WO1989001937A1

WO1989001937A1 - Herbicidal pyridinesulfonylureas

Info

Publication number: WO1989001937A1
Application number: PCT/US1988/001754
Authority: WO
Inventors: Paul Hsiao-Tseng Liang
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1987-08-28
Filing date: 1988-06-01
Publication date: 1989-03-09
Also published as: PL158414B1; JPH03500165A; PL272848A1; BG60563B1

Abstract

This invention relates to herbicidal pyridinesulfonylureas which are highly active as preemergence and postemergence herbicides.

Description

Title

HERBICIDAL PYRIDINESULFONYLUREAS Background of the Invention Pyridinesulfonylureas of the instant application show high activity as preemergence and postemergence herbicides. In particular, safety to corn is demonstrated by many of the herbicides.

EP-A-13, 480 discloses herbicidal sulfonamides of the formula

wherein

R₁ is H, Cl, Br, F, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, NO₂ or CO₂R₅.

U.S. 4,435,206, issued March 6, 1984 and U.S. 4,522,645, issued June 11, 1985, disclose 2- pyridinesulfonylureas substituted in the 3-position by R₁, wherein R₁ is H, Cl, Br, F, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, NO₂, CF₃, CO₂R₅ or SO₂NR₆R₇.

U.S. 4,339,267 discloses herbicidal sulfonamides of the formula

wherein

R ₄ is H, Cl, Br, F, C₁-C₄ alkyl, C₁-C₄ alkoxy,

NO₂, CO₂R₆ or SR₁₃. EP-A-30,433 discloses herbicidal sulfonamides of the formula

wherein

X is H;

R₁₄ is H or CH₃; and

R₃ is H, F, Cl, Br, CH₃, OCH₃, NO₂, CO₂E₁₁ or S(O)_nR_12.

U.S. 4,456,469 discloses herbicidal sulfonamides of the formula

wherein

R is C₁-C₆ alkyl, C₃-C₆ alkenyl, C₂-C₄ alkoxyalkyl, C₅-C₆ cycloalkyl, R'OCH₂CH₂OCH₂,

R'OCH₂CH₂OCH₂CH₂, (CH₂)_n CF₃,

CF₃CH₂, HGLCCF₂ or HCF₂; and Z is H, F, Cl, Br, CH₃, OCH₃ or SCH₃.

U.S. 4,487,626 discloses herbicidal sulfonamides of the formula

wherein

and

R₂ is H, F, Cl, Br, C₁-C₄ alkyl, C₁-C₄ alkoxy, NO₂, CO₂R₁₅, S(O)_mR₁₆, SO₂NR₁₈R₁₉ or SO₂N(OCH₃)CH₃.

U.S. 4,421,550 discloses herbicidal sulfonamides of the formula

wherein

Z IS

R₁₆ is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, F, Cl, Br, CF₃, CO₂R₂₀, SO₂NR₁₀R₁₁, SO₂N(OCH₃)CH₃ or S(O)_nR₁₃.

U.S. 4,496,392 discloses herbicidal sulfonamides of the formula

wherein

R ₃ i s Cl , SO₂CH₃ or SO₂N ( CH₃ ) ₂. EP-A-84,224 discloses herbicidal sulfonamides of the formula

wherein

A is and

R₁₆ is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, F, Cl, Br, CF₃, CO₂R₉, SO₂NR₁₀R₁₁, SO₂N(OCH₃)CH₃ or S(O)_nH₁₃.

EP-A-125,846 discloses herbicidal sulfonamides of the formula

wherein

and

R₃ is Cl, SO₂CH₃, SO₂N(CH₃)₂, OCH₃, NO₂ or N(CH₃)₂.

EP-A-155,767 discloses herbicidal sulfonamides of the formula

wherein

J is and

R₅ is H, CH₃, Cl, Br, CO₂R₁₅, C(O)NR₁₆R₁₇, SO₂NR₁₆R₁₇, SO₂N(OCH₃)CH₃, SO₂R₁₈ or NO₂ .

EP-A-161,905 discloses herbicidal sulfonamides of the formula

wherein

R₄ is CH₃, CH₂CH₃ OCH₃, OCH₂CH₃, F, Cl, Br,

SO₂NR₁₆R₁₇, SO₂N(OCH₃)CH₃, S(O)_nR₁₉, C₃-C₄ alkenyloxy or C₃-C₄ alkynyloxy.

EP-A-164,269 discloses herbicidal sulfonamides of the formula

wherein

R₄ is CH₃, CH₂CH₃, OCH₃, OCH₂CH₃, F, Cl, Br, SO₂NR₁₁R₁₂, SO₂N(OCH₃)CH₃ or S(O)_nR₁₃ . EP-A-171,286 discloses herbicidal sulfonamides of the formula

wherein

R₄ is CH₃, CH₂CH₃, OCH₃, OCH₂CH₃, F, Cl, Br,

SO₂NR₁₈R₁₉, SO₂N(OCH₃)CH₃, S(O)_nR₂₁, C₃-C₄ alkenyloxy, CH₂OCH₃ or CH₂OCH₂CH₃.

South African Patent Application 83/4305, published December 14, 1983, discloses herbicidal sulfonamides of the formula

wherein

R₂ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, halogen, NO₂, C₁-C₃ alkoxy, C(W)R₈, SO₂NR₆R₇, S(O)_n- C₁-C₃ alkyl or C(O)R₉;

R₃ is H, halogen, C₁-C₃ alkyl, OCH₃, NO₂ or CF₃;

R₅ is H, NO₂, F, Cl, Br, CH₃, CF₃, S(O)_nC₁-C₃ alkyl, C(O)C₁-C₄ alkoxy or C₁-C₃ alkoxy; Y is O or S. South African Patent Application 83/6639, published March 8, 1984, discloses herbicidal sulfonamides of the formula

wherein

A is a C₃-C₆ alkynyl radical, a C₁-C₆ alkyl radical which is substituted by halogen, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkoxy, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl or C₁-C₄ haloalkylsulfonyl, or is a C₂-C₄ alkenyl radical which is unsubstituted or substituted as for C₁-C₆ alkyl, or is a phenyl radical which is unsubstituted or substituted by halogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, an -X-C₁-C₄ alkyl, C₁-C₄ alkoxycarbonyl, amino, mono- or di(C₁-C₄ alkyl)amino, carbamoyl, mono- or di-(C₁-C₄ alkyl)carbamoyl„ sulfamoyl, mono- or di-(C₁-C₄ alkyl)sulfamoyl radical;

R₁ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, C₂-C₅ alkoxyalkoxy, C₁-C₅ alkylthio, C₁-C₅ alkylsulfinyl or C₁-C₅ alkylsulfonyl; and

X is O, S, SO or SO₂. U.S. 4,518,776 discloses a process for the preparation of herbicidal sulfonamides of the formula

wherein

R₁, in part, is S(O)_nC₁-C₄ alkyl, SO₂di-C₁-C₄ alkylamino or CO₂-C₁-C₂ alkyl; and

R₂ is H, halogen, CF₃, NO₂, C₁-C₄ alkyl or C₁-C₄ alkoxy.

This patent generically discloses some, but does not claim any, compounds of the instant invention.

EP-A-101,670, published February 29, 1984, discloses a process for the preparation of herbicidal sulf onamide s of the formula

wherein

R₁ is Q-C₁-C₄ alkyl, SO₂-di-C₁-C₄ alkylamino or CO₂-C₁-C₄ alkyl;

Q is S or S(O)_n; and

R₂ is H, halogen, CF₃, NO₂, C₁-C₄ alkyl or C₁-C₄ alkoxy.

This application generically discloses some of the compounds of the instant invention.

U.S. 4,521,597 discloses a process for the preparation of herbicidal sulfonamides of the formula

wherein

R₃ is H, F, Cl, Br, NO₂, OCH₃ or CF₃;

R₅ is S(O)_mC₁-C₅ alkyl, SO₂NR₈R₉ or COR₇; and

R₆, is H, F, CH₃ or OCH₃.

EP-A-184,385, published June 11, 1986, discloses the following compound for selective weed control in tomatoes and turf.

U.S.S.N. 874,307 discloses herbicidal o-alkylcarbonyl-pyridinesulfonylureas.

U.S.S.N. 943,137 discloses herbicidal o-substituted-pyridinesulfonylureas. SUMMARY OF THE INVENTION This application pertains to novel compounds of Formula I, agriculturally suitable compositions containing them and their method-of-use as preemergent and/or postemergent herbicides or plant growth regulants.

R is H or CH₃;

W is O or S;

R₁ is R_f or R_g; R_f is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, halogen, NO₂, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN;

R_g is C₁-C₃ haloalkyl, C₂-C₃ alkyl, cyclopropyl, C₁-C₃ alkyl substituted by C₁-C₃ alkoxy, OH, C₁-C₂ alkylthio or CN, CN, W₂R₁₁, amino, C₁-C₃ alkylamino or C₁-C₃ dialkylamino;

R₂ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₅ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e,

SO₂NR'₇R₈, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉, CO₂R'₉, CH₂F,

CF₂H, CH₂Cl, CCl₂H or C₂-C₄ haloalkyl; R₃ is C₁-C₄ alkylsulfinyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₄ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R8, SO₂NR'₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN,

CO₂R₉, CO₂R'₉ or C₁-C₄ haloalkyl;

R₄ i s C₁-C₄ alkylsulfinyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulf inyl, C₃-C₄ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₅ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl,

C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl,

C₃-C₅ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e,

SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₆ is C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₃-C₄ alkenylthio, C₃-C₄ alkenylsulfinyl, C₃-C₄ alkenylsulfonyl, C₃-C₄ alkynylthio, C₃-C₄ alkynylsnlfinyl, C₃-C₄ alkynylsulfonyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₅ cycloalkylsulfonyl, SO₂NR_dR_e, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R ₇ is H, C₂-C₃, cyanoalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl; R'₇ is C₁-C₄ alkyl; R₈ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl or cyclopropyl; or

R₇ and R₈ may be taken together as -(CH₂)₃-,

-(CH₂)₄-, -(CH₂)₅- or -CH₂CH₂OCH₂CH₂-;

R₉ is CH₂CH₂R₁₀, CH₂CF₃, C₃-C₄ haloalkyl,

C₃-C₄ alkynyl, C₂-C₄ alkylthioalkyl, C₃-C₅ cycloalkyl or C₄-C₇ cycloalkylalkyl;

R'₉ is C₁-C₄ alkyl, C₃-C₄ alkenyl, CH₂CH₂Cl,

CH₂CH₂Br , CH₂CH₂OCH₃ or CH₂CH₂OC₂H₅ ;

R₁₀ is OH, F, CN, OSO₂(C₁-C₃ alkyl) or OSO₂(C₁-C₃ haloalkyl); R₁₁ is C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl; W₁ is O or S; W₂ is O or S;

