The invention relates to certain 6-amino-substituted 2-pyridinesulfonylureas, intermediates thereof, and compositions and methods of their use.

BACKGROUND OF THE INVENTION 
This invention relates to novel pyridine sulfonylurea herbicidal compounds, 
agriculturally suitable compositions thereof and a method of using them to 
control the growth of undesired vegetation. 
New compounds effective for controlling the growth of undesired vegetation 
are in constant demand. In the most common situation, such compounds are 
sought to selectively control the growth of weeds in useful crops such as 
cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed 
growth in such crops can cause significant losses, reducing profit to the 
farmer and increasing costs to the consumer. In other situations, 
herbicides are desired which will control all plant growth. Examples of 
areas in which complete control of all vegetation is desired are areas 
around railroad tracks and industrial storage areas. There are many 
products commercially available for these purposes, but the search 
continues for products which are more effective, less costly and 
environmentally safe. 
The "sulfonylurea" herbicides are an extremely potent class of herbicides 
discovered within the last few years. A multitude of structural variations 
exist within this class of herbicides, but they generally consist of a 
sulfonylurea bridge, --SO.sub.2 NHCONH--, linking two aromatic or 
heteroaromatic rings. 
U.S. Pat. Nos. 4,579,583 and 4,690,707 disclose herbicidal 
pyridinesulfonylureas of the formula 
##STR1## 
wherein XA is NR.sub.6 R.sub.7 ; and 
R.sub.6 and R.sub.7 are independently H, C.sub.1 -C.sub.4 alkyl, C.sub.3 
-C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, C.sub.3 -C.sub.6 alkoxyalkyl, 
C.sub.1 -C.sub.4 cyanoalkyl, or taken together form a 5- or 6-membered 
heterocyclic ring which may also contain O, S, SO or NR.sub.8. 
U.S. Pat. No. 4,544,401 discloses herbicidal pyridine sulfonylureas of the 
formula 
##STR2## 
wherein R.sub.1 is NR.sub.6 R.sub.7 ; and 
R.sub.2 is H, Cl, Br or CH.sub.3. 
EP-A-101,670 discloses a process for the preparation of herbicidal 
sulfonylureas of the formula 
##STR3## 
wherein A is --C.dbd.N--; and 
R.sub.1 is NH(C.sub.1 -C.sub.4)alkyl or N(C.sub.1 -C.sub.4 alkyl).sub.2. 
U.S. Pat. No. 4,518,776 discloses a process for the preparation of 
herbicidal sulfonylureas of the formula 
##STR4## 
wherein A is --C.dbd.N--; and 
R.sub.1 is NH.sub.2, NH(C.sub.1 -C.sub.4)alkyl or N(C.sub.1 -C.sub.4 
alkyl).sub.2. 
SUMMARY OF THE INVENTION 
This invention relates to novel agriculturally suitable herbicidal 
compounds of the Formula 
##STR5## 
wherein W is O or S; 
R is H or CH.sub.3 ; 
R.sub.1 is H, F, Cl, Br, I, CN, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 
haloalkyl, OCH.sub.3, OCH.sub.2 CH.sub.3, OCH.sub.2 CF.sub.3, OCF.sub.2 H, 
SCH.sub.3, SCF.sub.2 H, C.sub.1 -C.sub.3 alkylsulfonyl or SO.sub.2 
CF.sub.2 H; 
R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.2 haloalkyl, CN, OH, 
C.sub.1 -C.sub.2 alkoxy, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, C.sub.1 
-C.sub.2 alkyl substituted by CN, C.sub.1 -C.sub.2 alkoxy or C.sub.1 
-C.sub.2 alkylthio, C.sub.3 -C.sub.4 cycloalkyl, C.sub.3 -C.sub.4 alkenyl, 
C.sub.3 -C.sub.4 alkynyl or C(O)R.sub.5 ; 
R.sub.3 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.2 haloalkyl; or 
R.sub.2 and R.sub.3 may be taken together as --(CH.sub.2).sub.n -- or 
##STR6## 
R.sub.4 is H, F, Cl or CH.sub.3 ; R.sub.5 is H, C.sub.1 -C.sub.3 alkyl, 
