CA1203535A - Herbicidal o-sulfamylmethylbenzenesulfonamides - Google Patents
Herbicidal o-sulfamylmethylbenzenesulfonamidesInfo
- Publication number
- CA1203535A CA1203535A CA000381468A CA381468A CA1203535A CA 1203535 A CA1203535 A CA 1203535A CA 000381468 A CA000381468 A CA 000381468A CA 381468 A CA381468 A CA 381468A CA 1203535 A CA1203535 A CA 1203535A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- och3
- sulfonylmethyl
- formula
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
HERBICIDAL o-SULFAMYLMETHYLBENZENESULFONAMIDES
Abstract of the Disclosure Compounds, of the formula wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, C1-C3 alkyl or C1-C3 alkoxy;
R1 is H or C1-C4 alkyl;
R2 is H or CH3;
R3 is C1-C4 alkyl or OCH3;
R4 is C1-C4 alkyl;
R8 is H, CH3 or OCH3;
A is <IMAGE<, or W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3, SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH=CH2;
y1 is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
provided that:
(1) when R3 is OCH3, then R4 is CH3;
(2) the total number of carbon atoms of R3 and R4 is five or less; and (3) when W is S, then R8 is H, are useful as agricultural chemicals and in particular as herbicides.
Abstract of the Disclosure Compounds, of the formula wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, C1-C3 alkyl or C1-C3 alkoxy;
R1 is H or C1-C4 alkyl;
R2 is H or CH3;
R3 is C1-C4 alkyl or OCH3;
R4 is C1-C4 alkyl;
R8 is H, CH3 or OCH3;
A is <IMAGE<, or W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3, SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH=CH2;
y1 is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
provided that:
(1) when R3 is OCH3, then R4 is CH3;
(2) the total number of carbon atoms of R3 and R4 is five or less; and (3) when W is S, then R8 is H, are useful as agricultural chemicals and in particular as herbicides.
Description
3S3~
, 1 Title HERBICIDAL o-SULFAMYLMETHYLBENZENESULFONAMIDES
Background of the ~nvention ~,2-Toluenedisulfonamide derivatives are useful as agricultural chemicals and in particular as herbicides.
French Patent No. 1,468,747, published 1967 February 10 discloses the following E~ substituted phenylsulfonamides, useful as anti-diabetic agents:
R ~ ~N
where R = H, halogen CF3 or alkyl.
Longemann et al., Chem Ab., 53, 18052 9 (1959), disclose a number of sulfonamides, including uracil dervatives and those having the formula:
o H3C ~ So2NHcNHR
~ N~
wherein R is butyl, phenyl or ~ \ ) and ~ R
Rl is hydrogen or methyl. When tested for hypoglycemic effect in rates (oral does of 25 mg/100 g), the compounds in which R is butyl or phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon, Pharm. 19, P.
121-5 (1962) [Chem. Ab., 59 1633 e~ describes the synthesis of N[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:
OCH
~ 3 C 3 ~ So2NH-c-NH ~ ~
120353~
~ased upon similarity to a known compound, the author predicted hypoglycemic activity for the foregoing com-pound.
Netherlands Patent 121,788, published September 15, 1966, teaches the preparation of compounds of Formula (i), and their use as general or selective herbicides:
R3 ~HR
wherein Rl and R2 may independently be alkyl of 1-4 carbon atoms; and R3 and R4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
Compounds of Formula (ii), and their use as anti-diabetic agents, are reported in J. Druq. Res. 6, 123(1974):
~ O
~ (ii) wherein R is pyridyl.
The presence of undesired vegetation causes sub-stantial damage to useful crops, especially agricul-tural products that satisfy man's basic food needs, such as soybeans, wheat and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by ~illing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are co~mmonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
Summary of the Invention This invention relates to novel compounds of Formula I and their agriculturally suitable salts, suitable agricultural compositions containing them and their method of use as general herbicides.
~ R2 (I) wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, Cl-C3 alkyl or Cl-C3 alkoxy;
Rl is H or Cl-C4 alkyl;
R2 is H or CH3;
R3 is Cl-C4 alkyl or OCH3;
R4 is Cl-C4 alkyl;
R8 is H, CH3 or OCH3;
A is ~V353~;
W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3, SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CcH2cH2cl or CCH2CH=CH2;
yl is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
. provided that:
(1) when R3 is OCH3, then R4 is CH3;
, 1 Title HERBICIDAL o-SULFAMYLMETHYLBENZENESULFONAMIDES
Background of the ~nvention ~,2-Toluenedisulfonamide derivatives are useful as agricultural chemicals and in particular as herbicides.
French Patent No. 1,468,747, published 1967 February 10 discloses the following E~ substituted phenylsulfonamides, useful as anti-diabetic agents:
R ~ ~N
where R = H, halogen CF3 or alkyl.
Longemann et al., Chem Ab., 53, 18052 9 (1959), disclose a number of sulfonamides, including uracil dervatives and those having the formula:
o H3C ~ So2NHcNHR
~ N~
wherein R is butyl, phenyl or ~ \ ) and ~ R
Rl is hydrogen or methyl. When tested for hypoglycemic effect in rates (oral does of 25 mg/100 g), the compounds in which R is butyl or phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon, Pharm. 19, P.
121-5 (1962) [Chem. Ab., 59 1633 e~ describes the synthesis of N[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:
OCH
~ 3 C 3 ~ So2NH-c-NH ~ ~
120353~
~ased upon similarity to a known compound, the author predicted hypoglycemic activity for the foregoing com-pound.
Netherlands Patent 121,788, published September 15, 1966, teaches the preparation of compounds of Formula (i), and their use as general or selective herbicides:
R3 ~HR
wherein Rl and R2 may independently be alkyl of 1-4 carbon atoms; and R3 and R4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
Compounds of Formula (ii), and their use as anti-diabetic agents, are reported in J. Druq. Res. 6, 123(1974):
~ O
~ (ii) wherein R is pyridyl.
The presence of undesired vegetation causes sub-stantial damage to useful crops, especially agricul-tural products that satisfy man's basic food needs, such as soybeans, wheat and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by ~illing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.
A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are co~mmonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.
Summary of the Invention This invention relates to novel compounds of Formula I and their agriculturally suitable salts, suitable agricultural compositions containing them and their method of use as general herbicides.
~ R2 (I) wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, Cl-C3 alkyl or Cl-C3 alkoxy;
Rl is H or Cl-C4 alkyl;
R2 is H or CH3;
R3 is Cl-C4 alkyl or OCH3;
R4 is Cl-C4 alkyl;
R8 is H, CH3 or OCH3;
A is ~V353~;
W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3, SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CcH2cH2cl or CCH2CH=CH2;
yl is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
. provided that:
(1) when R3 is OCH3, then R4 is CH3;
(2) the total number of carbon atoms of R3 and R4 is five or less; and
(3) when W is S, then R8 is H.
Preferred in increasing order for their higher activity and/or more favorable ease of synthesis.
(1) Compounds of the generic scope wherein Z is N, CH, CCl, CBr or CCH3, W is O, and R8 is H or CH3;
~2) Compounds of Preferred (1) wherein Z is CH or N, X is CH3 or OCH3, and R
and R2 are H;
(3) Compounds of Preferred t2) wherein A is ~ No~z N
and R and R8 are H;
Preferred in increasing order for their higher activity and/or more favorable ease of synthesis.
(1) Compounds of the generic scope wherein Z is N, CH, CCl, CBr or CCH3, W is O, and R8 is H or CH3;
~2) Compounds of Preferred (1) wherein Z is CH or N, X is CH3 or OCH3, and R
and R2 are H;
(3) Compounds of Preferred t2) wherein A is ~ No~z N
and R and R8 are H;
(4) Compounds of Preferred (3) wherein R3 is Cl-C3 alkyl or OCH3, and R4 is CH3; and
(5) Compounds of Preferred (4) wherein R3 is OCH3 or CH3.
Specifically Preferre~ for highest activity and/or most favorable ease of synthesis are:
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, m.p. 203-204C;
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, 10m.p. 171-176C;
2-t~Dimethylamino)sulfonylmethyl]-N-t(4-methoxy-
Specifically Preferre~ for highest activity and/or most favorable ease of synthesis are:
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, m.p. 203-204C;
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide, 10m.p. 171-176C;
2-t~Dimethylamino)sulfonylmethyl]-N-t(4-methoxy-
6-methylpyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide, m.p. 181-183C;
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide, m.p. 209-210C;
2-1(Dimethylamino)sulfonylmethyl]-N-t(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyllbenzenesulfonamide, m.p. 200-203C; and 2-t(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyllbenzene-sulfonamide, m.p. 200-205C.
This invention also relates to novel compounds of Formula II which are useful intermediates for the 5 preparation of the herbicidal compounds of Formula I.
R~ R2 (II) wherein 35L, R, Rl, and R2 are as previously defined, and Z is CH or N.
lZ03S3~;
This invention also relates to novel compounds of Formula III which are useful intermediates for the preparation of the~compounds of Formula I.
R R
5 ~ / 2 ~ ~ C-L
R ~ ;
(III) wherein L, R, Rl and R2 are as previously defined.
Detailed Description Svnthesis The compounds of Formula I, in which W = O, may be prepared as shown in Equation 1 by the reaction of an appropriately substituted benzenesulfonyl isocya-nate with an appropriate aminopyrimidine or aminotri-azine.
Equation 1 R~ /R2 ~C-S02NR3R4 I ~ I + ANH
o III VIII
~ ~R2 "~" C-so2NR3R4 )\ ~
. R SO2NHCNA
lZ03S35 wherein R is H, F, Cl, Br, N02, CF3, Cl-C3 alkoxy or Cl-C3 alkyl;
Rl is H or Cl-C4 alkyl;
R2 is H or CH3;
R4 is Cl-C4 alkyl;
R3 is CH30 or Cl-C4 alkyl;
provided that when R3 is CH30, then R4 is CH3, and provided that the total number of carbon atoms of R3 and R4 is five or less;
A is X yl yl N ~ N
X is H, Cl, Br, CH3, CH3CH2, Cl-C3 alkoxy, CF3, CH3S or CH30CH2;
Y is CH3, CH30 or Cl;
Z is N, CH, C-Cl, C-Br, C-CN, C-CH3, C-CH2CH3, C-CH2CH2Cl or C-CH2CH~CH2;
yl is H, CH3, CH30 or OCH2CH3;
and Q is 0 or CH2.
The reaction of Equation 1 is best carried out in an inert aprotic solvent e.g. methylene chloride, tetrahydrofuran or acetonitrile at a temperature between 20 and 80. ~ catalytic amou~t of 1,4-diazabicyclot2,2,2]octane (DABC0) may be used to accelerate the reaction. In cases in which the products are insoluble in the reaction solvent, they may be isolated by simple filtration. When the products are soluble, they may be isolated by 9evaporation of the solvent and trituration of the residue with solvents such as l-chlorobutane, ethyl-ether or methanol and filtration.