X is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ haloalkoxy, C₁-C₄ haloalkyl, C₂-C₄ haloalkylthio, C₁-C₄ alkylthio, halogen, C₁-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino or di(C₁-C₃ alkyl)amino;

Y is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ haloalkoxy, C₂-C₄ haloalkylthio, C₁-C₄ alkylthio, C₂-C₅ alkoxyalkyl, C₂-C₆ alkoxyalkoxy, amino, C₁-C₃ alkylamino, di(C₁-C₃ alkyl)amino, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₅ alkylthioalkyl, C₂-C₅ alkylsulfinylalkyl, C₂-C₅ alkylsulfonylalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkynyl, C₃-C₅ cycloalkyl , azido ,

N(OCH₃)CH₃; m is 2 or 3;

Q₁ and Q₂ are independently O or S; R_a is H or C₁-C₃ alkyl; R_b and R_c are independently C₁-C₃ alkyl;

R_d is H or C₁-C₂ alkyl;

R_e is C₁-C₂ alkoxy;

Z is CH, N, CCH₃, CC₂H₅, Cl or CBr;

Y₁ is O or CH₂;

X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H;

X₂ is CH₃, C₂H₅ or CH₂CF₃;

Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃, or CH₂CH₃;

X₃ is CH₃ or OCH₃;

Y₃ is H or CH₃; X₄ is CH₃, OCH₃, OC₂H₅, CH₂OCH₃ or Cl;

Y₄ is CH₃, OCH₃, OC₂H₅ or Cl; and their agriculturally suitable salts; provided that

1) when X is halogen, then Z is CH and Y is OCH₃, OC₂H₅, NH₂, NHCH₃ , N(CH₃)₂ or N(OCH₃)CH₃;

2) when W is S, then R is H, A is A-1, Z is CH or

N, and Y is CH₃, OCH₃, OC₂H₅, CH₂OCH₃, C₂H₅, CF₃, SCH₃, OCH₂CH-CH₂ , OCH₂CΞCH, OCH₂CH₂OCH₃,

CH(OCH₃)₂, or C

3) when the total number of carbon atoms of X and

Y is greater than four, then the combined number of carbons of R₁, R₂, R₃, R₄, R₅ or R₆ is less than or equal to six;

4) when J is J-1 and R₂ is C₁-C₄ alkylsulfonyl, SO₂NR_dR_e, SO₂NR'₇R₈ or CO₂R'₉, or when

J is J-2 and R₃ is CF₃, SO₂NR_dR_e, SO₂NR'₇R₈ or CO₂R'₉, then Y is other than C₂-C₅ alkylthioalkyl, C₂-C₅ alkylsulf inylalkyl,

C₂-C₅ alkylsul fonyla l kyl ,

2

5) when J is J-2 or J-3 and R₃ or R₄ is C₁-C₄ alkylsulfinyl, then X and Y are other than NH₂ or NHCH₃;

6) when J is J-2 and R₃ is C₁-C₄ alkylsulfinyl or

SO₂NR_dR_e, or R₇ is H, then X and Y are other than C₂-C₄ haloalkoxy;

7) when J is J-5, then R₇ is other than H and R₆ is other than SO₂NR_dR_e;

8) when J is J-2 and R₃, is SO₂NH₂ or SO₂NR_dR_e, or R₇ is H, then X is other than iodine;

9) when J is J-2 and R₇ is H or R₃ is SO₂NR_dR_e, then Y is other than C₁-C₄ alkynyl;

10) X₄ and Y₄ are not simultaneously Cl;

11) when J is J-1, J-2, J-3, J-4 and A is A-5, then R_f is other than H;

12) when J is J-1 or J-2, then A is other than A-6;

13) when J is J-1 and A is A-7, then R₂ is other than C₁-C₄ alkylsulfonyl;

14) when R₂ or R₃ is CO₂R'₉ or SO₂NR'₇R₈, then R₁ is R_g and when R₂ or R₃ is other than

CO₂R'₉ or SO₂NR'₇R₈, then R₁ is R_f; and

15) when J is J-2 and R₁ is adjacent to the sulfonylurea bridge, then R_g is C₁-C₃ haloalkyl, C₂-C₃ alkyl, cyclopropyl, CN, W₂R₁₁, amino, C₁-C₃ alkylamino or C₁-C₃ dialkylamino.

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-propyloxy or isopropyloxy.

Alkenyl denotes straight chain or branched alkenes, e.g. 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.

Alkylsulfonyl denotes methylsulfonyl, ethylsulfonyl and the different propylsulfonyl and butylsulfonyl isomers.

Cycloalkyl denotes cyclopropyl, cyclobutyl and cyclopentyl.

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 partially halogenated or fnlly substituted with halogen atoms which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFC1. Similarly, this definition applies to haloalkoxy and haloalkylthio. The total number of carbon atoms in a substituent group is indicated by the C_i-C_j prefix where i and j are numbers from 1 to 5. For example, C₁-C₃ alkylsulfonyl would designate methylsulfonyl through propylsulfonyl, C₂ alkoxyalkoxy would designate OCH₂OCH₃, C₂ cyanoalkyl would designate CH₂CN and C₃ cyanoalkyl would designate CH₂CH₂CN and CH(CN)CH₃.

Preferred Compounds Preferred for reasons of increased ease of synthesis and/or greater herbicidal efficacy are: 1. Compounds of Formula I where

X is C₁-C₂ alkyl, C₁-C₂ alkoxy, Cl, F, Br, I,

CH₂F, CF₃, OCH₂CH₂F, OCH₂CHF₂, OCH₂CF₃,

CH₂Cl or CH₂Br; and

Y is H, C₁-C₂ alkyl, C₁-C₂ alkoxy, CH₂OCH₃,

CH₂OCH₂CH₃, NHCH₃, N(OCH₃)CH₃, N(CH₃)₂, CF₃,

SCH₃, OCH₂CH=CH₂, OCH₂CΞCH, OCH₂CH₂OCH₃,

CH₂SCH₃, cyclopropyl, CΞCH or CΞCCH₃;

R_a is H or CH₃; and

Z is CH or N.

2. Compounds of Preferreid 1 where

W is O; R_f is H, CH₃, C₁ haloalkyl, halogen or OCH₃;

R_g is C₁-C₂ haloalkyl, ethyl, W₂R₁₁, CH₂OCH₃,

CH₂SCH₃, CH₂CN, C₁-C₂ alkylamino or N(CH₃)₂;

R₂ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl,

SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, SO₂NR'₇R₈,

OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂,

CN, CO₂R₉, CO₂R'₉, CHF₂, CF₂H, CH₂Cl,

CCl₂H or C₂-C₄ haloalkyl;

R₃ is C₁-C₄ alkylsulfinyl, SO₂NH₂, SO₂NR_dR_e,

SO₂R₇R₈, SO₂NR'₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉, CO₂R'₉ or C₁-C₄ haloalkyl;

R₄ is C₁-C₄ alkylsulfinyl, SO₂NH₂, SO₂N(OCH₃)CH₃,

SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl;

R₅ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl,

SO₂NH₂, SO₂N(OCH₃)CH₃, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₆ is C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₃-C₄ alkenylthio, C₃-C₄ alkenylsulfinyl, C₃-C₄ alkenylsulfonyl, C₃-C₄ alkynylthio, C₃-C₄ alkynylsulfinyl, C₃-C₄ alkynylsulfonyl,

SO₂N(OCH₃)CH₃, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl;

R₇ is H, C₂-C₃ cyanoalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl;

R₈ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl or cyclopropyl; and R₁₁ is C₁-C₃ alkyl, C₁-C₂ haloalkyl, allyl or propargyl. 3. Compounds of Preferred 2 where J is J-1. 4. Compounds of Preferred 2 where J is J-2.

5. Compounds of Preferred 2 where J is J-3.

6. Compounds of Preferred 2 where J is J-4.

7. Compounds of Preferred 2 where J is J-5.

8. Compounds of Preferred 3 where

R₇ is H, C₂-C₃ cyan oa l k yl , allyl or propargyl;

R'₇is C₁-C₃ alkyl;

R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl; R₉ is CH₂CH₂R₁₀, CH₂CH₂SCH₃, propargyl or cyclopropylmethyl;

R'₉ is C₁-C₃ alkyl, allyl, CH₂CH₂OCH₃ or

CH₂CH₂Cl; and

R₁₀ is OH, CN or OSO₂CH₃. 9. Compounds of Preferred 8 where A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃, NHCH₃ or

CH(OCH₃)₂. 10. Compounds of Preferred 9 where Z is CH.

11. Compounds of Preferred 9 where Z is N.

12. Compounds of Preferred 4 where

R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl; and R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl.

13. Compounds of Prefer1red 12 where

A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃ , NHCH₃ or

CH(OCH₃)₂.

14. Compounds of Preferred 13 where Z is CH.

15. Compounds of Preferred 13 where Z is N.

16. Compounds of Preferred 5 where R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl; and R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl.

17. Compounds of Preferred 16 where A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃ , NHCH₃ or CH(OCH₃)₂.

18. Compounds of Preferred 17 where Z is CH. 19, Compounds of Preferred 17 where Z is N.

20. Compounds of Preferred 6 where

R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl; a nd

R₈ i s C₁-C₄ a lkyl , a l lyl , pr opa rgyl or cyc lopr opyl . 21. Compounds of Preferred 20 where A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and

Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃, NHCH₃ or

CH(OCH₃)₂.

22. Compounds of Preferred 21 where Z is CH.

23. Compounds of Preferred 21 where Z is N.

24. Compounds of Preferred 7 where

R₆ is C₁-C₂ alkylthio, C₁-C₂ alkylsulfinyl, C₁-C₂ haloalkylthio, C₁-C₂ haloalkylsulfinyl, C₁-C₂ haloalkylsulfonyl, SO₂N(OCH₃)CH₃ or SO₂NR₇R₈; R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl;

R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl.

25. Compounds of Preferred 24 where A is A-1; X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and

Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃, NHCH₃ or CH(OCH₃)₂.

26. Compounds of Preferred 25 where Z is CH.

27. Compounds of Preferred 25 where Z is N. 28. Compounds of Preferred 1 where

J is J-1;

A is A-1;

Z is CH;

W is O; R₂ is C₁-C₄ alkylsulfinyl or C₁-C₄ alkylsulfonyl; and R_f is H, C₁-C₂ alkyl, C₁ haloalkyl, C₁-C₂ alkoxy or C₁-C₂ thioalkyl. 29. Compounds of Preferred 28 where

R_f is H;

R₂ is C₁-C₄ a lkylsulfonyl; X is OCH₃; and Y is OCH₃.

