JPH0639364B2 - Herbicide - Google Patents

Description

Detailed Description of the Invention

The present invention relates to herbicides, and more specifically,
formula

[0002]

[Chemical 2] Wherein R ₁ is H, CH ₃ , Cl, Br or F; R
₃ is CH ₃ or C ₂ H ₅ ; X and Y are each CH
₃ or OCH ₃ ; and Z is CH or N, provided that R ₃ is CH ₃ , X and Y are OCH ₃ and Z is CH, then R ₁ is other than H. The present invention relates to a herbicide containing a compound or an agriculturally suitable salt thereof as an active ingredient.

US Pat. No. 4,127,405 and US Pat. No. 4,169,719 disclose herbicidal benzenesulfonylureas.

European Patent Application Publication No. 165,753 published on December 27, 1985 (EP-A-165,753)
Is the expression,

[0005]

[Chemical 3] Wherein Q is an optionally substituted phenyl, or an optionally substituted saturated or unsaturated 5- or 6-membered heterocycle containing 1 to 3 heteroatoms. Disclosed are herbicidal thiophene sulfonamides, which are cyclic rings.

European Patent Application (EP-A) No. 83,9
Ceremony for No. 75 (July 20, 1983)

[0007]

[Chemical 4] Wherein Q is selected from various 5- or 6-membered aromatics or partially unsaturated heterocyclic rings containing 2 or 3 heteroatoms selected from O, S or NR. Certain benzene sulfonamides have been disclosed.

European Patent Application No. 85.476 (1
Ceremony on August 10, 983)

[0009]

[Chemical 5] In the formula, Q is various 5-membered aromatic heterocycles containing one heteroatom selected from O, S or NR, and dihydro and tetrahydro analogues thereof, or Q is one selected from O or S A benzenesulphonamide herbicide, which is a saturated or partially unsaturated 6-membered ring containing a heteroatom; and Q ¹ is a 6-membered aromatic heterocycle containing ¹ to 3 N atoms. Is disclosed.

South African Patent Application No. 83/8416
Ceremony on (May 12, 1983)

[0011]

[Chemical 6] Wherein A is a 5- or 6-membered heterocyclic ring system which is bonded through a carbon atom and which contains 1, 2 or 3 heteroatoms and is unsaturated or only partially saturated, A herbicide, benzenesulfonamide, is disclosed.

European Patent Application No. 116,518 (Swiss priority 2/4 / 83,8 / 22/84)

[0013]

[Chemical 7] In the formula, X is NR ₆ R ₇ , N (SO ₂ R ₉ ) ₂ or

[0014]

[Chemical 8] A is CO, SO ₂ , CONR ₂₃ or CO ₂ ; B is C ₁
-C is ₄ alkyl or C ₂ -C ₄ alkenyl; and C is CO, a CR ₂₁ R ₂₂ or SO _2, sulfonamide are disclosed a herbicide.

The formula in US Pat. No. 4,475,944

[0016]

[Chemical 9] Disclosed is a herbicide sulfamate having an ortho-heterocyclic ring, such as where W is O, S or NR ₁ .

European Patent Application Publication No. 164,268 published on December 11, 1985 (EP-A-164,268)
Has an expression,

[0018]

[Chemical 10] In the formula, Q is a saturated 5-membered or 6-membered ring containing 1 to 2 heteroatoms selected from 0-2S or 0-2O, or 0-1S, 0-10 or 0 Is an unsaturated 5- or 6-membered ring containing 1 to 3 heteroatoms selected from --3N, and Q is C ₁ -C ₄ alkyl, halogen, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio,
C ₁ -C ₂ haloalkoxy, C ₃ -C ₄ alkenylthio, C
Disclosed are herbicidal benzyl sulfonamides, optionally substituted with one or more groups selected from ₁ -C ₂ haloalkylthio or SCH ₂ CN.

European Patent Application Publication No. 165,753 published on December 27, 1985 (EP-A-165,753)
Has an expression,

[0020]

[Chemical 11] Wherein Q is Cl, CH ₃ O or phenyl optionally substituted by CH _3, saturated 5-membered ring containing one heteroatom selected from O or S, or 0-1S ,
An unsaturated 5- or 6-membered ring containing 1 to 3 heteroatoms selected from 0-1O or 0-3N,
And when Q is an unsaturated 5- or 6-membered ring, Q
Is C ₁ -C ₄ alkyl, halogen, C ₁ -C ₃ alkoxy,
C ₁ -C ₃ alkylthio, C ₃ -C ₄ alkenylthio, C ₁
-C ₂ haloalkoxy or may be optionally substituted by one or more groups selected from C ₁ -C ₂ haloalkylthio, herbicidal pyridine sulfonamides are disclosed in.

European Patent Application Publication No. 176,304 (EP-A-176,304), published on April 11, 1986, contains the formula

[0022]

[Chemical 12] In the formula, Q is a saturated 5- or 6-membered ring containing one hetero atom selected from 0-1S or 0-1O, or 0-1S, 0-1O or 0-3N. Is an unsaturated 5- or 6-membered ring containing 1 to 3 heteroatoms, and Q is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₃ -C ₄ alkenylthio, C ₃ -C ₄ alkenyloxy, C ₁ -C ₂ haloalkoxy, C ₁ -C ₂ haloalkylthio, C ₂ -C ₄ cyanoalkyl thio or C ₁ - Herbicidal pyrazole sulfonamides are disclosed, such as pyrazole sulfonamides, optionally substituted with one or more groups selected from C ₂ alkoxycarbonylmethylthio.

European Patent Application Publication No. 141,777 (EP-A-141,777), published on May 15, 1985, contains the formula:

[0024]

[Chemical 13] In the formula, Y is O or S, and R ¹⁷ is

[0025]

[Chemical 14] Ortho-benzyl-substituted sulfonylureas, which are 5- or 6-membered unsaturated heterocyclic groups including
bstituted sulfonylureas) have been disclosed. 1986
U.S. Pat. No. 4,602,936 issued Jul. 29, 2010
Issue is part of this disclosure.

South African Patent Application Publication No. 83/0441, published July 25, 1983, contains the formula:

[0027]

[Chemical 15] In the formula, R ₁ is H, halogen, NO ₂ , C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₅ alkenyl or C ₁
-C ₄ alkoxycarbonyl, R ₂ is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, each of which is unsubstituted or substituted by 1 to 3 halogen atoms, R ₃ Is halogen, H, NR ₄ R ₅ , C ₁ -C ₃ alkyl, which is unsubstituted or substituted by 1 to 3 alkoxy, unsubstituted or methoxy, ethoxy or substituted by 1-3 halogen atoms, a is a C ₁ -C ₄ alkylene or C ₂ -C ₄ alkenylene, or each of which is unsubstituted C ₁ -C ₄
Substituted by alkyl, m is 0 or 1,
E is N or CH, X is oxygen, sulfur, SO or SO
₂ and Q is, in part, a 5- or 6-membered heterocyclic ring bonded via carbon or nitrogen, and examples of such a heterocycle include furan, pyran, thiophene, triazole,
Pyridine, pyrroline, oxazole, isoxazole, thiazole, isothiazole, thiadiazole, oxathiol, pyrrole, imidazole, pyrazole,
Pyrazine, pyrimidine, pyridazine, symmetrical and asymmetrical triazines oxodiazole, oxazine, furazan,
Pyridine-N-oxide, thiophene-S-oxide,
Benzothiophene, benzofuran, isobenzofuran,
Chromene, chroman, indole, isoindole, indazole, quinoline, isoquinoline, phthalazine, quinoxaline, quinazoline, quinoline, benzothiazole and benzimidazole and their partially or fully hydrogenated and condensed homologues, Of the above herbicidal benzenesulfonamide are disclosed.

South African Patent Application Publication No. 85/2646, published October 11, 1985, contains the formula:

[0029]

[Chemical 16] Wherein R ₁ is H, halogen, NO ₂ , alkyl, alkoxy, alkoxycarbonyl or haloalkyl, X 1
Is O, S, SO or SO ₂ , Y is O or S, E is CH or N, R ₂ and R ₃ are independently alkyl, alkoxy or alkoxyalkyl, and A is alkylene or alkenylene. And m is 0 or 1, and Q is partially

[0030]

[Chemical 17] And each of which may be optionally substituted and /
Or optionally optionally partially hydrogenated, X ′ is O, S
Or NR, which is herbicidal benzenesulfonamide.

The presence of undesired plants causes substantial damage to useful crops, especially agricultural products, such as corn, soybeans, wheat, etc., which satisfy the basic human food needs. The modern population explosion and the consequent global food shortages call for improving the efficiency of production of these crops. Preventing or minimizing the loss of valuable crops by eradicating unwanted plants or inhibiting their growth is one way to improve this efficiency.

A wide range of substances are available which are useful for combating unwanted plants or for inhibiting (regulating) their growth. Such substances are commonly referred to as herbicides. However, there remains a need for effective herbicides that either destroy weeds or delay their growth without causing significant damage to the more useful crops.

The present invention relates to novel compounds of formula I, agriculturally suitable compositions containing them and their use as pre-emergence or post-emergence herbicides or as plant growth regulators.

Expression

[0035]

[Chemical 18] In the formula, J is

[0036]

[Chemical 19]

[0037]

[Chemical 20] W is O, S or NRx; Rx is H, O
H, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, allyloxy, propargyloxy, C ₁ -C ₃ haloalkyl, C
₁ -C ₃ haloalkoxy or NRyRz, where Ry is H
Or C ₁ -C ₃ alkyl, Rz is C ₁ -C ₃ alkyl, G is O, S, SO or SO ₂ ; m is 0 or 1; n is 0, 1 or 2 Yes; R is H or CH
₃ ; E is a single bond, CH ₂ or O; Q is

[0038]

[Chemical 21] R ₁ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl,
Halogen, nitro, C ₁ -C ₃ alkoxy, SO ₂ NRaR
b, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, CN, SCN, C
O ₂ Rc, C ₁ -C ₃ haloalkoxy, C ₁ -C ₃ haloalkylthio, amino, C ₁ -C ₃ alkylamino, di (C ₁ -C _1
3 alkyl) amino or C ₁ -C ₂ alkoxy, C ₁ -C ₂
Haloalkoxy, C ₁ -C ₂ alkylthio, C ₁ -C ₂ haloalkylthio or C ₁ -C ₂ alkyl substituted with CN; R ₂ is H, C ₁ -C ₃ alkyl, allyl or phenyl; R ₃ is H, C ₁ -C ₆ alkyl, C ₃ -C ₆
Cycloalkyl, C ₁ -C ₆ haloalkyl, CH ₂ - (C ₂
To C ₅ alkenyl), CH ₂ (C _{2 to} C ₅ haloalkenyl),
CH ₂ (C ₂ -C ₅ alkynyl), CH ₂ (C ₂ -C ₅ haloalkynyl), C ₆ H ₅ or C ₁ -C ₂ alkoxy, C ₁ -C ₂
Alkylthio, C ₁ -C ₂ alkylsulfinyl or C
C ₁ -C ₄ alkyl substituted with ₁ -C ₂ alkylsulfonyl; R ₄ is H, halogen, C ₁ -C ₆ alkyl, C ₃
To C ₆ cycloalkyl, C _{1 to} C ₆ haloalkyl, C _{2 to} C
₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₃ -C _{6 haloalkynyl, C 6 H 5, C 1} ~C 4 alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ Alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, OCH ₂ C
H ₂ O- (C ₁ -C ₂ alkyl) or di (C ₁ -C ₃ alkyl) amino; R ₅ is H, C ₁ -C ₃ alkyl or allyl; Ra is H, C ₁ -C ₄ alkyl, C ₂ -C ₃ cyanoalkyl, methoxy or ethoxy; Rb is H,
C ₁ -C ₄ alkyl or C ₃ -C ₄ alkenyl;
Or Ra and _{Rb - (CH 2) 3 -} , - (CH 2) 4 -, -
(CH ₂ ) ₅ — or —CH ₂ CH ₂ OCH ₂ CH ₂ — can be combined; Rc is C ₁ -C ₄ alkyl, C ₃ -C ₄
Alkenyl, C ₃ -C ₄ alkynyl, C ₂ -C ₄ haloalkyl, C ₁ -C ₂ cyanoalkyl, C ₅ -C ₆ cycloalkyl, be a C ₄ -C ₇ cycloalkylalkyl or C ₂ -C ₄ alkoxyalkyl ; A

