CA1255661A - Herbicidal n-hydroxy-n'-sulfonylguanidines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present application disclosed plant growth regulants and herbicides of the following formula:

wherein R'' is C1-C3 alkyl;
R is H or CH3;

L is R5 is C1-C4 alkyl, C1-4 alkoxy, OCH2CH2OCH3.
F, C1, Br, NO, CF3, CO2R19, SO2NR20R21.
SO2N(OCH3)CH3, OSO2R22, S(O)nR23, WCF3, WCH2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, R6 is H, F, C1, Br,CF3, CH3, OCH3, SCH3 or OCF2H;
R7 is H. CH3, OCH3, F, C1, Br. SO2N(CH3)2, OSO2CH3 or S(O)nCH3:
R8 is CH3, CH2CH3, OCH3, OCH2CH3, F, C1, Br, SO2NR20R21, SO2N9OCH3) or S(O)nR23;
R9 is C1-C3 alkyl, F, C1, Br, NO2.
CO2R19 SO2NR20R2l, SO2N(OCH)3 CH3 or S(O)n23;
R10 is C1, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, OSO2CH3, SO2CH3, SO2CH2CH3, OCH3 or CH3 or CH2CH3 R11 is H, CH3 or CH2CH3;
R12 is H, CH3 or CH2CH3;
R13 is H or CH3;
R14 is H or CH3;
R15 is H or CH3;
R16 is CH3 or CH2CH3;
R17 is H or C1-C4 alkyl;
R18 is H or CH3;
R19 is C1-C4 alkyl, CH2CH2OCH3, CH2CH2C1 or CH2CH=CH2;

R20 is C1-C3 alkyl;
R21 is C1-C3 alkyl;
R22 is C1-C3 alkyl or N(CH3)2;
R23 is C1-C3 alkyl or CH2CH=H2;
m is 0 or 1;
n is 0 or 2;
Q1 is O. S. SO2 or NR17;
Q2 is O, S or NR17; and W is O. S or SO2;

A is X is CH3, OCH3, OCH2CH3, C1, F. Br, OCF2H, CH2F or CF3;
Y is H, CH3, OCH3, OCH2CH3, CH2OCH3, CH2OCH2CH3, N(CH3)2, CH2CH3, CF3, SCH, OCH2CH=CH2, OCH2C?CH, OCH2CF3, OCH2CH2OCH3, CH2SCH3, OCF2H, SCF2H, CR24 (QCH3)2, , , or CR24 (QCH2CH3)2;

Q is O or S;
R24 is H or CH3;
Z is CH or N;
Y1 is CH2 or O;
X1 is CH3, OCH3, OCH2CH3 or OCF2H;
Y2 is H or CH3;
X2 is CH3, CH2CH3 or CH2CF3;
Y3 is OCH3, OCH2CH3, SCH3, CH3 or CH2CH3;
X3 is CH3 or CH3;
and their agriculturally suitable salts;
provided that 1) when L is L-1 and A is A-1, R5 is C2-C4 alky1, C2 -C4 alkoxy, OCH2CH2OCH3, OSO2R22, S(O)nR23, WCF2, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, , 2) when L is L-1 and A is A-2 or A-3, then R5 is C1-C4 alkyl, C2-C4 alkoxy, OCH2CH2OCH3, Br, OSO2R22, WCF3, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, 3) when L is L-3 and A is A-1, A-2 or A-3, then R8 is SO2NR20R21, SO2N(OCH3)CH3 or SO2R23;
4) when L is L-4, L-5 or L-6 and A is A-1, A-2 and A-3, then R9 is C1-C3 alkyl, F, Cl, Br, NO2, SO2NR20R21, SO2N(OCH3)CH3 or S(O)nR23;
and 5) when L is L2 then A is A5 or A6;

6) the total number of carbon atoms of R20 and R21 is less than or equal to four;
7) when M is 1, then R13 is H;
8) when L is L-19, then R17 and R18 are not simultaneously H; and 9) when X is Cl, F or Br, then Z is CH and Y is OCH3; OCH3CH3, N(CH3)2 or OCF2H.

Description

~25S~

Title BA-B479-A-~
HERBICIDAL N-HYDROXY-N'-SU~FONYLGUANIDINES
Backqround of the Invention This invention relates to certain novel N-hydroxy-N'-sulfonylguanidine compounds, to compo-s;tions containing ~uch compounds, and to a method of use of such compo~itions to control the growth o~
undesired vegetation.
U.S. Patent 4,127,405 issued November 28, 1978 disclose~ substituted triazinyl arylsulfonylurea com-pounds of the following formuia:
.. . .

W N
Rl-SO2-NH-C-NH~ O ~ ' while U.S. Patent 4,169,719 issued October 2, 1979 discloses substituted pyrimidinyl arylsulfonylurea compounds of the following formula:
X ..
W N
Rl-SO2-NH-c N

Z
The triazine and pyrimidine compounds within the sco~e of the ~405 and ~719 patents include those wherein W
can be oxygen or sulfur. .
U.S. Patent 4,310,346 issued January 12, 1982 discloses sulfonylisothiourea compounds of the formula SO A X

2 S-B N ~
~502N=C-NH~OZ

~Z~i66~

wherein B i~ Cl-C6 alkyl, CH2CH2OCH3, CH2CH2OCH2CH3, CH~CH2CH2OCH3, CH2Q, CH-Q

where Q i~
O ~ CH3 O
CO~-Cl 3 alkyl, -CN , -CN(Cl_3 alkYl)2 O O
10 -cNH(cl-c3 alkyl)- CN 2' phenyl, phenyl substituted with chlorine, CN, C2 4 alkenyl, C2 4 alkynyl. ORll, where Rll is Cl-C4 alkyl, -CH2OCH2CH2OCH3 or -CH2cH2cH2cH2cH3 South African Patent No. 79/2657, published June 30, 1980 discloses sulfonylisothiourea compounds of the formula X

Rl-SO2N=C-NH ~ ~ Z
Y , .
wherein R2 is Cl-C20 alkyl; CH2CH2OCH3:
25 CH2cH2ocH2cH3; CH2CH2CH2 3 CH2OA~ where A' is C1-Cl2 alkyl.
-CH2CH~OCH3, -CH2CH OCH CH , phenyl or phenyl substituted with 1-2 NO2, 1-2 Cl,.or 1-2 CH3:
CH2A, CH-A where A is CO2(H, C1-C4 alkyl).

O ~ C1-C4 alkyl ~ C1-C4 alkyl CN , CN
H \ Cl~Cq alkyl, S6~i3l , / 3 ,, CN , CNH~ , phenyl, CN, C2-C4 \ OCH3 alkenyl, Cl-C4 alkynyl, phenyl substi-tuted with 1-2 CH3, 1-2 N02, 1-2 OCH3, 1-2 chlorine or phenoxy.
U.S. 4,301,2~36 issued November 17, lg81 dis-closes O-alkylsulfonylisoureas of the formula RS02N=C-NHR
wherein W is Cl, Br or OR12; and R is Cl-C12 alkyl, C3-C4 alkenyl, CH2CH20CH3, 2CH20CH2CH3~ (CH2)30CH3~ benzyl, CHR13Co2R14, where R13 is H or CH3 and R14 is Cl-C4 alkyl.

The compounds taught in the above five refer-ences are useful as general or selective herbicides having both preemergent and postemergent-herbicidal activity or plant growth regulant activity.

~2~S6~

Summar~ of the Invention The novel sulfonylguanidine compound~ of the present invention incorporating a guanidyloxyl moiety are highly active herbicides in both preemergent and postemergent applications. Certain compounds addi-tionally exhibit selective herbicidal 6afety to wheat and barley. Speci~ically, the i~vention relates to novel compounds of formula I, agriculturally suitable compositions containing them and their method of-use .
as pre-emergent and~or post-emergent hecbicides or plant growth regulants.
N-OR' R

wherein ~ is H or CH3:
R' is H. C(O)Rl, C(O)NR2R3 or CO2R4;
Rl is Cl-C3 alkyl or CF3:
2 H~ CH3 or C2H5; .
R3 is Cl-C3 alkyl:
R4 is Cl-C3 alkyl;
L is ~ ; ~ ~ R8 L-l . L-2 L-3 ~ R 9 q ~ZS;S~6~

s ~ ~ E

14~ 5 N-E16 ~ O

L-9 L 10 L-ll .. R13 R13 ~ 5 ~ Cl ~ 5,N E16 L _ L-13 L-14 ~ R17 ~ ~ ~ RlB ;

- O O

R5 is C1-C4 alkyl, Cl-C4 alkoxy, OCHzCH2OCH3, F, Cl, Br, NO2, CF3, CO2Rlg, SO2NR20R21.
s~2N(ocH3)cH3~ 52R22~ 5()nR23 3 WCHF2, C3-C4 alkenyloxy. C3-Cg alkynyloxy.
Ci-C2 alkyl substituted wit~ OCH3 or ~SS6~

N-N N-N
OCH2CH3. C6H5~ ~ O ~ CH3 ' O

N-N r N
o,N ~ N~O , ~ S , ~ O

/~\ / =\ r N
-~`N,N-CH3 ' N~N ~ N`N >

. ~ , ~ or ~ ~ ;

R6 is H, F, Cl, Br, CF3, CH3, OCH3, SCH3 or OCF2H:
R7 is H, CH3, OCH3, F, Cl, Br, 5O2N~CH3)2, oso2cH3 Or s(o)ncH3;
R8 is CH3, CH2CH3, OCH3, OCH2CH3, F, Cl, 2 20R21' SO2N~OCH3)CH3 or S(O) R23 Rg is Cl-C3 alkyl, F, Cl, Br, NO2, 2 19 2 R20R21~ 52N(CH3)cH3 or S(O) R23;
Rlo is Cl, NO2, CO2CH3~ C2CH2CH3' SO N(CH3)2' OS2CH3- S02CH3, SO2CH2C 3 3 OCH2CH3:
R11 is H, CH3 or CH2CH3:
R12 is H~ CH3 or CH2cH3 R13 is H or CH3:
R14 is H or CH3:
R15 is H or CH3:
R16 is CH3 or CH2CH3:
R17 is ~ or Cl-C4 al~y~;
RlB is H or CH3;
Rlg is Cl-C4 alkyl, CH2CH2OCH3, CH2CH2Cl oc CH~CH=CH2:

~ZS5~

R20 is Cl-C3 alkyl ~21 i8 Cl-C3 alkyl R22 i~ Cl-C3 alkyl or N(CH3)2:
R23 is Cl-C3 alkyl or CH2CH5CH2:
m i~ 0 or 1;
n is 0 or 2;
Ql is O~ S~ SO2 or ~R17 Q2 is O, S OL NR17 and W is O, S or SO2:
N ~ N Xl ~ X

~ lC ~0~ ~ ~0~ ~

lS A-l A-2 A 3 Xl X2 OCH3 Y; 3 N ~

X is CH3, OCH3, OCH2CH3, Cl, F, ~r, OCF2H, CH2F o~ CF3;
Y is H, CH3, OCH3, OCH2CH3, CH20CH3, 2 2 3' ( 3)2' Z 3' 3' 3' OCH2CH=CH2, 0CH2C--CH. OCH2CF3, 0CH2CH20CH3, /
CH2SCH3, OCF2H, SCF2H, CR24(QCH3~2 \2 Q
Q ~ Q ~,CH~
CR24 ~ ' \24J or CR24(QCH~cH3~2;

Q is O or S;

~Z5S6~ 3L

R24 is H or CH3; . -Z is CH or N:
Yl is CH2 or O:
Xl is CH3, OCH3, OCH2CH3 or OCF2H;
Y2 is H o~ C~3:
2 i~ C~3, CH2CH3 or CH2CF3;
Y3 is OCH3. OCH2CH3. SCH3, CH3 o~
CH2CH3;
X3 is,CH3 or OCH3 provided that 1) the total numbe~ of carbon atoms of R20 and R21 is less than or equal to ~our;
2) when m is 1. ~hcn R13 is H; ~

3) when L is L-17, then R17 and R18 are not simultaneously H; and

4) when X i6 Cl, F or Br, then Z is CH and Y is OCH3. OCH2CH3, N(CH3)2 or OCF2H.

This invention also relates tO novel compounds 2~ of Formula II, suitable agricultural compositions , containing them and their method o use as genecal or selective preemergent or postemergent h-erbicides or plant growth regulants.