Specifically Preferred for reasons of greatest ease of synthesis and/or greatest herbicidal efficacy are:

• N-[(4,6-dimethoxypyriraidin-2-yl)aminocarbonyl]- 3-(1-proρylsυlfonyl)-2-pyridinesulfonamide;

• N-[(4,6-diraethoxypyrimidin-2-yl)aminocarbonyl]- 3-(1-propylsulfinyl)-2-pyridinesulfonamide;

• N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- 3-(ethylsulfonyl)-2-pyridinesulfonamide;

• N2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- N3-ethyl-2,3-pyridinedisulfonamide; • N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- 3-(methylsulfonyloxy)-2-pyridinesulfonamide; and

• N2-[(4,6-dimethoxypyrimidin-2-yl)- aminocarbonyl]-N3-methyl-2 , 3- pyridinedisulfonamide.

This invention also pertains to novel compounds of the following formulas

wherein X_a is Cl, NH₂, HNC(CH₃)₃ and NHCOC₆H₅; which are useful as intermediates to herbicidal sulfonylureas.

Specifically preferred are:

3-ethylsulfonyl-2-pyridinesulfonamide and N3-methyl-2,3-pyridinedisulfonamide. DETAILED DESCRIPTION OF THE INVENTION Synthesis Compounds of Formula I can be synthesized either by one or more of the methods described in U.S. 4,456,469, or by the reaction of sulfonamides II with the phenyl ester of the appropriate carbamic acid III in the presence of an equimolar quantity of a tertiary amine base such as 1,8-diazabicyclo[5.4.0Jundec-7-ene (DBU) as shown in Equation 1. Equation 1 O

wherein

J, R, and A are as previously defined. The reaction shown in Equation 1 is best carried out at 25°C in a solvent such as dioxane or acetonitrile for 1-2 hours under an inert atmosphere as described in European Patent Application No. 70,804 (published January 26, 1983). The desired products of Formula I can be conveniently isolated by acidifying the reaction solution with aqueous hydrochloric acid. Alternatively, the aqueous layer can be extracted with a solvent such as methylene chloride or ethyl acetate. Drying and evaporation of the solvent affords the desired products. The phenyl carbamates can be synthesized by treatment of the corresponding heterocyclic amines of Formula A-NHR with diphenyl carbonate or phenyl chloroformate in the presence of a ba s e such a s sod ium hyd r ide , pyrid ine , or potass ium carbonate with a catalytic amount of 4-dimethylaminopyridine. The mixture is stirred at temperatures between 25° and 65°C in a suitable solvent such as tetrahydrofuran for 12-36 hours. The required sulfonamides of Formula II can be synthesized by either one of the methods shown below in Equations 2 and 3.

Equation 2 depicts the reaction of sulfonyl chlorides of Formula IV with ammonia to give sulfonamides of Formula II. Equation 2

JSO₂Cl JSO₂NH₂

IV II wherein J is as previously defined.

The animation of Equation 2 is conveniently effected by adding at least two molar equivalents of either anhydrous ammonia or concentrated ammonium hydroxide to a solution of the sulfonyl chloride IV in a suitable solvent such as diethyl ether, tetrahydrofuran or methylene chloride at temperatures between -30° and 25ºC. The desired sulfonamides of Formula II are isolated either by filtration, in which case the by-product ammonium chloride is removed by washing with water, or extraction into a suitable organic solvent euch as methylene chloride or ethyl acetate. Drying and evaporation of the solvent then affords the products II which are usually sυfficiently pure to be carried directly on to the next step.

Sulfonamides of Formula II can also be prepared as shown in Equation 3 by treatment of the corresponding N-t-butylsulfonamides VI with an appropriate acid such as trifluoroacetic (TFA), polyphosphoric (PPA), or p- tolυenesulfonic acid (p-TSA). Equation 3

JSO₂NH-t-Bu JSO₂NH₂

VI p II

wherein

J is as previously defined.

The reaction of Equation 3 is conveniently carried out by stirring a solution of the compound of Formula VI in excess trifluoroacetic acid. (approximately 0.3M) at about 25°C for 1-72 hours. The desired sulfonamides of Formula II are then isolated by removal of the volatiles in vacuo and crystallization from a suitable solvent such as diethyl ether, 1-chlorobutane, or ethyl acetate. Alternatively, the N-t-butylsulfonamides of Formula VI can be treated with a catalytic amount of p-toluenesulfonic acid monohydrate in a solvent such as toluene or xylenes at reflux temperature for 1-6 hours. The desired products are then isolated in a manner analogous to the one described above. For use of polyphosphoric acid in the deprotection of N-t-butylsulfonamides, see J. G. Lombardino, J. Org. Chem., 36, 1843 (1971); for use of trifluoroacetic acid, see J. D. Catt and W. L. Matier, J. Org. Chem., 38, 1974 (1973).

Sulfonamides of Formula VI can be prepared by the reaction of sulfonyl chlorides of Formula IV with excess t-butyl amine as shown in Equation 4. Equation 4

JSO₂Cl JSO₂NH-t-Bu

IV VI where in

J is as previ oυsly def ined .

Sulfonyl chlorides of Formula IV can be prepared according to the procedures described in U.S. 4,456,469. Alternatively, the procedures of South African Patent Application 84/8844 may be utilized which describe the conversion of mercapto or arylmethylthio compounds to sulfonyl chlorides via treatment with hypochlorite solution.

Sulfonyl chlorides of Formula IVa may also be prepared via metallation of 2-fluoropyridine derivatives with lithium diisopropyl amide (LDA) according to the procedure of T. Gungor, F. Marsais and G. Queguiner, J. Organomet. Chem., 1981, 215, 139-150, followed by treafment with sulfur dioxide and N-chlorosυccinimide (NCS) as shown in Equation 5. Equation 5

wherein

R₁ is as previously defined.

Sulfonyl chlorides of Formula IVb can be prepared from compounds of Formula VII as shown in Equation 6 and described in U.S. 4,420,325. Equation 6

wherein

J is as previously defined; and [X] is a suitable halogenating reagent which would be obvious to one skilled in the art.

The sulfides of Formula VIII can be prepared by the reaction of a halo pyridine compound of Formula IX with an appropriate mercaptan in the presence of a base as described in U.S. 4,456,469 and shown in Equation 7. Equation 7

J-X' J-SR'

IX

VIII wherein

X' is F, Cl, or Br; and

R' is C₁-C₄ alkyl or benzyl.

The sulfides of Formula Villa can be prepared by metallation of the pyridine compound of Formula X with two equivalents of a strong base such as n-butyllithium or lithium diisopropylamide (LDA) as described by P. Breant, F. Warsais, and G. Queguiner, Synthesis, 1983, 822-824, followed by treatment with the appropriate disulfide as shown in Equation 8. Equation 8

wherein

R' is C₁-C₄ alkyl, C₃-C₅ cycloalkyl or benzyl; and

R₁ is as previously defined.

In an analogous Banner, sulfides of Formula Vlllb can be prepared as shown in Equation 9. Equation 9

wherein

R' is C₁-C₄ alkyl, C₃-C₅ cycloalkyl, or benzyl; and

R₁ is as previously defined.

Su lf ides of Formula VI I I c can be prepared by the metallation of a 2-fluoropyridine derivative as described previously and again followed by treatment with an appropriate disulfide as shown in Equation 10. Equation 10

wherein

R' is C₁-C₄ alkyl, C₃-C₅ cycloalkyl, or benzyl; and

R₁ is as previously defined. The sulfones and sulfoxides of General Formula XI can be prepared from the corresponding sulfides of Formula VIIId by any one of the numerous oxidation reagents [O] known in the art such as hydrogen peroxide or peracids, as shown in Equation 11. Equation 11

wherein

R₁ is as previously defined;

R' is C₁-C₄ alkyl or C₃-C₅ cycloalkyl; and n is 1 or 2.

The chloropyridine of Formula IXa can be prepared by diazotization of 3-amino-2-chloropyridine followed by displacement with cuprous cyanide as shown in Equation 12. The diazonium group can also be replaced by other groups such as SO₂Cl and N₃ by those skilled in the art via methods known in the literature.

Equation 12

wherein is as previously defined

The sulfides of General Formula Vlllf can be prepared as shown in Equation 13. Alkylation of a 3-hydroxy-2-mercaptopyridine derivative with alkyl halides utilizing a variety of bases such as potassium carbonate or potassiura t-butoxide afforded the sulfides of Formula VlIle which were then treated with the appropriate sulfonyl chlorides in the presence of an acid acceptor such as triethylamine to afford sulfides. of Formula Vlllf.

Equation 13

Wherein

R' is C₁-C₄ alkyl or benzyl;

X' is Cl , Br, or I; and

R₁ and R₈ are as previously defined. The esters of Formula Vlllg, Vlllh, and VIIIj can be prepared by either of the two methods shown in Equation 14. The first method involves metallation of a 2- fluoropyridine derivative as previously described in Equation 5, followed by treatment with ethyl or methyl chloroformate which afforded esters of Formula XIII. Mercaptide displacement as described in Equation 7 resulted in esters of Formula Vlllg. Acid catalyzed transesterification using the appropriate alcohol as the solvent afforded esters of Formula Vlllh.

The second method involves the alkylation of a 2-mercaptonicotinic acid derivative Vllli with alkyl halides utilizing a variety of bases such as potassium carbonate or potassium t-butoxide, followed by conversion to the acid halides by any number of standard reagents such as thionyl chloride, phosphorous trichloride or pentachloride, or oxalyl chloride. The acid chlorides were then treated with the appropriate alcohols in the presence of an acid acceptor such as triethylamine, to afford esters of Formula Vlllh. Conversion of the sulfides Vlllh to the sulfonamides VIIIj was carried out as previously described.

Equation 14 A.

v

V

₂

VIIIj wherein

R' is C₁-C₄ alkyl or benzyl;

R₉ can also be R'₉; and

X', R', R₁, R₉ and R'₉ are as previously defined. The sulfonamides of General Formula Xlla can be prepared as shown in Equation 15. However, for the preparation of primary or unhindered secondary sulfonamides, a protective group is needed for a later stage in the synthetic sequence. A representative example is shown in Εquation 16 where a t-butyl protective group is utilized for the synthesis of sulfonamide Ila. Equation 15

wherein

[D] is R_dR_e, R₇K₈, R'₇R₈, or H₂; and R₁, R_d, R_e, R₇, R₈ and R'₇ are as previously defined.

Equation 16

wherein

R₁ is as previously defined, The difluoro compounds of Formula XlVa in Equation 17 can be prepared using the reactions previously described. Treatment with one equivalent of various

R₁ nucleophiles (those that are available in the art) results in a mixture of products which can be separated. An example of the use of sodium methoxide as the reactive nucleophile is shown. Intermediates XlVb and XIVc can be separated and further derivatized as previously described.

Equation 17

XIVc wherein

R₂ is as previously defined.