[0039]

[Chemical formula 22] X is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁
To C ₄ haloalkoxy, C _{1 to} C ₄ haloalkyl, C _{1 to} C
₄ haloalkylthio, C ₁ -C ₄ alkylthio, halogen, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₅ alkoxyalkoxy, amino, C ₁ -C ₃ alkylamino, di (C ₁
˜C ₃ alkyl) amino or C ₃ -C ₅ cycloalkyl; Y is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkylthio. , C ₁ -C ₄ alkylthio, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₅ alkoxyalkoxy, amino, C ₁ -C ₃
Alkylamino, di (C ₁ -C ₃ alkyl) amino, C ₃ ~
C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, C ₂
To C ₅ alkylthioalkyl, C _{2 to} C ₅ alkylsulfinylalkyl, C _{2 to} C ₅ alkylsulfonylalkyl, C _{1 to} C ₄ haloalkyl, C _{2 to} C ₄ alkynyl, azido, cyano,

[0040]

[Chemical formula 23] Or —N (OCH ₃ ) CH ₃ ; p is 2 or 3; L ₁ and L ₂ are independently O or S; R ₆ is H
Or CH ₃ ; R ₇ and R ₈ are independently C ₁ -C ₃ alkyl; Z is CH, N, CCH ₃ , CC ₂ H ₅ , CCl or CBr; Y ₁ is O or CH ₂ ; X ₁ is CH ₃ ,
OCH ₃ , OC ₂ H ₅ or OCF ₂ H; X ₂ is CH ₃ ,
C ₂ H ₅ or CH ₂ CF ₃ ; Y ₂ is OCH ₃ , OC
₂ H ₅ , SCH ₃ , SC ₂ H ₅ , CH ₃ or CH ₂ CH ₃ ;
X ₃ is CH ₃ or OCH ₃ ; Y ₃ is H or CH ₃ ; X ₄ is CH ₃ , OCH ₃ , OC ₂ H ₅ , CH ₂ OCH ₃ or Cl; Y ₄ is CH ₃ , OCH ₃ , OC ₂ H ₅ or Cl; and Z ¹ is CH or N, a) when X is Cl, F, Br or I then Z is CH and Y is OCH ₃ , OC ₂ H ₅ , N (OCH ₃ ) CH ₃ , N
HCH ₃ , N (CH ₃ ) ₂ or OCF ₂ H; b) when X or Y is C ₁ haloalkoxy, Z is CH; c) J is J-9 and n is 0. Where Q is Q-1 or Q-2; d) when E is O, J is J-1; e) when W is S, A is A-1; R is H, and Y is CH ₃ , OCH ₃ , OC ₂ H ₅ , CH ₂ OCH ₃ ,
C ₂ H ₅ , CF ₃ , SCH ₃ , OCH ₂ CH = CH ₂ , OCH ₂ C
≡CH, OCH ₂ CH ₂ OCH ₃ , CH (OCH ₃ ) ₂ or

[0041]

[Chemical formula 24] F) If the total number of carbon atoms in X and Y is greater than 4, then the carbon content of R ₁ , R ₃ , R ₄ and R ₅ must each be less than or equal to 2; g) X ₄ and Y ₄ cannot be Cl at the same time; h) when J is J-1 and m is 0, then n is 0
And i) n is 0 and m is 1, then Q is Q-1
Or Q-2, and agronomically suitable salts thereof.

In the above definitions, the term "alkyl" used either alone or in synthetic terms such as "alkylthio" or "haloalkyl" refers to straight or branched chain alkyl, eg methyl. , Ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers.

Alkoxy stands for methoxy, ethoxy, n-propoxy, isopropoxy and the different butyl isomers.

Alkenyl stands for straight-chain or branched alkenes, for example vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl or hexenyl isomers.

Alkynyl represents straight-chain or branched alkyl, such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.

Alkylsulfonyl is methylsulfonyl,
Represents ethylsulfonyl or the different propylsulfonyl isomers.

Alkylthio, alkylsulfinyl, alkylamino and the like are similarly defined.

Cycloalkyl represents cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halogen" either alone or in synthetic words such as "haloalkyl" represents fluorine, chlorine, bromine or iodine.

In terms such as C ₂ -C ₃ alkylthioalkyl, the particular number of carbon atoms is meant to define the total number of carbon atoms in the substituent. For example, C ₂ ~
C ₃ alkylthioalkyl is CH ₂ SCH ₃ , CH ₂ SC ₂
H ₅ , CH ₂ CH ₂ SCH ₃ or CH (CH ₃ ) SCH ₃ , and C ₂ -C ₅ alkoxyalkoxy is OCH ₂
OCH ₃ to O (CH ₂ ) ₄ OCH ₃ or OCH ₂ O (CH ₂ )
₃ CH ₃ and various structural isomers contained therein.

Preferred for reasons of ease of synthesis and / or great herbicidal potency are: 1) Compounds of formula I wherein E is a single bond.

2) A compound of formula I wherein E is CH ₂ .

3) Compounds of formula I wherein E is O.

4) m is 0; W is O; and R
A preferred compound wherein H is H.

5) X is C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, cyclopropyl, Cl, F, Br, I, OCF ₂ H,
CH ₂ F, CF ₃ , OCH ₂ CH ₂ F, OCH ₂ CHF ₂ , OCH
₂ CF ₃ , CH ₂ Cl or CH ₂ Br, Y is H, C ₁ ~
C ₂ alkyl, C ₁ -C ₂ alkoxy, CH ₂ OCH _3, CH ₂
OCH ₂ CH ₃ , NHCH ₃ , N (OCH ₃ ) CH ₃ , N (C
_{H 3) 2, CF 3,} SCH 3, OCH 2 CH = CH 2, OCH 2 C≡
CH, OCH ₂ CH ₂ OCH ₃ , CH ₂ SCH ₃ ,

[0055]

[Chemical 25] OCF ₂ H, SCF ₂ H, OCF ₂ Br, C≡CH or C
A preferred compound of 4 which is ≡CCH ₃ .

6) R ₁ is H, CH ₃ , F, Cl, Br, OCH ₃ ,
SCH ₃ , CH ₂ CN, CH ₂ OCH ₃ , CF ₃ or OCF ₂
A preferred compound of 5 which is H; and n is 0.

7) R is H, C ₁ -C ₃ alkyl, C ₁ -C ₂
C ₁ -C ₂ alkyl substituted with alkoxy, CH ₂ CH ₂ Cl, CH ₂ CH ₂ F, CH ₂ CHF ₂ , CH ₂ CF ₃ , allyl or propargyl; and R ₄ is H, C ₁ -C ₃
Alkyl, C ₁ -C ₂ alkoxy, C ₁ -C ₂ alkylthio, N (CH ₃ ) ₂ , allyl, propargyl or C ₁ -C ₂ alkyl substituted with ₁ to 3 atoms of F, Cl or Br. 6 compounds.

8) A suitable compound of 7 wherein J is J-1.

9) A is A-1; Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H; Y is CH ₃ , OCH ₃ , C _{2
H 5, CH 2 OCH 3,} NHCH 3 or CH (OCH ₃₎ compounds of preferred 8 is _2.

10) Preferred compounds of 9 wherein Q is Q ₁ .

11) Preferred 9 compounds wherein Q is Q ₂ .

12) Preferred compounds of 9 wherein Q is Q ₃ .

13) Preferred 9 compounds wherein Q is Q ₄ .

14) Preferred compounds of 9 wherein Q is Q ₅ .

15) Preferred compounds of 9 wherein Q is Q ₆ .

16) Preferred compounds of 9 wherein Q is Q ₇ .

17) Preferred 7 compounds wherein J is J ₂ .

18) A is A-1, Z is CH or N
And X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , OC.
H ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (OC
H ₃₎ is _2, compounds of preferred 17.

19) Preferred 18 compounds wherein Q is Q ₁ .

20) Preferred 18 compounds wherein Q is Q ₂ .

21) Preferred 18 compounds wherein Q is Q ₃ .

22) Preferred 18 compounds wherein Q is Q ₄ .

23) Preferred 18 compounds wherein Q is Q ₅ .

24) Preferred 18 compounds wherein Q is Q ₆ .

25) Preferred 18 compounds wherein Q is Q ₇ .

26) Preferred compounds of 7 wherein J is J ₃ .

27) A is A-1, Z is CH or N
And X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , OC.
H ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (OC
H ₃₎ is _2, compounds of preferred 26.

28) Preferred 27 compounds wherein Q is Q ₁ .

29) Preferred 27 compounds wherein Q is Q ₂ .

30) Preferred 27 compounds wherein Q is Q ₃ .

31) Preferred 27 compounds wherein Q is Q ₄ .

32) Preferred 27 compounds wherein Q is Q ₅ .

33) Preferred 27 compounds wherein Q is Q ₆ .

34) Preferred 27 compounds wherein Q is Q ₇ .

35) Preferred 7 compounds wherein J is J ₄ .

36) A is A-1, Z is CH or N
And X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , OC.
H ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (OC
H ₃ ) ₂ of the preferred 35 compounds.

37) Preferred 36 compounds wherein Q is Q ₁ .

38) Preferred 36 compounds wherein Q is Q ₂ .

39) Preferred 36 compounds wherein Q is Q ₃ .

40) A suitable 36 compound wherein Q is Q ₄ .

41) Preferred 36 compounds wherein Q is Q ₅ .

42) A suitable 36 compounds wherein Q is Q ₆ .

43) Preferred 36 compounds wherein Q is Q ₇ .

44) Preferred compounds of 7 wherein J is J ₅ .

45) A is A-1, Z is CH or N
And X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , OC.
H ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (OC
H ₃₎ is _2, compounds of preferred 44.

46) A suitable 45 compound wherein Q is Q ₁ .

47) A suitable 45 compound wherein Q is Q ₂ .

48) A suitable 45 compound wherein Q is Q ₃ .

49) A suitable 45 compound wherein Q is Q ₄ .

50) A suitable 45 compound wherein Q is Q ₅ .

51) A suitable 45 compound wherein Q is Q ₆ .

52) A suitable 45 compound wherein Q is Q ₇ .

53) Preferred compounds of 7 wherein J is J ₆ .

54) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
A preferred 53 compound which is CH ₃ ) ₂ .

55) A preferred 54 compound wherein Q is Q ₁ .

56) A preferred 54 compound wherein Q is Q ₂ .

57) A preferred 54 compound wherein Q is Q ₃ .

58) A preferred 54 compound wherein Q is Q ₄ .

59) A preferred 54 compound wherein Q is Q ₅ .

