,3C8G,9C8G,9C9G,9C 9G,9C10C10C10C 5C7C 7C9C 7G,2C8G,7C8G,9C8G,9C 7G8G9G10E ##STR594## 1/2561/1281/641/321/81/41/2 10C10C10C10C 8G,8C8G,8H8G,8H8G,9H 8G,6C9G,9C1 0C10C 8G,5C8G,5C8G,9C8G,8C 9G,8C9G,9C10C10C 7G7G,2C9G,8C9G,7C 7G,3C7G,5C8 G,8C10C 9G,9C10C10C10C 7C8C10C10C 7G,6C7G,5C8G,9C8G,7C 6G,3C7G,2C8G8G POST-EMERGENCE Morning- Jimson- Rate kg/ha Mustard Cocklebur glory Cassia Velvetleaf Alfalfa Sesbania Kochia R. Thistle weed Nutsedge Wheat Barley ##STR595## 1/2561/1281/641/321/81/41/2 10C10C10C10C 10C10C10C10C 9C10C10C10C --10C10C-- 5G10C10C10C 10C10C10C10C ----10C-- 8C10C10C10C 7G,5C10G,5C10G, 7C10G,6C 7G,3C10G,8C10G,5C10G 2G2G,2C 6G,3C 06G,2C8G,3C ##STR596## 1/2561/1281/641/321/81/41/2 10C10C10C10C 10C10C10C10C 10C9C10C10C --10C---- 10C10C10C10C 10C10C10C10C 10C--10C-- 10C10C10C10C 10G,4C10G,8C1 0G,8C10G,9C 3G5G,3C10G,7C10C 005G,3C 5G5G,2C7G,3C
TEST F
Several compounds from within the scope of the invention are highly active against nutsedge, as evident from the following test.
Purple nutsedge tubers (Cyperus rotundus) were planted about 2 cm deep in Fallsington silt loam contained in plastic pots 10 cm in diameter. Five tubers were put in each pot. Compounds of this invention were sprayed dissolved in a non-phytotoxic solvent at a volume rate of 560 l/ha. in four different methods of treatment, i.e., soil surface spray, tuber/soil spray, soil incorporated and post-emergence. For the soil surface spray, the compounds were sprayed on the firmed soil surface immediately after planting. For the tuber/soil spray, the compounds were sprayed on the exposed tubers and subtending soil before the untreated covering soil was added. Soil incorporation treatments were mixed in the covering soil. Post-emergence treatments were sprayed on the nutsedge foliage and surrounding soil surface after the nutsedge had emerged and had reached the height of about 12 cm.
Immediately after spraying the surface spray, tuber/soil spray and soil incorporated treatments were misted with about 0.3 cm of water over a 90 minute period and then placed in the greenhouse. Post-emergence treatments were placed directly into the greenhouse and watered carefully so that treatments would not be washed from the foliage.
The following Table XVII gives results 4 weeks after treating nutsedge with compounds of this invention.
TABLE XVII______________________________________NUTSEDGE TEST RESPONSE RATING AFTER 4 WEEKS Soil Tuber SoilRate kg/ha Surface Spray Incorp. Post-emergence______________________________________ ##STR597##.004 8E,9G 10E 10E 4C,7G.008 10E 10E 10E 9C.016 10E 10E 10E 9C.032 10E 10E 10E 10C.064 10E 10E 10E 10C______________________________________ ##STR598##.004 8E,9G 10E 10E 5C,7G.008 10E 10E 10E 9C.016 10E 10E 10E 9C.032 10E 10E 10E 10C.064 10E 10E 10E 10C______________________________________ ##STR599##.004 9E,9G 8E,9G 8E,9G 8C.008 10E 10E 10E 10C.016 10E 10E 10E 10C.032 10E 10E 10E 9C.064 10E 10E 10E 10C______________________________________ ##STR600##.004 4C,7G 5C,8G 5C,8G 0.008 4C,7G 5C,8G 5C,8G 2G.016 4C,7G 5C,9G 5C,8G 2G.032 5C,8G 5C,9G 5C,9G 2C,5G.064 5C,8G 5C,9G 6C,9G 5C,7G______________________________________ ##STR601##.004 3C,6G 3C,7G 3C,7G 0.008 4C,8G 4C,8G 4C,8G 0.016 -- 4C,8G 4C,8G 2C,3G.032 4C,8G 4C,8G 4C,8G 3G.064 5C,8G -- 4C,8G 3C,4G______________________________________ ##STR602##.032 0 2G 0 0.125 2E,7G 4E,8G 8E,9G 9C.5 10E 10E 10E 10E______________________________________ ##STR603##.032 2G 2G 3G 0.125 10E 4E,8G 