C.sub.1 -C.sub.2 alkoxy, NH.sub.2, NHCH.sub.3 or N(CH.sub.3).sub.2 ; 
R.sub.6 is H, C.sub.1 -C.sub.2 alkyl or phenyl; 
R.sub.7 is H or CH.sub.3 ; 
n is 2, 3, 4 or 5; 
p is 0 or 1; 
##STR7## 
X is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 
haloalkoxy, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkylthio, 
C.sub.1 -C.sub.4 alkylthio, halogen, C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 
-C.sub.5 alkoxyalkoxy, amino, C.sub.1 -C.sub.3 alkylamino or di(C.sub.1 
-C.sub.3 alkyl)amino; 
Y is H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 
haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylthio, 
C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 -C.sub.5 alkoxyalkoxy, amino, 
C.sub.1 -C.sub.3 alkylamino, di(C.sub.1 -C.sub.3 alkyl)amino, C.sub.3 
-C.sub.4 alkenyloxy, C.sub.3 -C.sub.4 alkynyloxy, C.sub.2 -C.sub.5 
alkylthioalkyl, C.sub.2 -C.sub.5 alkylsulfinylalkyl, C.sub.2 -C.sub.5 
alkylsulfonylalkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkynyl, 
C.sub.3 -C.sub.5 cycloalkyl, azido, cyano, 
##STR8## 
or N(OCH.sub.3)CH.sub.3 ; m is 2 or 3; 
Q.sub.1 and Q.sub.2 are independently O or S; 
R.sub.a is H or C.sub.1 -C.sub.3 alkyl; 
R.sub.b and R.sub.c are independently C.sub.1 -C.sub.3 alkyl; 
Z is CH, N, CCH.sub.3, CC.sub.2 H.sub.5, CCl or CBr; 
Y.sub.1 is O or CH.sub.2 ; 
X.sub.1 is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 or OCF.sub.2 H; 
X.sub.2 is CH.sub.3, C.sub.2 H.sub.5 or CH.sub.2 CF.sub.3 ; 
Y.sub.2 is OCH.sub.3, OC.sub.2 H.sub.5, SCH.sub.3, SC.sub.2 H.sub.5, 
CH.sub.3 or CH.sub.2 CH.sub.3 ; 
X.sub.3 is CH.sub.3 or OCH.sub.3 ; 
Y.sub.3 is H or CH.sub.3 ; 
X.sub.4 is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3 or Cl; 
and 
Y.sub.4 is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 or Cl; 
and their agriculturally suitable salts; provided that 
(1) when X is halogen, then Z is CH and Y is OCH.sub.3, OC.sub.2 H.sub.5, 
NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, OCF.sub.2 H, OCF.sub.2 Br or 
N(OCH.sub.3)CH.sub.3 ; 
(2) when X and/or Y is C.sub.1 haloalkoxy, then Z is CH; 
(3) when W is S, then R is H, A is A-1, Z is CH or N, and Y is CH.sub.3, 
OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3, C.sub.2 H.sub.5, 
CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, OCH.sub.2 C.tbd.CH, 
OCH.sub.2 CH.sub.2 OCH.sub.3, CH(OCH.sub.3).sub.2 or 
##STR9## 
(4) when the total number of carbon atoms of X and Y is greater than four, 
then the combined number of carbons of R.sub.2 and R.sub.3 is less than or 
equal to six; and 
(5) X.sub.4 and Y.sub.4 L are not simultaneously Cl. 
In the above definitions, the term "alkyl," used either alone or in 
compound words such as "alkylthio" or "haloalkyl," denotes straight chain 
or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the 
different butyl isomers. 
Alkoxy denotes methoxy, ethoxy, n-propoxy, isopropoxy and the different 
butoxy isomers. 
Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 
1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers. 
Alkynyl denotes straight chain or branched alkynes, e.g., ethynyl, 
1-propynyl, 2-propynyl and the different butynyl isomers. 
The term "halogen," either alone or in compound words such as "haloalkyl," 
denotes fluorine, chlorine, bromine or iodine. Further, when used in 
compound words such as "haloalkyl" said alkyl may be monohalogenated or 
fully substituted with halogen atoms, which may be the same or different. 
Examples of haloalkyl include CH.sub.2 CH.sub.2 F, CF.sub.2 CF.sub.3 and 
CH.sub.2 CHFCl. 