The benzenesulfonyl isocyanates of Formula III
may be prepared as shown below in Equation 2, by phosgenation of the sulfonamides of Formula IV
in the presence of butyl isocyanate. The sulfonyl isocyanates of Formula IIImay also be prepared, as shown in Equation 3, by phosgenation of the butyl ureas of Formula V.
~ tion 2 Rl R2 ~ C - S2NR3R4 n C4Hg 1~1 ) R S2 2 COC12/xylene IV
Rl R2 C--So2~R3R4 ~ SO2NCO
III
wherein 30R, Rl, R2, R3 and R4 are as previously described.
`` lZ~3535 The above reaction is carried out by heating a mixture of the appropxiate sulfonamide (IV), an alkyl isocyanate e.g. butyl isocyanate and a catalytic amount of a tertiary amine such as 1,4-diaza~2,2,2]bi-S cyclooctane (DABC0) in xylene, or other inert solventof boiling point ~135 to approximately 135. Phosgene is then added to the mixture over a 1-6 hour period until an excess of phosgene is present as indicated by a drop in the boiling point to less than 130. The mixture is cooled and filtered to remove a small amount of insoluble by-products. The solvent and the alkyl isocyanate are distilled off in-vacuo leaving a residue of the crude, sulfonyl isocyanate, III, which can be used without further purification.
E~Luation 3 Rl R2 ~ C - S2NR3R4 n-C4H~NC0 R S02N 2 K2CO3/Y~R
IV
Rl ~R2 ~ C5O2NR3R4 COC12/DABCO
NHcNH-n-c4H9 Xylene V Rl R2 ~ C - 52NR3R4 o 52 III
where~n R, Rl, R2, R3 ~nd R4 ~re ~s previously ~escr$bea.
,J
:, ` ~
The compounds of Formula V are conveniently prepared by stirring a mixture of the sulfonamides, IV, anhydrous potassium carbonate,` and n-butyl isocyanate in acetone or methyl ethyl ketone at 25-80 until all of the isocyanate has reacted- The products are isolated by quenching in dilute mineral acid and recrystallizing the solid product. The com-pounds V are treated with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in a manner analogous to that described in ~quation 2.
The sulfonyl isocya~ates of Formula IIImay also be prep~red as shown in Equa_ion 4, by the method of Ulrich et al. lJ. Org. Chem. 34, 3200 (1969)].
Equation 4 ,Rl ~R2 SOC12 IV
Rl R2 ~C/ 52NR3R4 COC12 RSO2NSO Pyridine catalyst VI
Rl R2 ,~ C--S02NR3R4 ~1 III
The synthesis of heterocyclic amine derivati~es such as those depicted by Formula VIII has been re-viewed in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publ., New York and London. Aminopyrimidines are described by D. ~. Brown in "The Pyrimidines", Vol. XVI of the above series.
The synthesis of the bicyclic pyrimidines of FormulaUIII is described in the following references:
Braker, Sheehan, Spitzmiller and Lott, J. Am.
Chem. Soc. 69, 3072 (1947).
Mitter and Bhattacharya, Quart. J. Indian. Chem.
Soc. 4f 152 (1927).
Shrage and Hitchings, J. Org. Chem. 16, 1153 (1951).
Caldwell, Kornfeld and Donnell, J. Am. Chem.
Soc. 63, 2188 (1941).
Fissekis, Myles and Brown, J. Org. Chem. 29, 2670 (1964).
- ~ompol~ds of Formula I, in which W = O, can also be prepared by the method described in Equation 5.
(5a) Equation 5 25Rl-c-so2NR3R6 X
so2NH2 + O~C-N
IV VII
Rl-c-so2~R3R4 x2 O N ~
) ~ ~ SO2NH ~ -~ NO~2 R ~II
(5b) Ri-c-so2NR3R4 N~~
~,SO2~HCNH--( C) Z
Rl-c-so2NR3R4~OR12 [~So2~HC~H~ Z
R IX
(5c~
Rl-c-so2NR3R4 OR12 N--( 2 0~ ~,5O2NHCNH ~ Z
R IXa 2 5 Rl- I-SOzNR3R4 ~ OR12 R X
(5d) Rl-c-sO2NR3R4 Y4 O N
S ~ ~ . N
R IIa ,R2 Rl f 52~ 3 4 N ~ Y4 < C) Z
R XI
wherein R, Rl, R2, R3 and R4 are as descrlbed previously;
R12 is methyl;
R13 is Cl-C3 alkyl;
X is Cl or Br;
Y2 is H, Cl, Br, methyl, ethyl or CF3:
Y3 is Cl or Br;
Y4 is methyl, ethyl or CF3; and ' E is CH35-.
Reaction Step (5a) -In Reaction Step (5a), an aromatic sulfonamide of Formula IV is contacted with a heterocyclic iso-cyanate of Formula VII to yield an N-(halohetero-cyclicaminocarbonyl)aromatic sulfonamide of Formula The heterocyclic isocyanates used in Reaction(5a) may be prepared according to methods described in Swiss Patent 579,062, U.S. Patent 3,919,228, U.S. Patent 3,732,223 and Angew Chem. Int. Ed. 10, 402 (1976).
The aromatic sulfonamide and the heterocyclic isocyanate are contacted in the presence of an inert organic solvent, for example, acetonitrile, tetra-hydrofuran (THF), toluene, acetone or butanone.Optionally, a catalytic amount of a base, e.g. 1,4-diazabicyclo[2.2.2]octane (DABCO), potassium carbonate sodium hydride or potassium tert-butoxide, may be added to the reaction mixture. The quantity of base constituting a catalytic amount would be obvious to one skilled in the art. The reaction mixture is preferably maintained at a temperature of about 25 to 110C, and the product can generally be recovered by cooling and filtering the reaction mixture. For reasons of efficiency and economy, the preferred solvents are acetonitrile and THF, and the preferred temperature range is about 60 to 85C.
Reaction Steps (Sb) and (5c) In Reaction Steps (5b) and (5c), one or two of the halogen atoms on the heterocyclic ring of the compound of Formula II is displaced by a nucleophilic species. Generally, this may be done by contacting the compound of Formula II either with alkanol, R12OH, or with alkoxide, -OR12, where R12 is as defined above.
,A
Thus, in Reaction Step (5b), a comp~und of Formula II, substituted with one displaceable group, can be contaeted with at least one equivalent of alkanol, R120H. This reaction is sluggish, however, and it is preferred to contact the compound of For~ula II with at least two equivalents of alkoxide, -OR12. ~he alkoxide can ~e provided in a number of ways:
(a) The compound of ~ormula II can be suspended or disso~ved in an alkanol solvent, R12O~, in the presence of at least twc equivalents of alkoxide, -OR12. The zlkoxide can be added directly as alkali metal or alkaline earth metal alkoxide or can be ~en-erated by the addition to the alkanol solvent of at least two ecuivalents of ~ base capable of oenerating al-koxide frcm the sol~ent. Suitable bases include, DUt are not limited to, the alkali and alkaline earth metals, their hydrides and tert-butoxides. For example, when R12 is methyl, the compound of Formula II
could.be suspended or dissolved in methanol in the presence of two equivalents of sodiu~ methoxide.
Alternatively, two equivalents of sodiu~ hydride could be used in place of the sodium methoxide.
;
~203S35 (b) The compound of Formula II can be suspended or dissolved in an inert solvent in the presence of at least two equivalents of alkoxide, -OR12.
Suitable inert solvents include, but are not limited to, acetonitrile, T~F and dimethylformamide. The alkoxide may be added directly as alkali metal or alkaline earth metal alkoxide or may be generated from alkanol and a base 2s describe~
in (a) above. For example, when R12 is methyl, the compound of Formula II could be suspended or dissolved in THF in the psesence of two ecuiva-lents of sodium methoxide. Alterna- --tively, two equivalents each of methanol and sodium h dride could ~e used instead of sodium methoxide.
For reasons of economy and efficiency, procedure (a) is the more preferred method.
It should be noted that two equivalents of alkoxide are required for Reaction Step (5a) whereas only one equivalent of alka~ol is needed for the same process.
This difference is due to the reaction which is be-lieved to occur between the al~oxide an2 the sul-fonyl nitrogen of the sulfonamide of Formula VIII.
When alkoxide is used, the first e~u~alent of al-koxide removes a proton from the sulfonyl nitrogen, and it is only the second equivalent which effects displacement of the halogen. As a result, two eguivalents of alkoxide are requirea. ,he resulting salt must be acidified, e.g., with sulfuric, hydro-chloric or acetic acid, to yield a compoun2 of Formula IX. Applicant, of course, does not intenc to be boun2 by the ~echanism described a~ove.
12(~3535 In Reaction Step (5c) a compound of Formula IXa, su~stituted with at least one displacement gr~up, is contacted with either one equivalent of alkznol, P.130~, or with two ecuivalents of alkoxide, -OR13 where ~13 is as desc~ibed abo~e. The compound of Formula IXa is prepared according to Reaction Step (5b) from a compound of Formula IX where Y2 is Cl or Br. ~hen alkoxide, -OR13 is used, it may ~e prot-ided ir. either of the methods described above in connection with Reaction Step (5c), and the resulting salt can be acidi ied to yield a compound of Formula X.
When R12 ~ R13, Reaction Steps (5b) and (5c) m8y be combined. Thus, a compour.d of Formula II
m~y be contacted either with at le2st two es~ivalents lS oS Alkanol, R130H, or with at lezst three ecuivalents of alkoxide~ -OR13-~ hen a compound of Formula II contains two dis-place~ble g-oups, i.e., both X2 and Y2 are Cl or Br, certain reaction conditions will favor dis?lacement of only one of the group. These conditions a-e the use of low temperatures and, when alkoxide is used, the slow addition of the stoiehiometric amount of alXoxice or alkoxide-generating base to the medium containing the compound of ~or~ula II.
~5 When alkoxide is used, both Reaction Steps (5b) and (5c) are preferably run at temperatures within the range of about -10 to 80C, the range of about 0 to 25-C beins more preferrea. Reaction Steps 30 (Sb) and (5c) are more sluggish when alkanol is used instead of alkoxide, and more drastic conditions are reo,uired,for the reactio~ to go to completion. Thus, i.igher temperatures, up to and including the boiling point of the alkanol itself, are reguirec.
lZ03S35 Reaction Step (5d) Reaction Step ~Sd) involves the displacement of the halogen atom in a compound of Formul2 IIa by a methylthio nucleophile. The starting material, a com-pound of FormulaIIa, is prepared accordinq to ReactionStep (5a), and Y4 is limited to Cl-C2 alkyl and CF3.