SR'' L-S02N=C-N-A
R
II
wherein R~ is Cl-C3 alkyl;
R, L and A are defined for Formula I:
provided that 1) when L is L-l and A is A-l, R5 is C2-C4 alkyl, C2-C~ alkoxy, OCH2CH20CH3. 0502R22.
)n 23' WCF2. WCHF2, C3-C4 alkenyloxY.

5~ti1 C3-C4 alkynyloxy, Cl-C2 alkyl substituted with OCH3 or OCH2~H3~ C6H5~
~ ~ CH3 ~ o3 ~ ~N

~ o , ~ -CH3, _N~

~ , ~ or ~

2) when L is L-l and A is A-2 or A-3, then R5 is Cl-C4 alkyl, C2-C4 alkoxy, OCH2CH2OCH3, Br, OSO2R22, WCF3, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Cl-C2 alkyl substituted with OCH3 or OCH2CH3~ C6H5~
~CH3 ~ O~ ' . ~o~N ' ~N~ ' ~ S

N ~ ~N
, ~ ~ 3~ ~N~ N

~ or 3) when L is L-3 and A is A-l, A-2 or A-3, then R8 is So2NR2oR2l/ so2N(ocH3)cH3 or SO2R23;
4) when L is L-4, L-5 or L-6 and A is A~1, A-2 and A-3, then Rg is C1-C3 alXyl, F, Cl, Br, NO2, So2NR2oR2l~ so2N(ocH3~cH3 or S(O)nR23; and 5) when L is L2 then A is A5 or A6.

....

~ZS5~

Preferred for reason~ of their higher herbicidal activi~y, greater plant growth regulant activi~y or more favoeable ease of synthesis are:
1) Compounds o~ Formula I where R is H, R' is H
S and A i~ A-l.
2) Compounds of Preferred 1 where Y i~ C~3.
CH3~ CH2cH~' CH20CH~' ~CH2CF3 or CH(OCH3)2 and X is CH3. OCH3, Cl or CF3.
3) Compounds of Preferred 2 where L is ~-1.
L-2, L-3, L-5, L-8, L-10, L-ll, L-16 or L-17.
4) Compounds of Preferred 3 where L is L-l.
R5 is OCH3, OCH2CH3, Cl, N02, CF3, C02CH3.
C2CH2CH3' SOZN(CH3)2' S02N(OCH3~CH3' 2R22' S()nR23. 0CF2H, S(:F2H, N-N

OCH2CH=CH2. OCH2C_CH. ~ O ~ CH
O-N N-O N-N
~ ' ~ or ~ \
R22 is Cl-C3 alkyl;
: R23 is CH3 and n is 2. -5) Compounds of Preferred 3 where L is L-2 and R7 is Cl, CH3, OCH3, SCH3 or Br.

6) Compounds of Preferred 3 where L is L-3 and R8 is Cl, S02CH~ or 502N(CH332.

7) Compounds of Preferred 3 wheee L is L-5 and Rg is C02CH3 or C02CH2CH3.

8) Compounds of Preferred 3 where L is L-8.

9) Compounds of Preferred 3 where L is L-10.

10) Compounds of Preferred 3 where L is L-ll.

11) Compounds of Preferred 3 where L is L-16.

12) Compounds of Preferred 3 where L is L-17.

13) Compounds of Formula II whe~e R is H and A
3s is A-l.

1~S566~

14) Compounds of Preferred 13 where Y is CH3, 3, 2CH3, H20CH3, OCH2CF3 or CH(OCH3)2 and X is CH3, OCH3, Cl or CF3:

15~ Compounds of Preferred 14 where L is L-l and R5 i~ S2R22~ 52R23' CF2~' 2 OCH2CH-CH~. OCH2C--CH, "l~ ,~ . , ~ .

N-0 N=N
~ or ~ 5 , Specifically Preerred for reasons of their highest herbicidal activity or grea~est plant growth regulant activity or most favorable ease of synthesis are:
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]aminosul~onyl]benzoic acid - methyl ester:
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-l-(hydroxyimino)methyl]aminosulfonyl~benzoic acid methyl ester:
o N',N'-dimethyl-N-[[1-(4,6-dimethyl-1;3,5-triazin-2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzene-disulfonamide; and . N',N'-dimethyl-N-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzene-disulfonamide.

~Z~566~L
1~
Detailed Descr iPt ion of the Invention SYnthes i6 The compounds of Formula Ia may be prepared ~y the reaction of hydroxylamine with an appropriately substituted S-alkyl benzenesulfonyl isothioure~ of Fo~mula II. as shown in Equation 1.
Equation 1 N-OH
SR'' ll 10LS2N-- NH2H L502N ~ \ N-A
. N A. R
R

II Ia wherein L, R, R'' and A are as previously defined.

The reaction of Equation 1 is conducted by con-tacting 1-3 equivalents of hydroxylamine hydcochloride and an equivalent amount of sodium acetate with a com-pound of Formula II in a suitable solvent, e.g.
tetrahydrofuran, at 0-30 for 1-24 hours. The product may be isolated by removal of solvent and trituration of the residue with water.
The compounds of Formula II may be prepared by the methods described in U.S. 4,301.286. Alternatively, they may be prepared by the procedure outlined in Equation 2.
Equation 2 SR'' LS2Cl ~ HN ~ N-A ~ II

III IV
wherein L. R. R'' and A are as previously defined.

56~
i ~he reaction of Equation 2 may be carried out by contacting a sulfonyl chloride of Formula III with an appropriately substituted S-alkyl isothiourea of Formula IV in an inert solvent, e.g., methylene chloride or tetrahydrofuran, in the presence of an acid scavenger, e.g~, aqueous sodium bicarbonate or a tertiary amine, e.g., triethylamine, for 1-3 days at 20-40. The product is isolated by removal of solvent and trituration of the residue with water, or by 10 extraction from water with an organic solvent, concentration, and chromatography.
Reference to the following patents and patent applications is sug~ested for details regarding the preparation of the sulfonyl chlorides III: U.S. Patent 15 4,169,719 to G. Levitt issued October 2, 1979, U.S.
Patent 4,127,405 to G. Levitt, issued November 28, 1978; U.S. Patent 4,383,113 to G. Levitt issued May 10, 1983; U.S. Patent 4,394,506 to G. Levitt issued July 20 19, 1983; U.S. Patent 4,120,691 to G. Levitt, issued October 17, 1978; U.S. Patent 4,238,621 issued December 9, 1980; European Patent Application Number 80304286.0 (E.I. du Pont de Nemours and Company) published June 10, 1981; European Patent Application Number 79302769.9 25 (E.I. du Pont de Nemours and Company) published July 23, 1980; Canadian Paten~ 1128042; European Patent Application 82301500.3 IE.I. du Pont de Nemours and Company) published November 17, 1982; European Patent Application 81305160.4 (E.I. du Pont de Nemours and 30 Company) published May 12, 1982; and copending Canadian Patent Applications Serial No. 413,400, to M.P. Rorer filed October 14, 1982; Serial ~o. 413,385, to R.J.
Pasteris filed October 14, 1982; Serial No. 439829, filed October 27, 1983 and Serial t~o. 419,031, to M.P.
35 Rorer filed January 06, 1983.

~;~SS6g~l ~. ~4 The preparatio~ of the compounds of Formula IV
i6 ~hown in Equation~ 3, 4 and 5.

(3a) S
ll NC-N-A H25 ~ H2 N-A
pyridine R

V VI

'3b?
VI (~ )2S04 _ ~ IV

R''I
wherein R, R'' and A are as previously defined.

The reaction of Equation 3a may be carried out by saturation of a solution of a compound of Formula V
in pyridine with hydrogen sulfide, allowing to react for 1 to 5 days at 25 to 40, removal o~ pyridine in vacuo, and crystallization of the product with water or an organic solvent e.g. ether or methylene chloride. The resulting compound of Formula VI may be reacted according to Equation 3b with one eguivalent of a dialkyl sulfate or alkyl iodide at 20 to 80 for 1 to 3 days to provide the corresponding alkyl sulfate or iodide salt of IV. The free base may be obtained by extraction from aqueous ~odium bicarbonate with an organic ~olvent, e.g. e~hyl acetate. An alterna-tive synthesis of compounds o Formula VI is shown in Equation 4.

3s .

15 ~ ~Ss 6~;
E~_ion 4 4a) ~ 5 HN'~`N-A
RNH-A J ~ NCS ~ ~ R

VII VIII

(4b) . . H20 VIII NaOH or ~ VI
MgO
wherein R and A are as previously defined: and J is C6H5 or C6H5O.

The reaction of Equation 4a is carried out by contacting a compound of Formula VII with l-1.5 equivalents of benzoyl- or phenoxycarbonylisothio-cyanate at 30-80 for 1-24 hours in a suitable sol-vent, e.g. acetonitrile or tetrahydrofuran. The product may be isolated by cooling or concentration and filtration. The reaction of Equation 4b may be performed by heating the compound of Formula VIII in an aqueous medium, with or without a cosolvent, in the presence of 1 to 2 equivalents of an alkali metal hydroxide or an alkali earth oxide at 30 to 80~ for 1-24 hours. The product is isolated by cooling, neutralization to pH 8, and filtration in the case where an alkali metal hydroxide is used, and in the case where an alkali earth oxide is used, the reaction mixture is filtered and the filtrate is concentrated, cooled, and filtered.

~S5661 ` 16 Heterocyclic amine~ of Formula VII and method6 for preparing them are known in the art. The synthe-si of heterocyclic amines such a6 those of For~ula VII ha~ been reviewed in "The Chemi~ry of Hete~ocyclic Compounds~, a series published by Interscience Publ., New Yor~ and London. 2-Aminopyrimidine~ are de~cribed by D. J. Brown in "The Pyrimidines~, Vol. XVI of this series. 2-Amino-1,3,5-triazines can be prepared accordin~ to methods described by E. M. S~olin and L. Rapaport in "s-Triazines and Derivatives", Vol.
XIII of the same series. The synthesis of tciazines is also described by F. C. Schaefer, U.S. 3,154,5~7 and by R. R. Huffman and F. C. Schaefer; J. Orq. Che~., 28, 1816 (1963). See also copending C~dian Application N~r 416,863, filed ~r 02, 1982, ~pean Pabent Application N~r 80300505.7, published September 17, 1980 (Pub. ~o.
15,683), European Patent ~pplication Number 81303837.9, published March 3, 1982 (Pub. No. 46,677): European Patent Application Number 82306492.8, published July 27, 1983 (Pub. No. 8q,22q); and European Patent Application Numbec 82303611.6, published March 9, 1983 (Pub. No. 73,562), for description of met~ods for preparing heterocyclic amine derivatives.
A third method by which certain compounds of Formula IV may be obtained is shown in Equa~ion 5.
Equation S
.

X ..
~ SR
N N
~ N ~ R2NH~ ~NH _~ IV
Cl Y
IX
wherein R, R'~. X and Y are as previously defined.
.

16 ~Z~S6~

The reaction of Equation 5 may be carried out by contacting a chlo~otriazine of Formula IX with an S-alkyl isothiourea of Formula X in the same manner as was described in the reaction of Equation 2.
Compounds of Formulae Ib and Ic may be obtained from those of Formula Ia by the reactions of Equation 6.
Equation 6 (6a) lo N-OR' Ia R~Cl ~ LS02N N-A

Ib (6b). o N-o ~ NHR
R3NCO ~
Ia ~ ES02N N-A
H R
Ic wherein ( ) 1~ C(O)NR2R3, or C02R4, and L, R, R
R2, R3, R4, and A are as previously defined.