The total number of carbon atoms in a substituent group is indicated byy 
the C.sub.i -C.sub.j prefix where i and j are numbers from 1 to 4. For 
example, C.sub.3 -C.sub.4 alkenyl would designate propenyl through 
butenyl. 
Compounds of the invention preferred for reasons of increased ease of 
synthesis and/or greater herbicidal efficacy are: 
1. Compounds of Formula I wherein R.sub.4 is H; 
2. Compounds of Preferred 1 wherein R.sub.2 is C.sub.1 -C.sub.2 haloalkyl, 
OH, C.sub.1 -C.sub.2 alkoxy, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, 
C.sub.1 -C.sub.2 alkyl substituted by C.sub.1 -C.sub.2 alkylthio, C.sub.3 
-C.sub.4 cycloalkyl or C(O)R.sub.5 ; 
R.sub.3 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.2 haloalkyl; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n -- or 
##STR10## 
and n is 2 or 3. 
3. Compounds of Preferred 2 wherein 
W is O; 
X is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, F, Cl, Br, I, 
OCF.sub.2 H, CH.sub.2 F, CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 
CHF.sub.2, OCH.sub.2 CF.sub.3, CH.sub.2 Cl or CH.sub.2 Br; 
Y is H, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, CH.sub.2 
OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, NHCH.sub.3, N(OCH.sub.3)CH.sub.3, 
N(CH.sub.3).sub.2, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, 
OCH.sub.2 C.tbd.CH, OCH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 SCH.sub.3, 
C(O)R.sub.a, 
##STR11## 
OCF.sub.2 H, SCF.sub.2 H, OCF.sub.2 Br, cyclopropyl, C.tbd.CH or 
C.tbd.CCH.sub.3 ; and 
Z is CH or N. 
4. Compounds of Preferred 3 wherein 
R.sub.2 is NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, CF.sub.3, CF.sub.2 H, 
OH, OCH.sub.3, CH.sub.2 SCH.sub.3, cyclopropyl or C(O)R.sub.5 ; 
R.sub.3 is H, CH.sub.3 or CH.sub.2 CH.sub.3 ; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n -- or 
##STR12## 
R.sub.5 is H, CH.sub.3, OCH.sub.3, NH.sub.2, NHCH.sub.3 or 
N(CH.sub.3).sub.2 ; and 
R.sub.6 is H or C.sub.1 -C.sub.2 alkyl. 
5. Compounds of Preferred 4 wherein 
A is A-1; 
X is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, OCF.sub.2 H or OCH.sub.2 
CF.sub.3 ; and 
Y is CH.sub.3, OCH.sub.3, CH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, NHCH.sub.3 
or CH(OCH.sub.3).sub.2. 
6. Compounds of Preferred 5 wherein 
R is H; 
R.sub.1 is H; and 
p is O. 
7. Compounds of Preferred 1 wherein 
R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, CN, C.sub.1 -C.sub.2 alkyl 
substituted by CN or C.sub.1 -C.sub.2 alkoxy, C.sub.3 -C.sub.4 alkenyl or 
C.sub.3 -C.sub.4 alkynyl; 
R.sub.3 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.2 haloalkyl; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n -- or 
--CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --; and 
n is 4 or 5. 
8. Compounds of Preferred 7 wherein 
W is O; 
X is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, F, Cl, Br, I, 
OCF.sub.2 H, CH.sub.2 F, CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 
CHF.sub.2, OCH.sub.2 CF.sub.3, CH.sub.2 Cl or CH.sub.2 Br; 
Y is H, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, CH.sub.2 
OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, NHCH.sub.3, N(OCH.sub.3)CH.sub.3, 
N(CH.sub.3).sub.2, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, 
OCH.sub.2 C.tbd.CH, OCH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 SCH.sub.3, 
C(O)R.sub.a, 
##STR13## 
OCF.sub.2 H, SCF.sub.2 H, OCF.sub.2 Br, cyclopropyl, C.tbd.CH or 
C.tbd.CCH.sub.3 ; and 
Z is CH or N. 
9. Compounds of Preferred 8 wherein 
R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, CN, CH.sub.2 CN, CH.sub.2 OCH.sub.3, 
allyl or propargyl; and 
R.sub.3 is H, CH.sub.3 or CH.sub.2 CH.sub.3. 