60) A preferred 54 compound wherein Q is Q ₆ .

61) A preferred 54 compound wherein Q is Q ₇ .

62) Preferred compounds of 7 wherein J is J ₇ .

63) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
CH ₃₎ is _2, compounds of preferred 62.

64) A preferred 63 compound wherein Q is Q ₁ .

65) A preferred 63 compound wherein Q is Q ₂ .

66) A preferred 63 compound wherein Q is Q ₃ .

67) A preferred 63 compound wherein Q is Q ₄ .

68) A preferred 63 compound wherein Q is Q ₅ .

69) A preferred 63 compound wherein Q is Q ₆ .

70) A suitable 63 compound wherein Q is Q ₇ .

71) Preferred 7 compounds wherein J is J ₈ .

72) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
CH ₃₎ is _2, compounds of preferred 71.

73) A suitable 72 compound wherein Q is Q ₁ .

74) A preferred 72 compound wherein Q is Q ₂ .

75) A suitable 72 compound in which Q is Q ₃ .

76) A suitable 72 compound wherein Q is Q ₄ .

77) A suitable 72 compound in which Q is Q ₅ .

78) A preferred 72 compound wherein Q is Q ₆ .

79) A suitable 72 compound wherein Q is Q ₇ .

80) Preferred 7 compounds wherein J is J ₉ .

81) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
80 suitable compounds which are CH ₃ ) ₂ .

82) A suitable compound according to 81, wherein Q is Q ₁ .

83) A suitable compound according to 81, wherein Q is Q ₂ .

84) A suitable compound of 81, wherein Q is Q ₃ .

A preferred compound of 81, wherein Q is Q ₄ .

86) A suitable compound of 81, wherein Q is Q ₅ .

87) A suitable 81 compound wherein Q is Q ₆ .

88) A suitable compound of 81, wherein Q is Q ₇ .

89) Preferred compounds of 7 wherein J is J ₁₀ .

90) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
A preferred 89 compound which is CH ₃ ) ₂ .

91) Preferred 90 compounds wherein Q is Q ₁ .

92) Preferred 90 compounds in which Q is Q ₂ .

93) A suitable 90 compound wherein Q is Q ₃ .

94) Preferred 90 compounds wherein Q is Q ₄ .

95) Preferred 90 compounds wherein Q is Q ₅ .

96) Preferred 90 compounds wherein Q is Q ₆ .

97) Preferred 90 compounds wherein Q is Q ₇ .

98) Preferred 7 compounds wherein J is J ₁₁ .

99) A is A-1, Z is CH or N
X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O.
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
CH ₃ ) ₂ preferred 98 compounds.

100) Preferred 99 compounds wherein Q is Q ₁ .

101) A suitable 99 compound wherein Q is Q ₂ .

102) A suitable 99 compound wherein Q is Q ₃ .

103) A suitable 99 compound wherein Q is Q ₄ .

104) A suitable 99 compound wherein Q is Q ₅ .

105) A suitable 99 compound wherein Q is Q ₆ .

106) A suitable 99 compound wherein Q is Q ₇ .

107) Preferred compounds of 7 wherein J is J ₁₂ .

108) A is A-1, Z is CH or N, X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH. ₃ ,
OCH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH
A preferred 107 compound which is (OCH ₃ ) ₂ .

109) A suitable 108 compound wherein Q is Q ₁ .

110) A preferred 108 compound wherein Q is Q ₂ .

111) A preferred 108 compound wherein Q is Q ₃ .

112) A suitable 108 compound wherein Q is Q ₄ .

113) A suitable 108 compound, wherein Q is Q ₅ .

114) A suitable 108 compound wherein Q is Q ₆ .

115) A suitable 108 compound wherein Q is Q ₇ .

116) Preferred compounds of 7 wherein J is J ₁₃ .

117) A is A-1, Z is CH or N, X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H, and Y is CH ₃ , O
CH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (O
A preferred 116 compound which is CH ₃ ) ₂ .

118) A preferred 117 compound wherein Q is Q ₁ .

119) A preferred 117 compound wherein Q is Q ₂ .

120) A preferred 117 compound wherein Q is Q ₃ .

121) A suitable 117 compound wherein Q is Q ₄ .

122) A suitable 117 compound wherein Q is Q ₅ .

123) A suitable 117 compound wherein Q is Q ₆ .

124) A suitable compound of 117, wherein Q is Q ₇ .

125) m is 0; n is 0; J is J-1, J-2, J-3, J-8, J-10 or J-
11; W is O; R is H; R ₁ is H; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H or C ₁ -C ₃ alkyl A is A-1; Z is CH
Or N; X is CH ₃ , OCH ₃ , OCH ₂ CH ₃ , cyclopropyl, Cl or OCF ₂ H; and Y is CH ₃ , OCH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , Preferred two compounds which are NHCH ₃ or CH (OCH ₃ ) ₂ .

126) m is 0; R is H; R ₁
Is H; R ₃ is H or C ₁ -C ₃ alkyl; R ₄
Is H or C ₁ -C ₃ alkyl; A is A-1;
Z is CH or N; X is CH ₃ , OCH ₃ , OCH ₂ C
Preferred 3 compounds which are H ₃ , cyclopropyl, Cl or OCF ₂ H; and Y is CH ₃ , OCH ₃ , C ₂ H ₅ , CH ₂ OCH ₃ , NHCH ₃ or CH (OCH ₃ ) ₂ .

Particularly preferred are the following because they are very easy to synthesize and / or have great herbicidal efficacy: N-[(4-chloro-6-methoxypyrimidin-2-yl) aminocarbonyl] -2 -(1-Ethyl-1H-tetrazol-5-yl) benzenesulfonamide, melting point 223-225 ° C; -N-[(4.6-dimethoxypyrimidin-2-yl)
Aminocarbonyl] -2-methyl-6- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide, melting point 178-189 ° C, N-[(4-chloro-6-methoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl- 1H-tetrazol-5-yl) benzenesulfonamide, melting point 225-227 ° C .; N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide, melting point 207 to 210 ° C .; N-[(4,6-dimethylpyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide, melting point 224-226 ° C .; ・ N-[(4 -Methoxy-6-methylpyrimidin-2-yl) aminocal Sulfonyl] -1-methyl-4-(2-methyl-2H chromatography tetrazole -5 Iru) over 1H Pirazoru 5 over sulfonamide, melting point 181 over 183 ° C., · N chromatography [(4.6 over dimethoxypyrimidin--2 Iru)
Aminocarbonyl] -1-methyl-4- (2-methyl-2H-tetrazol-5-yl) -1H-pyrazole-5-sulfonamide, melting point, 171-173 ° C.

Synthesis Compounds of formula I may be synthesized by one or both of the methods shown in Schemes 1 and 2 below.

Scheme 1 illustrates the reaction of sulfonyl isocyanates and isothiocyanates of formula II with appropriate heterocyclic amines of formula III to give the desired sulfonylureas and sulfonylthioureas of formula I.

Reaction formula 1

[0181]

[Chemical formula 26] In the formula, J, W, R and A are as described above.

The reaction of Reaction Scheme 1 is best carried out in an inert aprotic solvent such as methylene chloride, tetrahydrofuran or acetonitrile at a temperature between 0 and 82 ° C. A catalytic amount of 1,4-diazabicyclo [2,2,2] octane [DABCO ^R ] may be used to accelerate the reaction. If the products are insoluble in the reaction solvent, these can be isolated by simple filtration. If the products are soluble, they can be isolated by evaporation of the solvent, disintegration with a solvent such as 1-chlorobutane, diethyl ether or ethyl acetate, and filtration.

The compounds of formula I are present in equimolar amounts of a tertiary amine such as 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) as shown in Scheme 2 below. It may be prepared below by reacting sulfonamide IV with a suitable phenyl ester of carbamic acid or thiocarbamic acid of formula V.

Reaction formula 2

[0185]

[Chemical 27] In the formula, J, R, W and A are as described above.

The reaction shown in Scheme 2 is as described in European Patent Application No. 70,804 (January 26, 1983) at 25 ° C. in a solvent such as dioxane or acetonitrile under an inert atmosphere. Best done.
The desired product of formula I may be conveniently isolated by acidifying the reaction solution with aqueous hydrochloric acid. Alternatively, the aqueous phase may be extracted with a solvent such as methylene chloride or ethyl acetate. Drying and evaporation of the solvent gives the desired product.

Phenyl carbamate and phenyl thiocarbamate of formula V are described in South African Patent Application No. 82/5
It can be prepared by methods known to those skilled in the art as described in 671 and 82/5045, or by modifications thereof.

In preparing the compounds of formula I, the J value (J ₁ ~
The appropriate method must be carefully selected in consideration of the characteristics of the substituents contained in J ₆ ), that is, Q and R ₁ and their chemical compatibility with the reaction conditions of Reaction Schemes 1 and 2.

The sulfonyl isocyanate of formula II is prepared by reacting a sulfonamide of general formula IV with n-butylisocyanate and a catalytic amount of 1,4-diazabicyclo [2,2,2] octane (DABCO) as shown in Reaction Scheme 3. It can be prepared by reacting with phosgene underneath.

Reaction formula 3

[0191]

[Chemical 28] Where J is as described above, but E is not oxygen.

The reaction represented by Reaction Scheme 3 is described in US Pat.
Best done by the method described in US Pat. No. 238,621.

Sulfonyl isocyanate II can also be prepared via phosgenation of preformed n-butylurea of formula VI as shown in Scheme 4.

Reaction formula 4

[0195]

[Chemical 29] Where J is as described above, but E is not oxygen.

The compound of formula VI is a suitable sulfonamide IV,
Mix a mixture of anhydrous potassium carbonate and n-butyl isocyanate in a suitable solvent such as acetone or methyl ethyl ketone until all isocyanate has reacted 25-
It is conveniently prepared by stirring at 80 ° C. The product is isolated by cooling in dilute aqueous acid and recrystallising the insoluble solid. Then, n-butylurea VI was mixed with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in the same manner as described in Reaction Scheme 3 for reference.
To process. Alternatively, treatment of the sulfonamide of formula IV with thionyl chloride provides an intermediate N-sulfinylsulfonamide.
VII is formed which upon exposure to phosgene in the presence of a catalytic amount of pyridine is a sulfonylisocyanate II (where W is O
Is caused).

Reaction formula 5

[0198]

[Chemical 30] The reaction formula 5 is H.264. Ulrich, B.I. Tatsuka (T
ucker) and A. Sayigh, Journal of Organic Chemistry (J. Org. Chem.), 3 .
4, 3200 may be performed best by the method of (1969).

Sulfonyl isothiocyanate II (W is S
Are known in the art and are prepared from the corresponding sulfonamide (V) by reaction with carbon disulfide and potassium hydroxide, followed by treatment of the resulting dipotassium salt with phosgene. Such a method is described in Arch. Pham. Two
99,174 (1966).

In preparing the compound of formula II, the J value (J ₁ ~
A suitable method must be carefully selected in consideration of the characteristics of the substituents contained in J ₆ ), that is, Q and R ₁ and its chemical compatibility with the reaction conditions of Reaction Schemes 3 to 5.

The required sulfonamides of formula IV can be synthesized by one or more of the following methods.

Reaction Scheme 6 represents the reaction of a sulfonyl chloride of formula VIII with ammonia to form a sulfonamide of formula IVa.

Reaction formula 6

[0204]

[Chemical 31] Where J is as described above, but E is not oxygen.