For ~his reaction, the compound of FormulaIIa is suspende~ or dissolved ir. ~n ir.est solvent, e-s-acetonitrile or ~EF. At least one ecuivalent o~
the r.u~leophilic species and at least t~o e~u Yaler.~s of a base are then cont2cted with the startins ma-te-ial. The first equi~alent of base is belie~ed to neutralize the sulfonamido proton. ~he seconc ecuiv21ent of base generates merc2r~ide ion from the mercaptan. Suitable bases include sodium hydride, sodium methoxide and sodium hydroxide.
Suitable reaction temperatures are within the r~nge of about -10 to 80C, with a range o' a~out 0 to 25C being preferred. ~he product may ~e isolatec by dilution of the reaction mixture with water, mild acidification and filtration.
The sulfonamides of Formula IV can be prepared by the four step reaction sequence shown in Equation 6.
3s lZ(~3535 Eauation 6 S2Cl - `S02-NR3R4 Rl~ I, l`c R2 ~ N2 ~ R
R XIIa XII XIII
R 1 2 3 4 ` R S12 3 4 Pd/C R
XIII XIV
Rl2 R3R4 S02-NR3R4 (6c) ~ 2 l) HN02/HCl R2 ~ S02C
R - 2) S02/CH3C02H/CuCl R
XV
XIV
S02-NR3R4 R l2 NR3 4 (6d)2 ~ S2 ' ~ R2 ~ 02NH2 IV
XV
whereln R, Rl, R2, R3 and R4 are as defined in Equations 1-5, wlth the exception that R cannot be N02.
1;2~35;~5 In step 6a, the _-nitrobenzylsulfonyl chlo-rides of Formula XII, which are well-known in the art, are treated with an amine of Formula XIIa in an inert organic solvent e.g. methylene chloride, ethyl ether or tetrahydrofuran at 0-50. The amine may be taken in excess to act as an acid acceptor; or, alterna-tively, a tertiary amine e.g. triethylamine or pyridine may be used as an acid acceptor. The by-product amine hydrochloride is filtered off or washed out of the solvent with water and the product isolated by evaporation of the solvent.
The reduction described in step 6b is accom-plished by treating a solution of the compounds of Formula XIII in a solvent e.g. ethanol, ethyl acetate, or diglyme, in a pressure vessel, with 50-1000 pounds per square inch of hydrogen at 25-150 in the presence of a hydrogenation catalyst e.g. 5-10% palladium absorbed on carbon. When the theoretical amount of hydrogen has been absorbed, the solution is cooled and the catalyst is removed by filtration. The product is then isolated by evaporation of the solvent.
In the case where R = NO2, the reduction of step 6b can be accomplished using ammonium sulfide or sodium hydrosulfide instead of catalytic hydro-genation. This type of procedure is described inOrganic Synthesis Coll. Vol. III, pgs. 242-3, John Wiley and Sons, Inc., New York and London (1955).
The diazotization and coupling with sulfur dioxide, described in step 6c, is accomplished in the following manner. A solution of the aniline of Formula XIV in a mixture of concentrated hydrochloric acid and glacial acetic acid is treated with a solu-tion of sodium nitrite in water at -5 to 0. After 3S3~
stirring for 10-15 minutes at 0 to insure complete diaæotization! this solution is added to a mixture of an excess of sulfur dioxide, and a catalytic amount of cuprous chloride in glacial acetic acid at 0-5.
The temperature is kept at 0-5 for 1/4 to 1 hour then raised to 20-25 and held at that temperature for 2-4 hours. This solution is then poured into a large excess of ice water. The sulfonyl chloride products, XV, can be isolated by filtration or by extraction into a solvent such as ethyl ether or methylene chloride followed by evaporation of the solvent.
The amination described in step 6d is con-veniently carried out by treating a solution of the sulfonyl chloride of Formula XV with an excess of anhydrous ammonia in a solvent e.g. ethyl ether or methylene chloride at 0-25. If the product sulfon-amide, IV, is insoluble it may be isolated by fil-tration followed by washing out the salts with water.
If the product sulfonamide is soluble in the reaction solution, it may be isolated by filtering off the precipitated ammonium chloride and evaporation of the solvent.
lZ03535 Compounds of Formula I, in which W = 0 and R8 = H, can also be prepared by the reaction of an appropriately substituted sulfonamide, IV, with the methyl carbamate of the appropriate aminoheterocycle, 5 XVI, in the presence of an equivalent of trimethyl-aluminum as shown in Equation 7.
Eauation 7 ~ /
.~C-S02NR3R4 ~ CH30CNH-A
IV XVI
Al(CH3)3 ~ / 2 CH2C12 ~ R - S02NHCNH-A
, Rl, R2, R3, R4 and A are as previously defined.
The reaction of Equation 7 is best carried out in an inert solvent e.g. methylene chloride at 10-45 and ambient pressure. The preferred mode of addition is to add the trimethylaluminum to a solution or slurry of the sulfonamide, IV, a mildly exothermic reaction occurs accompanied by the evolution of gas.
The addition of the heterocyclic carbamate, XVI, is then made and the mixture is stirred at ambient to reflux temperatures for 6 to 48 hours. The addition of aqueous acid e.g. dilute hydrochloric or acetic acid removes inorganic salts from the product con-tained in the organic phase. Evaporation of the methy-lene chloride yields the crude product which can be purified by recrystallization or column chromatography.
``` lZ~353~i As shown in Equation 8, compounds of Formula I, in which W is sulfur and R, Rl, R2, R3, R4 and A
are as previously defined and R8 is H are prepared by reaction of an appropriately substituted sulfon-amide, IV, with a heterocyclic isothiocyanate of Formula XVII.
Eauation 8 10R~ / 2 ~ ~ A-NCS
IV XVI I
R S02~HCNH-A
The reaction of Equation 8 is best carried out by dis-solving or suspending the sulfonamide and isothiocya-nate in a polar solvent e.g. acetone, acetonitrile, ethyl acetate or methyl ethyl ketone, adding an equi-valent of a base e.g. potassium carbonate and stir-ring the mixture at ambient temperature up to the reflux temperature for one to twenty-four hours. In some cases, the product precipitates from the reaction mixture and can be removed by filtration. The product is stirred in dilute mineral acid, filtered and washed with cold water. If the product does not precipitate from the reaction mixture it can be isolated by evap-oration of the solvent, trituration of the residue with dilute mineral acid and filtering off the insol-uble product.
~2~3535 The heterocyclic isothiocyanates which are used in the procedure of Equation 8 are prepared, for example, according to the method of Japan Patent Application Pub: Kokai 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow, Tetrahedron 29, 691-7 (1973).
Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g. hydroxide, alkoxide, carbonate or hydride) quaternary amine salts can be made by similar techniques.
Detailed examples of such techniques are given in United States Patent 4,127,405.
The compounds of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade and all parts are by weight unless other-wise indicated.
. ,~
l:~V3535 Example 1 2-Nitrophenylmethyl carbamimidothioate hydrochloride A solution of 34.3 9 of o-nitrobenzyl chloride and 15.2 g of thiourea in 250 ml of #2B alcohol was refluxed for 1 1/2 hours. The solution was cooled to 60 and 250 ml of l-chlorobutane added. Further cooling to 20 yielded a precipitate which was fil-tered, washed with l-chlorobutane and dried at 65 to give 38.1 9 of 2-nitrophenylmethyl carbamimidothioate hydrochloride, m.p. 190-192.
NMR (DMSO-d6)S: 4.85 (s, 1.8H, CH2);
2-1(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide, m.p. 209-210C;
2-1(Dimethylamino)sulfonylmethyl]-N-t(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyllbenzenesulfonamide, m.p. 200-203C; and 2-t(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyllbenzene-sulfonamide, m.p. 200-205C.
This invention also relates to novel compounds of Formula II which are useful intermediates for the 5 preparation of the herbicidal compounds of Formula I.
R~ R2 (II) wherein 35L, R, Rl, and R2 are as previously defined, and Z is CH or N.
lZ03S3~;
This invention also relates to novel compounds of Formula III which are useful intermediates for the preparation of the~compounds of Formula I.
R R
5 ~ / 2 ~ ~ C-L
R ~ ;
(III) wherein L, R, Rl and R2 are as previously defined.
Detailed Description Svnthesis The compounds of Formula I, in which W = O, may be prepared as shown in Equation 1 by the reaction of an appropriately substituted benzenesulfonyl isocya-nate with an appropriate aminopyrimidine or aminotri-azine.
Equation 1 R~ /R2 ~C-S02NR3R4 I ~ I + ANH
o III VIII
~ ~R2 "~" C-so2NR3R4 )\ ~
. R SO2NHCNA
lZ03S35 wherein R is H, F, Cl, Br, N02, CF3, Cl-C3 alkoxy or Cl-C3 alkyl;
Rl is H or Cl-C4 alkyl;
R2 is H or CH3;
R4 is Cl-C4 alkyl;
R3 is CH30 or Cl-C4 alkyl;
provided that when R3 is CH30, then R4 is CH3, and provided that the total number of carbon atoms of R3 and R4 is five or less;
A is X yl yl N ~ N
X is H, Cl, Br, CH3, CH3CH2, Cl-C3 alkoxy, CF3, CH3S or CH30CH2;
Y is CH3, CH30 or Cl;
Z is N, CH, C-Cl, C-Br, C-CN, C-CH3, C-CH2CH3, C-CH2CH2Cl or C-CH2CH~CH2;
yl is H, CH3, CH30 or OCH2CH3;
and Q is 0 or CH2.
The reaction of Equation 1 is best carried out in an inert aprotic solvent e.g. methylene chloride, tetrahydrofuran or acetonitrile at a temperature between 20 and 80. ~ catalytic amou~t of 1,4-diazabicyclot2,2,2]octane (DABC0) may be used to accelerate the reaction. In cases in which the products are insoluble in the reaction solvent, they may be isolated by simple filtration. When the products are soluble, they may be isolated by 9evaporation of the solvent and trituration of the residue with solvents such as l-chlorobutane, ethyl-ether or methanol and filtration.
The benzenesulfonyl isocyanates of Formula III
may be prepared as shown below in Equation 2, by phosgenation of the sulfonamides of Formula IV
in the presence of butyl isocyanate. The sulfonyl isocyanates of Formula IIImay also be prepared, as shown in Equation 3, by phosgenation of the butyl ureas of Formula V.
~ tion 2 Rl R2 ~ C - S2NR3R4 n C4Hg 1~1 ) R S2 2 COC12/xylene IV
Rl R2 C--So2~R3R4 ~ SO2NCO
III
wherein 30R, Rl, R2, R3 and R4 are as previously described.