10. Compounds of Preferred 9 wherein 
A is A-1; 
X is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, OCF.sub.2 H or OCH.sub.2 
CF.sub.3 ; and 
Y is CH.sub.3, OCH.sub.3, CH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, NHCH.sub.3 
or CH(OCH.sub.3).sub.2. 
11. Compounds of Preferred 10 wherein 
R is H; 
R.sub.1 is H; and 
p is O. 
12. Compounds of Formula I wherein 
R.sub.4 is F, Cl or CH.sub.3. 
13. Compounds of Preferred 12 wherein 
R.sub.2 is C.sub.1 -C.sub.2 haloalkyl, OH, C.sub.1 -C.sub.2 alkoxy, 
NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, C.sub.1 -C.sub.2 alkyl 
substituted by C.sub.1 -C.sub.2 alkylthio, C.sub.3 -C.sub.4 cycloalkyl or 
C(O)R.sub.5 ; 
R.sub.3 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.2 haloalkyl; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n --, or 
##STR14## 
and n is 2 or 3. 
14. Compounds of Preferred 13 wherein 
W is O; 
X is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, F, Cl, Br, I, 
OCF.sub.2 H, CH.sub.2 F, CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 
CHF.sub.2, OCH.sub.2 CF.sub.3, CH.sub.2 Cl or CH.sub.2 Br; 
Y is H, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, CH.sub.2 
OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, NHCH.sub.3, N(OCH.sub.3)CH.sub.3, 
N(CH.sub.3).sub.2, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, 
OCH.sub.2 C.tbd.CH, OCH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 SCH.sub.3, 
C(O)R.sub.a, 
##STR15## 
OCF.sub.2 H, SCF.sub.2 H, OCF.sub.2 Br, cyclopropyl, C.tbd.CH or 
C.tbd.CCH.sub.3 ; and 
Z is CH or N. 
15. Compounds of Preferred 14 wherein 
R.sub.2 is NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, CF.sub.3, CF.sub.2 H, 
OH, OCH.sub.3, CH.sub.2 SCH.sub.3, cyclopropyl or C(O)R.sub.5 ; 
R.sub.3 is H, CH.sub.3 or CH.sub.2 CH.sub.3 ; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n --, or 
##STR16## 
R.sub.5 is H, CH.sub.3, OCH.sub.3, NH.sub.2, NHCH.sub.3 or 
N(CH.sub.3).sub.2 ; and 
R.sub.6 is H or C.sub.1 -C.sub.2 alkyl. 
16. Compounds of Preferred 15 wherein 
A is A-1; 
X is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, OCF.sub.2 H or OCH.sub.2 
CF.sub.3 ; and 
Y is CH.sub.3, OCH.sub.3, CH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, MHCH.sub.3 
or CH(OCH.sub.3).sub.2. 
17. Compounds of Preferred 16 wherein 
R is H; 
R.sub.1 is H; and 
p is O. 
18. Compounds of Preferred 12 wherein 
R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, CN, C.sub.1 -C.sub.2 alkyl 
substituted by CN or C.sub.1 -C.sub.2 alkoxy, C.sub.3 -C.sub.4 alkenyl or 
C.sub.3 -C.sub.4 alkynyl; 
R.sub.3 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.2 haloalkyl; or 
R.sub.2 and R.sub.3 are taken together as --(CH.sub.2).sub.n -- or 
--CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --; and 
n is 4 or 5. 
19. Compounds of Preferred 18 wherein 
W is O; 
X is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, F, Cl, Br, I, 
OCF.sub.2 H, CH.sub.2 F, CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 
CHF.sub.2, OCH.sub.2 CF.sub.3, CH.sub.2 Cl or CH.sub.2 Br; 
Y is H, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, CH.sub.2 
OCH.sub.3, CH.sub.2 OCH.sub.2 CH.sub.3, NHCH.sub.3, N(OCH.sub.3)CH.sub.3, 
N(CH.sub.3).sub.2, CF.sub.3, SCH.sub.3, OCH.sub.2 CH.dbd.CH.sub.2, 
OCH.sub.2 C.tbd.CH, OCH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 SCH.sub.3, 
C(O)R.sub.a, 
##STR17## 
OCF.sub.2 H, SCF.sub.2 H, OCF.sub.2 Br, cyclopropyl, C.tbd.CH or 
C.tbd.OCH.sub.3 ; and 
Z is CH or N. 