The reaction of Equation 6a is carried out by contacting Ia with 1-10 equivalents of the appropriate carboxylic acid chloride .or anhydride, or alkyl chloro-formate, or dialkyl carbamoyl chloride in the pre~ence of an acid scavenger, e.g. pyridine or a ~ertiary amine, at O to 40 for 2 to 24 hours, adding ice-water, and filtering or extracting the product into an organic solvent.

s~

The reaction of Equation 6b may be conducted by treating a solution of Ia in an inert ~olvent e.g.
methylene chloride or acetonitrile with 1-1.5 equiva-lents of an alkyl isocyanate at 20-aoo for 1 to 2~
hours. The product is isolated by concentrating the reaction mixture and trituration with a solvent e.g.
ether or chlorobutane.
Agriculturally suitable salts of compounds of Formulae I and II are also useful herbicides. Salts of compounds of Formulae I and II can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formulae I
and II wi~h a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydride). Quater-nary amine salts can be made by similar techniques.
Salts of compounds of Formulae I and II can also be prepared by exchange of one cation for another.
Cationic exchange can be effected by direct treatment of an aqueous solution of a salt of a co~pound of For-mulae I and Il (e.g.. alkali metal or quaternary amine salt) with a solution containing the cation to be ex-changed.
This method is most effective when the desired salt containing the exchanged cation is insoluble in water, e.g., a copper salt, and can be separated by filtration.
Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formulae I
and II (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged. In this method, the cation of the resin is exchanged for that of the original salt and the desired product is eluted from the column. This method is particularlv useful ~2S.S6~i1 when the de~ired ~alt iz water-soluble, e.g., a po~a6-~ium, sodiu~ or calcium salt.
Acid addition salts, useful in this invention, can be obtained by reacting a compound o~ Formulae I
and II with a ~uitable acid, e.g., ~-toluenesulfonic acid, trichloroacetic acid or the like.
In the following examples, all parts are by weight and temperatures in C unless otherwise indicated.

ExamPle 1 2-Chloro-N-[[(4,6-dimethylpy~imidin-2-yl)a~ino]hydroxy-iminomethYllbenzenesulfonamide To a solution of 0.5 g of methyl N'-(2-chloro-phenylsulfonyl)-N-(~,6-dimethylpycimdin-2-yl)carbam-imidothioate in 10 ml of cetrahydrofuran was added 0.3 g of hydroxylamine hydrochloride and 0.3 g of sodium acetate. The mixture was stirred at room temperature for 2 hours, whereupon the product was precipitated with ice-watec, filtered, washed with water, and dried by suction to afford 0.3 g of the title compound, m.p.
165-167. NMR(CDC13/DMSO-d6) ~ 2.6 (s, 6), 6.S (~, 25 1), 7.4 (m, 3), 8.2 (m, 1), 10.2 (br, 1), 12.0 (br, 1). m/e: 355 (M ).

Example 2 N-(4,6-Dimethylpvrimidin-2-Yl)thiourea A suspension of 10 g of 2-cyanoamino-4,6-di-metbylpyrimidine in 50 ml of pyridine was saturated with hydrogen sulfide and stored for 1 hour at 25.
The H2S treatment was repeated twice more. and the mixture was allowed to stir at 25 for 16 houcs.
Methylene;-chloride was added. and the product was S66~

~ 20 filtered and washed with methylene chloride to affo~d 8 g of 4,6-dimethylpyrimidin-2-yl ~hiourea, m.p.
~260. IR (Nu~ol* mineral oil) 3280, 3180, 3120~ 1610 cm ExamPle 3 N-[(4-Methoxy-6-methylpyrimidin-2-yl~aminothioxo-methYllbenzamide To a hot solution of 1~ 9 of ammonium ~hiocya-nate in 300 ml of ace~onitrile was added 24 ml of ben-zoyl chloride. The mixture was heated on the steam bath for 30 minu~es and filtered. The filtrate Wa6 heated with 21 g of 4-methoxy-6-me~hylpyrimidine-2-amine for 30 minutes and cooled. The product was collected by filtration and washed wi~h a little acetonitrile to provide 28 g of N-[[(4-methoxy-6-methylpyrimidin-2-yl)amino~hiocarbonyl]amino]benz-amide, m.p. 193-195. IR (Nujol) ~290, 1720 cm 1.

Example 4 N-(4-MethoxY-6-methylpYrimidin-2-yl)thiourea A mixture of 25 g of the compound ~rom Example 3 and 55 ml of 10% aqueous sodium hydroxide was heated on the steam bath for 30 minutes, cooled, neutralized with aqueous HCl to p~ 8, filtered, washed with water, dried by suction, and washed with ether to aford 16 g of the title compound, m.p. 220d.
Anal. Calc~d.: C: 42.4, H: 5.06, N: 28.2, S: 16.2 Found: C: 42.6, H: 4.~, N: 28.8~ S: 15.3 mJe 198 (M ).

~denotes t,rade mark.

~2~S~6~L

ExamPle 5 Methyl 2-~[1-(4-methoxy-6-me~hylpyrimidin-2-ylimino)-1-(methYlthio~meth~llaminosulfonvllbenzoate To 9 g of the compound from Example 4 and 100 ml of tetrahydrofuran was added 7.6 g of dimethyl sulfate and the mixture was stirred for 2 days at room temper-ature. The product was filtered and washed with a little tetrahydrofuran to give 22 g of crude product.
Five grams of this material was suspended in 150 ml of methylene chloride and 1 ml of water, and 5 g of sodium bicarbonate and 6 g of methyl 2-chlorosulfonyl benzoate were added. The mixture was stirred for 24 hours, washed with dilute aqueous HCl, dried with sodium sulfate, filtered, and chromatographed on silica gel to afford 2.8 g of the title compound as a crystalline solid, m.p. 143-144.
Anal. Calc'd.: C: 45.22, H: 4.55, N: 14.06, S: 16.1 Found: C: 46.8, H: 4.35, N: 13.2, S: 16 m/e 395 (M -CH3) NMR(CDC13) o 2.35 (s, 3), 2.45 (s, 3), 3.90 (s, 3), 4.0 (s, 3) 6.35 (s, 1), 7.7 (m, 3), 8.2 (m, 1), 10.8 (brs, 1).

Example 6 25 Methyl N-(4,6-dimethoxy-1,3,5-triazin-2-yl)carbamimi-dothioate A mixture of 20 g of 2-chloro-4,6-dimethoxy-s-triazine, 20 g of S-methyl isothiouronium sulfate, 16 g of sodium carbonate, and 50 ml of water was stirred for 72 hours, concentrated at reduced pressure, and extEacted with 300 ml of methylene chloride. The organic layer was dried with Na2SO9, filtered, concentrated to dryness, and recrystallized from chlorobutane to afford 10 9 of title compound, m.p.
99-100. NMR(CDC13) ~ 2.6 (s, 3), 4.0 (s, 6), 8.2 (brs, 1).

~2~6~1 Using the procedure~ and exar~ple~ ~hown above, the compounds in Tables 1-13 can be prepaeed.

.. . . . .

.

i.

~Z~6t~

Table la R

10 5 6 R'' jR X Y m.p.(C) 2 .2. CH3 3 3 5cH2cH=cH2 H C2H5 H OCH3 C2H5 OS02-n-C3H7 H CH3 CH3 CH3 CH20CH3 OS02-n-C3H7 H CH3 H CH3 SCH3 2 3 H CH3 ~ 3 3 CH2CH3 5-Br CH3 H CH3 OCH3 n-C4Hg H n-c3H7 H OCH3 OCH3 20 ~-C3H7 H CH3 CH3 OCH3 CH3 OS02N(CH3)2 H CH3 H CH3 CH(CH2CH2) CH2cH3 H CH3 H CH3 OCH3 O-l-C3H7 H CH3 H OCH3 OCH3 25 O_i_C3H7 H CH3 3 C2 5 O-n-C4H9 H CH3 H CH3 CH(OCH3)2 O-n-C4H9 H CH3 H CH3 OC2H5 S02CF2H 5-CH3 CH3 ~3 CH3 S02CF2H H C2H5 H OCH3 C2~5 20C 3 H n-c3H7 H H3 OCH3 -56~

Table la (continued?

R5 R6 P~' ' R X Y m.P.(C~

CH20CH2CH3 H CH3 H Cl OCH3 CH20CH2CH3 H CH ~ H Cl CH3 OCF2H ~ 3 CH3 CH(OCH2CH20) .. . . . . .

~2S56t;3L

Table lb 5O2N ~ N 1 N ~ y R
.

10 R5 R6 R'' R X Y m.p. (C) SO?CH2CH-CH2 H CH3 3 C 3 OS02-n-C3H7 H CH3 CH3 C~3 CH2OCH3 OS02-n-C3H7 H CH3 H CH3 SCH3 CHzCH3 3-Br CH3 H CH3 OCH3 n-C4H9 H n-c3H7 ~ OCH3 OCH3 OSO2N(CH3)2 H CH3 H CH3 CH(OCH2CH2O) CH2cH3 H CH3 H CH CH
OCHzCH3 H C~3 H CH3 OCH3 o-i-C3H7 H CH3 H CH3 3 25 O_i_C3H7 ~ CH3 H OCH3 C2H5 O-n-C4Hg H CH3 H CH3 CH(OCH3)2 O-n-C4Hg H CH3 H CH3 OC2H5 CH2OCH3 H n-c3H7 H OCH3 OCH3 .

~ss~

Table lb (continued2 R5 R6 R'' R X Y m P.(C) CH20CH3 H C:H3 CH3 OCH3 CH3 CH20CH2CH3 H CE~3 H Cl OCH3 .. . . ...

3 s i .

lZS5i6~

Table lc X
a~ SR' R

m.p.
10 R R S 6 X Y Z (~C) CH3 . . .2 ? 3 CH3 H CH
C~i H OCH2CH=CH2 H CH3 CK3 N
CH3 HOCH2cH-cH 6-OCH3 CH3 CH3 CH

15 CH3 H N-N~ H CH3 OCH3 CH

3 /1 ~\
~O~
CH3 ~3 H 3 2 N
S ,.
CH3 ~3 H 3 2 2 3 N
o CH3 2 3 3-OCF2H OCH3 C(CH3)(0CH3)2 CH

3 S02CH2CH3 H OCH3 N(CH3)2 CH
30CH3 CH3 S02C~2CH3 H OCH3 C(CH3)(~CH3)2 N
CH3 H S02CH2CH3 HOCF2H CH~SCH2CH2Si CH

CH3 H S02CH2CH3 HOC2H5 C(CH3)(0CH2CH20) CH
j.

~2SS~i6~

T~ble ld SR'' LS2N ~ N ~
N~/ z R N ~

: m.p.
10 R'' R ~ X Y Z ~C) CH3 H L2:R7.-Cl, 3 CH

CH3 ~ L2 R7=so2N~cH3~2 C 3 3 CH
CH3 H L3 ~8=S2N~CH3)2 3 3 CH
CH3 H L3:R8=S02CH3 CH3 OCH3 CH
CH3 CH3 L3:X8=S02cH2c 3 C1 OCH3 CH
i-C3H7 H L4:R9=Br 3 3 CH
CH3 H 5 9 2 5 OCH3 CH2cH=c~l2 CH
CH3 H L6:Rg=Cl OCH3 OCH2 _ N
CH3 H L7:Rlo=co2c 3 OCH3 OCH2CF3 N
CH3 8 Q1 ~ m 0~ R11=R12=R13=cH3 OCH3 CH2SCH3 CH
CH3 H L9:Q2=S~ R14 R15 ' H CH
CH3 H L1o:~=0~ ~13=H~ R16 3 OCH3 SCF2H CH
CH3 H Lll:m=O, R13=H OCH3 C(CH3)~0CH3)2 CH
CH3 H L12:m=1, R13 C 3 3 3 CH
CH3 H L13:m-0, R13-H OCH3 N~CH3)2 CH
CH3 CH3 L14 R16 CH2 3 OCH3 C(CH3)~SCH3)2 CH
CH3 H Ll~:R17 CH3 OCF2H CH(SCH2CH2S) CH
CH3 H L16:~17=H CF3 CH2CH3 CH
CH3 ~ L17 R17=R18 C 3 F OCH3 CH
CH3. H L17 R17 ~18 3 OC2H5 C~CH3~(0CH2CH20) CH

;, .