8E,8G 9C.5 10E 10E 10E 10C______________________________________ ##STR604##.008 10E 10E 10E 10C.032 10E 10E 10E 10C.125 10E 10E 10E 10C.25 10E 10E 10E 10C______________________________________ ##STR605##.008 2C,4G 3C,7G 3C,8G 5C,7G.032 3C,6G 3C,7G 3C,7G 3C,6G.125 2C,8G 3C,8G 5E,9G 8C.5 2C,8G 5E,9G 5E,9G 5C,6G______________________________________ ##STR606##.004 8G 7G 8G 8C.008 8G 8G 8G 9C.016 8E,9G 6E,9G 8E,9G 9C.032 5E,9G 8E,9G 10E 10C______________________________________ ##STR607##.008 10E 10E 9E,9G 10C.032 10E 10E 10E 10C.125 10E 10E 10E 10C.25 10E 10E 10E 10C______________________________________ ##STR608##.008 10E 10E 10E 10C.032 10E 10E 10E 10C.125 10E 10E 10E 10C.25 10E 10E 10E 10C______________________________________ ##STR609##.008 3G 4G 5G 3G.032 7G 7G 7G 5C,6G.125 9G 9G 9G 10C______________________________________ ##STR610##.008 2C,5G 7G 7G 2C,5G.032 9G 10E 8E,9G 9C.125 10E 10E 10E 9C______________________________________ ##STR611##.008 8E,9C 10E 10E 10C.032 10E 10E 10E 10C.125 10E 10E 10E 10C______________________________________
TEST G
Purple nutsedge tubers (Cyperus rotundus, L.) were planted about 2 cm deep in Fallsington silt loam (about 1% organic matter from Delaware) and in Flanagan loam (about 4% organic matter) from Illinois. Five tubers were planted in each 10 cm diameter plastic pot. Treatments recorded in Table XVII were applied in three different ways, i.e., soil surface spray, tuber/soil spray and soil incorporated. In surface sprays, the material was sprayed on the firmed soil surface after planting, but before nutsedge emergence. In tuber/soil sprays, the material was sprayed on exposed tubers and subtending soil before the tubers were covered with untreated soil. Soil incorporated treatments were mixed in the covering soil.
Immediately after treating, the treated pots were misted with about 0.3 cm of water over a 90 minute period and placed in the greenhouse. The high degree of activity of these compounds on nutsedge is demonstrated by the ratings after 4 weeks as recorded in Table XVIII.
TABLE XVIII______________________________________Nutsedge Response Rating - After 4 WeeksSurface Spray Tuber/Soil Spray Soil Incorp.Rate, Low High Low High Low Highkg/ha OM OM OM OM OM OM______________________________________ ##STR612##.008 10E 4C,7G 10E 7E,9G 10E 9E,9G.016 10E 8E,8G 10E 10E 10E 8E,9G.032 10E 9E,9G 10E 10E 10E 10E ##STR613##.008 5C,8G 0 9E,9G 5E,7G 8E,9C 2C,3G.016 9E,9G 2C,4G 10E 10E 9E,9G 3C,3G.032 10E 10C 10E 9E,10C 10C 7E,3C,8G______________________________________
TEST H
Two ten-inch in diameter plastic pans lined with polyethylene liners were filled with prepared Fallsington silt loam soil. One pan was planted with seeds of wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), downy brome (Bromus tectorum), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) and ripgut brome (Bromus rigidus). The other pan was planted with seeds of wild buckwheat (Polygonum convolvulus), Kochia scoparia, smartweed (Polygonum pennsylvanicum), false chamomile (Matricaria inodora), jimhill mustard (Sisymbrium altissium), wild mustard (Brassica kaber), tansy mustard (Descurainnia pinnata), pigweed (Amaranthus retroflexus) and Russian thistle (Salsola kali). The above two pans were treated pre-emergence. At the same time two pans in which the above plant species were growing were treated post-emergence. Plant height at the time of treatment ranged from 1-15 cm depending on plant species.