`` lZ~3535 The above reaction is carried out by heating a mixture of the appropxiate sulfonamide (IV), an alkyl isocyanate e.g. butyl isocyanate and a catalytic amount of a tertiary amine such as 1,4-diaza~2,2,2]bi-S cyclooctane (DABC0) in xylene, or other inert solventof boiling point ~135 to approximately 135. Phosgene is then added to the mixture over a 1-6 hour period until an excess of phosgene is present as indicated by a drop in the boiling point to less than 130. The mixture is cooled and filtered to remove a small amount of insoluble by-products. The solvent and the alkyl isocyanate are distilled off in-vacuo leaving a residue of the crude, sulfonyl isocyanate, III, which can be used without further purification.
E~Luation 3 Rl R2 ~ C - S2NR3R4 n-C4H~NC0 R S02N 2 K2CO3/Y~R
IV
Rl ~R2 ~ C5O2NR3R4 COC12/DABCO
NHcNH-n-c4H9 Xylene V Rl R2 ~ C - 52NR3R4 o 52 III
where~n R, Rl, R2, R3 ~nd R4 ~re ~s previously ~escr$bea.
,J
:, ` ~
The compounds of Formula V are conveniently prepared by stirring a mixture of the sulfonamides, IV, anhydrous potassium carbonate,` and n-butyl isocyanate in acetone or methyl ethyl ketone at 25-80 until all of the isocyanate has reacted- The products are isolated by quenching in dilute mineral acid and recrystallizing the solid product. The com-pounds V are treated with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in a manner analogous to that described in ~quation 2.
The sulfonyl isocya~ates of Formula IIImay also be prep~red as shown in Equa_ion 4, by the method of Ulrich et al. lJ. Org. Chem. 34, 3200 (1969)].
Equation 4 ,Rl ~R2 SOC12 IV
Rl R2 ~C/ 52NR3R4 COC12 RSO2NSO Pyridine catalyst VI
Rl R2 ,~ C--S02NR3R4 ~1 III
The synthesis of heterocyclic amine derivati~es such as those depicted by Formula VIII has been re-viewed in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publ., New York and London. Aminopyrimidines are described by D. ~. Brown in "The Pyrimidines", Vol. XVI of the above series.
The synthesis of the bicyclic pyrimidines of FormulaUIII is described in the following references:
Braker, Sheehan, Spitzmiller and Lott, J. Am.
Chem. Soc. 69, 3072 (1947).
Mitter and Bhattacharya, Quart. J. Indian. Chem.
Soc. 4f 152 (1927).
Shrage and Hitchings, J. Org. Chem. 16, 1153 (1951).
Caldwell, Kornfeld and Donnell, J. Am. Chem.
Soc. 63, 2188 (1941).
Fissekis, Myles and Brown, J. Org. Chem. 29, 2670 (1964).
- ~ompol~ds of Formula I, in which W = O, can also be prepared by the method described in Equation 5.
(5a) Equation 5 25Rl-c-so2NR3R6 X
so2NH2 + O~C-N
IV VII
Rl-c-so2~R3R4 x2 O N ~
) ~ ~ SO2NH ~ -~ NO~2 R ~II
(5b) Ri-c-so2NR3R4 N~~
~,SO2~HCNH--( C) Z
Rl-c-so2NR3R4~OR12 [~So2~HC~H~ Z
R IX
(5c~
Rl-c-so2NR3R4 OR12 N--( 2 0~ ~,5O2NHCNH ~ Z
R IXa 2 5 Rl- I-SOzNR3R4 ~ OR12 R X
(5d) Rl-c-sO2NR3R4 Y4 O N
S ~ ~ . N
R IIa ,R2 Rl f 52~ 3 4 N ~ Y4 < C) Z
R XI
wherein R, Rl, R2, R3 and R4 are as descrlbed previously;
R12 is methyl;
R13 is Cl-C3 alkyl;
X is Cl or Br;
Y2 is H, Cl, Br, methyl, ethyl or CF3:
Y3 is Cl or Br;
Y4 is methyl, ethyl or CF3; and ' E is CH35-.
Reaction Step (5a) -In Reaction Step (5a), an aromatic sulfonamide of Formula IV is contacted with a heterocyclic iso-cyanate of Formula VII to yield an N-(halohetero-cyclicaminocarbonyl)aromatic sulfonamide of Formula The heterocyclic isocyanates used in Reaction(5a) may be prepared according to methods described in Swiss Patent 579,062, U.S. Patent 3,919,228, U.S. Patent 3,732,223 and Angew Chem. Int. Ed. 10, 402 (1976).
The aromatic sulfonamide and the heterocyclic isocyanate are contacted in the presence of an inert organic solvent, for example, acetonitrile, tetra-hydrofuran (THF), toluene, acetone or butanone.Optionally, a catalytic amount of a base, e.g. 1,4-diazabicyclo[2.2.2]octane (DABCO), potassium carbonate sodium hydride or potassium tert-butoxide, may be added to the reaction mixture. The quantity of base constituting a catalytic amount would be obvious to one skilled in the art. The reaction mixture is preferably maintained at a temperature of about 25 to 110C, and the product can generally be recovered by cooling and filtering the reaction mixture. For reasons of efficiency and economy, the preferred solvents are acetonitrile and THF, and the preferred temperature range is about 60 to 85C.
Reaction Steps (Sb) and (5c) In Reaction Steps (5b) and (5c), one or two of the halogen atoms on the heterocyclic ring of the compound of Formula II is displaced by a nucleophilic species. Generally, this may be done by contacting the compound of Formula II either with alkanol, R12OH, or with alkoxide, -OR12, where R12 is as defined above.
,A
Thus, in Reaction Step (5b), a comp~und of Formula II, substituted with one displaceable group, can be contaeted with at least one equivalent of alkanol, R120H. This reaction is sluggish, however, and it is preferred to contact the compound of For~ula II with at least two equivalents of alkoxide, -OR12. ~he alkoxide can ~e provided in a number of ways:
(a) The compound of ~ormula II can be suspended or disso~ved in an alkanol solvent, R12O~, in the presence of at least twc equivalents of alkoxide, -OR12. The zlkoxide can be added directly as alkali metal or alkaline earth metal alkoxide or can be ~en-erated by the addition to the alkanol solvent of at least two ecuivalents of ~ base capable of oenerating al-koxide frcm the sol~ent. Suitable bases include, DUt are not limited to, the alkali and alkaline earth metals, their hydrides and tert-butoxides. For example, when R12 is methyl, the compound of Formula II
could.be suspended or dissolved in methanol in the presence of two equivalents of sodiu~ methoxide.
Alternatively, two equivalents of sodiu~ hydride could be used in place of the sodium methoxide.
;
~203S35 (b) The compound of Formula II can be suspended or dissolved in an inert solvent in the presence of at least two equivalents of alkoxide, -OR12.
Suitable inert solvents include, but are not limited to, acetonitrile, T~F and dimethylformamide. The alkoxide may be added directly as alkali metal or alkaline earth metal alkoxide or may be generated from alkanol and a base 2s describe~
in (a) above. For example, when R12 is methyl, the compound of Formula II could be suspended or dissolved in THF in the psesence of two ecuiva-lents of sodium methoxide. Alterna- --tively, two equivalents each of methanol and sodium h dride could ~e used instead of sodium methoxide.
For reasons of economy and efficiency, procedure (a) is the more preferred method.
It should be noted that two equivalents of alkoxide are required for Reaction Step (5a) whereas only one equivalent of alka~ol is needed for the same process.
This difference is due to the reaction which is be-lieved to occur between the al~oxide an2 the sul-fonyl nitrogen of the sulfonamide of Formula VIII.
When alkoxide is used, the first e~u~alent of al-koxide removes a proton from the sulfonyl nitrogen, and it is only the second equivalent which effects displacement of the halogen. As a result, two eguivalents of alkoxide are requirea. ,he resulting salt must be acidified, e.g., with sulfuric, hydro-chloric or acetic acid, to yield a compoun2 of Formula IX. Applicant, of course, does not intenc to be boun2 by the ~echanism described a~ove.
12(~3535 In Reaction Step (5c) a compound of Formula IXa, su~stituted with at least one displacement gr~up, is contacted with either one equivalent of alkznol, P.130~, or with two ecuivalents of alkoxide, -OR13 where ~13 is as desc~ibed abo~e. The compound of Formula IXa is prepared according to Reaction Step (5b) from a compound of Formula IX where Y2 is Cl or Br. ~hen alkoxide, -OR13 is used, it may ~e prot-ided ir. either of the methods described above in connection with Reaction Step (5c), and the resulting salt can be acidi ied to yield a compound of Formula X.
When R12 ~ R13, Reaction Steps (5b) and (5c) m8y be combined. Thus, a compour.d of Formula II
m~y be contacted either with at le2st two es~ivalents lS oS Alkanol, R130H, or with at lezst three ecuivalents of alkoxide~ -OR13-~ hen a compound of Formula II contains two dis-place~ble g-oups, i.e., both X2 and Y2 are Cl or Br, certain reaction conditions will favor dis?lacement of only one of the group. These conditions a-e the use of low temperatures and, when alkoxide is used, the slow addition of the stoiehiometric amount of alXoxice or alkoxide-generating base to the medium containing the compound of ~or~ula II.
~5 When alkoxide is used, both Reaction Steps (5b) and (5c) are preferably run at temperatures within the range of about -10 to 80C, the range of about 0 to 25-C beins more preferrea. Reaction Steps 30 (Sb) and (5c) are more sluggish when alkanol is used instead of alkoxide, and more drastic conditions are reo,uired,for the reactio~ to go to completion. Thus, i.igher temperatures, up to and including the boiling point of the alkanol itself, are reguirec.
lZ03S35 Reaction Step (5d) Reaction Step ~Sd) involves the displacement of the halogen atom in a compound of Formul2 IIa by a methylthio nucleophile. The starting material, a com-pound of FormulaIIa, is prepared accordinq to ReactionStep (5a), and Y4 is limited to Cl-C2 alkyl and CF3.
For ~his reaction, the compound of FormulaIIa is suspende~ or dissolved ir. ~n ir.est solvent, e-s-acetonitrile or ~EF. At least one ecuivalent o~
the r.u~leophilic species and at least t~o e~u Yaler.~s of a base are then cont2cted with the startins ma-te-ial. The first equi~alent of base is belie~ed to neutralize the sulfonamido proton. ~he seconc ecuiv21ent of base generates merc2r~ide ion from the mercaptan. Suitable bases include sodium hydride, sodium methoxide and sodium hydroxide.
Suitable reaction temperatures are within the r~nge of about -10 to 80C, with a range o' a~out 0 to 25C being preferred. ~he product may ~e isolatec by dilution of the reaction mixture with water, mild acidification and filtration.
The sulfonamides of Formula IV can be prepared by the four step reaction sequence shown in Equation 6.