An alternative method to prepare esters of Formula XVd is shown in Equation 18. Mercaptide displacement of a 2,6-dihalopyridine can be achieved followed by conversion to the sulfonamide XVa as previously described. Treatment with two equivalents of a strong base such as n-butyllithium in a similar manner to that described by P. Breant, F. Harsalis, and G. Queguiner, Synthesis, 1983, 822-824, followed by treatment with carbon dioxide affords the acids of Formula XVb. The acids can then be treated with various R₁ nucleophiles such as alkoxides, mercaptides or amines to afford the acids of Formula XVc (using sodium methoxide as an example) which can then be esterified with the appropriate alcohols utilizing standard 1,3-dicyclohexylcarbodiimide (DCC) coupling conditions to afford esters of Formula XVd.

0 wherein

R₉ can also be R'₉; X' is F or Cl; and R', R₉ and R'₉ are as previously defined.

In an analogous manner, sulfonamides of General Formula XVIb can be prepared as shown in Equation 19. Treatment of XVa with strong base followed by an appropriate disulfide affords sulfides of Formula XVIa. Further elaboration utilizing chemistry previously described affords sulfonamides of Formula XVIb.

Equation 19

V

wherein

X' ie F or Cl; and

R' and [D] are as previously defined.

' A choice by one skilled in the art of the appropriate methods for preparing compounds of Formula I must take into account the nature of the substituents

R₁ through R₁₁, and Rd through Rg, and their chemical compatibility with the reaction conditions of Equations 1 through 19.

The heterocyclic amines of Formula A-NHR in Equation 1 above can be prepared by methods known in the literature, or simple modifications thereof, by those skilled in the art. For instance, EP-A No. 84,224 (published July 27, 1983) and W. Braker et al., J. Chem. Soc, 69, 3072 (1947) describes methods for preparing aminopyridines and triazines substituted by acetal groups such as dialkcxymethyl or 1,3-dioxolan- 2-yl, among other groups. Also, for example, South African patent application Nos . 82/5045 and 82/5671 describe methods for preparing aminopyrimidines and triazines substituted by haloalkyl or haloalkylthio groups such as OCH₂CH₂F, OCH₂CF₃, SCF₂H, or OCF₂H, among other groups. South African patent application No. 83/7434 (published October 5, 1983) describes methods for the synthesis of cyclopropylpyrimidines and triazines substituted by such groups as alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, dialkylamino or alkoxyalkyl.

The 5,6-dihydrofuro[2.3-d]pyrimidine-2-amines, the cyclopenta[d]pyrimidine-2-amines (A is A-2) and the 6,7-dihydro-5H-pyrano[2.3-d]pyrimidin-2-amines (A is A-3) can be prepared as described in EP-A No. 15,683. The furo[2.3-d]pyrimidin-2-amines (A is A-4) are described in EP-A No. 46,677.

Compounds of Formula A-NHR where A is A-5 are described in EP-A-73,562. Compounds where A is A-6 are described in EP-A-94,260.

In addition, general methods for preparing aminopyrimidines and triazines have been reviewed in the following publications: • The Chemistry of Heterocyclic Compounds", a series published by Interscience Publishers, Inc., New York and London;

• "Pyrimidines", Vol. 16 of the same series by D. J. Brown;

• "s-Triazines and Derivatives", Vol. 13 of the same series by E. M. Smolin and L. Rappoport; and • F. C. Schaefer, U.S. Patent 3,154,547 and

K. R. Huffman and F. C. Schaefer, J. Org. Chem., 28 , 1812 (1963), which describes the synthesis of triazines.

Preparation in view of the above would be obvious to one skilled in the art. Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by contacting compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of one cation for another. Cationic exchange can be effected by direct contact of an aqueous solution of a salt of a compound of Formula I (e.g., alkali or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water-soluble, e.g., a potassium, sodium or calcium salt.

Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.

The preparation of the compounds of this invention is further illustrated by the following specific examples. Temperatures are reported in degrees Celsius; abbreviations for nuclear magnetic resonance (NMR) are: s = singlet, d = doublet, t = triplet, m = multiplet, and peak positions are reported as parts per million downfield from internal tetramethylsilane. Infrared (IR) peak positions are given in reciprocal centimeters (cm^-1).

Example 1 Preparation of 2-Fluoro-3-(propylthio)pyridine

To a stirred solution of 59 ml (0.113 mol) of 1.9 molar lithium diisopropyl amide (in hexanes) in 150 mls dry tetrahydrofuran cooled to -70° under nitrogen was added dropwise a solution of 10.0 g of 2-fluoropyridine (0.103 mol) in 30 mls dry tetrahydrofuran such that the temperature was maintained below -65º. The solution was stirred at -70° for 4 hours and a solution 17 g of n-propyldisulfide (0.113 mol) in 45 mls dry tetrahydrofuran was added dropwise. while maintaining the temperature below -65°. After stirring another hour at -70°, the solu- tion was poured into water and extracted with ether. The combined organic phases were washed with brine, dried over magnesium sulfate, and evaporated to afford 14.5 g (82%) of a red oil: NMR (CDCl₃, 200 MHz), 1.0 (3H, m), 1.7 (2H, m), 2.9 (2H, m), 7.1 (1H, m), 7.7 (1H, m) , 8.0 (1H, m); IR (neat) 1565, 1560, 1410, 1245 cm^-1.

Example 2 Preparation of 2-(Phenylmethylthio)-3-(propylthio)- pyridine

To a stirred suspension of 0.62 g (0.013 mol) of 50% sodium hydride (in mineral oil), which had been washed with hexanes, in 20 mis dry dimethylformamide cooled to -5° under nitrogen was added dropwise 1.6 g (0.013 mol) benzyl mercaptan such that the temperature was maintained below 5º. The suspension was stirred at room temperature for 1 hour, cooled to 0°, and a solution of 2.0 g (0.012 mol) of the product from Example 1 was added dropwise while maintaining the temperature between 0° and 5°. After warming to room temperature, the solution was poured into water and extracted with ether. The combined organic layers were washed with water and with brine, dried over magnesium sulfate, and evaporated to an oil which was purified by flash chromatography to afford 0.9 g (27%) oil: NMR (CDCl₃, 200 MHz), 1.02 (3H, t, J=7 Hz), 1.6 (2H, m), 2.9 (2H, t, J=7 Hz), 4.45 (2H, s), 6.9-7.6 (7H, m), 8.3 (1H, m); IR (neat) 1560, 1370 cm^-1.

Example 3

Preparation of N-(1,1-Dimethylethyl)-3-(propyl- sulfinyl)-2-PyridinesuIfonamide

To a vigorously stirred mixture of 0.5 g (0.0018 mol) of the product from Example 2 in 9 mis methylene chloride and 4 mis water cooled to 0° was added 0.7 mis (0.008 mol) concentrated hydrochloric acid followed by the dropwise addition of 8.9 mis (0.006 mol) of a 5% sodium hypochlorite solution such that the temperature was maintained between 0º and 5º. After the mixture was stirred for an additional 30 minutes at 0° the reaction was poured into water and extracted with methylene chloride. The combined organic layers were washed with brine, dried over magnesium sulfate, and filtered. The filtrate was stirred and cooled to -70° under nitrogen and 0.53 g (0.0072 mol) of t.-butyl amine was added dropwise and the mixture was allowed to warm to room temperature. The reaction was poured into water and extracted with methylene chloride. The organic layers were combined and washed with brine, dried over magnesium sulfate, and evaporated to a mixture which was purified by flash chromatography to afford 0.4 g (69%) white solid: m.p. 138-140°; NMR (CDCl₃, 200 MHz) 1.09 (3H, m), 1.7 (1H, m), 2.0 (1H, m), 2.8 (1H, m), 3.3 (1H, m), 5.2 (NH), 7.7 (1H, m), 8.6 (1H, m), 8.8 (1H, m); IR (nujol) 3400, 1375, 1325, 1160, 1065, 1015 cm^-1.

Example 4 Preparation of 3-(Propylsulfonyl)-2-pyridinesulfonamide To a stirred solution of 8.8 g (0.029 mol) of the product from Example 3 in 400 mls methylene chloride cooled to -5°, under nitrogen, vaε added €.6 g (0.038 mol) of 3-chloroperbenzoic acid and stixred at room temperature for 20 hours. The reaction mixture was poured into water and extracted with methylene chloride. The organic layers were combined and washed with saturated sodium bisulfite and brine, dried over magnesium sulfate, and evaporated to a solid mixture which was washed with hexanes to afford a white solid. The solid was dissolved and stirred in 150 mls trifluoroacetic acid for 72 hours. The solution was evaporated and triturated with ether to afford -5.3 g (46%) white solid: m.p. 153-157°; NMR (CDCl₃, 200 MHz) 1.06 (3H, t, J=7 Hz ), 1.8 (2H, m), 3.7 (2H, m) 5.8 (NH₂), 7.8 (1H, m), 8.6 (1H, m), 8.95 (1H, m); IR (nujol) 3390, 3180, 1360, 1310, 1175, 1150 cm^-1.

Example 5

Preparation of N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(propylsulfonyl)-2-pyridinesuIfonamide

To a stirred suspension of 0.4 g (0.0015 mol) of the product from Example 4 and 0.63 g (0.0023 mol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbaroate in 4 mls acetoni tr i l e wa s added 0. 35 g ( 0.0023 mol ) of 1, 8- diazabicyclo[5.4.0]undec-7-ene and stirred for 30 minutes. The solution was diluted with water and acidified with 1 normal hydrochloric acid. The resulting precipitate was collected and washed with water and ether to afford 0.45 g (67%) white solid: m.p. 168-170°; NMR (CDCl₃, 200 MHz), 1.07 (3H, t, J=7 Hz), 1.85 (2H, m), 3.7 (2H, m), 3.97 (6H, s), 5.8 (1H, s), 7.26 (NH), 7.8 (1H, m), 8.6 (1H, m), 8.9 (1H, m), 12.9 (NH); IR (nujol) 3320, 1740, 1610, 1580, 1375, 1195, 1170 cm^-1.

Example 6 Preparation of 3-ethylthio-2-flυoropyridine

Using the procedure of Example 1, 40.0 g of 2-fluoropyridine (0.412 mol) was converted to 46.5 g (72%) of the title compound as an oil: NMR(CDCl₃, 200 MHz) 1.3 (3H, t, J = 7 Hz), 2.95 (2H, q, J = 7 Hz), 7.1 (1H, m), 7.7 (1H, m), 8.0 (1H, m); IR (neat) 1585, 1565, 1410, 1230 cm^-1. Example 7 Preparation of 3-ethylthio-2-(phenylmethylthio)- pyridine

Using the procedure of Example 2, 25.0 g (0.160 mol) of the product from Example 6 was converted to 44.8 g (100%) of the title compound as a yellow liquid: NMR (CDCl₃, 200 MHz) 1.28 (3H, t, J = 7 Hz), 2.9 (2H, q, J = 7 Hz), 4.45 (2H, B), 7.0-7.6 (7H, m), 8.35 (1H, m); 1R (neat) 1610, 1405 cm^-1.