-Tabl~ le SR'' LS02N~N-A
R

m.p.
L R'' R A (C) Ll aS=C02CH3' a6=H CH3 H ~4:Xl=C~3. Y2 Ll R5=S2C~3' R6-H CH3 H A5:X2=CH2CH3, Y3=SCH3 Li:R5=N02, R6=H CH3 H A6:X3=OCH3 Ll:RS=Br, R6=H CH3 H A3:Xl=OCH3 Ll:RS=Cl, R6=H CH3 H As:x2=cH3~ Y3 2 5 Ll R5=C2H5' R6=H CH3 H A2:Xl=CH3~ 1 Ll:R5=SCF3, R6=H C2H5 H A3:Xl OC 2 L17:R17=H~ R18 CH3 CH3 H A2:~1=OCH3, Yl CH2 16 17 3 CH3 H A3:Xl=OCF2H
2 7 3 CH3 H A4:Xl=CH3~ Y2 3 L3:R8=F CH3 H A5:X2=CH2CH3~ Y3 3 L :R ~ C H CH3 H A5:X2=CH3~ Y3 CH2 3 L5:R9=S02CH3 CH H A :X --OCH
L6:R9=S02CH3 CH3 H A2:Xl=CH3~ Yl L7:Rlo=OCH2CH3 CH3 H A3:~1 3 ~8 Ql S'~Rll=R12=CH3~ m=1, R13=H CH3 H A6:~3=CH3 L9 Q2=o~ R14=R15 CH3 CH3 H A4:X1=0CH3. Y2 3 10 16 2 5' 13 3' CH3 H A5:~2=CH3. Y3 SC 3 Lll:m=l, R13=H CH3 H A2:Xl=CH3' Yl 2 L12:m=0~ R13 C 3 CH3 H ~2:Xl~ocH3~ Yl 2 30 L13:m=1, R13=H CH3 H A5:~2=CH2CF3' Y3 2 3 L14 R16=C~3 CH3 H A~:Xl=OCH3, Y2=H
L15 R17ScH3 CH3 H A4:Xl=0CH3. Y2 ~L2~5~6~

Table 2a H~ ll-OI~' 6 2~, , " R

10 R5 R6 R H CH3 3 1zl_167'~

Ccl H HH H OCH3 3 142-144 F H H H CE~3 CH3 B ~ H H H OCH 3 3 NO H H H CH3 CH(OC~2CH2O) NO2 HH CH3 H oCH3 C2H5 CF3 H H H OCH j 3 oO,c,3H3 HH HH HH CH3 CH (OCH3 ) 2 OCH3 H U H Cl OCH3 O_~ c~H <I~ CII]
C~ H H ~U~ C

~s~

Table 2a (cont;nued) R5 R6 R R' X Y m.P.(C) S02N(CH3)2 H ~E 3 ~3 S02N(CH3)2 H H CH3 CH3 S02N(CH3~2 H H H CH3 OCH3 166-168 S02N(CH3)2 H H H OCH3 OCH2C~E3 SO2N(CH3)2 H H H CH3 CH~OCH2CH20) 2 ( 2 H3)2 H CH3 H CH3 C2H5 S02N(CH2CH3)2 H H OCH3 OC2H5 2 ( 2 3)2 H H 3 CH3 C02CH2CH3 H H H CH3 CH(OCH3)2 2 H3 H H H Cl CH3 2 H3 H H H Cl OCH3 C02-i-C3H7 H H H CH3 CH3 $02N(OC~13)CH3 ~I H 3 CH3 C2CH2CH=CH2 H H 3 CH3 2 2 H2Cl ~E H H OCH3 OCH3 CO2-n-C4Hg H H 3 CH3 ~ 3 H H 3 2H5 z 2C CH2 H H 3 3 S2CH2CH=CH2 H H H CH3 OCH3 SCF3 H H H CH3 CH(CH2CH2) 2 HF2 j, H 3 CH3 C2~5 31 2S~ii6~;~

~ble 2a ~continued~

6 B jR' X Y m D. (-C?
_C H H H 3 3 n-C4Hg H H ~ CH3 OCH3 OS02NSCH3)2 H H H CH3 CH(OCH3)2 OS02NtCH3)2 H H H Cl CH3 OS02CH~CH3)2 H H H Cl OCH3 OS02CH3 H 3 OCH3 ~CH3 OS02CH~ , ~ , H 3 CH3 CH20CH3 H H H CN3 O~H3 CH3 ~ H H 3 CH3 lS S02-~-C3H7 H ~l 3 3 Cl H H CH3C0 3 3 131-136d Cl S-CF3 H H CH3 OCH3 Cl H H CH30COOCH3 OC2H5 Cl 6-SCH3 H H 3 3 Br H H (CH3)2NCO OCH3 CH3 B~ 3-OCH3 H 3 3 N02 H H CH3NHCO CH3 CH(CH2CH2) CF3 6-Cl H C2H5CO OCH3 CH3 OCH3 5-Cl H H CH3 CH(OCH3)2 30 OCH3 3-Cl H H Cl CH3 OCH3 H H CH3CO Cl OCH3 OC?HS 5-F H H 3 2 3 2 5 S-F H Et2NC 3 H3 OC2H5 3-Br 3 3 3 o-i-C3H7 H H EtOCO 3 3 ~25~66~l TAblQ ?a ~continued) R5 R6 R R~ X y ~ .~^C) O-n-C H N H - 3 7 CH3 OCH3 O-n-C H 6-CH3 H 3 3 O-l-C H 3-CF3 H 3 CO 3 H3 O-~-C4H9 6-CF3 H H 3 H3 S02N(CH3)i 6-SCH3 3 CH3 SOzN(CH3)2 5-SCH3 H CH3CO CH3 CH3 S02N(CH3)2 6-OCH3 H H CH3 OCH3 S02N(CH3)2 H H (CH3)2NCO OC~3 OCH3 S02N(CH3)2 3-OCH3 H H OCH3 OCH2CH3 S02N~CH3)2 H H CH3NHCO CH3 CH(CH2CH2) So2N(cH2cH3)2 3-CH3 3 CH3 C2H5 S02N(CH2cH3)2 5-CH3 CF3CO OCH3 OC2H5 C02CH2CH3 5-Cl H H CH3 CH~OCH3)2 2 3 6-Cl H H Cl CH3 2 H3 H H CH30CO Cl OCH3 C02-i-C3H7 5-F H (C2H5)2Nc CH3 C~3 C02-i-C3H7 3-Br 3 3 3 So2N(ocH3)cH3 H _ 3 7 3 3 C2CH2CH=CN2 6-CH3 H 3 3 C02-n-C4H9 6-CF3 H H 3 3 ~Z5S6~L

T~ble ?a ~continued) S 6 R R' X Y m P.~-C) S2C~2CH'C~2 5-SCH3 H CH3C0 3 H3 S2CH2CH~CH2 6-OCH3 3 OCH3 S2C~12CH2CH3 H H (CH3)2NCO OCH3 CH3 SCF3 H H CH3NHCO CH3 CH~OCH2CH20) S02CHF2 3 3 CH3 C2Hs ~-C3H7 . 6-C1 H 3 3 n~C4H9 H H C2H5CO CH3 OCH3 OS02N~CH3)2 6-Cl H H Cl CN3 OS02N(CH3)2 H H CH30CO Cl OCH3 OS02CN(CH3)2 5-F H CH3C0 3 2 3 2 3 3-Br 3 3 3 2 3 H H n-C3H70CO OCH3 CH3 2 3 H. H 3 7 CH3 OCH3 S02-i-C3H7 S-CF3 H 3 H3 ~ DPt~ re~er to molecular ion in electron-impact m~ss spectrum.

i' ~2~i~6~L

Table ?b R ~ 5 N-OR'~ 1 10 Rs R6 R ~ X Y m.P.(C) Cl H . H H3 CH3 Cl H H H CH3 OCH3 Cl H H CH3 OC2H5 Cl H H H3 OCH3 137-140 F H H H CH3 OC~3 Br H H 3 3 Br H H 3 CH3 NO2 H H H CH3 CH(CH2CH2) . CF3 H H H OCH3 OC2H5 .
: CF3 H H H OCH3 CH3 OCH3 H H H CH~ CH(OCH3)2 30 O-i-C3H7 H H 3 3 O-n-C3H H H H CH3 OCH3 O-l;l-C3H7 H H H CH3 CH3 O- i -C H H H H 3 OCH3 O_i_C4Hg H H 3 CH3 lZ55~61 Table 2b tcontinued) R5 6 R R' X Y m p (C) ,_ _ _ _ _ 2~H3 H H H3 OC2H5 SO2N(CH3)2 H H H OCH OCH ~ 3.0 and S2N(CH3)2 H ~ 3 3 4.0 (1:1)*~
S02N~CH3)2 H H H CH3 OCH3 S02N(CH3)2 H H H OCH3 OCH2CH3 S02N(CH3)2 H H H CH3 CH(OC~2CH20 o-2N(CH2~H332 H CH3 ~ CH3 C2~5 02N(CH2CH3)2 H ~ H OCH3 OC2H5 2N(CH2CH3)2 H H OCH3 C~3 C02CH2CH~ H H H CH3 OCH3 C02CH2CH3 H H H CH3 CH(OCH3)2 2C~3 H H H CH3 CH20CH3 C02-i-C3H7 H H H CM3 CH3 C02-i-C3H7 H CH3 H OCH3 OCH3 S02N(OCH3~CH3 H H OCH3 CH3 C2CH2CH=CH2 H H H CH3 CH3 C2CH2CH2Cl H H 3 OCH3 CO2-n-C4H9 H H 3 3 So2cH2cH-cH2 H H H CH3 CH3 S2cH2cH=cH2 H H H CH3 OCH3 z 3 H H 3 OCH3 SCF3 H H H CH3 CH(OC~2CHzO) ~2~S6~i~

T~ble 2b ~continued ?

R R6 a R X Y m ~.~ C) 5 i_C ~ H ~ 3 3 n~G4H9 H H 3 H3 OS02N~CN3)2 H H H CH3 CH~OCH3)~
OS02N~CH3)2 H H 3 3 OS02CH~CH3)2 H H H CX3 OCH3 OS02CH3 . H . C 3 H3 OCH3 Cl 3-CF3 H CH3 CH3 Cl S-CF3 H H CH3 OCH3 Cl H H CH30CO OCH3 OC2HS
20 Cl 6-SCH3 H H OCH3 OCH3 F 5-SCH3 H CH3C0 3 ~3 Br H H (CH3)2NCO OCH3 CH3 8r 3-OCH3 H 3 CH3 No2 H H CH3NHCO CH3 CH(CH2CH2) N2 3 3 CH3 C2Hs CF3 6-Cl H C2H5CO OCH3 CH3 ~CH3 5-Cl H H CH3 CH(OCH3)2 OCH3 6-Cl H H 3 3 OCH3 H H ~ 3 7 CH3 OCH3 C2H5 3-Br 3 3 3 ~L2556~

.

l~ble 2b (continued) R R6 ~ R~ X Y m p.('C) O-i-C3H~ H H EtOCO 3 3 O-n-C3H7 H H - 3 7COCH3 OCH3 : O-n-C3H 6-CH3 ~ 3 ~3 o-i-c h 3-CF3 H CH30C0 3 3 O-i-C4~9 5-CF3 H H 3 3 CO~C.H3 H H C~130CO OCH3 OC2N5 S02N(CH3)2 6-SCH3 H 3 H3 S02N(CH3)2 S-SCH3 H 3 CH3 CH3 502N~CH3)2 6-OCH3 H H CH3 OCH3 S02N(CH3~2 H H (CH3)2NCO OCH3 OCH3 S02N~CH3)2 3-OCH3 H H OCH3 OCH2CH3 S02N~CH3)2 H H CH3NHCO CH3 CH~OCH2CH20) S02N~CH2cH3)2 3-CH3 3 CH3 C2HS
so2N~cH2cH3)2 S-CH3 H - 3 7 OCH3 OCzH5 C02CH2CH3 H H CF3COCH3 OC~3 C02CH2CH3 S-Cl H C2H5CCH3 CH(OCH3)2 2 3 6-Cl H H 3 3 C02-i-C3H7 S-F H HCH3 CH3 C02-i-C3H7 3-8r 3 3 3 S02N(OCH3)CH3 H H Et2NC0 3 3 C02CH2CH20CH3 H H n-C3H70CO CH3 OCH3 C2CH2CH=CH2 6-CH3 H 3 3 C2CH2CH2Cl H H CH30C0 3 3 C02-n-C4Hg H H C2H5C0 3 3 2 3 " s-cF3 H H CH3 OCH3 ~zss~

able 2b (continued) S 6 R R' X Y m p. ( -C) S2CH3 6-scH3 H 3 3 5 S2CH2CH=CH2 5-SCH3 H H 3 3 S2CH2CH=CH2 6-OCH3 H SCH3)2NCo CH3 OCH3 ~2CH2cH2cH3 H H H 3 3 SCF3 H H CH3NHCO CH3 CH~OCH2Ci320) CH3 5-CH3 h 2 5 OCH3 OC2H5 i-C3H7 6-Cl H H OCH3 3 n~C4H9 H H ~ 3 7 CH3 OCH3 OS02N~CH3)2 6-Cl H C2H5CO CH3 CH3 os02N(cH3)2 H H ~ 3 7 CH3 OCH3 OS02CH(CH3)2 S-F H H 3 2 3 2 3 3-Br CH3 C2H5NHCO 3 3 2 3 H H (C2H5)2NCO OCH3 CH3 CH20CH3 H H C~3COCH3 OCH3 S02-i-C3H7 H H n-C3H7N~CO oCH3 CH3 X*Data refer to characteristic si~nals in NMR spectrwm (CDC13) in ppm downfield from tetramethylsilane.