3s lZ(~3535 Eauation 6 S2Cl - `S02-NR3R4 Rl~ I, l`c R2 ~ N2 ~ R
R XIIa XII XIII
R 1 2 3 4 ` R S12 3 4 Pd/C R
XIII XIV
Rl2 R3R4 S02-NR3R4 (6c) ~ 2 l) HN02/HCl R2 ~ S02C
R - 2) S02/CH3C02H/CuCl R
XV
XIV
S02-NR3R4 R l2 NR3 4 (6d)2 ~ S2 ' ~ R2 ~ 02NH2 IV
XV
whereln R, Rl, R2, R3 and R4 are as defined in Equations 1-5, wlth the exception that R cannot be N02.
1;2~35;~5 In step 6a, the _-nitrobenzylsulfonyl chlo-rides of Formula XII, which are well-known in the art, are treated with an amine of Formula XIIa in an inert organic solvent e.g. methylene chloride, ethyl ether or tetrahydrofuran at 0-50. The amine may be taken in excess to act as an acid acceptor; or, alterna-tively, a tertiary amine e.g. triethylamine or pyridine may be used as an acid acceptor. The by-product amine hydrochloride is filtered off or washed out of the solvent with water and the product isolated by evaporation of the solvent.
The reduction described in step 6b is accom-plished by treating a solution of the compounds of Formula XIII in a solvent e.g. ethanol, ethyl acetate, or diglyme, in a pressure vessel, with 50-1000 pounds per square inch of hydrogen at 25-150 in the presence of a hydrogenation catalyst e.g. 5-10% palladium absorbed on carbon. When the theoretical amount of hydrogen has been absorbed, the solution is cooled and the catalyst is removed by filtration. The product is then isolated by evaporation of the solvent.
In the case where R = NO2, the reduction of step 6b can be accomplished using ammonium sulfide or sodium hydrosulfide instead of catalytic hydro-genation. This type of procedure is described inOrganic Synthesis Coll. Vol. III, pgs. 242-3, John Wiley and Sons, Inc., New York and London (1955).
The diazotization and coupling with sulfur dioxide, described in step 6c, is accomplished in the following manner. A solution of the aniline of Formula XIV in a mixture of concentrated hydrochloric acid and glacial acetic acid is treated with a solu-tion of sodium nitrite in water at -5 to 0. After 3S3~
stirring for 10-15 minutes at 0 to insure complete diaæotization! this solution is added to a mixture of an excess of sulfur dioxide, and a catalytic amount of cuprous chloride in glacial acetic acid at 0-5.
The temperature is kept at 0-5 for 1/4 to 1 hour then raised to 20-25 and held at that temperature for 2-4 hours. This solution is then poured into a large excess of ice water. The sulfonyl chloride products, XV, can be isolated by filtration or by extraction into a solvent such as ethyl ether or methylene chloride followed by evaporation of the solvent.
The amination described in step 6d is con-veniently carried out by treating a solution of the sulfonyl chloride of Formula XV with an excess of anhydrous ammonia in a solvent e.g. ethyl ether or methylene chloride at 0-25. If the product sulfon-amide, IV, is insoluble it may be isolated by fil-tration followed by washing out the salts with water.
If the product sulfonamide is soluble in the reaction solution, it may be isolated by filtering off the precipitated ammonium chloride and evaporation of the solvent.
lZ03535 Compounds of Formula I, in which W = 0 and R8 = H, can also be prepared by the reaction of an appropriately substituted sulfonamide, IV, with the methyl carbamate of the appropriate aminoheterocycle, 5 XVI, in the presence of an equivalent of trimethyl-aluminum as shown in Equation 7.
Eauation 7 ~ /
.~C-S02NR3R4 ~ CH30CNH-A
IV XVI
Al(CH3)3 ~ / 2 CH2C12 ~ R - S02NHCNH-A
, Rl, R2, R3, R4 and A are as previously defined.
The reaction of Equation 7 is best carried out in an inert solvent e.g. methylene chloride at 10-45 and ambient pressure. The preferred mode of addition is to add the trimethylaluminum to a solution or slurry of the sulfonamide, IV, a mildly exothermic reaction occurs accompanied by the evolution of gas.
The addition of the heterocyclic carbamate, XVI, is then made and the mixture is stirred at ambient to reflux temperatures for 6 to 48 hours. The addition of aqueous acid e.g. dilute hydrochloric or acetic acid removes inorganic salts from the product con-tained in the organic phase. Evaporation of the methy-lene chloride yields the crude product which can be purified by recrystallization or column chromatography.
``` lZ~353~i As shown in Equation 8, compounds of Formula I, in which W is sulfur and R, Rl, R2, R3, R4 and A
are as previously defined and R8 is H are prepared by reaction of an appropriately substituted sulfon-amide, IV, with a heterocyclic isothiocyanate of Formula XVII.
Eauation 8 10R~ / 2 ~ ~ A-NCS
IV XVI I
R S02~HCNH-A
The reaction of Equation 8 is best carried out by dis-solving or suspending the sulfonamide and isothiocya-nate in a polar solvent e.g. acetone, acetonitrile, ethyl acetate or methyl ethyl ketone, adding an equi-valent of a base e.g. potassium carbonate and stir-ring the mixture at ambient temperature up to the reflux temperature for one to twenty-four hours. In some cases, the product precipitates from the reaction mixture and can be removed by filtration. The product is stirred in dilute mineral acid, filtered and washed with cold water. If the product does not precipitate from the reaction mixture it can be isolated by evap-oration of the solvent, trituration of the residue with dilute mineral acid and filtering off the insol-uble product.
~2~3535 The heterocyclic isothiocyanates which are used in the procedure of Equation 8 are prepared, for example, according to the method of Japan Patent Application Pub: Kokai 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow, Tetrahedron 29, 691-7 (1973).
Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g. hydroxide, alkoxide, carbonate or hydride) quaternary amine salts can be made by similar techniques.
Detailed examples of such techniques are given in United States Patent 4,127,405.
The compounds of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade and all parts are by weight unless other-wise indicated.
. ,~
l:~V3535 Example 1 2-Nitrophenylmethyl carbamimidothioate hydrochloride A solution of 34.3 9 of o-nitrobenzyl chloride and 15.2 g of thiourea in 250 ml of #2B alcohol was refluxed for 1 1/2 hours. The solution was cooled to 60 and 250 ml of l-chlorobutane added. Further cooling to 20 yielded a precipitate which was fil-tered, washed with l-chlorobutane and dried at 65 to give 38.1 9 of 2-nitrophenylmethyl carbamimidothioate hydrochloride, m.p. 190-192.
NMR (DMSO-d6)S: 4.85 (s, 1.8H, CH2);
7.4-8 (m, 4.2H, 4 aromatics);
9.7 ~broad s, 4.OH, 4 NH's).
Example 2 N,N-Dimethyl-2-nitrobenzenemethanesulfonamide To a slurry of 34.7 9 of the compound of Exam-ple 1 in 350 ml of water was added 20.5 ml of liquid chlorine at 10-15 over a 45 minute period. After stirring an additional 15 minutes at 10, the preci-pitated sulfonyl chloride was filtered off and washedwell with water. The wet sulfonyl chloride filter cake was suspended in 200 ml of ether and contacted with 18.0 ml of liquid dimethylamine at 5-15. ~fter stirring at room temperature for 1 1/2 hours, the pre-cipitate was filtered off and washed well with water,then l-chlorobutane. Oven drying at 60 overnight gave 15.9 g of N,N-dimethyl-2-nitrobenzenemethanesul-fonamide, m.p. 129-132.
NMR (DMSO-d6)~: 2.7 (s, 6.2H, SO2NMe2);
4.8 (s, l.9H, -CH2-);
7.6-8.3 (m, 3.9H, 4 aromatics).
Anal. Calcd. for CgH12N2O4S: C, 44.28;
H, 4.96; N, 11.47; S, 13.13.
Found: C, 44.6 44.5;
H, 4.8; N, 11.4; S, 13.3.
4.7; 11.4 13Ø
lZ03535 Example 3 N,N-Dimethyl-2-aminobenzenemethanesulfonamide In a pressure bottle, a mixture of 116 g of the product of Example 2, 1400 ml of 2-methoxyethyl ether and 10 9 of 10% palladium on carbon was shaken at 110 under 500 p.s.i. hydrogen until the hydrogen was no longer absorbed. The catalyst was filtered off and the filtrate stripped under reduced pressure to a volume of 200 ml. This residue was poured into 600 ml of ice and the precipitate filtered off and dried to give 84 g of crude product, m.p. 70-78. Recrystalli-zation from ~600 ml of l-chlorobutane gave 60.6 g of N,N-dimethyl-2-aminobenzenemethanesulfonamide, m.p.
92-100.
NMR (DMSO-d6)~: 2.7 (s, 5.8H, SO2NMe2);
4.3 (s~ 2.1H, CH2);
4.9-5.2 (broad s, 2.0H, NH2);
6.4-7.3 (m, 4.1H, 4 aromatics).
1~3S3S
Example 4 2-l(Dimethylamino)sulfonylmethyllbenzenesulfonamide To a solution of 53.5 9 of the product of Exam-ple 3 in a mixture of 225 ml of concentrated hydro-chloric acid and 75 ml of glacial acetic acid wasadded a solution of 21.4 g of sodium nitrite in 70 ml of water at -5 to 0. The solution was stirred at 0 for 15 minutes, then poured into a mixture of 6 9 of cuprous chloride, 48 ml of liquid sulfur dioxide in 300 ml of glacial acetic acid at 0-5. This mixture was stirred at 0 for 1 hour, then at 25 for 2 hours before being poured into 2 liters of ice-water. The precipitate was filtered and washed with water then suspended in 250 ml of ether and treated with 11.0 ml of liquid anhydrous ammonia at 5-15. After stirring at 25 for 30 minutes the precipitate was filtered off and washed well with ether then water. Oven drying at 60 gave 40.2 g of 2-1(dimethylamino)sulfonylmethyl~-benzenesulfonamide, m.p. 145-150.
NMR (DMSO-d6)~: 2.7 (s, 6.0H, SO2NMe2);
4.8 (s, 1.8H, -CH2-);
7.2-8.1 (m, 6.2H, 4 aromatics +
S02NH2) .
Example 5 2-t(Dimethylamino)sulfonylmethyl)benzenesulfonyl isocyanate A solution of 14.0 9 of the product of Example 4, 5.0 g of n-butyl isocyanate and 0.1 g of DABCO in 90 ml of mixed xylenes was heated- to 136. ~o this solution was added 3.6 ml of liquid phosgene over a 2 hour period to maintain the temperature between 125 and 136. The temperature was kept at 130 for 1/2 hour after the addition. The solution was cooled, and filtered under a nitrogen atmosphere and concentrated, at 60-7~ in vacuo to give 16.0 g of crude 2-~dime-thylamino)sulfonylmethyl]benzenesulfonyl isocyanate as a moisture sensitive oil. An infrared peak at 2200 cm 1 confirmed the presence of the -SO2NCO group.