Example 8 Preparation of N-(1,1-Dimethylethyl)-3-ethylsulfinyl- 2-pyridinesulfonamide Using the procedure of E ple 3, 35.0 g (0.134 mol) of the product from Example 7 was converted to 21.2 g (56%) of the title compound: m.p. 129-131°; NMR (CDCl₃, 200 MHz) 1.23 (9H, s), 1.28 (3H, t, J = 7 Hz), 2.9 (1H, m), 3.3 (1H, m), 5.2 (NH), 7.7 (1H, m), 8.55 (1H, m), 8.75 (1H, m); 1R (nujol) 3100, 1320, 1155 cm^-1.

Example 9 Preparation of N-(1,1-Dimethylethyl)-3-ethylsulfonyl- 2-pyridinesulfonamide Using the first half of the procedure of Example 4 (i.e., the 3-chloroperbenzoic acid reaction), 9.0 g (0.033 mol) of the product from Example 9 was converted to 10.1 g (100%) of the title compound: m.p. 58-63°; NME (CDCl₃. 200 KHz) 1.2 (3H, t, J = 7 Hz), 1.2 (9H, s), 3.7 (2H, q, J = 7 Hz), 6.1 (NH), 7.7 (1H, m), 8.55 (1H, m), 8.95 (1H, m); 1R (nujol) 3300, 1560, 1350, 1300, 1170, 1140 cm^-1. Example 10

Preparation of 3-ethylsulfonyl-2-pyridinesulfonamide Using the second half of the procedure of

Example 4 (i.e., the trifluoroacetic acid reaction),

9.0 g (0.029 mol) of the product from Example 9 was converted to 4.2 g (58%) of the title compound: m.p.

211-212.5°; NMR (DMSO-d₆, 200 MHz) 1.15 (3H, t, J = 7 Hz), 3.4 (NH₂), 3.7 (2H, q, J = 7 Hz), 7.9 (1H, m), 8.5 (1H, m), 8.95 (1H, m); IR (nujol) 3370, 3190,

1350, 1310, 1180 cm^-1.

Example 11

Preparation of N-[(4,6-dimethoxypyrimidin-2-yl)- aminocarbonyl]-3-ethylsulfonyl-2-pyridinesuIfonamide

Using the procedure of Example 5, 0.60 g (0.0024 mol) of the product from Example 10 was converted to

0.70 g (70%) of the title compound: m.p. 160-162°;

NMR (CDCl₃, 200 MHz) 1.35 (3H, t, J = 7 Hz), 3.7 (2H, q, J = 7 Hz), 3.97 (6H, s), 5.8 (1H, s), 7.3

(NH), 7.75 (1H, m), 8.6 (1H, m), 8.9 (1H, m), 12.95

(NH); IR (nujol) 3260, 1740, 1610, 1360, 1195, 1175 cm^-1.

Example 12 Preparation of 2,6-Difluoro-3-pyridinecarboxylic acid, methyl ester

To a stirred solution of 91 ml (0.182 mol) of 2.0 molar lithium diisopropylamide (in hexanes) in 200 mL dry tetrahydrofuran cooled to -70° under nitrogen was added dropwise a solution of 20.0 g of 2,6-difluoropyridine (0.174 mol) in 75 mL dry tetrahydrofuran such that the temperature was maintained below -60°. The solution was stirred at -70° for 3 hours and was then added via a cannula to a solution 21.7 g (0.230 mol) of methyl chloroformate in 100 mL dry tetrahydrofuran cooled to -70° under nitrogen. After stirring another hour at -70°, the mixture was poured into water and extracted with ether. The combined organic layers were washed with brine, dried over magnesium sulfate, and evaporated to a semisolid which was purified by flash chromatography to afford 13.0 g (43%) orange oil: NMR (CDCl₃, 200 MHz) 3.95 (3H, s), 6.9 (1H, m), 8.5 (1H, m); IR (neat) 1745, 1730, 1610, 1415,

1290 cm^-1.

Example 13 Preparation of 2-Fluoro-6-Methoxy-3-Pyridinecarboxylic Acid, Methyl Ester

To a stirred solution of 15.0 g (0.0867 mol) of the product from Example 12 in 240 mL dry tetrahydrofuran cooled to -78° was added dropwise 22.7 mL (0.0993 mol) of 25% sodium methoxide in methanol solution over 45 minutes. After warming to -20°, the mixture was poured into ice water, acidified with 1 normal hydrochloric acid and extracted with ether. The combined organic layers were washed with brine, dried over magnesium sulfate, and evaporated to a semisolid which was purified by flash chromatography to afford 3.2 g (17%) light yellow solid: m.p. 81-82°; NMR (CDCl₃, 200 MHz) 3.9 (3H, s), 3.98 (3H, s), 6.67 (1H, d, J=9 Hz), 8.25 (1H, m); IR (nujol) 1715, 1615, 1290 cm^-1. Example 14

Preparation of 6-Methoxy-2-(Phenylmethylthio)-3- Pyridinecarboxylic Acid, Methyl Ester

To a stirred mixture of 0.8 g (0.0161 mol) of

50% sodium hydride (in mineral oil), which had been washed with hexanes, in 20 mL dry dimethylformamide cooled to -5° under nitrogen was added dropwise 1.9 mL (0.0161 mol) benzyl mercaptan The suspension was stirred at room temperature for 1 hour, cooled to 0º, and a solution of 3.2 g (0.0147 mol) of the product of Example 13 in 20 mL dry dimethylformamide was added dropwise. After warming to room temperature, the solution was poured into water and extracted with ether. The combined organic layers were washed with water and with brine, dried over magnesium sulfate, and evaporated to an oil which was purified by flash chromatography to afford 3.0 g (64%) of a yellow solid: m.p. 67-71°; NMR (CDCl₃, 200 MHz) 3.88

(3H, s), 3.96 (3H, s), 4.46 (2H, s), 6.44 (1H, d,

J=9Hz), 7.2-7.5 (5H, m), 8.1 (1H, d, J=9HZ); IR (nujol) 1700, 1580, 1305, 1255 cm^-1.

Example 15

Preparation of 2-[1,1-Pimethylethyl)Aminosulfonyl]-6- Methoxy-3-Pyridinecarboxylic Acid, Methyl Ester

To a vigorously stirred mixture of 3.7 g (0.0129 mol) of the product from Example 14 in 79 mL methylene chloride and 41 mL water cooled to 0° was added 6.3 mL ( 0 . 0759 mol ) concentrated hydr ochl or ic ac id f ol lowed by the dropwise addition of 79 mL (0.053 mol) of a 5% sodium hypochlorite solution such that the temperature was maintained below 5°. After the mixture was stirred for an additional 30 minutes at 0° the reaction was poured into water and extracted with methylene chloride. The combined organic layers were washed with brine, dried over magnesium sulfate, and filtered. The filtrate was stirred and cooled to -70° under nitrogen, and 4.7 (0.0645 mol) of t-butyl amine was added dropwise. The reaction mixture was allowed to warm to -20°, poured into water, acidified with 1 normal hydrochloric acid, and extracted with methylene chloride. The combined organic layers were washed with brine, dried over magnesium sulfate, and evaporated to a semisolid which was purified by flash chromatography to afford 3.0 g (77%) yellow solid: m.p. 128-130°; NMR (CDCl₃, 200 MHz) 1.27 (9H, s), 3.94 (3H, s), 4.05 (3H, s) 5.75 (NH), 6.9 (1H, d, J=9 Hz), 7.95 (1H, d, J=9 HZ); IR (nujol) 3260, 1740, 1605, 1325, 1125 cm^-1.

Example 16 Preparation of 2-(Aminosulfonyl)-6-Methoxy-3-Pyridine- Carboxylic Acid, Methyl Ester

A solution of 2.9 g (0.0096 mol) of the product from Example 15 was stirred in 50 mL trifluoroacetic acid at room temperature for 20 hours. The solution was evaporated to afford 2.4 g (100%) white solid: m.p. 142.5-144.5°; NMR (CDCl, 200 MHz) 3.97 (3H, s),

4.1 (3H, s), 5.6 (NH₂), 6.9 (1H, d, J=9Hz), 8.1 (1H, d, J=9Hz); 1R (nujol) 3305, 3205, 1715, 1590, 1355, 1320, 1175 cm^-1.

Example 17

Preparation of 2-[[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyI]aminosuIfonyl]-6-Methoxy-3-Pyridinecarboxylic Acid, Methyl Ester

To a stirred suspension of 0.4 g (0.0016 mol) of the product from Example 16 and 0.54 g (0.002 mol) of phenyl(4,6-dimethoxypyrimidin-2-yl) carbamate in 4 mL acetonitrile was added dropwise 0.30 g (0.002 mol) of

1,8-diazobicyclo[5.4.0]undec-7-ene and stirred for 30 minutes. The solution was diluted with water and ac id if ied with 1 norma l hyd r ochlor ic acid . The resulting precipitate was collected and washed with water and with ether to afford 0.57 g (84%) white solid: m.p. 194-196°; NMR (CDCl₃, 200 MHz), 3.83 (3H, s), 3.95 (9H, s), 5.8 (1H, s), 6.95 (1H, d, J=9 Hz), 7.4 (NH), 8.1 (1H, d, J=9 Hz), 12.8 (NH); IR (nujol) 3140, 1740, 1720, 1640, 1360, 1195, 1140 cm ^-1.

Example 18

Preparation of N-(1,1-Dimethylethyl)-2-Fluoro-3- PyridinesuIfonamide

To a stirred solution of 396 mL (0.740 mol) of

1.9 molar lithium diisopropylamide (in hexanes) in 1.5

L dry tetrahydrofuran cooled to -70° under nitrogen was added dropwise a solution of 65 g (0.670 mol) of

2-fluoropyridine in 150 mL dry tetrahydrofuran such that the temperature was maintained below -65°. The suspension was stirred at -70° for another 3.5 hours and 86 g (1.34 mol) of sulfur dioxide was added while maintaining the temperature below -65°. After stirring another 15 minutes at -70°, the reaction was allowed to warm to 0° and evaporated to half the original volume and diluted with ether. The white precipitate was collected under nitrogen, washed with ether, and dried. The solid was dissolved in 800 mL acetic acid and cooled to 10-20°. To this stirred solution was added portionwise 99.4 g (0.740 mol) of

N-chlorosuccinimide while maintaining the temperature below 20°. After stirring another 30 minutes, the suspension was evaporated, diluted with water and extracted with methylene chloride. The combined organic phases were washed with saturated aqueous sodium bicarbonate solution until no more gas evolution, washed with brine, dried over magnesium sulfate, and filtered. The filtrate was cooled to -70° under nitrogen and to this stirred solution was added dropwise 199 g (2.7 mol) of t-butylamine. The suspension was poured into ice water, acidified with concentrated hydrochloric acid, and extracted with methylene chloride. The combined organic layers were washed with brine, dried over magnesium sulfate, and evaporated to an oil which was purified by flash chromatography to afford 29.1 g (19%) of a brown solid which was further washed with cold n-butylchloride to afford 22.4 g (14.5%) of a white solid: m.p. 95-97°; NMR (CDCl₃, 200 MHz) 1.25 (9H, s), 4.9 (NH), 7.35 (1H, m), 8.3-8.5 (2H, m).