~;Z55~61 Table 2c S R ~ ~I~ 1 N 1 H R

m p H H OCH2CH=CH2 H CH3 CH3 N
H OCH2CH_CH 6-OCH3 CH3CH3 CH
lS H H C6H5 H CH3 3 . N
H H ~N-N~ H CH3 OCH3 CH

H ~N-N~ 3 3 N
H H Cl H OCH3 OCH2C-CH N
CONHCH3 H Cl H OCH3 CH2cF3 CH
H H Cl H 3 2 2 3 N
25 H H Cl H OCH3 CH2SCH3 CH
: H H F H OCH3 OCF2H CH

H H F 3-OCF2H .OCH3 C(CH3~0CH3)2 CH

30 H H Br H OCH3 N(CH3)2 CH
H . 3 H OCH3 C(CH3)(SCH3)2 N
H 3 OCF2H CH(SCH2CH2S) CH

35 H 3 H OC2H5 C(CH3)(0CH2CH20) CH

~lZ~S6~

~ble 2c ~continued) R' R S 6 ~ Y Z m p.~'C) S H ~ H CH3 H CH

-N ~ 3 3 CH
H Hr N H CH3 OCH3 CH
~N~
COCF HO-n-C H7 3 3 CH
H HO-n-C3H7 H OCH3 CH2cH=cH2 CH
H HO-n-C3H~ H OCH3 OCH2C-CH N
H H. OCH3 ~-Br OCH3 OCH2cF3 N

H H CF3 3 .( 3)2 CH
33 H OCH3 C~CH3)~SCH3)2 CH
H CH3 CO2CH3 H OCF2H CH(SCH2CH2S) CH

H CH3 CO2CH3 H OC2H5 C(CH3)(0CH2CH20) CH
H H ~ H CH3 H N

30 H H ~ 3 3 N

H H ~3 H CH3 OCH3 CH
S

.- 2 2 2 3 3 CH
HC02CH2CH=CH2 HOCH3 OCH2CH=CH2 CH
.

~2S~

Tdble 2c . ( cont ~ nu~d~

R' j~ 5 6 jX Y Z m p.('C) H ~i CO2C112CH=CH2 H OCH3 OCH2C--CH N
H H S02N(CH3)2 H OCH3 OC112CF3 N
% H SO2N(CH3)2 3 2 2 3 N
H H SO2N(CH3)2 H OCH3 CH2SCH3 N
H H SO2N(OCH3)CH3 HOCH3 OCF2H CH
H SO2N(CH3)C2H5 H OCH3 SCF2H CH
H H SCF3 H OCH3 ~CH3) (CH3)2 CH

2 2 2 OCN3 N ( CH3 ) 2 CH
H3 C 2 2C 3 H OCH3 C ( CH3 ) ( SCH3)2 CH
'H H CO2CH2CH3 H OCF2H CH(SCH2CH2S) CH

H H S2CH3 H F OC.13 CH
CO-i-C3H7 H S2CH3 H OC2HS C(CH3) ~OCH2CH20) CH
' H H ~ H CH3 H N
o,N
H H ~ 3 3 N
,O
H H N=N~6-OCF2H CH3 OCH3 CH
25 ~ S
H H r N\ 3 3 CH
~o H - H OC2H5 NOCH3 C~2SCH3 CH

H H CH3 H oCH3 C(CH3)(0CH3)2 N
3 5 H Hi' CH3 H . OCH3 CF3 N

~S56~31 Tabl~ 2c (continued?

R' R Rs R6 X Y Z m D. (-C) H H CH3 H OCH3 N ( CH3 ) 2 N
51 ~N3 i_C3H7 H OCH3 C(CH3)(SCH3j2 CH
H H l-C3H? H OCF2H CH(SCH2CH2S) CH
H H i-C3H7 H CF3 CH2~H3 CH
H H l_C3H7 H F OCH3 CH
10 H H n-C4Hg H OC2HS C(CH3) (OCH2CH20) N

.. . . ..

~3 ~LZS~66~

T~ble 3 ~-OR' ~
5SO NH ~ N ~/ Z
~ ~ R7 R N ~

lo R~ a R' ~ Y Z m.P. ~C) CH3 H CN(~H3)2 OCH3 CH3 N
OCH3 N N Cl CH3 CH

Br H H F OCH3 CH
SO2N(CH3)2 H H CH3 OCH3 CH

CH3 H H CF3 N~CH3)2 . CH

F 2 2 3 3 CH(OCH3)2 CH

Br H H OCH3 CH2cH2cH3 N
2N(CH3)2 H H OCH3 CH2SCH3 N

SCH3 H H OCH2CH3 ~O ~ CH

CH3 - ~ H CH3 OCH3 N

~ 4 ~2~566~L

T~bls b N-OR' N X

S02N~N-</ Z
R N ~

m p 10 8 R R' X Y Z ~gC) .. O--\
CH3 H CON(CH3)2 OCH3 o ~ N
CH2CH3 H H Cl OCH3 CH

Cl H H CH3 CH3 CH
Br H H OCF2H CH3 C~
20 So2N~cH2cH3)2 H H CH2F OCH3 CH
S02NtCH3)2 CH3 H OCH2CH3 OCH3 N
S02N~OCH3)CH3 H H CF3 OCH3 CH
SCH2CH=CH2 H H OCH3 OCH3 CH

25 S-n-C3H7 .H H OCH3 C2H5 N

CH3 H H OCH3 C(CH3)(SCH3)2 CH
F H H OCH~CH3 OCF2H CH
H H C~3 2 5 2 CH
Br H H CH3 CH3 N

~Z551~61 'r~ble 5 N-OR~ _~
LS02NHJ~Ny Z
R N~

m.p.
; L 9 R R' ~ Y Z ~-C) L4 F . . H CN~CH3)2 OCH3 OC~3 N
L4 NO2 H H Cl OCH3 CH

L4 SO2N(CH3)2 H H OCH3 C~.2SCH3 CH
L4 S-i-C3H7 H H F CH3 CH
L n-C H H H CH3 N~CH3)2 CH
L5 Cl H H OCF2H CH20CH3 CH
L5 Br H H CH2F CH20C~13 CH
L~ CO2CH3 3 2 3 2 3 N
L5 S02N~C~H5)2 H H CF3 CH3 CH
. L5 SO2N~OCH3)CH3 H H OCH3 CH3. CH

25 Ls SO2CH3 H H OCH3S ~ N

L6 F H H OCH3 CH~OCH3)2 CH
L6 C2~1~C3H7 H H OCH2CH3 OCH3 CH
L6 SO2CH3 H H CH3 OC~3 CH
L6 S2N(CH3)2 H H CH3 OCH3 t N
L6 Br R H CH3OCH3 N

~;~S~i~6~L

4~
T~bl~ 6 ~ CH SO NH ~ N ~/
R N ~

R m.p.
10 10 ~ R' X y z NO H CON(CH3)2 OCH3 CH3 N
2 3 H H Cl CH3 CH

S2N(CH3)2 H H OCH3 CH3 CH
: OSo2cH3 H H F OCH3 CH

S02CH2CH3 H H OCL`2H OCH3 CH

CH2cH3 3 CH2cH3 OCH3 N
CH2cH3 H H CF3 CH2SCH3 CH
OCH2cH3 H H OC~I3 CF3 CH
OCH3 2 2 3 3 C~2CH3 CH

30 CO~CH3 H H ~H3 OCH3 N

~ZS56~

Table 7 S H~1~503~NHJ~ Z
R N ~
y ,l.. Rll . R12 R13 R R~ ~ m p O H H H ~ H CH3 OCH3 CH
S H H H H CN~CH3)2 OCH3 OCH3 N
S2 H .H H H H Cl OCH3 CH

2 3 c,l3 H H H CF2H CH3 CH

NH H CH3 H H H CH3 C(CH3~0CH3)2 CH
3 .3 H H H CH3 CH3 N

Tflble 8 R1~3 N-OR' ~
S02NHJI~N <Y Z
R N =~
Y

Q2 R14 Rls % R~ ~ m.p O H H H H Cl CH3 CH

O CH3 H U H OCH3 CH(OCH3)2 CH

' ~;~S5~

Tabl~

LS02NHJ~N~ Z
R N =~
y L jm 13 16 B R i_ L-10 1 ~ -CH3 H 3 2 3 CH3 N
L-10 O H 3 H Cl CH3 CH
L-ll O CH3 - H H CH3 CH3 CH
L-Il O CH3 - H H OCH3 CH(OCH3)2 CH
L-ll O CH3 - H H F OCH3 CH
L-ll O H - H H CH3 OCH3 CH

L-13 1 H - H H OCH3 OC~3 CH

i-~ZS5~

Sl T~ble 10 N-OR' LS02NH ~ N ~/ Z
R N ~

L R17 RlB R R' X Y Z ~C) lS H, ~ -CON(CH3)2 OCH3 CH3 N
lS H H Cl CH3 CH
lS H H CH3 CH3 CH
H H OCH3 CH(OCH3)2 CH
LlS H H H F OCH3 CH.
lS H H CH3 OCH3 CH
LlS CH3 - H H OCF2H OCH3 CH

L16 CH3 - H H .CF3 2 3 CH
16 3 H H OCH3 OCH3 ..... CH
L16 CH3 _ H 2 2 3 3 OCH3 CH

17 3 3 H OCH2CH3 CH3 CH
17 3 H H . CH3 CH3 CH

i ~Z~;566~

Table 11 H R
~ N-9R' R~So2NHJ~N-A
R

R5 6 R a~ A
CH3 ~ H HA2: yl=C~2; X1 CH3 1-C3H7 H . HA2: Yl=O; Xl=OCH3 OC H H H H 2 1 2; 1 2 O-n-C4Hg N H H A3 1 3 F 3-CF3 H C2CH3 A3: Xi=CH2 3 15 Cl H H C2CH3 A4: X1-CH3; 2 N02 H CH3 C2CH3 A4: Xl CH3; 2 3 CF3 H H C2CH3 A5: X2=CH3; Y3 OCH3 C2CH3 H H C2CH3 A5: X2=CH3; Y3 SCH3 - C02CH2CH3 3-CH3 H C2CH3 A5: X2=CH3; Y3 C2HS
20 S02N(CH3)2 H H C2CH3 A6 X3 CH3 S02N(C2H5)2 H H C2CH3 A6: X3=OCH3 oSo2cH2cH3 3 C2CH3 A2 Y1=; Xl=CH2CH3 SCH3 6-C1 H C 2C 3 2 1 2; 1 3 2 3 H H H A2: Y~=; Xl=CH3 25 OCHF2 H H COCH3 A3 X1=OCF2H
OCH2CH=CH2 H H H A : X -OCH

6 5 H H H A4: Xl=OCH3; Y2=CH3 N-N\ H H H A4: ~1=OCF2H; Y~=H
~ .
~ H H H A5: X2=cH2cP3; Y3 3 : 52 ~25566~
, Tsble_12 ~-OR' Jl LS02NH ~ `'N-A
R