20. Compounds of Preferred 19 wherein 
R.sub.2 is H, C.sub.1 -C.sub.4 alkyl, CN, CH.sub.2 CN, CH.sub.2 OCH.sub.3, 
allyl or propargyl; and 
R.sub.3 is H, CH.sub.3 or CH.sub.2 CH.sub.3. 
21. Compounds of Preferred 20 wherein 
A is A-1; 
X is CH.sub.3, OCH.sub.3, OCH.sub.2 CH.sub.3, Cl, OCF.sub.2 H or OCH.sub.2 
CF.sub.3 ; and 
Y is CH.sub.3, OCH.sub.3, CH.sub.2 CH.sub.3, CH.sub.2 OCH.sub.3, NHCH.sub.3 
or CH(OCH.sub.3).sub.2. 
22. Compounds of Preferred 21 wherein 
R is H; 
R.sub.1 is H; and 
p is O. 
Compounds of the invention specifically preferred for reasons of greatest 
ease of synthesis and/or greatest herbicidal efficacy are 
N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-(dimethylamino)-2-pyrid 
inesulfonamide, m.p. 141.degree.-143.degree. C.; 
6-(dimethylamino)-N-[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]c 
arbonyl]-2-pyridinesulfonamide, m.p. 186.degree.-188.degree. C.; and 
N-[[[(4-ethoxy-6-(dimethylamino)-1,3,5-triazin-2-yl]amino]carbonyl]-6-(met 
hylamino)-2-pyridinesulfonamide, m.p. 116.degree.-117.degree. C. 
This invention also comprises intermediates of Formula II utilized in the 
preparation of the compounds of Formula I. 
##STR18## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and p are as previously 
defined; and 
X.sub.5 is Cl, NH.sub.2 or NHC(CH.sub.3).sub.3 ; 
provided that when 
R.sub.1 is H, R.sub.3 is H, R.sub.4 is H, p is O and X.sub.5 is NH.sub.2, 
then 
R.sub.2 is other than H. 
The compounds of this invention are highly active as preemergent and/or 
postemergent herbicides or plant growth regulants. Some of the compounds 
demonstrate selective safety toward cereal crops, maize (corn), cotton and 
oilseed rape. The invention comprises in addition to the novel compounds 
agriculturally suitable compositions containing said novel compounds and a 
method of using said compounds and/or compositions as preemergent and/or 
postemergent herbicides or plant growth regulants. 
DETAILED DESCRIPTION OF THE INVENTION 
Compounds of Formula I can be prepared by the methods described in 
Equations 1 and 2. 
Equation 1 
##STR19## 
The reaction shown in Equation 1 is carried out by contacting a phenyl 
carbamate or phenyl thiocarbamate of Formula (2) with an aminoheterocycle 
of Formula (3) in an inert organic solvent such as dioxane or 
tetrahydrofuran at temperatures of about 20.degree. C. to 100.degree. C. 
for a period of about one-half to twenty-four hours. The product can be 
isolated by evaporation of the reaction solvent and purified by 
triturating the residue with solvents such as 1-chlorobutane or ethyl 
ether and filtering, by recrystallizing from mixtures of solvents such as 
1,2-dichloroethane, 1-chlorobutane and heptane or by chromatography on 
silica gel. 
Equation 2 
##STR20## 
The reaction of Equation 2 can be carried out by contacting a sulfonamide 
of Formula (4) with a heterocycle phenyl carbamate of Formula (5) in the 
presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), by methods analogous 
to those described in South African Patent Application 830441. The phenyl 
carbamates of Formula (5) can be prepared by methods (or modifications 
thereof) described in South African Patent Application 825671 and South 
African Patent Application 825045. 
Phenylcarbamates and phenylthiocarbamates of Formula (2) (Equation 1) can 
be prepared from sulfonamides of Formula (4) (Equation 2) by methods 
described (or modifications thereof) in U.S. Pat. No. 4,443,243. The 
sulfonamides (4) can be prepared via the routes shown in Equations 3-7, or 
by modifications thereof. 