Example 19

Preparation of N-(1,1-Dimethylethyl)-2-Fluoro-N-Methyl- 3-Pyridinesulfonamide

To a stirred suspension of 3.4 g (0.071 mol) of

50% sodium hydride (in mineral oil), which had been washed with hexanes, in 120 mL dry dimethyldormamide cooled to 0° under nitrogen was added dropwise a solution of 15.0 g (0.065 mol) of the product from

Example 18 in 120 mL dry dimethylformamide. After stirring at room temperature for 1 hour, the mixture was cooled to 0° and 12.2 g (0.086 mol) of methyl iodide was added dropwise. After warming to room temperature the reaction was poured into ice water and extracted with ether. The combined organic layers were washed with brine, dried over magnesium sulfats, and evaporated to 15.9 g (99%) oil; NMR (CDCl₃, 200

MHz), 1.32 (9H, s), 3.1 (3H, s), 7.3 (1H, m), 8.3-8.4

(2H, m); 1R (neat) 1590, 1570, 1335, 1155 cm^-1. Exampl e 20

Preparation of N-(1,1-Dimethylethyl)-N-Methyl-2- (Phenylmethylthio)-3-PyridinesuIfonamide

Using the same procedure as in Example 14, 15.9 g (0.065 mol) of the product from Example 19 was converted to 19.5 g (86%) yellow solid: m.p. 92-94°; NMR (CDCl₃), 200 MHz) 1.26 (9H, s), 3.1 (3H, s), 4.5 (2H, s), 7.0-7.5 (6H, m), 8.2 (1H, m); IR (nujol) 1570, 1385, 1315, 1150, 1120 cm^-1.

Example 21

Preparation of N2, N3-Bis(1,1-Dimethylethyl)-N3-Methyl- 2,3-Pyridinedisulfonamide

Using the same procedure as in Example 15, 19.5 g (0.056 mol) of the product from Example 20 was converted to a tan solid which was washed with n-butylchloride to afford 13.1 g (66%) white solid: m.p. 155-156.5°;

NMR (CDCl₃, 200 MHZ) 1.23 (9H, s), 1.33 (9H, s), 3.1

(3H, s), 6.0 (NH), 1H, m), 8.5 (1H, m), 8.8 (1H, m);

1R (nujol) 3320, 1340, 1325, 1160, 1120 cm^-1.

Example 22

Preparation of N3-Methyl-2,3-Pyridinedisulfonamide

A stirred solution of 13.1 g (0.036 mol) of the product from Example 21 in 150 mL trifluoroacetic acid was refluxed for 5 hours. After cooling to room temperature, the solution was evaporated to a solid which was washed with ether to afford 9.6 g (100%) white solid: m.p. 220-223°; NMR (DMSO-d₆, 200 MHz),

2.5 (3H, d), 6.9 (NH), 7.65 (NH₂), 7.85 (1H, m), 8.45 (1H, m), 8.9 (1H, m); IR (nujoi) 3380, 3320, 3180, 1355, 1170 cm^-1. Example 23

Preparation of N2-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-N3-MethyI-2,3-Pyridinedisulfonamide

To a stirred suspension of 4.15 g (0.0165 mol) of the product from Example 22 and 5.0 g (0.018 mol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate in 50 mL acetonitrile was added dropwise 2.8 g (0.018 mol) of 1,8-diazabicyclo 15.4.0] undec-4-ene and stirred for 30 minutes. The solution was diluted with water and acidified with 1 normal hydrochloric acid. The resulting precipitate was collected and washed with water and with ether to afford 6.4 g (82%) white solid: m.p. 147-148.5°; NMR (CDCl₃, 200 MHz) 2.7

(3H, d, J=7 Hz), 3.97 (6H, s), 5.8 (1H, s), 6.15 (1H, m), 7.3 (NH), 7.7 (1H, m), 8.55 (1H, m), 8.8 (1H, m),

13.1 (NH); IR (nujol) 3310, 1740, 1610, 1340, 1190,

1165 cm^-1.

By applying the procedures of Examples 1 through

23 and Equations 1 through 19, the compounds in Tables I through X can be prepared by one skilled in the art.

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly.

Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to

20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

* 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 some times desirable, and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either 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 0ºC. "McCutcheon's Detergents and Emυlsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood. "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example. Littler. U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook". 5th Ed., McGraw-Hill. New York, 1963, pp. 8-57ff. For further information regarding the art of formulation, see for example: H. M. Loux, U.S. Patent 3,235,361,

February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3.309,192, March 14, 1967, Col. 5. line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; G. C. Klingman, "Weed Control as a Science", John Wiley and « Sons, Inc., New

York, 1961, pp. 81-96; and J. D. Fryer and S. A. Evans, "Weed

Control Handbook". 5th Ed., Blackwell Scientific Publications. Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example 24

High Strength Concentrate

N2-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]- N3-methyl-2,3-pyridinedisulfonamide 99% trimethylnonyl polyethylene glycol ether 1% The surfactant is sprayed upon the active ingredient in a blender and the mixture s if ted through a U . S. S. no. 40 sieve (0.42 mm openings) prior to packaging. The concentrate may be formulated further for practical use. Example 25 Wettable Powder 2-[[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonyl]-3-pyridinecarboxylic acid, methyl ester 65% dodecylphenol polyethylene glycol ether 2% sodium ligninsulfonate 4% sodiυm silicoalυminate 6% montmorillonite (calcined) 23%

The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example 26 Agueous Suspension

N2-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-

N3-methyl-2,3-pyridinedisulfonamide 50.0% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. Example 27 Oil Suspension N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(1- propylsulfonyl)-2-pyridinesulfonamide methyl ester 35% blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6% xylene 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 3 microns. The product can be used directly, extended with oils, or emulsified in water. Example 28

Oil Suspension

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- 3-(1-methylsulfonyloxy)-2-pyridinesulfonamide methyl ester 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example 29 Agueous Suspension

N-[(4,6-dimethoxypyrimidin-2-yl)arainocarbonyl]- 3-(1-ethylsulfonyl)-2-pyridinesulfonamide methyl ester 25% hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5%

The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns. Example 29 Wettable Powder N2-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-

N3-methyl-2,3-pyridinedisulfonamide 40.0% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54%

The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging. All compounds of the invention may be formulated in the same manner.

Example 30 Granule wettable powder of Example 29 15% gypsum 69% potassium sulfate 16%

The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 cm (U.S.S.#18 to 40 sieves), the granules are removed, dried, and screened. Oversized material is crushed to produce additional material in the desired range. These granules contain % active ingredient.

Example 31 Wettable Powder N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl- 3-(ethylsulfonyl)-2-pyridinesulfonamide methyl ester 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The ingredients are blended, coarsely hammermilled and the air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. Example 32

Extruded Pellet N-[(4,6-diraethoxypyrimidin-2-yl)aminocarbonyl-

3-(ethylsulfonyl)-2-pyridinesulfonamide 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled. Example 33 Wettable Powder N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-

3-(1-ethylsulfonyl)-2-pyridinesulfonamide 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended and then ground in a hammermill to produce particles with an average particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before being packaged.

Example 34 High Strength Concentrate N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-

3-(1-ethylsulfonyl)-2-pyridinesulfonamide 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are blended and ground in a hammer mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways.

Example 35 Wettable Powder 2-[[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonyl]-3-pyridinecarboxylic acid, methyl ester 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

Example 36 High Strength Concentrate

N2-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]- N3-methyl-2,3-pyridinedisulfonamide 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

Utility

Test results indicate that the compounds of the present invention are highly active preemergent or postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Some of the compounds have utility for selective weed control in plantation crops. Solanaeeae family crops such as tomatoes, potatoes and peppers, other crops such as wheat, barley, corn, cotton or soybeans, and their fallow land. In particular, some of the compounds of this invention control weeds in corn (maize) both pre- and postemergence without significant crop damage. Some of the compounds of this invention also control weeds in potato (Solanum tuberosum) and tomato (Lycopersicon esculentum) without significant crop damage. They are particularly useful to control such problem weeds as the foxtail (Setaria spp.), fall panicum (Panicum dichotomiflorum), barnyardgrass (Echinochloa crusgalli), seedling johnsongrass (Sorghum halepense) and shattercane (Sorghum bicolor). They can be used preemergence or postemergence and are most effective when applied postemergence to young weeds. They are also effective on certain broadleaf weeds such as lambsquarters (Chenopodium album), pigweed (Amaranthus spp.) and velvet leaf (Abutilon theophrasti).

Alternatively, the subject compounds are useful to modify plant growth.

The rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth modifiers or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of a lication, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.001 to 20 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required. The compounds of the invention may be used in combination with any other commercial herbicide, examples of which are those of the triazine, triazole, imidazolinone, uracil, urea, amide, diphenylether, cineole, carbamate and bipyridylium types. They are particularly useful in combination with the following herbicides.