The compounds applied were diluted with a nonphytotoxic solvent and sprayed over-the-top of the pans. An untreated control and a solvent alone control were included for comparison. All treatments were maintained in the greenhouse for 20 days at which time the treatments were compared to the controls and the effects visually rated. The recorded data are presented in Table XIX. Here again, the potential utility of certain test compounds for weed control in wheat and barley is evident.
TABLE XIX Rate kg/ha wheat barley wild oats downy brome cheatgrass blackgrass annual bluegrass green foxtail quackgrass Italian ryegrass PRE-EMERGENCE ##STR614## 1/161/8 9E,9G9E,9G 7H,8G8H,8G 4H,7G7H,8G 9E,9G10E 7G,8G9E,9G 5H,8G8H,9G 5 C,7G7C,8G 8C,8G8C,9G 5H,7G7H,8G 6H,7G8H,8G ##STR615## 1/641/321/16 000 000 000 001G 001G 002G 001G 001G 000 000 ##STR616## 1/641/321/16 000 01G1G 02G3G 1G3G5G 1C,2G1C,3G2C,4G 2G3G4G 2G3G5G 001G 02 0G 02G3G Rate jimhill Russian kg/ha ripgut brome wild buckwheat Kochia smartweed false chamomile mustard wild mustard tansy mustard pigweed thistle PRE-EMERGENCE ##STR617## 1/161/8 8C,9G10C 4C,7G5C,8G 9C,9G9C,9G 7C,8G9C,9G 9C,9G9C,9G 10C10C 8C,8G9C,9G 10C10C 8C,9G10C 7C,7G8C,8G ##STR618## 1/641/321/16 000 3C,5G7C,8G7C,8G 5C,7G7C,8G9C 4C,7G10C10C 9G9G9G 10C10C10C 10C10C10C 7C,9G10C10C 7G5C,8G10C 3G4G7C,5G ##STR619## 1/641/321/16 000 9C9C10C 9C10C10C 9C10C10C 9G9G10C 10C10C10C 10C10C10C 1 0C10C10C 8C9C10C 3C,5G7C,7G8C,8G Rate kg/ha wheat barley wild oats downy brome cheatgrass blackgrass annual bluegrass green foxtail quackgrass Italian ryegrass POST-EMERGENCE ##STR620## 1/161/8 9C10C 9C10C 9C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C ##STR621## 1/641/321/16 001C 000 001C 000 000 000 002G 1C1C2C,3G 000 000 ##STR622## 1/641/321/16 001C 000 002C 002G 0 01C,2G 002G 003G 01C3C 001G 002G Rate jimhill Russian kg/ha ripgut brome wild buckwheat Kochia smartweed false chamomile mustard wild mustard tansy mustard pigweed thistle POST-EMERGENCE ##STR623## 1/161/8 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C ##STR624## 1/641/321/16 000 9C10C10C 10C10C10C 9C9C10C 10C10C10C 10C10C10C 10C10C10C 10C10C10C 9C10C10C 9C10C10C ##STR625## 1/641/321/16 000 10C10C10C 10C 10C10C 10C10C10C 10C10C10C 10C10C10C 10C10C10C 10C10C10C 10C10C10C 10C10C10C
TEST I
Five-inch diameter plastic pots were filled with a 50--50 mixture of Fallsington silt loam soil and sand and seeds of the following planted (one plant species per pot): milkweed vine (Morrenia odorata), plantain (Plantago spp.), burdock (Arctium minus), field bindweed (Convolvulus arvensis), dandelion (Taraxacum officinale), horsenettle (Solanum carolinense), bermudagrass (Cynodon dactylon), quackgrass (Agropyron repens), dallisgrass (Paspalum dilatum) and johnsongrass (Sorghum halepense). The pots were placed in the greenhouse and the plants grown for several weeks.
The compound evaluated was diluted with a nonphytotoxic solvent and sprayed on the plant foliage. Untreated and solvent controls were included for comparison. One and eight weeks after treatment, a visual rating of the compound's effects on plant growth were made. These ratings are presented in Table XX. The data indicate the high activity of the test compound for the control of established broadleaved and grass perennial weeds.