The amination of reaction formula 6 is diethyl ether,
This can be done by adding at least 2 molar equivalents of anhydrous ammonia or concentrated ammonium hydroxide to a solution of the sulfonyl chloride VIII in a solvent such as methylene chloride or tetrahydrofuran at a temperature between -30 and 25 ° C. formula
The sulfonamide of IVa is isolated either by filtration to remove the ammonium chloride byproduct by washing with water, or by extraction into an organic solvent such as methylene chloride.
Drying and evaporation of the solvent gives the sulfonamide IVa,
This is usually pure enough to carry out the next step directly.

The sulfonyl chloride of formula VIII can be prepared by reaction scheme 7,
It may be prepared by one or more of the methods shown in 8 and 9.

As shown in Reaction Scheme 7, an appropriately substituted N-of Formula IX in the presence of cupric chloride or cuprous chloride.
Reaction of the arylhydroxylamine and subsequent displacement with sulfur dioxide yields the desired sulfonyl chloride of formula VIII.

Reaction formula 7

[0209]

[Chemical 32] The reaction of Scheme 7 involves combining the appropriate aryl hydroxylamine with aqueous concentrated hydrochloric acid and acetic acid, and at -10 to 10 ° C.
By adding an aqueous solution of sodium nitrite. After stirring for 10 minutes to 2 hours, the reaction mixture was stirred at -5 to -5.
At 20 ° C. add to a mixture of acetic acid, catalytic amounts of cuprous or cupric chloride and excess sulfur dioxide. After stirring for 0.5-24 hours, the mixture is diluted with cold water and the product is extracted into a solvent such as methylene chloride or ethyl ether.

The sulfonyl chloride solution thus obtained can be treated as in Scheme 6 to prepare the desired sulfonamide IVa.

By the diazotization of an appropriately substituted amine derivative of the formula X and subsequent reaction with sulfur dioxide in the presence of cupric chloride or cuprous chloride as shown in Scheme 8 A VIII product results.

Reaction formula 8

[0213]

[Chemical 33] The reaction of Reaction Scheme 8 can be carried out by a method similar to that described in European Patent Application Nos. 83,975 and 85,476 (August 10, 1983). Reaction formula 8
At 5 to 5 ° C., the amine X substituted in concentrated hydrochloric acid at
Treated with a solution of sodium nitrite in water. After stirring at about 0 ° C. for 10 minutes to 1 hour, the solution is stirred in acetic acid for about 1 hour.
At 0 ° C. add to the mixture of excess sulfur dioxide and catalytic amount of cupric or cuprous chloride. At a temperature between 10 and 25 ° C.
After stirring for 25-24 hours, the solution was poured into excess ice water. The sulfonyl chloride VIII may be isolated by filtration, or extraction into a solvent such as methylene chloride or ether, followed by drying and evaporation of the solvent.

Alternatively, the diazotization of the appropriately substituted amine hydrochloride salt of formula Xa can be carried out under anhydrous conditions, as shown in formula 8a, followed by sulfur dioxide and cupric chloride. The reaction yields the desired product of formula VIII.

Formula 8a

[0216]

[Chemical 34] Amine hydrochloride Xa is diazotized with an alkyl nitrite in a suitable solvent such as acetonitrile or acetone and the resulting diazonium salt is reacted with sulfur dioxide and cupric chloride to give the sulfonyl chloride VIII. M. Doyle is a journal of organic
Chemistry, Volume 42, 2426, 2431 (197)
7) [J. Org. Chem. 42 , 2426, 2431 (1977)] describes the conditions for performing similar Meerwein reactions.

The sulfonyl chloride may also be an appropriately substituted aryl or heterocyclic substrate as shown in Reaction Scheme 9 below.
It can be prepared by metal-halogen exchange or direct lithiation of XI and scavenging with sulfuryl chloride.

Reaction formula 9

[0219]

[Chemical 35] In the formula, J is as described above, provided that R ₁ is CO ₂ Rc, C ₁
-C ₃ haloalkyl, Br, nitro, not a C ₁ -C ₃ alkylsulfonyl or CN.

The lithiation shown in reaction formula 10 was carried out by S.I.
H. Bhattacharya et al., Journal
Of Chemical Society (J. Chem. Soc.)
(C), the method of 1265 (1968) or H.M. Gschwind and H.M. Rodriguez, Organic Reactions,
Volume 26, Wiley, New York, 197
9, as well as the methods described in the references cited therein.

Compounds of formula VIII may be prepared via the oxidative chlorination of a suitable thioether or mercaptan of formula XII as depicted in Scheme 10.

Reaction formula 10

[0223]

[Chemical 36] Where J is as described above, R ₁₅ is H, C ₂ -C ₄ alkyl or benzyl, and R ₁ is not C ₁ -C ₃ alkylthio or C ₁ -C ₃ alkylsulfinyl.

The reaction of Scheme 10 is a solution of thioether XII in a solvent such as acetic acid in the presence of at least 2.5 equivalents of water and at least 3.0 equivalents of chlorine at 0-30 ° C.
It can be performed by treating for 25 to 5 hours. The reactants were poured into ice-water and the product was isolated by extraction with a suitable solvent such as methylene chloride, dried and the solvent evaporated to give the product sufficiently pure for the next step directly. Give rise to things.

Arylmethanesulfonyl chloride of formula VIIIb
Is more suitable for the simple two-step process outlined in Scheme 11.
May be prepared from benzyl bromide of formula XIII substituted with
It Reaction formula 11

[0226]

[Chemical 37] Wherein, J'CH ₂ is J-1 to J-6 is defined for E is CH _2; R ₁ and Q are R ₁ is C ₁ -C ₃ alkylthio or C ₁ -C ₃ alkylsulfinyl Huy As above with the exception that it is not nil; and M is Cl or Br.

Conversion of an alkyl halide of formula XIII to an isothiouronium of formula XIV is described by T.W. B. Ji Young Song
son) and J. M. Spraque, Journal
Of the American Chemical Society (JA
m. Chem. Soc. ), 58 , 1348 (1936); 59 , 1
837 and 2439 (1937); 61 , 176 (1939).
It can be performed by the method of. The oxidative chlorination of isothiouronium salts such as XIV to give the sulfonyl chloride of formula VIIIb is best performed by the method of Jyonson described in Journal of American Chemical Society, 61 , 2548 (1939).

The required tetrazole substituted intermediates are characterized by the nature of the aromatic ring in the J (J-1 to J-6) system and the J (J-1 to J-6) on which the tetrazole is substituted. It may be prepared by a variety of methods depending on the nature of the other substitutions present. These intermediates can be prepared by those skilled in the art by the methods referred to in the following references on tetrazole chemistry: R. Benson, "Heterocyclic compounds (H
eterocyclic Compounds) "[R. C. Elderfield Edition] 8 , 1-104, John Wiley and Sons, New York, (1967); N. Butler,
"Advances in Heterocyclic
Chem. ), 21 , 323-436, Academic Press (1977); N. Butler, “Comprehensive Heterocyclic Chemistry
Chem. ) ”[K. T. Potts Edition] 5 , 791-8
38, Pergamon Press (198)
4) and F.I. R. Benson, “High Nitrogen Compounds (High Nitr
ogen Compounds) ", Jyon Wheelie and Sons, New York (1983).

The heterocyclic group of formula III in the above reaction scheme 1
Min is well known in the literature by those familiar with the field
Method, or a simple modification thereof. example
For example, European Patent Application No. 84,224 (July 1983)
March 27) and W.A. Breaker, Jer
The Null of American Chemical Society,
69, 3072 (1947) include acetal groups such as di-
Alkoxymethyl or 1,3-dioxirane-2-i
Of aminopyridines and triazines substituted by
The manufacturing method is described. Also, for example, a South African patent was issued.
Haro on Wish Nos. 82/5045 and 82/5671
Alkyl or haloalkylthio such as OCH₂CH₂F, O
CH₂CF₃, SCF₂H or OCF₂Aminopi substituted by H
Methods of making limidines and triazines are described. South Africa
Frika Patent Application No. 83/7434 (October 1983)
Alkyl, haloalkyl, alkoxy,
Haloalkoxy, alkylamino, dialkylamino
Or substituted by groups such as alkoxyalkyl
A method for synthesizing lopropylpyrimidine and triazine is described.
Has been done.

5,6-dihydrofuro [2,3-d] pyrimidin-2-amine, cyclopenta [d] pyrimidine-2
-Amine (III, A is A-2) and 6,7-dihydro-5H-pyrano [2,3-d] pyrimidin-2-amine (I
II, A is A-3) is European Patent Application No. 15,6
It may be prepared as described in No. 83. Flow [2,3-
d] Pyrimidin-2-amine (III, A is A-4) is described in European Patent Application No. 46,677.

Compounds of formula III wherein A is A-5 are described in European Patent Application No. 73,562. Compounds of formula III wherein A is A-6 are described in European Patent Application No. 9
No. 4,260.

In addition, general methods for the preparation of aminopyrimidines and triazines are described in the following publications: "The Chemistry of Heterocyclic Compounds (The Chemistry of Het
erocyclic Compounds) ", Interscience (Inter
science) publishers, series published by New York and London; "Pyrimidines", D.M. J. Brown (Br
Vol. 16 of the same series by own ;; "s-Triazines and Des.
rivatives) ", E.I. M. Smolin and L.L. Volume 13 of the same series by Rappoport; C. Shaefer, US Pat. No. 3,1
54,547 and K.S. R. Huffman and F.F. C. The synthesis of Schiffer, Journal of Organic Chemistry, 28 , 1812 (1963), triazine is described.

The agriculturally suitable salts of the compounds of formula I are also useful herbicides and may be prepared by a number of methods known in the art. For example, a metal salt may be prepared by contacting a compound of formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion, such as a hydroxide, alcoholate or carbonate. Quaternary amine salts can be prepared by similar techniques.

Salts of compounds of formula I may also be prepared by exchanging one cation for another. Cation exchange may be carried out by contacting an aqueous solution of a salt of a compound of formula I (eg an alkali or quaternary amine salt) directly 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.

An aqueous solution of a salt of a compound of formula I (eg an alkali metal or quaternary amine salt) may also be passed through a column packed with a cation exchange resin containing the cations exchanged for the original salt, and The exchange can be done by eluting the desired product from the column. In this method, the desired salt is an aqueous solution. It is particularly useful when it is a potassium, sodium or calcium salt, for example.

Acid addition salts useful in the present invention can be obtained by reacting a compound of formula I with a suitable compound such as p-toluenesulfonic acid, trichloroacetic acid and the like.

The preparation of compounds of the present invention is further illustrated by the following specific examples.

[0238]

【Example】

Example 1 1- (2-chlorosulfonylphenyl) -5-methyl-1
H-tetrazole 2.3 g of 1- (2-hydroxyaminophenyl) -5-methyl-1H-tetrazole in 12 ml of 37% hydrochloric acid and 5 ml of acetic acid 2.3 g of sodium nitrite in 10 ml of water at 0-5 ° C.
Was added. The resulting solution was stirred at -5 to + 5 ° C for 1 hour,
Then, with stirring, at <5 ° C., it was added in one portion to a mixture of 25 ml of acetic acid, 0.5 g of cupric chloride and 5 ml of liquefied sulfur dioxide. In the meantime, the mixture was stirred for 2 hours while warming to room temperature, then poured into ice and 150 ml of water and extracted twice with 150 ml of methylene chloride. Methylene chloride solution with 100 ml of water three times, saturated aqueous sodium bicarbonate solution 10
2 times with 0 ml, followed by 100 ml of saturated aqueous sodium chloride solution
And washed once with 100 ml of water. The methylene chloride solution was then dried over magnesium sulfate and filtered to produce a solution containing the desired sulfonyl chloride. This solution was used to prepare the sulfonamide of Example 2 without further treatment.