J
~20353S
Example 6 2-~(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-E~yrimidin-2-yl)aminocarbonyl~benzenesulfonamide A mixture of 2.6 g of the product of Example 5, 5 0.9 9 of 2-amino-4,6-dimethoxypyrimidine and a few crystals of DABCO in 15 ml of'dry acetonitrile was heated at 50-55 for 1 hour under a nitrogen atmos-phere, then stirred overnight at room temperature.
The precipitate was filtered off, washed with aceto-10 nitrile and dried to give 2.1 9 of 2-l(dimethylamino)-sulfonylmethyl]-N-l(4,6-dimethoxypyrimidin-2-yl)amino-carbonyl~benzenesulfonamide, m.p. 172-176.
NMR (DMSO-d6)C~: 2.8 (s, 6.3H, SO2NMe2);
4.0 (s, 5.6H, Het-OCH3's);
5.0 (s, 2.0H, -CH2-);
6.1 (s, 0.8H, Het-H);
7.7-8.6 (m, 4.4H, 4 aromatics);
10.8 and 13.2 (broad singlets, NH's).
Anal. Calcd. for C16H21N5O7S2: C, 41.80;
H, 4.61; N, 15.24; S, 13.96.
Found: C, 41.8;
42.2;
H, 4,6; N, 16.1; S, 14Ø
4.5; 16.1; 14.3.
Using the procedures and examples described above and choosing the appropriate aminoheterocycle and sulfonyl isocyanate or sulfonamide, the compounds described in Tables I-VI may be prepared.
lZ03535 Table Rl-C-S02NR3R4 X
~,S02NHCN--( O ~
~ F~ ~ ~
a m.p.
R Rl 2 4 W 3 ~ X Y (C) H H H CH3- o CH3 H CH30 CH30 200-203(d) H H H CP.3- o CH3 H CH30 CH3 200-205~d) H H H CH3- o CH3 H CH3 CH3 209-210(d) H H H CH3- o CH30 H CH30 CH30 H H H CH3- 0 (CH )2CH- H CH30 CH30 H H H CH3- 0 CH3(CH2)3- H CH30 CH30 2 5 5-Cl H H CH33- CH3 H CH30 CH30 5-Br H H CH - 0 CH3 H CH30 CH30 5_CF23 H H CH33- CH3 H CH 0 CH 0 5-CH30 H H CH3- o CH3 3 3 5 C2H5 H CH3- o CH3 H CH30 CH30 5- ~0- H H CH3- CH3 CH 0 CH 0 5-C2H5- H H CH3- o CH3 CH 0 CH 0 5 5- ~ H H CH3- o CH3 H 3 3 Table I (continued) m.p.
R Rl R2 R4 W R3 R8 X Y ~C) 3-Cl H H CH3- 0 CH3 H CH30 CH30 4-Cl H . H CH3- 0 CH3 H CH30 CH30 6-Cl H H CH3- 0 CH3 H CH30 CH30 H H H CH3 0 CH3 H Cl CH30 H H H CH3 0 CH3 H Br CH30 H H H CH3 0 CH3 H CH3CH2o 3 H H H CH3 0 CH3 H ~~{~ CH3 H' H H CH3 0 CH3 H CH3S CH30 H C ~5 H CH3 0 CH3 H CH3 CH30 H n-c3H7 H CH3 0 CH3 CH30 CH30 H n-C4Hg H CH3 0 CH3 ,H CH30 CH30 H H H CH3 0 CH3 CH30 CH30 C~30 1203~;35 Table lI
Rl-C-S02NR3R4 X
W N--( ~,S02NHCN--~ C) Z
m.p.
10 R Rl R2 R4 W ~ 8 X Y Z ( C) H H CH - o CH3 H CH30 CH30 CH 172-176(d) HH H H CH3- CH3 H CH30 CH3 CH 181-183td) H H H CH - o CH3 H CH3 CH3 CH 203-204(d) H 'H H CH33- CH30 H CH30 CH30 CH
H H H CH3- 0 (CH3)2CE~- H CH30 CH30 CH
H H H CH3- 0 Ca3(CH2)3- H CH30 CH30 CH
H H CH3- o CH3 H CH30 CH30 CH
CH3 CH3 3 o CH3 H CH30 CH30 CH
2 5 5-F H H CcHH33- CH H CH30 CH30 CH
55-Cl HH HH CH33- C3 H CH30 Ca30 CH
3 0 5-CH30 H H CH3- o CH3 H CH30 CH30 CH
5 C2H5 H CH3- o CH3 H CH30 CH30 CH
5- )-0- H H CCH33- o C33 H CH30 CH30 CH
5-C2H5- H HH CcHH33_ CH3 H CH30 CH30 CH
Table II (continued) m.p.
R ~1 R2 R4 W R3 R8 X Y Z (C) 3-Cl H H CH3- 0 CH3 H CH30 CH30 4-Cl H H CH3- 0 CH3 H CH30 CH30 CH
6-Cl H H CH3- 0 CH3 H CH30 ~H3 H H H CH3 0 CH3 H Cl C 3 H H H CH3 0 CH3 H Br CH30 H H H CH3 0 CH3 H >-- ~ CH3 CH
H H H CH o CH3 H CH3~H2- CH3 CH
H H H CH3 0 CH3 H H CH3 C-Cl H H ,H CH3 0 CH3 H H CH3 C-CH3 H H H CH3 0 CH3 H H CH3 C~H2CH3 H H H CH3 0 CH3 H Cl Cl C CH2CH2 H H H CH3 0 CH3 H H CH3 c-cH2cH
H H H CH3 0 CH3 H CH3 CH3 c-cH2cH2cl H H H CH3 0 CH3 H H CH3 C~H2cH~cH2 H n-C3H7 H CH3 3 3 CH30 H n-C4Hg H CH3 0 CH3 H CH30 CH30 H H H CH3 0 CH3 3 3 c~3 3 5 H H H CH3 0 CH3 CH3 CH30 C~3 ~203535 Table II (continued) R Rl R2 R4 W R3 R8 X Y Z (C) ~Z(~3~i3~i Table III
Rl-C-S02NR3R4 Y
S ¦ W N--~S02NHCN--< 0 ~
m-P-R RI R2 R4 W 3 R8_ Q (C) lS ~ 'H H CH3- CH30 H CH3 H H H CH3- 0 C~3 2 H CH30 H H H CH3- 0 (CH3) 2CH- H CH30 H H H CH3- o CH3(CH2)3- H CH30 HHl CH3 CH3 CH3 0 3 H C 3 2 5 55_Fcl HH HH CH3 CcHH3- H CH30 0 5-Br H H C 3 CH3- H CH30 0 5_CF2 H H CH3 CH3- H CH30 0 3 a CB 3 CH3- H CH30 0 5-)-- H H CH3 CH3- H CH30 0 `.
lZ03535 Table III (continued) m.p.
R R1 R2 R4 W R3 R8 Y' Q (C) 3-Cl H H CH3- 0 CH3- H C 3 4-Cl H H CH3- 0 CH3- H CH3 5-Cl H H CH3- 0 CH3- H CH30 H n-C3H7 CH3 0 CH3 H CH30 H n-c4H9 H CH3 0 CH3 H CH30 0 H H H CH3 3 CH30 C2HsOCH2 Table IV
C!S2NR3R4 Y ' R~ S0 2NH~C~N, ~0~
H H n-C4Hg CH3 0 H CH30 HH HH HH cHH 33 CH 3 CCH2H 50 HH C~. H CH3 ccH33 S0 HH ccH330 HH n ~,4H9 3 ccH33 oo HH CcHH3300 3-Cl N N CCCCNN33 CCNN333 O N CN ~0 3o HH HH HH CcHH33 CHH33 CH3 CH3 H H H CH3 CH3 C~30 CH30 Table V
R~ /R2 R ~ n ~<
So2NH-c-NH - ~o Z
N ~
Cl 10 R Rl R2 R3 R4 Z
15 H H H n-C4Hg CH3 CH
H H H i_C3H7 CH3 CH
20 H n-C4Hg H CH3 CH3 CH
3-Cl H H CH3 CH3 CH
4-Cl H H CH3 CH3 CH
5-Cl H H CH3 CH3 CH
25 6-Cl H H CH3 CH3 CH
H H H n-C4Hg CH3 N
3o H H H l-C3H7 CH3 N
H n-C4Hg H CH3 CH3 N
1;2~35~3~
Table V ~continued) R Rl R2 R3 R4 z 3-Cl H H CH3 CH3 N
4-Cl H H CH 3 CH3 N
5-Cl H H CH3 CH3 N
6-Cl H H CH3 CH3 N
Table VI
R~C-S02NR3R4 R Rl R2 R3 R4 15 H H H l-C3H7 CH3 H H H n-C4Hg CH3 o H n-C4Hg H CH3 CH3 3-Cl H H CH3 CH3 4-Cl H H CH3 CH3 5-Cl H H CH3 CH3 6-Cl H H CH3 CH3 5-Br H H CH3 CH3 5-i_C3H70 H B CH3 CH3 5-i_C3H7 H H CH3 CH3 Formulations Useful formulations of the compounds of Formula I
can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concen-trates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare.
High strength compositions are primarily used as intermediates for further formulation. The formula-tions, br~adly, contain about 0.1~ to 99% by weight of active ingredient(s) and at least one of a) about 0.1~ to 2~ surfactant(s) and b) about 1~ to 99.9 solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Table VII
Active*
Ingredient Diluent(s) Surfactant(s) Wettable Powders20-90 0-74 1-10 Oil Suspensions, Emulsions, Solu-tions (including Emulsifiable Concentrates 3-50 40-95 0-15 Aqueous Suspensions 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 3D Compositions 90-99 0-10 0-2 Active ingredient plus at least one Gf a surfactant or a diluent equals 100 weight percent.
~203535 Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.
Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey.
The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Sol-vents Guide", 2nd Ed., Interscience, New York, 1950.
Solubili~y under 0.1~ is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishi~g Co., Inc., New York 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, ~Agglomeration", Chemical Engineering, December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, ~ew York, 1973, pp. 8-57ff.
lZ03535 For further information regardin~ the art o~
formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5, line 43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 5B, 132, 13B-140, 162-164, 166, 167 and 169-182.
H. Gysin and E. Xnusli, U.S. Patent 2,891,855, June 23, 1959, Col. 5, line 66 thr~ugh Col. 5, line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wil~y ~ Sons, Inc., New York, 1~61, pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Hand~ook"j 5th Ed., Blackwell Scientific Publica-tions, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
Example 7 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-~(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyllbenzene-sulfonamide 80%
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2~
synthetic amorphous silica 3%
kaolinite 134 The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns and then reblended.
Example 8 Wettable Powder 2-1(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl)-S benzenesulfonamide 50%
sodium alkylnaphthalenesulfonate 2%
low viscosity methyl cellulose 2%
diatomaceous earth 46~
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles of active essentially all below 10 microns in diameter.
The product is reblended before packagino.