Common Name Chemical Name alachlor 2-chloro-2',6'-diethyl-N-(methoxymethyl)- acetanilide atrazine 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine butylate s-ethyl-diisobutylthiocarbamate cyanazine 2-[[4-chloro-6-(ethylamino)-s-triazin-2- yl]amino]-2-methylpropionitrile dicamba 3,6-dichloro-o-anisic acid

EPTC S-ethyl dipropylthiocarbamate linuron 3-(3,4-dichlorophenyl)-1-methoxy-1- methylurea metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-1-methylethyl)acetamide metribuzin 4-amino-6-tert-butyl-3-(methylthio)-astriazine-5(4H)-one Common Name Chemical Name tridiphane 2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane

2,4-D (2,4-dichlorophenoxy)acetic acid bromoxynil 3,5-dibromo-4-hydroxyphenylcyanide paraquat 1,1'-dimethyl-4,4-bipyridinium ion glyphosate N-(phosphonomethyl)glycine DCPA dimethyl tetrachloroterephthalate dalapon 2,2-dichloropropionic acid dinoseb 2-(1-methylpropyl)-4,6-dinitrophenol diphenamid N,N-dimethyl-2,2-diphenylacetamide pendimethalin N-(1-ethylproρyl)-3,4-dimethyl-2,6- dinitrobenamine oryzalin 3,5-dinitro-N,N-dipropylsulfanilamide trifluralin α,α,α-trifluoro-2,6-dinitro-N,N- dipropyl-p-toluidine chloramben 3-amino-2,5-dichlorobenzoic acid napropamide 2-(α-naphthoxy)-N,N-diethylpropionamide pebulate S-propyl butylethylthiocarbamate chlorpropham isopropyl m-chlorocarbanilate bensulide S-(O,O-diisopropyl phosphorodithioate) ester of N-(2-mercaptoethyl)benzenesulfonamide

Trade Name Chemical Name

Harmony™ 3-[[(4-methoxy-6-methyl-1,3,5-triazin2-yl)aminocarbonyl]aminosulfonyl]-2- thiophenecarboxylic acid, methyl ester

Cinch^® 1-methyl-4-(1-methylethyl)-2-exo-[(2- methylphenyl)-methoxy]-7-oxabicyclo¬

[2.2.1]heptane ----- 2-ethoxy-N-[[4-(2,2,2-trifluoroethoxy)- 6-raethoxy-1,3,5-triazin-2-yl]aminocarbonyl]benzenesuIfonamide

Test A Seeds of large crabgrass (Diσitaria sanσuinalis), barnyardgrass (Echinochloa crus-galli), giant foxtail (Setaria faberi), wild oats (Avena fatua), cheatgrass (Bromus secalinus) or downy brorne (Bromus tectorum), velvetleaf (Abutilon theophrasti), cultivated morningglory (Ipomoea coccinea, variety Scarlet O'Hara), cocklebur (Xanthium pensylvanicum). G522 sorghum (Sorghum vulgare, variety Funk G522), G4646 corn (Zea mays, variety Funk G4646), Williams soybeans (Glycine max, variety Williams), USH11 sugarbeet (Beta vulgaris, variety Union Sugarbeet Co. USH11), Coker cotton (Gossypium hirsutum. variety Coker 315), dry seeded rice (Oryza sativa. variety California Rice Coop. M101), Era wheat (Triticum aestivum, variety Era spring), Klages barley (Hordeum vulgare, variety Klages spring) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0 = no injury, to 10 = complete kill. Tl^e accompanying descriptive symbols have the following meanings: C = chlorosis/necrosis;

B = burn; D = defoliation;

E = emergence inhibition;

G = growth retardation;

H = formative effect;

U = unusual pigmentation;

X = axillary stimulation;

S = albinism; and 6Y = abscised buds or flowers. "POSOL" and "PRSOL" in Table A denote post- and preemergence treatments, respectively.

1

It is noted that a few compounds such as compounds 6, 19, 20, 26, 32, 37-39, 44, 49, 54-59, 76-78 and 88 show little or no herbicidal activity at the rate tested. It is thought they would show more herbicidal activity at higher rates.

Test B

Postemergence Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge (Cyperug rotundus) tubers, large crabgrass (Digitaria sanguinalis). sicklepod (Cassia obtusifolia), jimsonweed (Datura stramonium), velvetleaf (AbutiIon theophrasti), lambsquarters (Chenopodium album), dry seeded rice

(Oryza sativa, variety California Rice Coop. M101) and teaweed (prickly sida, Sida spinosa). The second pot was planted with green foxtail (Setaria viridis), cocklebur (Xanthium pensylvanicum), cultivated morningglory (Ipomoea coccinea, variety Scarlet

O'Hara), Coker cotton (Gossypium hirsutum, variety Coker 315), johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crus-galli), G4646 corn (Zea mays, variety Funk G4646), Williams soybeans (Glycine max, variety Williams) and giant foxtail

(Setaria faberi). The third pot was planted with Era wheat (Triticum aestivum, variety Era spring), Klages barley (Hordeum vulgare, variety Klages spring), wild buckwheat (Polgonum convolvulus), cheatgrass (Bromus secalinus) or downy brome (Bromus tectorum), USHll sugarbeet (Beta vulgaris, variety Union Sugarbeet Co. USHll), wild oats (Avena fatua), field violet (Viola arvensis) or chickweed (Stellaria media), blackgrass (Alopecurug myosuroides), and Altex rape (Brassica napus, variety Altex). The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a non-phytotoxic solvent. Preemergence

Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge tubers, crabgrass, sicklepod, jimsonweed, velvetleaf, lambsquarters, rice and teaweed (prickly sida). The second pot was planted with green foxtail, cocklebur, morningglory, cotton, johnsongrass, barnyardgrass, corn, soybean and giant foxtail. The third pot was planted with wheat, barley, wild buckwheat, cheatgrass or downy brome, sugarbeet, wild oat, field violet or chickweed, blackgrass and rape. The three pans were sprayed preemergence with the chemicals dissolved in a non-phytotoxic solvent.

Treated plants and controls were maintained in the greenhouse for 24 days, then all rated plants were compared to controls and visually rated for plant response. Response ratings are based on a scale of 0 to

100 where 0 = no effect and 100 = complete control. A dash (-) response means no test.

Response ratings are contained in Table B.

306

Test C

Postemergence

Six round pots (17 cm diameter by 15 cm deep) were used to grow plants to the treatment stage. Four were planted with seeds or tubers of four species each and another with soybeans using Sassafras sandy loam as the growing media. The sixth pot was planted to corn using a Tama silt loam. During spraying, the soil of this pot was temporarily covered with perlite then later removed so any effects noted would be from foliar uptake only. A separate pot of corn (25.5 cm diameter by 19.5 cm deep) grown in Sassafras sandy loam was also included to determine foliar/soil treatment effects on plant growth. Plants were grown 10 to 20 days and were in the 2 to 5 leaf stage when sprayed postemergence with compounds of the invention. Species included were as follows: G4646 Corn [maize] (Zea mays, variety Funk G4646), Williams Soybeans (Glycine max, variety Williams), Green foxtail (Setaria viridis), Giant foxtail (Setaria faberi), Fall Panicum (Panifium dichotomiflorum), Crabgrass (Digitaria sanguinalis), Barnyardgrass (Echinochloa crus-galli). Johnsongrass (Sorghum halepense), G522 Sorghum (Sorghum vulgare, variety Funk G522), Nutsedge (Cyperus rotundus), Velvetleaf (Abutilon theophrasti), Cocklebur (Xanthium pensylvanicum) , Smartweed (Polygonum persicaria, Lambsguarter (Chenopodium album), Pigweed (Amaranthus retroflexus), Ivy Morningglory (Ipomoea hederacea), Jimsonweed (Datura stramonium), Ragweed (Ambrosia artemisiifolia). Preemergence

Plantings were made as above except all in Tama silt loam. Compounds were sprayed preemergence the day after planting then all pots were watered to simulate rainfall.

After treatment all plantings were maintained in a greenhouse about 20 days then visually rated for plant response. Ratings are based on a scale of 0 to 100 where 0 = no effect and 100 = complete control. Response ratings are shown in Table C.

Test D

Potatoes (Solanum tuberosum, cult. 'Green Mountain') were grown in Metro 350 medium in 20 cm plastic pots. Potatoes were 17 days old at time of spraying. Barnyardgrass (Echinochloa crus-galli), johnsongrass (Sorghum halepense), giant foxtail (Setaria faberii), crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti). cocklebur (Xanthium pensylvanicum), and morningglory (Ipomoea hederacea) were grown in Sassafras sandy loam (pH 6.5, 1% organic matter) in plastic-lined 25 cm pots. These plants were 9 days old at the time of spraying.

Compounds were sprayed at 62, 16, 4, and 1 g/ha. Compounds were sprayed at each rate on one pot containing potato plants and at the same time on one pot containing the remaining species. Compounds were dissolved in a non-phytotoxic solvent, 4.0% and was sprayed at 374 1/ha. Plants were maintained in a greenhouse and were evaluated 11 days after spraying. All sprayed plants were evaluated for injury as compared to control plants. Injury was measured visually using a 0 to 100% scale where 0 = no effect and 100 = complete control. Results are shown in Table D.

Test E

Tomatoes (Lycopersicon esculentum cult. 'Rutgers') and peppers (Capsicum frutescens cult. 'Yolo') were grown in Metro 350 medium in 10 cm plastic pots. Tomatoes and peppers were 19 days old at time of spraying. Purple nutsedge (Cyperus rotundus), crabgrass (Digitaria sanguinalis), sicklepod (Cassia tora), prickley sida (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), lambsquarter (Chenopodium album), green foxtail (Setaria viridis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crus-galli), giant foxtail (Setaria faberii), wild buckwheat (Polygonum convolvulus), downy brome (Bromus tectorum), wild oat (Avena fatua), chickweed (Stellaria spp.), and blackgrass (Alopecurus myosuroides), were grown in sassafras sandy loam (pH 6.5, 1% organic matter) in plastic-lined 25 cm pots. These plants were 7 to 11 days old at the time of spraying.

Compounds were sprayed at 62, 16, 4, and 1 g/ha. Compounds were sprayed at each rate on one pot containing tomatoes, one pot containing peppers, and on three pots containing the remaining species. Compounds were dissolved in a non-phytotoxic solvent, and were sprayed at 374 1/ha. Plants were maintained in a greenhouse and were evaluated 16 days after spraying.

All sprayed plants were evaluated for injury as compared to control plants. Injury was measured visually using a 0 to 100% scale where 0 = no effect and 100 = complete control. Results are shown in Table E.

Claims

WHAT IS CLAIMED:

1. A compound selected from

R is H or CH₃;

W is O or S;

R₁ is R_f or R_g;

R_f is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, halogen,

NO₂, C₁-C₃ alkoxy, C₁-C₃ alkylthio or CN;

R_g is C₁-C₃ haloalkyl, C₂-C₃ alkyl, cyclopropyl, C₁-C₃ alkyl substituted by C₁-C₃ alkoxy, OH, C₁-C₂ alkylthio or CN, CN, W₂R₁₁, amino, C₁-C₃ alkylamino or C₁-C₃ dialkylamino; is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl,

C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl,

C₃-C₅ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR'₇R₈, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉, CO₂R'₉, CH₂F, CF₂H, CH₂Cl, CCl₂H or C₂-C₄ haloalkyl;

R₃ is C₁-C₄ alkylsulfinyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₄ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, SO₂NR'₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉, CO₂R'₉ or C₁-C₄ haloalkyl;

R₄ is C₁-C₄ alkylsulfinyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₄ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₅ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₅ cycloalkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₆ is C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkylsulfonyl, C₃-C₄ alkenylthio, C₃-C₄ alkenylsulfinyl, C₃-C₄ alkenylsulfonyl, C₃-C₄ alkynylthio, C₃-C₄ alkynylsulfinyl, C₃-C₄ alkynylsulfonyl, C₃-C₅ cycloalkylthio, C₃-C₅ cycloalkylsulfinyl, C₃-C₅ cycloalkylsulfonyl,

SO₂NR_dR_e, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl;

R₇ is H, C₂-C₃ cyanoalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl;

R'₇ is C₁-C₄ alkyl;

R₈ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl or cyclopropyl; or R₇ and R₈ may be taken together as -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -CH₂CH₂OCH₂CH₂-;