Example 2 1- (2-Aminosulfonylphenyl) -5-methyl-1
25 ml of H-tetrazole 28% ammonium hydroxide was added to the methylene chloride solution obtained from Example 1, the mixture was stirred for 2 hours and concentrated in vacuo to yield a mixture of oil and solid. 2.2 g of the desired product which is isolated by filtration and is washed with water and melts at 141 DEG-148 DEG C.
Was generated. Infrared absorption peaks at 3260 and 3360 cm ^-1 are consistent with NH ₂ and at 1160 and 1350 cm
^-1 was consistent with the desired product SO ₂ . Calculated by elemental analysis for C ₈ H ₉ N ₅ O ₂ S: C, 40.15; H, 3.79; N, 2
9.26; S, 13.39. Found: C, 40.43; H, 3.8.
4; N. 29.61; S, 13.04.

Example 3 5- (2-chlorosulfonylphenyl) -2-methyl-2
H-tetrazole and 5- (2-chlorosulfonylphenyl)
Nyl) -1-methyl-1H-tetrazole 5- (2- dissolved in 12 ml of 37% hydrochloric acid and 5 ml of acetic acid
Hydroxyaminophenyl) -2-methyl-2H-tetrazole and 5- (2-hydroxyaminophenyl) -1
-Methyl-1H-tetrazole mixture-5g-5g-5
2.3 g of sodium nitrite dissolved in 10 ml of water were added with stirring at ° C. After 1 hour at 0-5 ° C., the solution was 25 ml acetic acid, 0.5 g cupric chloride and 5 ml sulfur dioxide chloride.
To the above mixture in portions. After the addition was complete, the cooling bath was removed and the reaction mixture was warmed to 31 ° C, whereupon the cooling bath was used again and stirring was continued for up to two and a half hours after the addition was complete. The mixture was then poured onto ice water and treated as described in Example 1 except that the desired methylene chloride solution was concentrated in vacuo to produce a solidified oil. This product (3.28) is a mixture of the desired sulfonyl chlorides.
g) was pure enough for the preparation of the sulfonamide of Example 4.

Example 4 5- (2-Aminosulfonylphenyl) -2-methyl-2
H-tetrazole and 5- (2-aminosulfonylphene)
Nyl) -1-methyl-1H-tetrazole The solid product obtained in Example 3 was treated with tetrahydrofuran 5
Dissolve in 0 ml, and 28% ammonium hydroxide 20
Aliquots were added to ml. The mixture was stirred for 1 hour and concentrated in vacuo. Water was added to the residue, the mixture was filtered, and the solid was washed with a small amount of cold water to give 1.3 g of a mixture of isomers. The infrared absorption spectra shown by the peaks at 3260 and 3360 cm ^-1 are consistent with NH ₂ ,
And 1160 and 1330 corresponded to the desired product SO ₂ groups. Calculated elemental analysis for C ₈ H ₉ N ₅ O ₂ S:
C, 40.15; H, 3.79; N. 29.26; 13.3
9.

Found: C, 40.49; H, 3.86; N.V. 29.99; S.
13.75.

Example 5 5- (2-Aminosulfonylphenyl) -1-methyl-1
4- (2-Ethylthiophenyl) -1-methyl-1H-tetrazole in 40 ml of H-tetrazolepropionic acid and 1.08 g of water.
To 4 g, 5.2 ml of liquid chlorine (1.367 g / ml) was slowly added dropwise at -10 ° C. After the addition, the mixture was warmed to room temperature and then poured into about 100 g of ice. The resulting sulfonyl chloride was extracted with methylene chloride, washed with water, and the methylene chloride solution was added to 45 ml of concentrated aqueous ammonium hydroxide solution while maintaining the reaction temperature below 25 ° C. using ice bath cooling. The methylene chloride was evaporated to give a solid product, which was removed from the aqueous residue by filtration and washed with water. 3.72 g of the product melts at 176 DEG-179 DEG C. and corresponds to the desired sulfonamide 3210.
And an absorption peak by an infrared spectrum at 3300 cm ^-1 .

Example 6 5- (2-Aminosulfonyl-4-methylphenyl) -1
-Methyl-1H-tetrazole- 5- (4-methyl-2-propylthiophenyl) -1-methyl-1H-tetrazole cooled to -10 ° C 4.68
g, 40 ml of propionic acid and 1.08 g of water in a mixture of 5.2 ml of chlorine (liquefaction) while maintaining the reaction temperature at -10 to 0 ° C.
Was added dropwise. After half an hour, the reaction mixture was warmed to room temperature and stirred for 1 hour. It was then poured into 200 ml of ice and water and extracted with methylene chloride.
Methylene chloride solution at 10 ° C concentrated ammonium hydroxide 45
Add to ml and stir overnight. The mixture is concentrated in vacuo to an oil residue which is taken up in 100 ml of methylene chloride, 100 ml of water and 100 of saturated aqueous sodium hydroxide solution.
Wash 3 times with ml. The methylene chloride solution is then dried over magnesium sulphate, filtered and the filtrate evaporated to 1
This produced 4.1 g of the desired product, which melts at 61-171 ° C.

NMR (CDCl ₃ ): δ 2.56 (s, CH ₃ on phenyl); 3.99
(s, CH ₃ on tetrazole); 5.6 (s, w, NH ₂ ); and 7.
3-8.1 (m, 3CH on phenyl).

Example 7 5- (2-Aminosulfonyl-3-methylphenyl) -1
-Methyl -1H-tetrazole Reacts with a mixture of 14.6 ml concentrated (12M) hydrochloric acid at 0 ° C, 6.1 ml acetic acid, 25 ml ethyl ether and 5- (2-amino-3-methylphenyl) -1-methyl-1H-tetrazole. While maintaining the temperature below 10 ° C., 2.8 g of sodium nitrite dissolved in 12.2 ml of water was added dropwise.
Stirring was continued for 1 hour after the addition was complete. This mixture was then slowly added to 30.5 ml acetic acid containing 0.6 g cupric chloride and 6.1 ml liquefied sulfur dioxide. After stirring for 2 hours at ambient temperature, the mixture was poured into 200 ml of ice-water and extracted twice with 125 ml of methylene chloride. Next, the organic phase is water 20
2 times with 0 ml and 1 with 200 ml of saturated aqueous sodium chloride solution
Wash once with 200 ml of aqueous sodium bicarbonate solution, followed by 200 ml of water and 200 ml of saturated aqueous sodium chloride solution. The organic phase was then added dropwise to concentrated aqueous ammonium hydroxide solution, the mixture was stirred overnight and evaporated to a solid, which was washed with water and dried. The crude product thus obtained melts at 140-161 ° C,
The yield was 6.26 g. Mass spectral analysis showed a molecular weight of 253 (calculated 253) for the product.

Example 8 N-[(4,6-dimethoxypyrimidin-2-yl) ami
Nocarbonyl] -2- (2-methyl-2H-tetrazole
-5-yl) benzenesulfonamide 25 ml of acetonitrile at ambient temperature and pressure 5- (2-
0.48 g of aminosulfonylphenyl-2-methyl-2H-tetrazole and 0.54 g of phenyl N- (4,6-dimethoxypyrimidin-2-yl) carbamate are added, followed by 0.3 ml of DBU. After stirring for 3 hours, the reaction mixture was added to 25 g of ice and adjusted to pH 3 with hydrochloric acid. The precipitate thus obtained is filtered, washed with water,
Then it was dried to yield 0.66 g of the desired product, mp 214-222 ° C. 1720, 1600 and 15
Infrared absorption at 80 cm ^-1 was consistent with the desired structure.

NMR (CDCl ₃ ): δ3.91 (s, 2XCH ₃ O) 5.82 (s, CH, pyrimidine) 4.43 (s, CH ₃ on N-2 of tetrazole)) 4.38 ( s, CH ₃ on N-1 of tetrazole).

One CH showing the ratio of 2-methyl-2H-tetrazole to 1-methyl-1H-tetrazole of 2: 1 by integration of the peaks at 4.43d and 4.38d.
It reached ₃ . This mixture is suitable for the purposes of the invention. If necessary, the isomer mixture obtained in Example 6 could be separated into its component parts by chromatography.

Example 9 N-[(4,6-dimethoxypyrimidin-2-yl) ami
Nocarbonyl] -2- (5-methyl-1H-tetrazole
-1-yl) benzenesulfonamide To 048 g of 1- (2-aminosulfonylphenyl) -5-methyl-1H-tetrazole in 25 ml of acetonitrile at ambient temperature and pressure phenyl N- (4,6-dimethoxypyrimidine-2- Ill) carbamate 054g and DBU
0.3 ml was added. The reaction mixture was stirred for 3 hours and iced 25 g
In addition, the solution was adjusted to pH 3 with hydrochloric acid.
The precipitate thus obtained is filtered, washed with water and dried to yield 0.74 g of the desired product, mp 213-216 ° C. The infrared absorption spectrum showed peaks at 1710, 1605 and 1570 cm ⁻¹ , which corresponded to the desired product. _{NMR (CDCl 3): δ2.48 (} s, tetrazole on _{(CH 3) 3.82 (s,} 2XCH 3 O) 5.81 (s, CH- pyrimidine).

Example 10 N-[(4-Methoxy-6-methyl-1,3,5-tria]
Din-2-yl) aminocarbonyl] -2- (5-methyl
-1H-tetrazol-1-yl) benzenesulfonami
De acetonitrile 25ml of l- (2-aminosulfonyl-phenylalanine) -5-methyl -1H- tetrazole 048g and phenyl N-(4-methoxy-6-methyl-1,3,5
To 0.52 g of -triazin-2-yl) carbamate was added 0.3 ml of DBU at ambient temperature and pressure. The mixture is stirred for 3 hours, then 25 g of ice are added and acidified with hydrochloric acid. The precipitate thus obtained is filtered, washed with water and dried in vacuo to yield 0.65 g of the desired product, melting at 207-209 ° C. Infrared absorption spectra are 1700, 1600 and 1 that match the desired structure
It showed an absorption at 550 cm ^-1 .

Example 11 N-[(4-chloro-6-methoxypyrimidin-2-i
) Aminocarbonyl] -2- (1-methyl-1H-teto
Lazol-5-yl) benzenesulfonamide 0.4- (2-aminosulfonylphenyl) -1-methyl-1H-tetrazole in 20 ml dry acetonitrile 0.4
To 8 g and 0.56 g of phenyl N- (4-chloro-6-methoxypyrimidin-2-yl) carbamate were added 0.3 ml of DBU with stirring at ambient temperature. After stirring for 16 hours, the mixture was poured into 25 g of ice, followed by 10 ml of 2N hydrochloric acid.
Was added. The precipitate thus formed was filtered off, washed with water and dried to yield 0.74 g of the desired product, mp 225-227 ° C.

NMR (CDCl ₃ ): δ 3.88 (s, CH ₃ on tetrazole); 3.
95 (s, CH ₃ O); 6.52 (s, pyrimidine CH); 7.2
-7.5 (m, CH and NH of phenyl); 7.84 (m, 2CH of phenyl); 8.6 (m, CH of phenyl); and 11.96.
(s, NH).