Example g Granule ~
wettable powder of Example 85%
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 granules in a double-cone blender. The granules are dried and packaged.
Example 10 Extruded Pellet 2-l(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-ben-zenesulfonamide 25%
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium~magnesium bentonite 59~
The ingredients are blended, hammer-milled and then moistened with about 12~ water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
S Example ll Oil Sus ension p 2-[(Dimethylamino)sulfonylmethyl~-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 25 polyoxyethylene sorbitol hexaoleate 5 highly aliphatic hydrocarbon oil 70~
The ingrPdients are ground tcgether in a sand mill until the solid particles have been reduced to under ab~t 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
Example 12 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-l(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 20~
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3 attapulgite 69~
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce parti~les essen-tially all below 100 microns, the material is re-blended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
3~
lZ03535 Example 13 Low Strength Granule 2-l(Dimethylamino)sulfonylmethyl]-~-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 1%
N,N-dimethylformamide 9%
attapulgite granules 904 (U.S.S. 20-40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
_ Example 14 Acueous Suspension 2-[(Dimethylamino)sulfonylmethyl]-N-t(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 40%
polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether 0.5 disodium phosphate 1 monosodium phosphate 0.5 polyvinyl alcohol 1.0~
Water 56.7%
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
Example 15 - 30 solution 2-[(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyll-benzenesulfonamide, sodium salt 5%
water 95%
lZ03535 The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
Example 16 Low Strength Granule 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 0.1%
attapulgite granules 99.9 (U.S.S. 20-40 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 ~as been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
Example 17 Granule 2-l(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-1,3,5-triazin-2~yl)aminocarbonyl]benzene-sulfonamide 80%
wetting agent 1%
crude ligninsulfonate salt (containing 5-20% of the natural sugars) 10~
attapulgite clay 9%
The ingredients are blended and milled o pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidiza-tion and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water constant is reduced to the desired level, generally less than 1%. The material is then discharged, w reened to the desi~ed size range, gener-ally 14-100 mesh (1410-149 microns), and packaged for use.
Example 18 High Strength Concentrate 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzene-sulfonamide 99 silica aerogel 0~5%
synthetic amorphous silica 0.5%
The ingredients are blended and ground in a ha~mer-mill to produce a material essentially all passing a ~.S.S. No. 50 screen (0.3 mm opening~.
The concé~trate may be formulated further if necessary.
Example 19 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methyl-lJ3,5-triazin-2-yl)aminocarbonyl]-0 benzenesulfonamide 90%dioctyl sodium sulfosuccinate O.lZ
synthetic fine silica 9~97O
The ingredients are blended and ground in a hammer-mill to produce particles essentially all be-low 100 microns. The material is sifted through a.S.S. No. 50 screen and then packaged.
Example 20 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
lZ03S35 Example 21 Oil Suspension 2-~(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 35 blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6 xylene 59%
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified i~ water.
Example 22 Dust 2-[(Dimethylamino)sulfonylmethyl]-N-1(4,6-dimethYl-pyrimidin-2-yl)aminocarbonyllbenzene-sulfonamide 10~
attapulgite 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 pyrophyllite until homogeneous.
so ~tility The compounds of the present invention are active herbicides. They have utility for broadspectrum pre-and/or post-emergence weed control in areas where com-5 plete control of all vegetation is desired, su~h asaround fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highway and railroad structures.
By properly selecting rate and time of application. Some compounds of this invention may be used to modify plant growth beneficially, and also selectively contrDl w~ in crop6 such as wheat and b~rley.
The precise amount of the compound of Formula I
to be used in any given ~ituation will vary accordins to the particular end result desired, the amount of foliage p~nt, the w~ bo be oontr~lled, the crop species involved, the soil type, the fonN~ation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.05 to 20 kg/ha with a preferred range of 0.1 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistence in soil is desired.
The compounds of Formula I may be combined with other herbicides and are particularly useful in combi-nation with 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines such as 2-chloro-4-(ethyl-amino)-6-(isopropylamino)-s-triazine (atrazine); the uracils such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil); N-(phosponomethyl)glycine (glyphosate);
3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(lH,3~)-dione (hexazinone); N,N-dimethyl-2,2-12~3535 diphenylacetamide (diphenamide); 2,4-dichlorophenoxy-acetic acid (2,4-d) (and closely related compounds);
4-chloro-2-butynyl-3-chlorophenylcarbamate (barban);
S-(2,3-dichloroallyl)diisopropylthiocarbamate (diallate) S-(2,3,3-trichloroallyl)diisopropyl-thiocarbamate (triallate); 1,2-dimethyl-3,5-di-phenyl-l~-pyrazolium methyl sulfate (difenzoquat methyl sulfate); methyl 2-~4-(2,4-dichlorophenoxy)-phenoxylpropanoate (diclofop methyl); 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)one (metri-buzin); 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron); 3-isopropyl-lH-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide (bentazon); a,a,a-trifluoro-2,6-dini~ro-N,N-dipropyl-~-toluidine (trifluralin);
1,1'-dimethyl-4,4'-bipyridinium ion (paraquat);
monosodium methanearsonate (~SMA); 2-chloro-2',6'-diethyl (me~hoxymethyl)acetanilide (alachlor); 1,1-dimethyl-3-(a,a,a-trifluoro-_-tolyl)-urea (fluome-turon); and 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, methyl ester (acifluorfen-methyl).
-The activity of these compounds was discovered in greenhouse tests. The test procedure is described and the data obtained are shown below.
Test A
Seeds of crabgrass ~Digitaria spp.), barnyard-grass (Echinochloa crusqalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea sp.), cocklebur (Xanthium spp.), sorghum, corn, soy-bean, rice, wheat and nutsedge tubers (CYperus rotundus) were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent solution of the compounds of Table A. At the same time, cotton having five leaves (in-cluding cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass, barnyardgrass and wild oats with two leaves, cassia with three leaves ~including cotyledonary ones), morningglory and cocklebur with four leaves (including the cotyledonary ones), sorghum and corn with four leaves, soybean with 20 two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three to five leaves were sprayed with a non-phytotoxic solvent solution of the compounds of Table A. Other containers of the above mentioned weeds and crops were treated pre- or 25 post-emergence with the same non-phytotoxic solvent so as to provide a solvent control. A set of untreated control plants was also included for comparison.
Pre-emergence and post-emergence treated plants and controls were maintained in a greenhouse for sixteen 30 days, then all treated plants were compared with their respective controls and rated visually for response to treatment utilizing the following rating system:
0 S no effect;
10 s maximum effect;
C = chlorosis or necrosis;
E = emergence inhibition;
. G growth retardation;
H = formative effects:
X 8 axillary stimulation and 6Y = abscised buds or flowers.
The data obtained are summarized in Table A.
ComPound 1 O N_~/
~ SO2NHCNH ~ O ~
CH2SO2N(cH3)2 OCH3 20 ComPound 2 ~ SO2NHCNH ~ O N
CH2So2N(cH3)2 OCH3 ComPound 3 ~ ~ ~
CH2so2N(cH3)2 CH3 .
Compound 4 oCH
~SO2NHCNH--~O<
CH2so2N (CH3) 2 C 3 10 ComPound 5 O N--~S02NHCNH--< O>
_~ N~
CH2SO2N (CH3) 2 CH3 ComPound 6 ~CH3 SO2NHCNH--~O N
CH2SO2N (CH3) 2 CH3 lZ03535 Table A
Compound 1 ~ Compound 2 5 Rate kg/ha 0.1 2 0.1 2 POS$-EMERGENCE
Bush bean 5C,9G,6Y 4C,9G,6Y lC,4G,6Y 4S,9G,6Y
Cotton 5C,9G 5C,8G lC 5C,8G
Morningglory 4C,9~ SC,9G 2C,5G 3C,6G
Cocklebur 3C,9G 4C,9G 0 lC
Cassia 3C,7H 3C,6G lC lC
Nutsed5e lC,9G lC,9G 0 lC,5G
Crabgrass lC,3G 8G 0 0 Barnyardgrass 3C,9H 9C 0 0 Wild Oats 0 0 0 0 Wheat 0 0 0 0 Corn 2C,7H 5U,9C 0 0 Soybean 3C,9G 4C,9G lC,lH 2C,4G
15 Rice lC,5G 8G 0 2G
Sorghum 5C,9G 9C 0 lC,2G
PRE-EMERGENCE
Morningglory 2C,5H 9G 0 3C,6G
Cocklebur lC,3H 9H 0 6G
Cassia 6C 3C,8G 0 2C
Nutsedge 10E 10E 0 3G
20 Crabgrass lC 2C,8G 0 0 Barnyardgrass 3C,8H 5C,9H 0 lC,2G
Wild Oats lC 3C,7G 0 3G
Wheat lC` 4G 0 4G
Corn 2C,9H 9H 0 3C,9H
Soybean 3C,5H 9H 0 2C,3G
Rice 2C,6G 10E 0 3G
Sorghum 2C,9G 5C,9H 0 3C,8G
Table A (continued) Compound ~ Compound 4 Rate kg/ha 0.1 2 0.1 2 Moc in~lo~y 3C,8E 6C,9G 2C,4H lC,4G
Cassl 2C,6G 3C,8G 2G
Barnyardgrass lC 6H 2C,9H 0 lC,4G
Rice 2C,8G,5X 2C,8G lC,3G 2C 4G
PRE-EMERGE~CS 3C,5H 9GH lC 4C,9G
C--b~ras~ 922CC 36G 108 12Cc . 8G
Barnyardgrass 2C,6H 54Cc,98HG lo 4G
Siybe~n 233Ccc,,686Gd lC 7G 211GC 64GG ~312bc 21Cc Sorghum 5C,8H 4C,9H lC,3G 9G,3C
Table A (continued) Compound 5 Compound 6 Rate kg/ha 0.1 2 2 POST-EMERGENCE
Bush bean 3G 2C,9G 0 Cotton lC 2C,lH 0 Morningglory lC,9H 2C 0 Cocklebur lC lC 0 Nutsedge 0 lC,5G 0 CrabgraSs Barnyardgrass 0 0 0 Wild Oats 0 0 0 Wheat 0 0 0 Corn 0 0 0 Soybean lC 0 0 15 Sorghum lC lC,3G 0 PRE-EMERGENCE
Morningglory lC 3C,8G 0 CCaCsksleabUr 9H 0 Nutsedge 0 5G 4G
Crabgrass 0 2C,6G lC,3G
Wild Oats 0 4G 0 WchOerant 21c 22Gc,8H 02c,4G
Sorghum 122CCc l3Hcc~7G 121Hc,5G
9.7 ~broad s, 4.OH, 4 NH's).