R₉ is CH₂CH₂R₁₀, CH₂CF₃, C₃-C₄ haloalkyl,

C₃-C₄ alkynyl, C₂-C₄ alkylthioalkyl, C₃-C₄ cycloalkyl or C₄-C₆ cycloalkylalkyl;

R'₉ is C₁-C₄ alkyl, C₃-C₄ alkenyl, CH₂CH₂Cl, CH₂CH₂Br, CH₂CH₂OCH₃ or CH₂CH₂OC₂H₅; R₁₀ is OH, F, CN, OSO₂(C₁-C₃ alkyl) or OSO₂(C₁-C₃ haloalkyl);

R₁₁ is C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl;

W₁ is O or S;

W₂ is O or S;

A A A

A A

X is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ haloalkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkylthio, C₁-C₄ alkylthio, halogen, C₂-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino or di(C₁-C₃ alkyl) amino; Y is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ haloalkoxy, C₂-C₄ haloalkylthio, C₁-C₄ alkylthio, C₂-C₅ alkoxyalkyl, C₂-C₅ alkoxyalkoxy, amino, C₁-C₃ alkylamino, di(C₁-C₃ alkyl) amino, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₂-C₅ alkylthioalkyl, C₂-C₅ alkylsulfinylalkyl, C₂-C₅ alkylsulfonylalkyl, C₁-C₄ haloalkyl, C₂-C₄ alkynyl, C₃-C₅ cycloalkyl, azido,

N(OCH₃ )CH₃ ; m is 2 or 3 ;

Q₁ and Q₂ are independently O or S; R_a is H or C₁-C₃ alkyl;

R_b and R_c are independently C₁-C₃ alkyl;

R_d is H or C₁-C₂ alkyl;

R_e is C₁-C₂ alkoxy;

Z is CH, N, CCH₃, CC₂H₅, CCl or CBr; Y₁ is O or CH₂;

X₁ is CH₃, OCH₃, OC₂H₅ or OCF₂H; X₂ is CH₃, C₂H₅ or CH₂CF₃;

Y₂ is OCH₃, OC₂H₅, SCH₃, SC₂H₅ , CH₃ or CH₂CH₃; X₃ is CH₃ or OCH₃; Y₃ is H or CH₃;

X₄ is C_H3, OCH₃, OC₂H₅, CH₂OCH₃ or Cl; Y₄ is CH₃, OCH₃, OC₂H₅ or Cl; and their agriculturally suitable salts; provided that

1) when X is halogen, then Z is CH and Y is OCH₃, OC₂H₅, NH₂, NHCH₃, N(CH₃)₂ or N(OCH₃)CH₃;

2) when W is S, then R is H, A is A-1, Z is CH or N, and Y is CH₃, OCH₃ , OC₂H₅, CH₂OCH₃ , C₂-C₅, CF₃, SCH₃, OCH₂CH=CH₂, OCH₂C≡CH, OCH₂CH₂OCH₃, CH(OCH₃)₂ or

3) when the total number of carbon atoms of X and

Y is greater than four, then the combined number of carbons of R₁, R₂, R₃, R₄, R₅ or R₆ is less than or equal to six; 4) when J is J-1 and R₂ is C₁-C₄ alkylsulfonyl, SO₂NR_dR_e, SO₂NR'₇R₈ or CO₂R'₉, or when

J is J-2 and R₃ is CF₃, SO₂NR_dR_e, SO₂NR'₇R₈ or CO₂R'₉, then Y is other than C₂-C₅ alkylthioalkyl, C₂-C₅ alkylsulfinylalkyl, C₂-C₅ alkylsulfonylalkyl,

a

6) when J is J-2 arid R₃ is C₁-C₄ alkylsulfinyl or SO₂NR_dR_e, or R₇ is H, then X and Y are other than C₂-C₄ haloalkoxy;

8) when J is J-2 and R₃ is SO₂NH₂ or SO₂NR_dR_e, or R₇ is H, then X is other than iodine;

9) when J is J-2 and R₇ is H or R₃, is SO₂NR_dR_e, then Y is other than C₁-C₄ alkynyl;

10) X₄ and Y₄ are not simultaneously Cl;

11) when J is J-1, J-2, J-3, J-4 and A is A-5, then R_f is other than H;

12) when J is J-1 or J-2, then A is other than A-6;

13) when J is J-1 and A is A-7, then R₂ is other than C₁-C₄ alkylsulfonyl; 14) when R₂ or R₃ is CO₂R'₉ or SO₂NR'₇R₈, then R₁ is R_g and when R₂ or R₃ is other than

CO₂R'₉ or SO₂NR'₇R₈, then R₁ is R_f; and 15) when J is J-2 and R₁ is adjacent to the sulfonylurea bridge, then R_g is C₁-C₃ haloalkyl, C₂-C₃ alkyl cyclopropyl, CN, W₂R₁₁, amino, C₁-C₃ alkylamino or C₁-C₃ dialkylamino.

2. A compound of Claim 1 where

X is C₁-C₂ alkyl, C₁-C₂ alkoxy, Cl, F, Br, I, CH₂F, CF₃, OCH₂CH₂F, OCH₂CHF₂, OCH₂CF₃, CH₂Cl or CH₂Br; and Y is H, C₁-C₂ alkyl, C₁-C₂ alkoxy, CH₂OCH₃, CH₂OCH₂CH₃, NHCH₃, N(OCH₃)CH₃, N(CH₃)₂, CF₃,

SCH₃, OCH₂CH=CH₂, OCH₂C=CH, OCH₂CH₂OCH₃,

CH₂SCH₃, cyclopropyl, CΞCH or CΞCCH₃;

R_a is H or CH₃; and

Z is CH or N.

3. A compound of Claim 2 where W is O; R_f is H, CH₃, C₁ haloalkyl, halogen or OCH₃;

R_g is C₁-C₂ haloalkyl, ethyl, W₂R₁₁, CH₂OCH₃ ,

CH₂SCH₃, CH₂CN, C₁-C₂ alkylamino or N(CH₃)₂; R₂ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, SO₂NH₂, SO₂NR_dR_e, SO₂NR₇R₈, SO₂NR'₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂,

CN, CO₂R₉, CO₂R'₉, CHF₂, CF₂H, CH₂Cl,

CCl₂H or C₂-C₄ haloalkyl;

R₃ is C₁-C₄ alkylsulfinyl, SO₂NH₂, SO₂NR_dR_e,

SO₂R₇R₈, SO₂NR'₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉, CO₂R'₉ or C₁-C₄ haloalkyl; R₄ is C₁-C₄ alkylsulfinyl, SO₂NH₂, SO₂N(OCH₃)CH₃, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁) (OC₁-C₄ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₅ is C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl,

SO₂NH₂, SO₂N(OCH₃)CH₃, SO₂NR ₇R₈, OSO₂R₈, SO₂OR₈, N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₆ is C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylthio, C₁-C₄ haloalkylsulfinyl, C₁-C₄ haloalkyl onyl, C₃-C₄ alkenylthio, C₃-C₄ alkenylsulfinyl, C₃-C₄ alkenylsulfonyl, C₃-C₄ alkynylthio, C₃-C₄ alkynylsulfinyl, C₃-C₄ alkynylsulfonyl, SO₂N(OCH₃)CH₃, SO₂NR₇R₈, OSO₂R₈, SO₂OR₈,

N₃, P(W₁)(OC₁-C₂ alkyl)₂, CN, CO₂R₉ or C₁-C₄ haloalkyl; R₇ is H, C₂-C₃ cyanoalkyl, C₃-C₄ alkenyl or C₃-C₄ alkynyl; R₈ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl or cyclopropyl; and R₁₁ is C₁-C₃ alkyl, C₁-_C2 haloalkyl, allyl or propargyl.

4. A compound of Claim 3 where J is J-1.

5. A compound of Claim 3 where J is J-2.

6. A compound of Claim 3 where J is J-3.

7. A compound of Claim 3 where J is J-4.

8. A compound of Claim 3 where J is J-5.

9. A compound of Claim 4 where

R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl;

R'₇ is C₁-C₃ alkyl;

R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl; R₉ is CH₂CH₂R₁₀, CH₂CH₂SCH₃, propargyl or cyclopropylmethyl; R'₉ is C₁-C₃ alkyl, allyl, CH₂CH₂OCH₃ or CH₂CH₂Cl; and

R₁₀ is OH, CN or OSO₂CH₃.

10. A compound of Claim 9 where A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and

Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃, NHCH₃ or

CH(OCH₃)₂.

11. A compound of Claim 10 where Z is CH.

12. A compound of Claim 10 where Z is N.

13. A compound of Claim 5 where

R₇ is H, C₂-C₃ cyanoalkyl, allyl or propargyl; and

R₈ is C₁-C₃ alkyl, allyl, propargyl or cyclopropyl.

14. A compound of Claim 13 where A is A-1;

X is CH₃, OCH₃, OCH₂CH₃, Cl or OCH₂CF₃; and

Y is CH₃, OCH₃, CH₂CH₃, CH₂OCH₃ , NHCH₃ or

CH(OCH₃)₂.

15. A compound of Claim 14 where Z is CH.

16. A compound of Claim 14 where Z is N.

17. A compound of Claim 2 where J is J-1;

A is A-1;

Z is CH;

W is O;

R₂ is C₁-C₄ alkylsulfinyl or C₁-C₄ alkylsulfonyl; and R_f is H, C₁-C₂ alkyl, C₁ haloalkyl, C₁-C₂ alkoxy or C₁-C₂ thioalkyl.

18. A compound of Claim 17 where R_f is H; R₂ is C₁-C₄ alkylsulfonyl;

X is OCH₃; and

Y is OCH₃.

19. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(1-propylsulfonyl)-2-pyridinesulfonamide.

20. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(1-ρropylsulfinyl)-2-pyridinesulfonamide.

21. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide.

22. The compound of Claim 1 which is N2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-N3-ethyl-2,3- pyridinedisulfonamide.

23. The compound of Claim 1 which is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(methylsulfonyloxy)-2-pyridinesulfonamide.

24. The compound of Claim 1 which is N2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-N3-methyl-2,3- pyridinedisulfonamide.

25. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 1 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

26. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 2 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

27. A composition suitable for controlling the growth of undesired vegetation which comprises an ef fective amount of a compound of Claim 3 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

28. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 4 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

29. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 5 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

30. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 6 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

31. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 7 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

32. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 8 and at least one of the following: surfactant, solid inert diluent or liquid inert diluent and mixtures of the foregoing.

33. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 1.

34. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 2.

35. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 3.

36. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 4.

37. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 5.

38. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 6.

39. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 7.

40. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 8.

41. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound selected from Claims 19 to 24.

42. A method for controlling the growth of undesired vegetation which comprises applying to the corn crop to be protected an effective amount of a compound selected from Claims 19, 21 or 24.