Example 12 N-[(4,6-dimethoxypyrimidin-2-yl) ami
Nocarbonyl] -5-chloro-2- (4-methyl-5-
Oxo-1H, 4H-tetrazol-5-yl) benzenes
1 in Ruhon'amido acetonitrile 10 ml (2-aminosulfonyl-5-chlorophenyl) -4-methyl -1H- tetrazole -5 (H) - one 0.29g and phenyl N-(4, 6
-Dimethoxypyrimidin-2-yl) carbamate 0.2
To 7 g of the stirred solution was added 0.1 ml DBU at ambient temperature. The mixture was stirred for 2 hours, poured into 20 g of ice and acidified with 2N hydrochloric acid. The precipitate is removed by filtration,
Washed with water and dried to yield 0.37g of product, mp 178-180 ° C.

NMR (CDCl ₃ ): δ 3.63 (s, CH ₃ on tetrazole); 3.
_{92 (s, 2XCH 3 O)} ; 5.81 (s, pyrimidine CH);
7.4-8.6 (m, 3CH of phenyl); and 12.6 (s, w,
NH).

Example 13 3- (2-Methyl-2H-tetrazol-5-yl) -1
-Phenyl-1H-pyrazole-5-sulfonamide 12N hydrochloric acid 3.1 ml, acetic acid 12.5 ml, formic acid 3.7 ml and 5-amino-1-phenyl-3- (2-methyl-2H-).
To a mixture of 4.5 g of tetrazol-5-yl) -1H-pyrazole was added dropwise at -8 to -6 ° C 1.4 g of sodium nitrite in 2.5 ml of water. The mixture was stirred for 15 minutes and then added to 20 ml of acetic acid containing 3.7 ml of sulfur dioxide (liquid) and 0.75 g of cupric chloride anhydride. After stirring for 30 minutes and warming, the mixture was poured into an ice and water mixture and the precipitate was removed by filtration. After washing with water, dissolve the solid in tetrahydrofuran and -78 ° C.
It was cooled to and ammonia (liquefied, 1.0 ml) was added dropwise. The mixture was left at ambient temperature overnight and filtered to yield a brown solid. This solid showed peaks at 3300 and 3200 cm ^-1 corresponding to NH ₂ and 1370, 1185 and 1170 cm ^-1 corresponding to SO ₂ .

Example 14 5-Amino-1-methyl-4- (2H-tetrazole-
5-yl) pyrazole To 51.4 g of 5-amino-4-cyano-1-methylpyrazole in 300 ml of dimethylformamide at room temperature was added 31.0 g of sodium azide, followed by 25.0 g of ammonium chloride. The mixture was heated to 125 ° C. for 60 hours. The mixture was allowed to cool to room temperature and poured into a mixture of ice and water. The solution was adjusted to pH 9 and concentrated to a brown solid. Dissolve the residue in a minimum amount of water and
Acidified to pH 3 with hydrochloric acid. The solution was concentrated and the tan solid was extracted with methanol. Concentration gave 83.4 g of a tan solid with a melting point> 250 ° C. The product was used in the next reaction without further purification.

¹ HNMR (CDCl ₃ ): δ 7.70 (s, 1H, H on pyrazole) 6.10 (broad s, 2H, NH ₂ ) 3.64 (s, 3H, CH ₃ on pyrazole) ) Example 15 5-Amino-1-methyl-4- (2-methyl-2H-te
Trazol-5-yl) pyrazole 5-amino-1-methyl-4- (2H-tetrazol-5-yl) in 800 ml of dimethylformamide at room temperature
To a solution of 83.4 g of pyrazole, potassium carbonate 69.0
g, followed by 28.6 ml of iodomethane.
The mixture was stirred at room temperature overnight. Concentration of the mixture gave a waxy solid which was dissolved in the minimum amount of water. The aqueous phase was extracted with ethyl acetate. The organic layer is dried over magnesium sulfate, filtered and concentrated to a light yellow color (light
60.0 g of a yellow) solid was obtained. Chromatography of 20 g of crude product on silica gel afforded 6.6 g of the title compound as a white solid, mp 173-174 ° C.

¹ HNMR (CDCl ₃ ): δ 7.79 (s, 1H, pyrazole hydrogen) 4.80 (broad s, 2H, NH ₂ ) 4.15 (s, 3H, CH ₃ on pyrazole) 3 .70 (s, 3H, CH ₃ on tetrazole) Example 16 4- (2-Methyl-2H-tetrazol-5-yl)-
1-Methylpyrazole-5-sulfonamide 12N hydrochloric acid 5.2 ml, acetic acid 21.0 ml, formic acid 6.0
To a mixture of ml and 5-amino-1-methyl-4- (2-methyl-2H-tetrazol-5-yl) pyrazole 5.6 g 2.3 g sodium nitrite in 4.0 ml water at -10 ° C to -8 ° C was added dropwise. The mixture is stirred for a further 15 minutes and then 33 ml of acetic acid containing 6.2 ml of sulfur dioxide (liquid) and 1.25 g of cupric chloride dihydrate.
added to 1 After stirring for another hour and warming to room temperature, the mixture was poured into a slurry of ice and water. The precipitate was removed by vacuum filtration. The solid was air dried then dissolved in tetrahydrofuran, cooled to -70 ° C and ammonia (liquefied 1.7 ml) was added dropwise. The mixture was left at room temperature overnight. The mixture was filtered and then concentrated to give a tan solid. When recrystallized from methanol,
3.51 g of the title compound was obtained, mp 138-139 ° C.

¹ HNMR (CDCl ₃ ): δ 8.00 (s, 1H, H on pyrazole) 6.61 (s, 2H, SO ₂ NH ₂ ) 4.40 (s, 3H, CH ₃ ) 4. 20 (s, 3H, CH ₃ ) Example 17 N-[(4-methoxy-6-methylpyrimidin-2-y
Amino)]-1-methyl-4- (2-methyl)
Lou 2H-tetrazol-5-yl) pyrazole-5-
To a suspension of 0.24 g of the compound from Example 16 and 0.26 g of 4-methoxy-5-methylpyrimidin-2-ylcarbamic acid phenyl ester in 5.0 ml of sulfonamide acetonitrile, 1,8-diazabicyclo [5.4.0]. Undecor 7-ene 0.15 ml was added. After stirring for a further 2 hours, the mixture was diluted with 5 ml of water and acidified with 1N hydrochloric acid. The solid is collected by filtration, washed with water and ether to give 0.17 g of the title compound, mp 181-183 ° C.
Was obtained as a white solid.

[0261]¹ HNMR (200 MHz, DMSO-d₆): Δ 12.3 and 11.1 (s, 2 × 1H, NH) 8.15 (s, 1H, H on pyrazole) 6.90 (s, 1H, H on pyrimidine) 4.28 (s). 3H) 4.22 (s, 3H) 4.05 (s, 3H) 2.50 (s, 3H) IR (nujor): 1710 cm^-1 Example 18 N-[(4,6-dimethoxypyrimidin-2-yl) a
Minocarbonyl ]-1-methyl-4- (2-methyl-2
H-tetrazol-5-yl) pyrazole-5-sulfo
Namide Compound from Example 16 in 5.0 ml of acetonitrile
0.24 g and 4,6-dimethoxy-2-pyrimidinyl
To a suspension of 0.28 g of carbamic acid phenyl ester,
1,8-diazabicyclo [5.4.0] undeca 7-
0.15 ml of ene was added. After stirring for another 2 hours, mix
The mixture was diluted with 5.0 ml of water and acidified with 1N hydrochloric acid.
It was Collect the solid, wash with water and ether to give the title compound.
0.29 g of the compound is a white solid having a melting point of 171-173 ° C.
It was obtained.

¹ HNMR (200 MHz, DMSO-d ₆ ): δ 13.2 and 10.8 (s, 2 × 1H, NH) 8.10 (s, 1H, H on pyrazole) 6.05 (s, 1H, H on pyrimidine) 4.30 (s, 3H) 4.28 (s, 3H) 3.94 (s, 6H, CH ₃ O) IR (nujol): 1715 cm ^-1 Reaction formula above and examples Alternatively, by using the method described in the improved method thereof, those skilled in the art can prepare the compounds shown in the following table.

[0263]

[Table 1]

[0264]

[Table 2]

[0265]

[Table 3]

[0266]

[Table 4]

[0267]

[Table 5]

[0268]

[Table 6]

[0269]

[Table 7]

[0270]

[Table 8]

[0271]

[Table 9]

[0272]

[Table 10]

[0273]

[Table 11]

[0274]

[Table 12]

[0275]

[Table 13]

[0276]

[Table 14]

[0277]

[Table 15]

[0278]

[Table 16]

[0279]

[Table 17]

[0280]

[Table 18]

[0281]

[Table 19]

[0282]

[Table 20]

[0283]

[Table 21]

[0284]

[Table 22]

[0285]

[Table 23]

[0286]

[Table 24]

[0287]

[Table 25]

[0288]

[Table 26]

[0289]

[Table 27]

[0290]

[Table 28]

[0291]

[Table 29]

[0292]

[Table 30]

[0293]

[Table 31]

[0294]

[Table 32]

[0295]

[Table 33]

[0296]

[Table 34]

[0297]

[Table 35]

[0298]

[Table 36]

[0299]

[Table 37]

[0300]

[Table 38]

[0301]

[Table 39]

[0302]

[Table 40]

[0303]

[Table 41]

[0304]

[Table 42]

[0305]

[Table 43]

[0306]

[Table 44]

[0307]

[Table 45]

[0308]

[Table 46]

[0309]

[Table 47]

[0310]

[Table 48]

[0311]

[Table 49]

[0312]

[Table 50]

[0313]

[Table 51]

[0314]

[Table 52]

[0315]

[Table 53]

[0316]

[Table 54]

[0317]

[Table 55]

[0318]

[Table 56]

[0319]

[Table 57]

[0320]

[Table 58]

[0321]

[Table 59]

[0322]

[Table 60]

[0323]

[Table 61]

[0324]

[Table 62]

[0325]

[Table 63]

[0326]

[Table 64]

[0327]

[Table 65]

[0328]

[Table 66]

[0329]

[Table 67]

[0330]

[Table 68]

[0331]

[Table 69]

[0332]

[Table 70]

[0333]

[Table 71]

[0334]

[Table 72]

[0335]

[Table 73]

[0336]

[Table 74]

[0337]

[Table 75]

[0338]

[Table 76]

[0339]

[Table 77]

[0340]

[Table 78]

[0341]

[Table 79]

[0342]

[Table 80]

[0343]

[Table 81]

[0344]

[Table 82]

[0345]

[Table 83]

[0346]

[Table 84]

[0347]

[Table 85]

[0348]

[Table 86]

[0349]

[Table 87]

[0350]

[Table 88]

[0351]

[Table 89]

[0352]

[Table 90]

[0353]

[Table 91]

[0354]

[Table 92]

[0355]

[Table 93]

[0356]

[Table 94]

[0357]

[Table 95]

[0358]

[Table 96]

[0359]

[Table 97]

[0360]

[Table 98]

[0361]

[Table 99]

[0362]

[Table 100]

[0363]

[Table 101]

[0364]

[Table 102]

[0365]

[Table 103]

[0366]

[Table 104]

[0367]

[Table 105]

[0368]

[Table 106]

[0369]

[Table 107]

[0370]

[Table 108]

[0371]

[Table 109]

[0372]

[Table 110]

[0373]

[Table 111]

[0374]

[Table 112]

[0375]

[Table 113] Preparations Useful preparations of compounds of Formula I and II may be prepared in conventional manner. They are powders, granules, tablets, solutions, suspensions,
Includes emulsions, wettable powders, concentrated emulsions and the like. Many of these can be applied directly. The spray formulations can be extended in a suitable medium and are used in spray volumes of a few liters to a few hundred liters / ha. High-strength compositions are mainly used as intermediates for preparations. Generally speaking, the preparations contain about 0.
1 to 99% by weight and at least one of (a) about 0.1 to 20% surfactant and (b) about 1 to 99.9% solid or liquid inert diluent. More particularly they will contain these components in proportions approximately given below: * Active ingredient + at least one of surfactant or diluent = 100% by weight Of course, low or high amounts of active ingredient may also be present, depending on the intended use and the physical properties of the compound. A high ratio of surface-active to active ingredient is particularly desirable and is achieved by incorporation in the preparation or by mixing in tanks.