TABLE XX______________________________________PERENNIAL BROADLEAF AND GRASS TEST ##STR626## Plant Response Ratings 1 Week 8 WeeksPlant species 1/8 kg/ha 1/4 kg/ha 1/8 kg/ha 1/4 kg/ha______________________________________Milkweed 0 0 10C 10CvinePlantain 0 0 10C 10CBurdock 0 0 4C 10CField 0 2C 7C 8CbindweedDandelion 0 0 10C 10CHorsenettle 0 1C 5C 10CBermudagrass 5C 6C 5C,7G 6C,8GQuackgrass 6C 7C 10C 10CDallisgrass 6C 6C 8C,8G 10CJohnsongrass 8C 9C 10C 10C______________________________________
TEST J
The high herbicidal activity of one of the compounds from within the scope of the invention was confirmed in a field test. The material was applied pre-emergence to a silt loam. Three days after treatment the area was irrigated with 2.5 cm of water. Four weeks later, the percentage of control was estimated for each species, as shown in Table XXI.
TABLE XXI______________________________________PRE-EMERGENCE TREATMENTS ON CROPS ANDWEEDS -% CONTROL ##STR627## kg ai/ha Untreated .031 .063 .125 .25______________________________________Crabgrass 0 100 100 100 100Foxtail 0 100 100 100 100Nutsedge 0 98 100 100 100Pigweed 0 100 100 100 100Ragweed 0 100 100 100 100Velvetleaf 0 98 98 100 100Lambsquarter 0 100 100 100 100Purslane 0 100 100 100 100Smartweed 0 100 100 100 100Barnyardgrass 0 100 100 100 100Ryegrass 0 100 100 100 100Wild Oats 0 98 100 100 100Spinach 0 100 100 100 100Flax 0 90 100 100 100Endive 0 100 100 100 100Cabbage 0 100 100 100 100Red Beets 0 100 100 100 100Carrots 0 100 100 100 100Lima Beans 0 50 60 70 90Snap Beans 0 90 85 95 100Tomatoes 0 100 100 100 100Peanuts 0 70 80 90 90Potatoes 0 90 90 100 100Cucumber 0 100 100 100 100Squash 0 100 100 100 100Sugarbeets 0 100 100 100 100Soybeans 0 90 95 98 98Alfalfa 0 100 100 100 100Clover 0 100 100 100 100Lespedeza 0 100 100 100 100Cotton 0 80 90 90 95Oats 0 100 100 100 100Okra 0 90 90 100 100Rice 0 100 100 100 100Wheat 0 90 100 100 100Sorghum 0 100 100 100 100Corn 0 100 100 100 100Sunflower 0 70 90 95 100Safflower 0 100 100 100 100______________________________________
TEST K
The response of a number of noxious weed species to post-emergence applications of the same compound as used in Test J was studied in another field test. At the time of treatment, one month after mowing, the mixed vegetation was approximately 15 cm tall. The chemical was applied in water containing 0.2% of Surfactant WK.RTM. at an overall volume of 500 1/ha. Each treatment was replicated three times. Approximately 5 cm of rainfall was recorded 4 days after treatment and an additional 37 cm fell before weed control ratings were made 16 weeks after treatment. The figures are presented in Table XXII.
TABLE XXII______________________________________BROAD-SPECTRUM WEED CONTROL TESTMEAN % WEED CONTROL ##STR628## UntreatedRate kg/ha Check .5 1.0 2.0______________________________________Overall 0 81 90 94Grasses 0 81 84 93Broadleaves 0 91 96 98Purpletop 0 73 80 92Broomsedge 0 71 73 86Golden rod 0 100 100 100Dewberry 0 97 100 100Poison Ivy 0 67 85 95______________________________________Weeds Per Sq. Ft. in untreated check:Purpletop .7Broomsedge .7Golden Rod 1.0Dewberry .5Poison Ivy 1.0

Number	Name	Date
4383113	Levitt	May 1983
4591378	Levitt	May 1986
4627873	Levitt	Dec 1986
4645530	Wolf	Feb 1987
4647303	Levitt	Mar 1987

	Number	Date	Country
Parent	452106	Dec 1982
Parent	98781	Nov 1979

	Number	Date
Parent	29281	Apr 1979
Parent	15341	Mar 1979
Parent	965070	Nov 1978
Parent	910965	May 1978

Agricultural sulfonamides

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