Equation 3 
##STR21## 
wherein: X is F or Cl, and 
L is a leaving group such as Cl, Br, I, alkyl sulfide, etc.; 
and with the provision that when R.sub.1 =H, then Step (3c) is omitted. 
Dihalopyridine (6) (The Chemistry of Heterocyclic Compounds, Vol. 14, 
Wiley-Interscience, New York (1964)) is contacted with benzyl mercaptan in 
the presence of potassium tert-butoxide in a solvent such as 
dimethylformamide to produce the sulfide (7). The product is isolated by 
partitioning the reaction mixture between water and ether (Equation 3a). 
The sulfide (7) is converted to tert-butyl sulfonamide (8) by treatment 
with hypochlorite solution followed by tert-butylamine using the methods 
described in South African Patent Application 848845 (Equation 3b). 
Metallation of compound (8) by treatment with two equivalents of a strong 
base such as n-butyllithium or lithium diisopropylamide (LDA) followed by 
treatment with an appropriate electrophile (R.sub.1 -L) produces compound 
(9). An appropriate choice of electrophile R.sub.1 -L would be evident to 
one skilled in the art (Equation 3c). 
Contacting tert-butylsulfonamide (9) with trifluoroacetic acid affords 
sulfonamide (10). The product may be isolated by evaporation of the 
volatiles followed by trituration of the residue with an organic solvent 
such as ether (Equation 3d). 
Treatment of (10) with at least two equivalents of ammonia or of a primary 
or secondary amine or with the anion of a primary or secondary amide or of 
a cyanamide produces sulfonamide (4) (p=0). The product may be isolated by 
evaporating the volatiles in vacuo and triturating the residue with water 
or by partitioning the mixture between water and an organic solvent 
(Equation 3e). 
Equation 4 
##STR22## 
wherein: X and X.sub.1 may be independently F, Cl or Br. 
The dihalopyridine (11)(The Chemistry of Heterocyclic Compounds, Vol. 14, 
Wiley-Interscience, New York (1964)) is contacted with benzyl alcohol in 
the presence of an acid acceptor such as potassium carbonate in an inert 
solvent such as dimethyl sulfoxide to produce the ether (12). The product 
is isolated by partitioning the reaction mixture between water and ether 
(Equation 4a). 
The compound (12) is converted to sulfide (13) as described previously for 
Equation 3a (Equation 4b). 
Treatment of (13) with concentrated hydrochloric acid produces the 
pyridinol (14). The product is isolated by partitioning the reaction 
mixture between water and an organic solvent (Equation 4c). 
The pyridinol (14) is converted to chloride (15) by refluxing with thionyl 
chloride in the presence of dimethylformamide (DMF). The product is 
isolated by evaporation of the volatiles in vacuo and partitioning the 
residue between water and an organic solvent (Equation 4d). 
The chloride (15) is converted to sulfonamide (9) (X.dbd.Cl) as described 
previously for Equation 3b (Equation 4e). 
Equation 5 
##STR23## 
wherein: X is F, Cl or Br. 
The hydroxypyridine (16) (The Chemistry of Heterocyclic Compounds, Vol. 14, 
Wiley-Interscience, New York (1964)) is converted to mercaptopyridine (17) 
by treatment with phosphorous pentasulfide or via the thiocarbamate 
according to the procedure of Newman, et al. in J. Org. Chem. 31 3980 
(1966) (Equation 5a). 
Mercaptopyridine (17) is converted to sulfonamide (9) as described 
previously for Equation 3b (Equation 5b). 
Equation 6 
##STR24## 
wherein: X is f, Cl or Br. 
Sulfonamide (9) may be converted to the N-oxide (18) by methods such as 
those described (or modifications thereof) in Evans, et al., Rec. Trav. 78 
408 (1959). Some of the oxidants of choice for this transformation are 
m-chloroperoxybezoic acid, peracetic acid, etc. (Equation 6a). 
Compound (18) may be converted to sulfonamide (19) as described previously 
for Equation 3d (Equation 6b). 
Sulfonamide (19) may be converted to sulfonamide (4) (p=1) as described 
previously for Equation 3e (Equation 6c). 
Equation 7 
##STR25## 
wherein: X is F or Cl, and 
L is as previously defined. 