L R R' A
L-2: R7=S02N(CH3)2 H H A2: yl=CH2; Xl 3 10 L-2: R -OSO CH H H ~2: Yl=O; Xl=OCH3 L-2: R7=Cl . . .. H H 2 1 C82; ~1=0CF2H
L i- R7=Br H H 3 1 3 L-3 R8=CH3 H C02CH3 A3: Xl=OCH2CH3 L 3 8 3 H CO~CH3 A4: ~1=OCH3; Y2 15 L-3: R8=S02CH2CH3 CH3 C02CH3 .A4: Xl=CH3; 2 3 L-4: R9=C02CH3 H C02CH3 ~S X2=CH3; Y3 OC 3 .. L-S: R9=C02-i-C3H7 2 3 S 2 3; 3 3 L-6: R9=Cl H C02CH3 A5 X2=CH3; Y3 2 5 L-4: Rg=NO2 H C02CH3 A6 ~3 CH3 20 L-S: R9-S02N~CH3)2 H C02CH3 A6 X3 OCH3 9 2 5 CH3 co2cH3 A2 Yl=O; Xl 2 3 10 2 3 H C02CH3 A2 Yl=CH2; 1 3 L-7: Rlo=S2N~CH3)2 H H A2: Yl=; Xl 3 L-7: Rlo=OS02CH3 H COCH3 A3 Xl=OCF2H
25 L-8: Rll=R12=R13-CH3; m ; Ql 3 1 3 L-9: R14=CH3; R15=H; Q2 3 H H A4: Xl=OCH3; Y2 3 L-10: R16=C2HS; R13=H; m=l H H A4: Xl=OCF2H; Y~=H
L-ll R13=H; m=O H H A5: ~2=CZHS; Y3=C2HS
13 3; H H S ~2=CH2cF3; Y3=cH3 30 L-13 R13=CH3; m=O H H A5: X2=CH3; Y3 C2HS
L-14 R16=CH3 H H 6 3 3 L-lS: R17=H H H A2: Yl=CH2; Xl=CH3 L-lS: R~7=H H H A2: Yl.=O; Xl=OCH3 L-lS: R17=H H H 2 1 2' 1 2 ~2S5~

T~ble 12 ~contlnued) L R R' A

L-16: R1~CH3 H C02C~3 A3 Xl~OCH2 3 1~ 3 H C02CH3 A4: ~l~OcH3; Y2 L-17: R17~H; al8=CH3 CH3 C02CH3 A4: Xl=CR3; Y2GCH3 L-17: R17=H; R18 CH3 H CO CH A5: ~2-C83; Y3=CH3 L-17: R17=H; R18 CH3 H C02CH3 AS: X2=CH3; Y3 SC 3 L-8: R11=R12-R13=H; m=l; Ql 2 C02CH3 AS: X2=Cff3i ~3 C2 5 L-8: Rll=R12.-Rl~=Hi m=1; Ql S 2 C2CH3 A6 ~3=CH3 L-8i Rll=al2=al3=H; m=l; Ql S2 C02cH3 A6 ~3 OCH3 L-9: R14'R15=H; Q2 CH3 C02CH3 A2 Y1=0; Xl 2 3 L-9: R14=R15=H; Q2 H C02CH3 A2 Y1=CH2; ~1 3 L-9: R14=R15 H; Q2 H H A2: Yl=O; Xl C 3 13 16 3; H COCH3 A3: Xl=OCF2H
L-lO: R13=R16=CH3; H H A3 X1 3 13 16 3; H H A4: X1=0CH3; Y2 3 L 11: R13 H3; H H A4: Xl=OCF2H; Y2 ~L-ll R13=CH3; m~O H H A5: ~2=C2Hs; Y3 C2 5 13 3; H H A5: X2=CH2CF3; Y3 3 L-12 R13=H; m=l H H A5: Xz=CH3; Y3 C2 5 L-13 R13=H; m=1 H H 6 3 3 L-14: R16=H H H 6 3 3 s4 ~56~

Formulation~
Useful fo~mulation~ of the compounds of Formula I can be prepared in conventional way~. They include du~ts, granule~, pellet~, solu~ions, suspensions, 5 emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly.
Sp~ayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundeed liters per hectare. High strength 10 compositions ace primarily used as intermediates for further formulation. The formulations, broadly, con-tain about 0.1% to 99% by weight of ac~ive ingre-dient(s) and at least one of ~a) about 0.1% to 20%
surfactant(s) and (b) about 1% to 99.9S solid or li-15 quid diluent(s). More specifically, they will containthese ingredients in the following approximate propor-tions:
Table 13 Weight Percent*
Active Inqredient Diluent(c~ Surfactant(s) Wettable Powders20-90 0-74 1-10 Oil SuspensionsL3-50 40-95 0-15 Emulsions, Solutions, 25 (includiny Emulsifiable Concentrates) Aqueous Suspension 10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 0.1-95 5-99.9 0-15 High Strength so-gg 0-10 0-2 Compositions Active ingredient plus at least one of a Sucfactant or a Diluent equals 100 weight percent.

~ZS5~6~

Lower or higher levels of active ~ngredient can, of cour~e, be present depending on the intended use and the physical properties o the compound. Higher ratios of 6urfactant to active ingredient are 60me-times de6irable, and are achieved by incorporatio~in~o the ~ormulation 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 10 Jersey, but other solids, either mined or manufac-tured, may be used. The more absorptive diluents a~e preferred for wettable powders and ~he denser ones for dusts. Typical liquid diluents and solvents are de-scribed in Marsden, "Solvents Guide," 2nd Ed., Inter-15 science, New York, 1950. Solubility under 0.1~. ispreferred or suspension concentra~es: solution con-centrates are preferably stable against phase separa-tion at 0C. "McCutcheon's Detergents and Emulsifiers Annual~l, MC Publi6hing Corp., Ridgewood, New Jersey, 20 as well as Sisely and Wood, ~'Encyclopedia of Surface Active Agents~, Chemical Publishing Co., Inc., New York, 1969, list surfactants and recommended uses.
All formulations can contain minor amounts of addi-tives to reduce foaming, caking, corrosion, microbio-25 logical growth, etc.
The me~hods of making such compositions are wellknown. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a ham~er or 30 fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,0a4)~ Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E.
35 Browning, "Agglomeration~, Chemical Enqineerinq, S6~

December 4, 1967, pp. 147ff. and 'IPer~y'~ Chemical Engineer'~ Randbook", 5th Ed . ~ McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of 5 formulation, ~ee ~or example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 ~hrouqh Col. 7, line 19 and Examples 10 through 41;
R. ~. Luckenbaugh, U.S. Patent 3,309,192, 10 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, 162-16~, 166, 167 and 169-182:
H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, l9S9, Col. 3, line 66 through Col. S, line 17 lS 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 Hand-20 book", 5th Ed., Blackwell Scientific Publications.Oxford, 196B, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
ExamPle 7 25 Wettable Powder 2-t[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-imino)methyl]aminosulfonyl]benzoic acid, methyl ester 8~%
sodiu~ alkylnaphthalenesulfonate ~ 2%
sodium ligninsulfonate 2S
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended. hammer-milled until all the solids are essentially under 50 microns, re-35 blended, and packaged.

~5Si~6:~

5~
Example 8Wettable Powder 2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]aminosulfonyl3benzoic acid, methyl e~ter 50%
sodium alkylnaphthalenesulfonate 2%
low viscosity methyl cellulose 2%
diatomaceous earth 46%
The inqredients are blended, coarsely hammel-10 milled and then air-milled to produce paeticles essen-tially all below 10 microns in diameter. The product is rebiended before packaging.
ExamPle 9 Granule Wettable Powder of Example 8 5%
attapulgite granules 95%
(U.S.S. 20-40 mesh: 0.84-0.42 mm) A slurry of wettable powder containing ~25%
solids is sprayed on the surface of attapulgite 20 granules in a double-cone blender. The granules are dried and packaged.
Examvle 10 Extruded Pellet ~',N'-dimethyl-N-r[1-(4,6-dimethyl-1,3,5-triazin-2-yl)-amino]-1-~hydroxyimino)methyl]-1,2-benzenedi~ulfon-amide 25%
anhydrous sodium sulfate 10~
crude calcium ligninsulfonate5%
sodium alkylnaphthaienesulfonate 1%
calcium/magnesium bentoni~e S9 . The ingredients are blended, hammer-milled and then moistened with about 12~ water. The mixture is extruded as cylinders abou~ 3 mm diameter which are cut to produce pellets about 3 mm long. These may be 35 used directly after drying, or the dried pellets may 3L~5S6~i~

be crushed to pa~ a U.S.S. No. 20 sieve (O.B4 mm opening~). 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 11 Oil susPension N',~'-dimethyl-N-[[1-(4-methoxy-6-me~hylpyrimidin-2-yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5~
highly aliphatic hydrocarbon oil 70S
The ingredients are ground together in a ~and mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension 15 may be applied directly, but preferably after being e~tended with oils oc emulsified in water.
ExamPle_12 Wettable Powder 2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-imino)methyl]aminosulfonyl~benzoic acid, methyl ester .- 20%
sodium alkylnaphthalenesulfonate ~%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3%
attapulgite 69%
The ing~edients are thoroughly blended. After grinding in a hammer-mill to produce particles essen-~ially all below 100 microns, ~he material is re-blended and sifted through a U.S.S. No. 50 sievè ~0.3 30 mm opening) and packaged.

;566~

Exa~Ple 13 Low Strenqth Granule N'~N'-dimethyl-N-[rl-(4,6~dimethyl-1,3,5-triazin-2-yl)-amino~-l-(hydroxyimino)methyl]-1,2-benzenedisulfon-amide 1%
N,N-dimethylformamide 9S
attapulgite granules 90%
(U.5.5. 20-40 sieve~
The active ingredien~ is dissolved in the sol-10 vent and the solution is sprayed upon dedusted gran-ules in a double cone blender. After spraying of the soiution has been completed, ~he blender is allowed to run for a short period and then the granules are pack-aged.
ExamPle 14 Aqueous SusPension N',N'-dimethyl-N-t[1-(4-methoxy 6-methylpyrimidin-2-yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamide 40S
20 polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether 0.5%
disodium phosphate 1%
monosodium phosphate 0.5%
polyvinyl alcohol 1.0%
25 water ' 56.7%
The ingredients are blended and ground toge~her in a sand mill to produce particles essentially all under 5 microns in size.

~L~Z556~L

Example 15 olution 2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino~-1-(hydroxyimino)methyl]aminosulfonyl]benzoic acid, methyl ester 5 water 95 The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
Example 16 Low Strenqth Granule 2-[[1-(9,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-imino)methyl]aminosulfonyl]benzoic acid, methyl ester ~ 0.1~
attapulgite granules 99.9%
(U.S.S. 20-~0 mesh) The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution 20 has been completed, the material is warmed to evapor-ate the solvent. The material is allowed to cool and then package~.
E~
Granule 2-[[1-(4-methoxy'6-methylpyrimidin-2-yl)amino]-1-(hydroxyimino)methyl]aminosulfonyl]benzoic acid, methyl es~er 80%
wetting agent 1%
crude ligninsulfonate sal~ (containing 10%
5-20% of the natural sugars) attapulgite clay 9%
The ingredients are blended and milled to pass through a 100 mesh screen. This material is t~en added to a fluid bed granulator, the air flow is ad-justed to gently fluidize the material, and a fine spcay of water i~ sprayed onto the fluidized ma-terial. The fluidizatisn and speaying are continued until granules of the desired size range are made.
The spraying is stopped, but fluidization is con-S tinued, optionally wi~h heat, until the water contentis eeduced ~o the desired level, generally less than 1~. The ma~erial is then discharged, screened to the desi~ed size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
ExamPle 18 Hiqh Strenqth Concentrate . . .
N' ,N' -dimethyl-N-t[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-sulfonamide 99%
silica aerogel 0.5%
synthetic amorphous silica 0.5s The ingredients are blended and ground in a hammer-mill to p~oduce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The 0 concentcate may be ~ormu~ated further if necessary.
ExamPle 19 Wettable Powder N',N~-dimethyl-N-[tl-(4,6-dimethyl-1,3,5-triazin-2-yl)-amino]-l-(hydroxyimino)methyl]-1,2-benzenedisulfon-amide 90Sdioctyl sodium sulfosuccinate 0.1%
6ynthetic fine silica 9.9%
The ingredien~s are blended and ground in a hammer-mill to produce particles essentially all below 30 100 microns. The material is sif~ed ~hrough a U.S.S.
No. 50 screen and then packaged.

~SS66gL

ExamPle 20 Wettable Powder 2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-imino)methyl]aminosulfonyl~benzoic acidO methyl es~er ~0%
sodium lign;nsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles 10 essentially all below 10 microns in size. ~he material is replended and then packaged.
Example 21 oi 1 SusPension N',N'-dimethyl-N-[~l-(dimethyl-1,3,5-triazin-2-yl)-amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-amide 35%
blend of polyalcohol carboxylic 6%
esters and oil soluble petroleum sul~onates 20 ~ xylene 59%
The ingredient~ are combined and ground togetherin a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils~ or emulsified in water.
Example 22 Dust 2-t[1-(4-me~hoxy-6-methylpyrimidin-2-yl)amino~-1-(hydroxyimino)methyl]aminosulfonyl]benzoic acid, methyl ester 10%
attaQulgi~e 10~
. Pyrophyllite 80%
The active ingredient is blended with attapul-gite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyro-phyllite until homogeneous.