Typical solid diluents are Watkins (Watk
ins) et al., “Handbook of Insecticide Dust D
iluents and Carriers ", 2nd edition, Dorland Brooks, Caldwell, NJ, although other solids, natural and synthetic, may also be used. Adsorbent diluents are also suitable for use.Typical liquid diluents and solvents are Marsden
(Marsden), "Solvents guide", 2nd edition, Interscience, NY, 1950.
Listed in the year. Solubility below 0.1% is suitable for concentrated suspensions; concentrated solutions are preferably stable to phase separation at 0 ° C. "McCutcheon's Detergents
and Emulsifiers Annual ", Al-Alezd Publishing Company
(Allured Publ. Corp., NJ) and Sisli
(Sisely) and Wood, "Encyclopedia of
Surface Active Agents ", Chemical Publishing Company (Chem
ical Publ. Co. Inc. N. Y. ), 1964
The surface activity and its recommended use are indicated. All preparations may contain minor amounts of additives to reduce foaming, cake formation, corrosion, microbial growth and the like.

Methods for making such compositions are well known. Liquid formulations are prepared by simply mixing the components. The finely divided solid composition is prepared by mixing using a hammer mill or a fluid energy mill and usually milling. Suspending agents are produced by wet milling [see Littler, US Pat. No. 3,060,0.
No. 84]. Granules and tablets may be prepared by spraying the active substance onto a preformed granular carrier or by the agglomeration method. See J. E. By Browning,
"Agglomeration", Chemical Engineering, December 4, 147 (1967), and Perry.
Chemical Enginer's Handbook, 5th Edition, 8-5
P. 7, McGraw-Hill, N .;
Y. ), 1973.

For further literature on preparation techniques, see
See, for example: M. Loux, U.S. Pat. No. 3,235,361, column 6, line 16 to column 7, 19
Rows and Examples 10-41; W. Lucky Bow (Lucke
nbaugh), U.S. Pat. No. 3,309,192, column 5, 43.
Line to column 7, line 62 and Examples 8, 12, 15, 39, 4
1, 52, 53, 58, 132, 138-140, 16
2-164, 166, 167, 169-182; Gysin and E. Knusli, US Patent No. 2,
891,855, column 3, line 66 to column 5, line 17 and Examples 1-4; G.I. C. "Wee" by Klingman
d Contral as as Science ", Jiyoung Wheelie
And Sons (John Wiley and Sons, Inc.,
New York), 1961, 81-96; D.
Fryer and S.I. A. By Evans,
"Weed Contral Handbook", Bracquewell
Scientific Publications (Blackwel
l Scientific Publications, Oxford), 1968
Year 101-103.

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

Example 19 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 80% alkylnaphthalene Sodium Sulfonate 2% Sodium Lignin Sulfonate 2% Synthetic Amorphous Silica 3% Kaolinite 13% The above ingredients are mixed, ground with a hammer mill until all solids are substantially below 50 microns and remixed. , And packaged.

Example 20 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (5-methyl-1H-tetrazol-1-yl) benzenesulfonamide 50% alkylnaphthalene Sodium Sulfonate 2% Low Viscosity Methyl Cellulose 2% Diatomaceous Earth 46% Mix the above ingredients and coarsely grind with a hammer mill, then with an air mill to produce particles that are essentially all 10 microns or less in diameter. It was The product was remixed prior to packaging.

Example 21 Granules Wettable Powder of Example 20 (above) 5% Attapulgite particles (US standard sieve 20-40 mesh; 0.84-0.42 mm) 95% of wettable powder containing 25% solids The slurry was sprayed onto the surface of the attapulgite particles while mixing in a double cone mixer. The particles were dried and packaged.

Example 22 Extruded tablet N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (5-methyl-1H-tetrazol-5-yl) benzenesulfonamide 25% anhydrous sodium sulfate 10% Crude Calcium Lignin Sulfonate 5% Sodium Alkylnaphthalene Sulfonate 1% Calcium / Magnesium Bentonay 59% The above ingredients are mixed and treated with a hammer mill, then about 1
Moistened with 2% water. This mixture was extruded as a cylinder with a diameter of 3 mm and cut into tablets with a length of 3 mm.
It can be used directly after drying, or the dried tablets can be crushed into US Standard Sieve No. 20 (opening 0.84).
mm). Particles that remained on US Standard Sieve No. 40 (0.42 mm opening) were packaged for use and the bottom sieve was circulated.

Example 23 Oily suspension N-[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 25% poly Oxyethylene sorbitol hexaoleate 5% Higher aliphatic hydrocarbon oil 70% The above ingredients were milled together in a sand mill to reduce solid particles to about 5 microns or less. The resulting thick suspension was applied directly, preferably after oiling or emulsification in water.

Example 24 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (5-methyl-1H-tetrazol-1-yl) benzenesulfonamide 20% alkylnaphthalene Sodium Sulfonate 4% Sodium Lignin Sulfonate 4% Low Viscosity Methyl Cellulose 3% Attapulgite 69% The above ingredients were thoroughly mixed. After milling in a hammer mill until essentially everything is below 100 microns particles, the material is remixed and US Standard Sieve No. 50
(Opening 0.3 mm) and packaged.

Example 25 Low Concentration Granules N-[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 1% N , N-Dimethylformamide 9% attapulgite particles (U.S. standard sieve 20-40 mesh) 90% The active ingredient was solvated and sprayed onto the desalted particles in a double cone mixer. After the solution spraying was complete, the mixer was run for a short time and then the particles were packaged.

Example 26 Aqueous Suspension N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 40% poly Acrylic paste 0.3% Dodecylphenol Polyethylene glycol ether 0.5% Disodium phosphate 1% Monosodium phosphate 0.5% Polyvinyl alcohol 1.0% Water 56.7% Mix the above ingredients and sandmill Crushed together in
Essentially everything was sized to be 5 microns in size.

Example 27 Liquid formulation N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide, sodium salt 5% water 95% Add the salt directly to the water with stirring to form a solution,
It was then packaged for application.

Example 28 Low Concentration Granules N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 0.1 % Attapulgite particles (American standard sieve 20-40 mesh) 99.9% The active ingredient was dissolved in the solvent and the solution was sprayed onto the de-powdered particles in a double cone mixer. After the liquid spray was complete, it was heated to evaporate the solvent. It was cooled and then packaged.

Example 29 Granules N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 80% Wetting agent 1 % Crude lignin sulfonate (containing 5 to 20% natural sucrose) 10% Attapulgite clay 9% The above ingredients were mixed and milled through a 100 mesh sieve. This was then added to a fluid bed granulator, the air flow was adjusted so that it was generally fluid, and a fine spray of water was sprayed onto the fluidized material. Flowing and atomization continued until particles in the desired size range were obtained. The spraying was stopped, but the flow continued, possibly with heating, until the water content was reduced to the desired concentration, generally less than 1%. It was then removed, sieved to the desired particle size range, typically 14-100 mesh (1410-149 microns), and packaged for application.

[0391] Example 30 High thickeners N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl -1H- tetrazol-5-yl) benzenesulfonamide 99% silica Aerogel 0.5% Synthetic Amorphous Silica 0.5% The above ingredients are mixed in a hammer mill and milled to produce essentially all that passes through US sieve No. 50 (opening 0.3 mm). Let This concentrate was further made into a composition as required.

Example 31 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 90% sulfosuccinic acid Sodium Dioctyl 0.1% Synthetic Fine Silica 9.9% The above ingredients were mixed in a hammer mill and ground to produce particles, essentially all below 100 microns. This was passed through a U.S. Standard Sieve No. 50 and then packaged.

Example 32 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 40% lignin sulfone Sodium acid 20% Montmorillonite clay 40% Mix the above ingredients thoroughly and crush roughly with a hammer mill,
It was then milled in an air mill to produce particles of essentially all 10 microns or less. Remix this stuff,
It was then packaged.

Example 33 Oily Suspension N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 35% poly Mixture of alcohol carboxylic acid ester and oil-soluble petroleum sulfonate 6% xylene 59% The above ingredients were compounded in a sand mill and ground together to produce particles that were essentially all 5 microns or less. . The product can be applied directly, oil-extended or emulsified in water.

Example 34 Dust N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (1-methyl-1H-tetrazol-5-yl) benzenesulfonamide 10% attapulgite 10% stone brush Stone 80% active ingredient was mixed with attapulgite and then passed through a hammer mill to produce substantially all particles below 200 microns. The ground concentrate was then mixed with powdered stylus until uniform.

The results of the use test showed that the compound of the present invention was a highly active pre-emergence or post-emergence herbicide or a plant growth regulator. These can be used in areas where complete extermination of all plants is expected, such as around fuel storage tanks, around ammunition depots,
Exhibits a wide range of utility for pre-emergence and / or post-emergence control of weeds in industrial storage areas, parking lots, outdoor theaters, billboard areas, highways and railroad areas. Some of the compounds are also useful for the selective control of pre-emergence and / or post-emergence of weeds in crops such as corn, rice, wheat, barley and rape. Also, many of the compounds are useful for improving plant growth. The ratio of the compound of the present invention to be used is as a plant growth improver or herbicide, coexisting crop species, weed species to be controlled, weather and climate, selected formulation, application method, amount of leaves present, etc. It is determined by many factors, including Generally speaking, the compound should be used in an amount of about 0.001 to 10 kg / ha, in which case when used on light soils and / or soils of low organic matter content Lower doses are used when improving growth or when only short-term persistence is needed.

The compounds of this invention may be combined with other commercially available herbicides such as the triazines, triazoles, uracils, ureas, amides, diphenyl ethers, carbamates, phenoxyacetic acid and bipyridylium types, and other sulfonylurea herbicides. Can also be used. These are particularly useful when combined with the following herbicides.