In cases where the substituent R.sub.1 is sensitive to oxidation, this 
substituent may be introduced subsequent to the N-oxidation reaction. 
Thus, the sulfonamide (8) is converted to the N-oxide (20) by methods 
described for Equation 6a (Equation 7a). 
The N-oxide (20) is metallated and reacted with an electrophile (R.sub.1 
-L) to produce sulfonamide (18) as described previously for Equation 3c 
(Equation 7b). 
For further details pertaining to lithiations of pyridine ring systems see, 
Epsztajn et al., Tetrahedron Lett., 4739 (1980); snieckus et al., J. Am. 
Chem. Soc., 102, 1457 (1980); Kuraishi et al., Tet. Lett., 2049 (1983); 
Meyers et al., J. Org. Chem., 47, 2633 (1982); Taylor et al., J. Org. 
Chem., 48, 4156 (1983) and Breant et al., Synthesis, 822 (1983). 
For a general treatment of pyridines and pyridine N-oxides see, Katritzky, 
A. R., and Rees, C.W., "Comprehensive Heterocyclic Chemistry", Vol. 2, 
Pergamon Press, Oxford, New York, Part 2A, 1984. 
Phenyl carbamates and phenyl thiocarbamates (5) of Equation 2 can be 
prepared from heterocyclic amines (3) by methods, or modifications thereof 
known to those skilled in the art, described in South African Patent 
Application 82/5671 and South African Patent Application 82/5045. 
The synthesis of heterocyclic amines such as those represented by Formula 3 
(Equation 1) has been reviewed in "The Chemistry of Heterocyclic 
Compounds," a series published by Interscience Publ., New York and London. 
Aminopyrimidines are described by D. J. Brown in "The Pyrimidines," Vol. 
XVI of the series mentioned above which is herein incorporated by 
reference. The 2-amino-1,3,5-triazines of Formula 3, where A is A-1 and Z 
is N, can be prepared according to the methods described by E. M. Smolin 
and L. Rapaport in "s-Triazines and Derivatives," Vol. XIII. 
Pyrimidines of Formula 3, where A is A-1 and Y is an acetal or thioacetal 
substituent, can be prepared by methods taught in European Patent 
Application No. 84,224 (published July 27, 1983). 
Pyrimidines of Formula 3, where A is A-1 and Y is cyclopropyl or OCF.sub.2 
H can be synthesized according to the methods taught in U.S. Pat. No. 
4,515,626 and U.S. Pat. No. 4,540,782, respectively. 
Compounds of Formula 3, where A is A-2 or A-3, can be prepared by 
procedures disclosed in U.S. Pat. No. 4,339,267. 
Compounds of Formula 3, where A is A-4, can be prepared by methods taught 
in U.S. Pat. No. 4,487,626. 
Additional references dealing with the synthesis of bicyclic pyrimidines of 
Formula 3, where A is A-2, A-3, or A-4 are Braker, Sheehan, Spitzmiller 
and Lott, J. Am. Chem. Soc., 69, 3072 (1947); Mitler and Bhattachanya, 
Quart. J. Indian Chem. Soc., 4, 152 (1927); Shrage and Hitchings, J. Org. 
Chem., 16, 1153 (1951); Caldwell, Kornfeld and Donnell, J. Am. Chem., 
Soc., 63, 2188 (1941); and Fissekis, Myles and Brown, J. Org. Chem., 29, 
2670 (1964). 
Compounds of Formula 3, where a is A-5, can be prepared by methods taught 
in U.S. Pat. No. 4,421,550. 
Compounds of Formula 3, where A is A-6, can be prepared by methods taught 
in U.S. Pat. No. 4,496,392. 
Compounds of Formula 3, where A is A-7, can be prepared by methods taught 
in EP-A-125,864. 
Agriculturally suitable salts of compounds of Formula I are also useful 
herbicides and can be prepared by well-known methods including those 
described in U.S. Pat. No. 4,127,405. 
The following Example illustrates the synthesis of the compounds of this 
invention. Temperatures are reported in degrees Celsius. Abbreviations for 
nuclear magnetic resonance (NMR) are s=singlet, d=doublet, dd=doublet of 
doublets, br=broad, and peak positions are reported as parts per million 
downfield from internal tetramethylsilane. The NMR spectra were measured 
at 200 MHz.