~3 ~2~S~

Exam~le 23 Emulsifiable Concentrate N',N' -dimethyl-N-[ tl-(4-methoxY-6-1nethylpyrimidin-2-yl)amino]-l-(hydroxyimino)~ethyl]-1,2-benzenedi-sulfonamide 20Schlorobenzene 74%
sorbitan monostearate and polyoxyethylene condensates thereof 6~
The ingredients are combined and stirred to pro-10 duce a solution which can be emulsified in water foeapplication.
. . .
_tilitY
The compounds of the present invention are 15 active herbicides. They have utiiity for broad-spectrum pre-and/or post-emergence weed control in areas where complete control of all vege~ation is de-sired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-20 in theaters, around billboards, highway and railroad structuces. Alte~natively, the subject compounds are useful for the selective pre- or post-emergence weed control in crops, such as wheat and barley.
The rates of application for the compounds of 25 the invention are determined by a number of factors, including their use as selective or general herbi-cides, the crop species involved, ~he types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount o~ foliage pre-30 sent, etc. In general terms, the su~ject compounds should be applied at levels of around 0.03 to 5 kg/ha, the lower rates being sùggested for use on lighter soils and/or those having a low organic mattec con-tent, for selective weed control or for situations 35 where only short-term persis~ence is required.

~2S56~

The compounds of the invention may be used in combination with any other commercial herbicide exa~-ples of which are tho~e of the triazine, triazole.
uracil, urea, amide, diphenylether, carbamate and 5 bipyridylium ~ypes.
The herbicidal properties of the subject compounds were discovered in a number oÇ greenhouse test~. The test procedures and results follow.

.
.. . .

~2~5~

est ~
Seeds of crabgrass (Di~itacia 6pp. ), barnyard-grass (Echinochloa crus~alli), wild oats (Avena ~ L, sicklepod (Cassia obtusi~olia~, morningqlory (IPomoea 5 spp.), cocklebur (Xanthium pens~lvanicum), sorghu~, corn, soybean, sugar beet, rice, w~eat, and purple nutsedge (CYperus rotunduY) tuber were planted and treated preemergence with the test chemi~als dissolved in a non-phyto~oxic solvent. At the same time, these 10 crop and weed species, along with cotton and bush bean, 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 15 which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0 = no injury, to 10 = complete kill. The accompanying descriptive 0 symbols have the following meanings:
C = chlorosis/necrosis;
E = emergence inhibition:
G = growth retardation;
H = formative effect;
U = unusual pigmentation; and 6Y= abscised buds or flowers.
Note that co~pounds tested are highly ac~ive herbicides at the low rates of application selected for this tes~.

~ z556~

Compounds Compound 1 NOH N~ 3 ~ S 2 ~ N H - C - NH -< .0~>
Cl CH3 10 Compound 2 NOH Nl 3 ~S02-NH-C-NH -< ,0~
Cl OCH3 Compound N O H N
'. ~Sb2-NH-C-NH~O~
N
Cl orH3 Compound g , ~ NCH N ~
<~ S 2- N H- C -N H~O N
: Cl OC H3 3 0 Compound 5 N OC C H~
N

3 5 .. Cl CH3 ~Z~ 6~
6a Compounds (con~tinued) Compound 6 CH
NOH N--~ 3 ~ n ~O~

COOI:H3 CH3 CmPOUnd 7 OCH3 NOH N~
~S02-NH-C-NH <O~

Compound 8 OCH
NOH N l 3 ~S02-NH-C-NH~O~
5o2NtcH3)2 CH3 .. ..
Compound 9 OCH
~_ NOH N~ ~

502NtCH3)2 OCH3 566~

Table A

Cmpd. 1 Cmpd. 1 Cmpd. 2 Cmpd. 3 S Rate kg/ha .05 0.4 .05 .05 POST-EMERGENCE
Bush bean 3C,7H,6Y 9C 9C 9C
Cotton 5C,7H 6C,9G 4C,9G 3C,9G
Morningglory 3C 4C,8G 2C,9G 3C,8H
10 Cocklebur 3G 8G 3C,9G 3C,8H
Sicklepod 2C 3C,8G 2C,8G 4C,9G
Nutsedge 2C,6G 10C 4C,9G 9C
Crabgcass 0 2C,8G lC,3H 2C,3G
Barnyardgrass 2C,6H 9C 5C,9H 2C,9H
Wild Oats lC lC,7G 0 2C,4G
Wheat lC lC,9G 0 3G
Corn 2U,BH 6U,9G 3U,9G 2U,9G
15 Soybean lC,3H 4C,9G 2C,9H 3C,9H
Rice 2C,8H 5C,9G 3C,9G 4C,9G
Sorghum lU,9G SU,9G . 2C.9G 2C,9G
Sugar beet - - - -PRE-EMERGENCE
Morningglory 3C 8G 9G 9G
20 Cocklebur 2C,7H 8H 9H
Sicklepod 2C,5G 3C,9G 2C,BG 9G
Nut~edge SG 3C,9G 2C,5G 10E
Crabg~ass 0 3C lC,3G lC,SG
Barnyardgrass 3C,6H 3C,9H SC,9H 9H
Wild Oats 0 2C,7G SC,9G 8G
Wheat 3G 2C,8G 4C,9G 2C,8G
Corn 2C,6G lC,9G 2C,9G 2C,9H
25 Soybean 2C 3C,6G 3C,8H 7H
~ice 4C,6G 10E SC,9G 10E
Sorghum 2C,7H 3C,9H 4C,9G lC,9H
Sugar beet - - - -Table A (conti~ L

Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 5 Rate kg/ha .05 .05 .05 .05 POST-EMERGENCE
Bush bean lC 5C,9G,6Y 3C,6H,6Y 9C
Cotton 4C,8G ~C,8H ZC, SG 6C, 9G
Morningglory 3C,8G 3C,5G 3G 2C,7G
10 Cocklebur 2C 5G 4G ~C, 9H
Sicklepod 5C,9G lC 3G 9C
Nut~edge 0 3C,8G 7C,9G lOC
Cfabgras~ 3C 2H lOC 4C,9G
Barnyardgrass 2C,5H 3C,8H 4H 9C
Wild Oat~ 0 2C O 5C,9H
Wheat O lC O 5C,gG
Corn 2G 3C 8H 2C 8H 5C 9G
lS Soybean 3C,8G 2C 7H 2C 2H 5C 9G
Rice ~ 3G 3C,9H 2C,8H 5C,9G
Sorghum 3G 3C,9G 2C,9H 4U,9G
Sugar beet - - 2C lOC
PRE-EMERGENCE
Morningglory 9G 3C 2C,~G 8H
20 Cocklebur 9H 9H 9H 8H
Sicklepod 9G 3C,8~ 2C,5G 2C,9G
Nutsedge 9G 3C,8G 2C,5G lOE
Crabgrass 3G 2C lC 2C
Barnyardgrass 2C,5G 5C,9H 2H ~C,9H
Wild Oats lC 2C,8G 2C, 8G 3C,9G
Wheat lC 3C,9G 9G 2C,9H
Corn 2C,8G 4C.9H 9G 3C,9H
25 Soybean 8H 3C,SH 4C,7G 3C,7H
Rice 6G 5C,9H 3C,8H lOE
Sorghum 2C,5G 4C,9H 2C,9~ 2C,9G
Sugar beet - - 2C,9G 9C

~i5~

Table A (cont;nued~

Cmpd. 8 Cmpd. 9 5 Rate kg~ha .05 .05 POST~EMERGENCE
Bush bean 5C,9G,6Y 5C,9G,6Y
Cotton 9C
Morningglory 5C,9G 5C,9G
Cocklebur ~C,9G 4C,9G
10 Sicklepod 3C,8G 4C,3H
Nu~sedge 2C,7G 5G
Cr~bgrasfi 2C,9G 2C,8G
Barnyardgrass 2C,9H 5C,9H
Wild Oats 2C,8G O
Wheat 5C,9G 0 Corn 3U,9H 9C
15 Soybean 2C,9H 9C
Rice SC,9G SC,9G
Sorghum 2C,9G 9C
Sugar beet 3C,9G ~C
PRE-EMERGENCE
Morningglory 9C 9C
Cocklebur 9H
20 Scklepod 5C,9G 2C,9G
Nutsedge 10E 6G
Crabgrass 3C,9G 2C,6G
Barnyardgrass 9C,9H 3C,9H
Wild Oats 3C,9G 3C,9G
Wheat 10C lC,6G
Corn 9G SC,9H
25 Soybean 3C,9H 9H
Rice 10E 10E
Sorghum 5C,9H 5C,9H
Sugar beet 5C,9G 9C

.

12SS66~

Test B
Two plastic bulb pans were filled with ferti-lized and limed Woodstown sandy loam. One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds. The other pan was planted with cotton, soybeans, purple nuts~!dge (CYPerus rotundus), and several broadleaf weeds. The following grass and broadleaf weeds were planted: crabqrass (Diqitaria sanquinalis), barnyardgrass (Echinochloa crusqalli), ~0 wild oats (Avena fatua), johnei;ongrass (Sorqhum hale-pense), dallisgrass (PasPalum dilatatum), giant fox-tail (Setaria faberii), cheatgra~s (~romus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium Pen sylvanicum), pigweed (Amaranthus retroflexus), morn-ingglory (Ipomoea hederacea), sicklepod (Cassia obtu-sifolia), teaweed, (Sida sPinosa), velvetleaf (Abu-tilon theophrasti), and jimsonweed (Datura stramo-nium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat.
20 Another 12.5 cm pot was planted with sugar beets. The above four containers were treated preemergence with several test compounds within the scope o~ the inven-tion.
Twenty-eight days after treatment, the plants 25 were eva~uated and visual}y rated for response to the chemical treatments utilizing the rating system de-scribed previously for Test A. The data are sum-marized in Table B.

5~6~L

Table ~

PRE-EMERGENCE ON
WOODSTO'~N S~NDY_LOAM

Compound 1 Compound 2 Rate kg/ha 0.120 0.500 0.030 0.120 lo Crabgra~s 2G 5G 2G 4G
Barnyardgrass 8G,3H 10C 7G,3H 9G,SH
Sorghum - - 7G,5H 9G,5H
Wild Oats 2G 5G 4G SG
Johnsongrass SG,3~ 8G,3H 4G,3H 6G,2H
Dallisgrass 6G 8G,5H 2G 4G
Giant ~oxtail 6G,SH 8G,5H 4G 6G,3H
Ky~ bluegrass 8G,8C 10C 6G 7G
Cheatgrass 6G,3C 10C 8G,8C 8G,9C
Sugar beets 8G,8C 10C 8G,8C 10C
Corn 7G,SH 9G,8C 6G,3H 7G,3H
Mustard 9G,9C 10C 9G,8C 9G,9C
Cocklebur 6G 7G,3H ~G SG
20 Pigweed 8G 10C
Nutsedge 7G 10E 7G 7G
Cotton 3G 8G 3G SG,3H
Morningglory 0 6G,SH 4G 9G,5C
Sicklepod 6G 7G 7G 8G,3H
Teaweed 5G 8G,3H 5G lOC
Velvetleaf 6G,SH 9G,9C SG,5H aG,9C
Jimsonweed 6G 7G 7G BG,8C
2S Soybean 3G 6G,SH 3G,3H 6G,SH
Rice 9G,9C 10C 7G,8C 10C
Wheat 4G 6G 0 4G

~L~5S6~L

Table B (continued~

PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM

Compound 3 Compound 4 Rate kg/ha 0.030 0.120 0.007 0.030 Crabgrass 0 6G 0 0 Barnyardgrass 6G,2H 8G,SH 0 3G
Sorghum 6G,3H 9G,SH 0 0 Wild Oats 3G 6~ 0 0 Johnsongrass ~G,2H 7G,5H 0 0 Dallisgrass 0 SG 0 0 Giant oxtail 3G 7G,3H 0 0 Ky. blueg~ass SG,3H 7G,3H 4G O
Cheatgrass 8G,8C 8G,9C 0 0 Sugar beets 10C 10C 6G 8G
Corn 5G,3H 7G,3H 2G 3G
Mustard 9G,SH 9G,9C 9G gG,9C
Cocklebur 0 3G 0 ZG
20 Pigweed 10E 10E - -Nutsedge 9G,9E 10E 0 5G
Cotton 2G 4G 2G 5G
Morningglory 3G 3G 0 7G
Sicklepod 8G 8G 5G 6G
Teaweed 7G 8G 6G 9G
Velvetleaf 7G,5H 9G,8C SG,5H 8G
Jimsonweed 5G 6G 0 4G
Soybean 3G 6G,5H 5G 8G
Rice 8G,8C 10E 0 SG
Wheat 2G 4G 0 0 ~25SG61 Table 8 (continued2 PRE-EMERGENCE ON
WOODSTOWN_SANDY LOAM