Common name Chemical name Arachra 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetoanilide atrazine 2-chloro-4- (ethylamino) -6- (isopropylamino) -s- Triazine butyrate s-Ethyl-diisobutylthiocarbamate Cyanazine 2-{[4-chloro-6- (ethylamino) -s-triazin-2-yl] amine} -2-methylpropionitrile dicarba 3,6-dichloro-o -Anisic acid EPTC s-Ethyldipropylthiocarbamate Linuron 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurine Methracler 2-chloro-N- (2-ethyl-6-methylphenyl)- N- (2-methoxy-1-methylethyl) acetamide metribuzin 4-amino-6-t-butyl-3- (methylthio) as-triazin-5 (4H) -one tridiphene 2- (3,5-dichlorophenyl) -2- (2,2,2-trichloroethyl) oxirane 2,4-D (2,4-dichlorophenyl) Enoxy) acetic acid thiobencarb S-4-chlorobenzyldiethylthiocarbamate molinate S-ethyl N, N-hexamethylenethiocarbamate butachlor N- (butoxymethyl) -2-chloro 2 ', 6'-diethylacetoanilide naproanilide N-phenyl-2- (1 naphthyloxy ) Propionamide pyrazolate 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazolu 5-yl-4-toluenesulfonate pretilachlor 2-chloro 2 ', 6'-diethyl-N- (n-propoxyethyl) acetanilide oxydiazone 3- [2,4-dichloro -5- (1-Methylethoxy) -phenyl] -5- (1,1-dimethylethyl) -1,3,4-oxadiazol-2 (3H) -one Trade name Chemical name Harmony ^TM 3-{[(4-methoxy-6-methyl -1,3,5-Triazin-2-yl) aminocarbonyl] aminosulfonyl} -2-thiofenecarboxylic acid, methyl ester Cinchi ^R exo 1-methyl-4- (1 (Cinch) ^R- methylethyl) -2-[(2 -Methylphenyl) methoxy] -7-oxabicyclo [2.2.1] heptane MY-93 S- (1-methyl-1-phenethyl) piperidine-1-carbothioate CH-83 S- (2-methylpropyl) -hexanehydro-1H-azepine-1-carbothioic acid , Ester X-52 2,4-dichlorophenyl-3-methoxy-4-nitrophenyl ether SC-2957 S-benzyl-N-ethyl-N-propylthiocarbamate HW-52 N- (2,3-dichlorophenyl)-(ethoxymethoxy) benzamide NTN-801 2- (benzothiazol-2-yl) -N-methyl- N-phenylacetamide SL-49 2- [4-[(2,4-dichlorophenyl) carbonyl] -1,3-dimethyl-1H-pyrazol-5-yloxy] -1-phenylethanone BAS-514 3,7-dichloro-8-quinolinecarboxylic acid The herbicidal properties of this compound were found in many greenhouse tests. The test methods and results are as follows.

[0399]

[Table 114]

[0400]

[Table 115]

[0401]

[Table 116]

[0402]

[Table 117]

[0403]

[Table 118]

[0404]

[Table 119]

[0405]

[Table 120]

[0406]

[Table 121]

[0407]

[Table 122] Test A Himesekiba (Digitaria spp.), Barnyard grass (Sataria fa
berii) (if present), Echinochlo (Echinochlo)
a crusqalli), Japanese cypress (Bromus secalinu)
s), oats (Avena fatua), velvet leaf (A)
btilon theophrasti), morning glory (Ipomoea spp.),
Xanthium pensylvanicum, sorghum, corn, soybean, sugar beet, cotton, rice, barley (if present), wheat and pearl nut (Cyperus rot)
undus) lumps were planted and subjected to pre-emergence treatment with test chemicals dissolved in a solvent that was harmless to the plants. At the same time these crops and weed species were treated in soil / leaves. At the time of treatment the plants ranged in height from 2 to 18 cm. Treated plants and controls were kept in the hotbed for 16 days, after which all species were compared to controls and the response to treatment was assessed visually. The evaluation summarized in Table A is 0.
= Based on a numerical scale from no damage to 10 = complete eradication. The accompanying letter symbols have the following meanings: C = yellowing / disruption; B = burn; D = leaved leaf; E = inhibition of germination; G = delayed growth; H = effect of formation; U = abnormal pigmentation; X = axillary stimulation;
S = pigmentation; and 6Y = buds or flowers with abscesses.

[0408]

[Table 123]

[0409]

[Table 124]

[0410]

[Table 125]

[0411]

[Table 126]

[0412]

[Table 127]

[0413]

[Table 128]

[0414]

[Table 129]

[0415]

[Table 130]

[0416]

[Table 131]

[0417]

[Table 132]

[0418]

[Table 133]

[0419]

[Table 134]

[0420]

[Table 135]

[0421]

[Table 136]

[0422]

[Table 137]

[0423]

[Table 138]

[0424]

[Table 139]

[0425]

[Table 140]

[0426]

[Table 141]

[0427]

[Table 142]

[0428]

[Table 143]

[0429]

[Table 144]

[0430]

[Table 145]

[0431]

[Table 146]

[0432]

[Table 147]

[0433]

[Table 148]

[0434]

[Table 149]

[0435]

[Table 150]

[0436]

[Table 151]

[0437]

[Table 152]

[0438]

[Table 153]

[0439]

[Table 154]

[0440]

[Table 155]

[0441]

[Table 156]

[0442]

[Table 157]

[0443]

[Table 158]

[0444]

[Table 159]

[0445]

[Table 160]

[0446]

[Table 161]

[0447]

[Table 162]

[0448]

[Table 163]

[0449]

[Table 164]

[0450]

[Table 165]

[0451]

[Table 166]

[0452]

[Table 167]

[0453]

[Table 168]

[0454]

[Table 169]

[0455]

[Table 170]

[0456]

[Table 171]

[0457]

[Table 172]

[0458]

[Table 173]

[0459]

[Table 174]

[0460]

[Table 175]

[0461]

[Table 176]

[0462]

[Table 177]

[0463]

[Table 178]

[0464]

[Table 179]

[0465]

[Table 180]

[0466]

[Table 181]

[0467]

[Table 182]

[0468]

[Table 183]

[0469]

[Table 184]

[0470]

[Table 185]

[0471]

[Table 186]

[0472]

[Table 187]

[0473]

[Table 188]

[0474]

[Table 189] Test B After germination, two round-bottomed pans (diameter 25 cm, depth 12.5 cm) were filled with Sassafras sandy loam soil. In one pot, blackgrass (Alopecurus myosuroides), sugar beet, tuber (Cyperus rotundus) tubers, rape (Brassicanapus), and crabgrass (Digitaria sanquinal).
is), cucumber pottus (Cassia obtusifolia), tayweed (Sida Spinosa), white-necked morning glory (Datura stramonium), velvet leaf (Abutilo)
n theophrasti) and Anoenokokurogusa (Setaria fa
berii) planted. Other pots such as wheat, barley, cotton,
Rice, corn, soybean, oats (Avenafatu
a), fir (Xanthium pensylvanicum), morning glory
(Ipomoea hederacea), Seymour Sorghum (Sorghum ha
lepense) and the shrimp (Echinochloa crusqalli). The plant was grown for about 14 days. The plants were then sprayed with chemicals dissolved in a solvent that was harmless to the plants after germination.

Two round-bottom pans (diameter 25 cm, depth 12.5 cm) before germination were filled with Sassafras sandy loam soil. In one pot, blackgrass, sugar beet, nutsedge, oilseed rape, crabgrass, cichlid pod, tayweed, white-billed morning glory, velvet trefoil and Aquinoe foxtail were planted. Other pots such as wheat, barley, cotton, rice,
Soybeans, oats, onions, morning glory, sorghum and barnyard grass were planted. The two pots were sprayed with chemicals dissolved in a solvent that was harmless to the plants before germination.

Treated plants and controls were kept in the hotbed for 28 hours, then all treated plants were compared to controls and evaluated visually for plant response. Response ratings were based on a scale of 0-100 with 0 = no effect and 100 = full control. A dash (-) response means do not test.

Response assessments are included in Table B.

[0478]

[Table 190]

[0479]

[Table 191]

[0480]

[Table 192]

[0481]

[Table 193]

[0482]

[Table 194]

[0483]

[Table 195]

[0484]

[Table 196]

[0485]

[Table 197]

[0486]

[Table 198]

[0487]

[Table 199]

[0488]

[Table 200]

[0489]

[Table 201]

[0490]

[Table 202]

[0491]

[Table 203]

[0492]

[Table 204]

[0493]

[Table 205]

[0494]

[Table 206]

[0495]

[Table 207]

[0496]

[Table 208]

[0497]

[Table 209]

[0498]

[Table 210]

[0499]

[Table 211]

[0500]

[Table 212]

[0501]

[Table 213]

[0502]

[Table 214]

[0503]

[Table 215]

[0504]

[Table 216]

[0505]

[Table 217] Test C Maize and sorghum herbicide tests include preemergence and postemergence evaluations of the following species.

[0506]

[Table 218]

[0507]

[Table 219] Postemergence The postemergence plants were grown in Sssafras sandy loam soil. Corn and soybeans were grown in separate 25 cm diameter vessels. Sorghum and seven grass weed species were grown in two 18 cm diameter vessels, four per vessel. 7 broadleaf weed species, 4 species per container, 2
It was grown in two 18 cm diameter vessels. One additional planting of corn was made in an 18 cm diameter container. The soil surface of this additional container of corn was covered with the absorbent, perlite, prior to spraying treatment, so that the test chemical entered the plant only via the foliage. Plants were allowed to grow for 10-21 days depending on the species and then spray-treated with the test chemical dissolved in a non-phytotoxic solvent. Before germination (p
reemergence) preemergence planting
(s) is fertilized Tama silt loam soil
Let it grow. These plants were identical to the plants mentioned in the post-emergence test, except for the corn plant with perlite over the soil surface. These plantings were made on the day of spraying or prior to spraying the test chemical dissolved in the non-phytotoxic solvent.

Evaluation Treated plants and controls were kept in the greenhouse for 2-4 weeks.
The plant response assessment by visual inspection was performed on a percentage scale of 0-100 compared to controls. 0 is harmless and 100 is dead.

[0509]

[Table 220]

[0510]

[Table 221]

[0511]

[Table 222]

[0512]

[Table 223]

[0513]

[Table 224] Test D 16 cm with drain opening with plug near bottom of side wall
Diameter Wagner pots in Woodstown sandy loam soil (Woods
(town sandy loam) was partially filled. About 1 for each pot
Add 500 ml of water to bring the water level up from the soil surface to 3c
It was set to be above m. Japanese rice (Japonica rice) and Indian rice (Indica rice) seedlings were manually transplanted into pots. Seeds of a large number of barnyard grasses (Echinochloa crsgalli) were also added to each pot. At the same time, the seeds of the seedlings or tubers of following the (tubers) were transplanted into the muddy soil: Alisma orientale (water plantain) [Arisuma Toribare (Alisma tr
ivale)], Sushirupusu (Scirupus) [Kangarei (Scirupu
s mucranatus)], Kayatsuri (Cyperus) [smallflower umbrellaplant (C
yperus difformis )]. The weed species selected for this test are economically important in major rice growing areas. Chemical treatment has two additional species: water chess.
tnut) ( Eleocharis spp ) and arrowhead (Sagittari latifolia)
a latifolia)] within a few hours after transplantation, it was formulated in a non-phytotoxic solvent and applied directly to paddy water. Immediately after treatment, drain holes were opened to reduce the water level by 2 cm. Water was then added to bring the water level back to the original height.
The discharge and refill process was repeated the next day. The pot was then kept in the greenhouse.

The application rates and plant response assessments made 21 days after treatment are summarized in Table D. Response ratings are based on a scale of 0-100 with 0 being no effect and 100 being complete control.

[0515]

[Table 225]

Claims (1)

[Claims] 1. The formula: Wherein R ₁ is H, CH ₃ , Cl, Br or F; R
₃ is CH ₃ or C ₂ H ₅ ; X and Y are each CH
₃ or OCH ₃ ; and Z is CH or N, provided that R ₃ is CH ₃ , X and Y are OCH ₃ and Z is CH, then R ₁ is other than H. A herbicide, which comprises a compound or an agriculturally suitable salt thereof as an active ingredient.