Compound 5 Rate kg/ha 0.030 0.120 Crabgras6 ~ o Barnyardg~ass 2G 3H,BG
Sorghum 2G ~H.8G
Wild Oa~s 0 2G
Johnsongrass 0 2H,4G
Dallisg~ass 4G 8G
15 Giant foxtail 3H,4G 5H,8G
Ky. bluegrass 6G lOE
Cheatgrass SG 8G
Sugar beets 5G 8G
Corn 3G 3H,7G
Mustard 9G,9C 9G,9C
Cocklebur 2G 2G
Pigweed - -20 Nutsedge 2G 6G
Cotton 3G SG
Morningglory 2G 2G -Sicklepod 2G SG
Teaweed O O
Velvetleaf O SG
Jimsonweed 0 4G
25 Soybean 3G 3G
Rice 8G 9G,9C
Wheat 2G 3G

~L~5~

Test C
The test chemicals, dissolved in a non-phyto-toxic solvent, were applied in an overall spray to the oliage and surrounding soil ~f selected plant spe-S cies. One day after trea~ment, piants were checkedfor rapid burn inju~y. Approximately fourteen days after treatmen~ all species were visually compared to untreated controls and rated for response to treat-ment. The rating system was as described previously for Test A. The data are presented in Table C.
All plant species were seeded in Woodseown sandy loam soil and grown in a greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abu-tilon theoPhcasti), sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory (IPomoea hederacea~, jimsonweed (Datura stramonium), cocklebur ( _nthium pens~lvanicum), crabgrass (Diaitaria spp.), nutsedge (C~perus ~otundus), bacnyardgcass (Echino-chloa crus~alli), giant foxtail (Setaria faberii), and wild oats (Avena fatua). The following species were grown in soil in a paper cup tl2 cm diameter by 13 cm deep): sunflower, sugar beets, and rape. All plants were sprayed approximately 14 days aftec planting.
Additional plant species, such as johnsongrass and field bindweed, are sometimes added to this test in order to evaluate unusual selectivity.

~566~

Table C

Over-the-Top Soil~Foliage Treatment Gompound 2 Compound 5 Rate, kg/ha 0.015 0.004 0.06 0.015 : Soybeans 8G,6C 6G 3G O
10 Velvetleaf O O 4G O
Sesbania O - O
Sicklepod- O O O O
Cotton 3G 3G 3G 3G
Morningglory 2G C 4G 3G
Alfalfa 7G 5G 4G 3G
Jimsonweed 3G O O O
Cocklebur O - 2G 3G
Sunflower 2G O 3G lG
Rape 2G O SG O
Sugar beets 2G O
Corn 2G O lC O
Crabgrass 4G O O O
Rice 6G 2G 6G 6G
Nutsedge O O O O
Barnyardgrass 0 3G O O
Wheat O O O O
Giant Foxtail 2G 4G O O
Wild Oats O O O O
Sorghum 3G 5G 8G 6G
Johnsongrass O O O O
Field Bindweed 3G O O O

.

66~

Test D
Two ten-inch in diameter plastic pans lined with polyethyleae liners were filled with ptepa~ed Wood~-town sandy loam soil. One pan was planted with seeds 5 of wheat (Triticum aestivum), barley (Hordeum vul-qare), wild Odts (Avena fatua3, downy beome (_romus tectorum), cheatgrass (Bromus secalinus)~ blackgrass (AloPecurus mvosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), quackgrass 10 (AqroPyron rePens), Italian ryegrass (Lolium multi-florum) and ripg~t brome (Bromus riqidus), The other pan was planted with seeds of Russian thistle (Salsola kali), tansy mustard tDescuraina pinnata), cleavers (Galium ~ ), tumble mustard (SisYmbrium altis-15 sium), kochia (Kochia scoparia), shepherd~s purse(Capsella bursa-pastoris) Matricaria inodora, black nightshade (Solanum niqrum), yellow rocket (8arbarea vulqaris), rapeseed (~rassica naPus), and wild buck-wheat (PolYqonum convolvulus). The above two pans 20 were treated preemergence. At the same time, two pans in which the above plant species were growing were treated postemergence. Plant height at the time of treatment ranged from 1-15 cm depending on plant species.
The compound~ applied were diluted with a non-phytotoxic solvent and sprayed over the top of the pans. An untrea~ed control and a solvent-alone con-trol were included for comparison. All ~reatments were maintained in the green~louse for 19-21 days at 30 which time Che treatments were compared to the con-trols and the efects visually rated. The recorded data are presented in Table D. Some o~ the compounds tested have utility for selective weed control in cereal crops such as wheat and barley.

~5~6~

Table D

Compound 2 S Pre-Eme~gence Post-Emergence Rate kg/ha 0.060 0.015 0.060 0.015 whea~ 7G 2G 6G 3G
barley lC,7G 2G 6G 3G
10 wild oats lC,7G 5G 5G 2G
downy brome 2C,9G 8G BG 7G
cheatgrasfi lC,9G 8G 8G 7G
b~ackgrass 2C,8G 7G SG 3G
annual bluegrass 8G 7G 7G 3G
green Soxtail 2C,8G 2C,4~ 2C,8G 4G
quackgrass 9G 8G 8G 6G
Italian ryegrass lC,aG 7G 4C,8G 7G
lS cipgut brome 8G 8G 2C,8G 7G
Russian thistle 2C,3G 2G 8C,8G 4C,5G
tansy mustard 2C,9G 9G BC,8G SC,7G
Galium aparine 6G 8G 7G 4G
tumble mustard lC,8G 9G lOC 7G
kochia 7G SG 3C,8G 4G
shepherd's purse 2C,9G 9G 4C,9G 7G
20 Matricaria inodora 7G 7G 8C,8G 2C,7G
bla~k nightshade 8G 5G 6G 6G
yellow rocket 9G 8G 7G SG
rapeseed 2C,9G 9G l~C 2C,8G
wild buckwheat 7G 6G 7G 4G

.

~L ~2 LJ~ ~i 6 6 31.

Table D (continued) Compound 3 S Pre-Emergence Post-Emergence Rate kg/ha 0.060 O.OlS 0.060 0.015 wheat 3G 0 3G 0 barley 3G 0 5~ 0 wild oats 5G 3 4G 0 downy brome gG ~G 9G 7G
cheatgrass 2C,9G 7G 8G 6G
blackgrass 7G 6G 6G 3G
annual bluegrass 7G 6G 2C,8G 3G
green foxtail 2C,6G 3G 2C,6G 6G
quackgrass 9G 8G RG 7G
Italian ryegrass ~G 8G 2C,BG 6G
15 ripgut brome 8G 6G 7G 6G
Russian thistle lC,2G 0 ~C,8G
tansy mustard 9G 9G lOC 9G
Galium aparine lOE 8G 6G SG
tumble mustard 2C,9G 9G lOC 9G
kochia 8G 2C,5G 2C,8G 5G
shepherd's purse 9C,9G 9C,9G lOC 2C,8G
20 Matricaria inodoea 8G 9G 8C,8G 8C,8G
black nightshade 6G 3G 7G 6G
yellow rocket sG 7G 8C,8G 8C,8G
rapeseed 3C,9G 9G lOC lOC
wild buckwheat 6G 4G 2C,8G 7G

~Z~56~

Table D (continued) Compound 5 Pre-Emergence Pos~-EmergenCe Rate kg/ha 0.060 0.250 0.060 0.250 wheat lC,2G SG 2G 7G
barley 6G 2C.8G 3G 7G
10 wild oats SG 7G 3G 5G
downy brome SG 8G 5G 6G
cheatgras~ 6G 8G 5G 7G
blackgras6 SG lC,7G 6G 2C.7G
annual bluegrass 6G lC,8G 4G 3C,8G
green foxtail 0 2C,6G 0 2C,SG
quackgrass 45 8G 2G 6G
Italian ryegrass 8G 2C,9G 2C,6G 2C,8G
15 ripgut brome 6G lC.8G SG 7G
Russian thistle 0 2C,5G 0 lOC
tansy mustard 8G 2C,9G SG 8G
Galium aparine 9G lOE 0 3G
tumble mustard 7G 9G 0 6G
kochia - - - o shepherd's purse 2C,9G lOC SG lOC
20 Matricarla inodora 8G 9G 3G 9G
black nightshade 0 5G 0 4G
yellow rocke~ 8G 9G o 6G
rapeseed 2C,8G 9G 7G- 9C,9G
wild buckwheat 0 6G 0 3G

This application is a division of copending Canadian Application Serial No. 443,738 filed 1983 December 20.

Claims (4)

CLAIMS:

1. A compound having the formula:

II
wherein R'' is C1-C3 alkyl;
R is H or CH3;
L is R5 is C1-C4 alkyl, C1-C4 alkoxy, OCH2CH2OCH3, F, Cl, Br, NO2, CF3, CO2R19, SO2NR20R21, SO2N(OCH3)CH3, OSO2R22, S(O)nR23, WCF3, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, R6 is H, F, Cl, Br, CF3, CH3, OCH3, SCH3 or OCF2H;
R11 is H, CH3 or CH2CH3;
R12 is H, CH3 or CH2CH3;
R13 is H or CH3;
R14 is H or CH3;
R15 is H or CH3;
R16 is CH3 or CH2CH3;
R17 is H or C1-C4 alkyl;
R18 is H or CH3;
R19 is C1-C4 alkyl, CH2CH2OCH3, CH2CH2Cl or CH2CH=CH2;

R20 is C1-C3 alkyl;
R21 is C1-C3 alkyl;
R22 is C1-C3 alkyl or N(CH3)2;
R23 is C1-C3 alkyl or CH2CH=CH2;
m is 0 or 1;
n is 0 or 2;
Q1 is O, S, SO2 or NR17;
Q2 is O, S, or NR17; and W is O, S or SO2;

A is X is CH3, OCH3, OCH2CH3. Cl, F, Br, OCF2H, CH2F or CF3;
Y is H, CH3, OCH3, OCH2CH3, CH2OCH3, CH2OCH2CH3, N(CH3)2, CH2CH3, CF3, SCH3, OCH2CH=CH2, OCH2C?CH, OCH2CF3, OCH2CH2OCH3, CH2SCH3, OCF2H, SCF2H, CR24(QCH3)2, or CR24(QCH2CH3)2;
Q is O or S;
R24 is H or CH3;
Z is CH or N;
Y1 is CH2 or O;
X1 is CH3, OCH3, OCH2CH3 or OCF2H;
Y2 is H or CH3;
X2 is CH3, CH2CH3 or CH2CF;
Y3 is OCH3, OCH2CH3, SCH3, CH3 or CH2CH3;
X3 is CH3 or OCH3;
and their agriculturally suitable salts;
provided that 1) when L is L-1 and A is A-1, R6 is C2-C4 alkyl, C2-C4 alkoxy, OCH2CH2OCH3, OSO2R22, S(O)nR23, WCF2, WCF2, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, 2) when L is L-1 and A is A-2 or A-3, then R5 is C1-C4 alkyl, C2-C4 alkoxy, OCH2CH2OCH3, Br, OSO2R22, WCF3, WCHF2, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C2 alkyl substituted with OCH3 or OCH2CH3, C6H5, 3) the total number of carbon atoms of R20 and 4) R21 is less than or equal to four;
when m is 1, then R13 is H;
5) when L is L-19, then R17 and R18 are not simultaneously H; and 6) when X is Cl, F or Br, then Z is CH and Y is OCH3 ; OCH3CH3, N(CH3)2 or OCF2H.

2. A compounu of Claim 1 where R is H and A
is A-1.

3. A compound of Claim 2 where Y is CH3, OCH3, OCH2CH3, CH2OCH3, OCH2CF3 or CH(OCH3)2 and X is CH3, OCH3, Cl or CF3.

4. A compound of Claim 3 where L is L-1 and R5 is OSO2R22, SO2R23, OCF2H, SCF2H, OCH2CH=CH2, OCH2C?CH,