Example 2 N,N-Dimethyl-2-nitrobenzenemethanesulfonamide To a slurry of 34.7 9 of the compound of Exam-ple 1 in 350 ml of water was added 20.5 ml of liquid chlorine at 10-15 over a 45 minute period. After stirring an additional 15 minutes at 10, the preci-pitated sulfonyl chloride was filtered off and washedwell with water. The wet sulfonyl chloride filter cake was suspended in 200 ml of ether and contacted with 18.0 ml of liquid dimethylamine at 5-15. ~fter stirring at room temperature for 1 1/2 hours, the pre-cipitate was filtered off and washed well with water,then l-chlorobutane. Oven drying at 60 overnight gave 15.9 g of N,N-dimethyl-2-nitrobenzenemethanesul-fonamide, m.p. 129-132.
NMR (DMSO-d6)~: 2.7 (s, 6.2H, SO2NMe2);
4.8 (s, l.9H, -CH2-);
7.6-8.3 (m, 3.9H, 4 aromatics).
Anal. Calcd. for CgH12N2O4S: C, 44.28;
H, 4.96; N, 11.47; S, 13.13.
Found: C, 44.6 44.5;
H, 4.8; N, 11.4; S, 13.3.
4.7; 11.4 13Ø
lZ03535 Example 3 N,N-Dimethyl-2-aminobenzenemethanesulfonamide In a pressure bottle, a mixture of 116 g of the product of Example 2, 1400 ml of 2-methoxyethyl ether and 10 9 of 10% palladium on carbon was shaken at 110 under 500 p.s.i. hydrogen until the hydrogen was no longer absorbed. The catalyst was filtered off and the filtrate stripped under reduced pressure to a volume of 200 ml. This residue was poured into 600 ml of ice and the precipitate filtered off and dried to give 84 g of crude product, m.p. 70-78. Recrystalli-zation from ~600 ml of l-chlorobutane gave 60.6 g of N,N-dimethyl-2-aminobenzenemethanesulfonamide, m.p.
92-100.
NMR (DMSO-d6)~: 2.7 (s, 5.8H, SO2NMe2);
4.3 (s~ 2.1H, CH2);
4.9-5.2 (broad s, 2.0H, NH2);
6.4-7.3 (m, 4.1H, 4 aromatics).
1~3S3S
Example 4 2-l(Dimethylamino)sulfonylmethyllbenzenesulfonamide To a solution of 53.5 9 of the product of Exam-ple 3 in a mixture of 225 ml of concentrated hydro-chloric acid and 75 ml of glacial acetic acid wasadded a solution of 21.4 g of sodium nitrite in 70 ml of water at -5 to 0. The solution was stirred at 0 for 15 minutes, then poured into a mixture of 6 9 of cuprous chloride, 48 ml of liquid sulfur dioxide in 300 ml of glacial acetic acid at 0-5. This mixture was stirred at 0 for 1 hour, then at 25 for 2 hours before being poured into 2 liters of ice-water. The precipitate was filtered and washed with water then suspended in 250 ml of ether and treated with 11.0 ml of liquid anhydrous ammonia at 5-15. After stirring at 25 for 30 minutes the precipitate was filtered off and washed well with ether then water. Oven drying at 60 gave 40.2 g of 2-1(dimethylamino)sulfonylmethyl~-benzenesulfonamide, m.p. 145-150.
NMR (DMSO-d6)~: 2.7 (s, 6.0H, SO2NMe2);
4.8 (s, 1.8H, -CH2-);
7.2-8.1 (m, 6.2H, 4 aromatics +
S02NH2) .
Example 5 2-t(Dimethylamino)sulfonylmethyl)benzenesulfonyl isocyanate A solution of 14.0 9 of the product of Example 4, 5.0 g of n-butyl isocyanate and 0.1 g of DABCO in 90 ml of mixed xylenes was heated- to 136. ~o this solution was added 3.6 ml of liquid phosgene over a 2 hour period to maintain the temperature between 125 and 136. The temperature was kept at 130 for 1/2 hour after the addition. The solution was cooled, and filtered under a nitrogen atmosphere and concentrated, at 60-7~ in vacuo to give 16.0 g of crude 2-~dime-thylamino)sulfonylmethyl]benzenesulfonyl isocyanate as a moisture sensitive oil. An infrared peak at 2200 cm 1 confirmed the presence of the -SO2NCO group.
J
~20353S
Example 6 2-~(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-E~yrimidin-2-yl)aminocarbonyl~benzenesulfonamide A mixture of 2.6 g of the product of Example 5, 5 0.9 9 of 2-amino-4,6-dimethoxypyrimidine and a few crystals of DABCO in 15 ml of'dry acetonitrile was heated at 50-55 for 1 hour under a nitrogen atmos-phere, then stirred overnight at room temperature.
The precipitate was filtered off, washed with aceto-10 nitrile and dried to give 2.1 9 of 2-l(dimethylamino)-sulfonylmethyl]-N-l(4,6-dimethoxypyrimidin-2-yl)amino-carbonyl~benzenesulfonamide, m.p. 172-176.
NMR (DMSO-d6)C~: 2.8 (s, 6.3H, SO2NMe2);
4.0 (s, 5.6H, Het-OCH3's);
5.0 (s, 2.0H, -CH2-);
6.1 (s, 0.8H, Het-H);
7.7-8.6 (m, 4.4H, 4 aromatics);
10.8 and 13.2 (broad singlets, NH's).
Anal. Calcd. for C16H21N5O7S2: C, 41.80;
H, 4.61; N, 15.24; S, 13.96.
Found: C, 41.8;
42.2;
H, 4,6; N, 16.1; S, 14Ø
4.5; 16.1; 14.3.
Using the procedures and examples described above and choosing the appropriate aminoheterocycle and sulfonyl isocyanate or sulfonamide, the compounds described in Tables I-VI may be prepared.
lZ03535 Table Rl-C-S02NR3R4 X
~,S02NHCN--( O ~
~ F~ ~ ~
a m.p.
R Rl 2 4 W 3 ~ X Y (C) H H H CH3- o CH3 H CH30 CH30 200-203(d) H H H CP.3- o CH3 H CH30 CH3 200-205~d) H H H CH3- o CH3 H CH3 CH3 209-210(d) H H H CH3- o CH30 H CH30 CH30 H H H CH3- 0 (CH )2CH- H CH30 CH30 H H H CH3- 0 CH3(CH2)3- H CH30 CH30 2 5 5-Cl H H CH33- CH3 H CH30 CH30 5-Br H H CH - 0 CH3 H CH30 CH30 5_CF23 H H CH33- CH3 H CH 0 CH 0 5-CH30 H H CH3- o CH3 3 3 5 C2H5 H CH3- o CH3 H CH30 CH30 5- ~0- H H CH3- CH3 CH 0 CH 0 5-C2H5- H H CH3- o CH3 CH 0 CH 0 5 5- ~ H H CH3- o CH3 H 3 3 Table I (continued) m.p.
R Rl R2 R4 W R3 R8 X Y ~C) 3-Cl H H CH3- 0 CH3 H CH30 CH30 4-Cl H . H CH3- 0 CH3 H CH30 CH30 6-Cl H H CH3- 0 CH3 H CH30 CH30 H H H CH3 0 CH3 H Cl CH30 H H H CH3 0 CH3 H Br CH30 H H H CH3 0 CH3 H CH3CH2o 3 H H H CH3 0 CH3 H ~~{~ CH3 H' H H CH3 0 CH3 H CH3S CH30 H C ~5 H CH3 0 CH3 H CH3 CH30 H n-c3H7 H CH3 0 CH3 CH30 CH30 H n-C4Hg H CH3 0 CH3 ,H CH30 CH30 H H H CH3 0 CH3 CH30 CH30 C~30 1203~;35 Table lI
Rl-C-S02NR3R4 X
W N--( ~,S02NHCN--~ C) Z
m.p.
10 R Rl R2 R4 W ~ 8 X Y Z ( C) H H CH - o CH3 H CH30 CH30 CH 172-176(d) HH H H CH3- CH3 H CH30 CH3 CH 181-183td) H H H CH - o CH3 H CH3 CH3 CH 203-204(d) H 'H H CH33- CH30 H CH30 CH30 CH
H H H CH3- 0 (CH3)2CE~- H CH30 CH30 CH
H H H CH3- 0 Ca3(CH2)3- H CH30 CH30 CH
H H CH3- o CH3 H CH30 CH30 CH
CH3 CH3 3 o CH3 H CH30 CH30 CH
2 5 5-F H H CcHH33- CH H CH30 CH30 CH
55-Cl HH HH CH33- C3 H CH30 Ca30 CH
3 0 5-CH30 H H CH3- o CH3 H CH30 CH30 CH
5 C2H5 H CH3- o CH3 H CH30 CH30 CH
5- )-0- H H CCH33- o C33 H CH30 CH30 CH
5-C2H5- H HH CcHH33_ CH3 H CH30 CH30 CH
Table II (continued) m.p.
R ~1 R2 R4 W R3 R8 X Y Z (C) 3-Cl H H CH3- 0 CH3 H CH30 CH30 4-Cl H H CH3- 0 CH3 H CH30 CH30 CH
6-Cl H H CH3- 0 CH3 H CH30 ~H3 H H H CH3 0 CH3 H Cl C 3 H H H CH3 0 CH3 H Br CH30 H H H CH3 0 CH3 H >-- ~ CH3 CH
H H H CH o CH3 H CH3~H2- CH3 CH
H H H CH3 0 CH3 H H CH3 C-Cl H H ,H CH3 0 CH3 H H CH3 C-CH3 H H H CH3 0 CH3 H H CH3 C~H2CH3 H H H CH3 0 CH3 H Cl Cl C CH2CH2 H H H CH3 0 CH3 H H CH3 c-cH2cH
H H H CH3 0 CH3 H CH3 CH3 c-cH2cH2cl H H H CH3 0 CH3 H H CH3 C~H2cH~cH2 H n-C3H7 H CH3 3 3 CH30 H n-C4Hg H CH3 0 CH3 H CH30 CH30 H H H CH3 0 CH3 3 3 c~3 3 5 H H H CH3 0 CH3 CH3 CH30 C~3 ~203535 Table II (continued) R Rl R2 R4 W R3 R8 X Y Z (C) ~Z(~3~i3~i Table III
Rl-C-S02NR3R4 Y
S ¦ W N--~S02NHCN--< 0 ~
m-P-R RI R2 R4 W 3 R8_ Q (C) lS ~ 'H H CH3- CH30 H CH3 H H H CH3- 0 C~3 2 H CH30 H H H CH3- 0 (CH3) 2CH- H CH30 H H H CH3- o CH3(CH2)3- H CH30 HHl CH3 CH3 CH3 0 3 H C 3 2 5 55_Fcl HH HH CH3 CcHH3- H CH30 0 5-Br H H C 3 CH3- H CH30 0 5_CF2 H H CH3 CH3- H CH30 0 3 a CB 3 CH3- H CH30 0 5-)-- H H CH3 CH3- H CH30 0 `.
lZ03535 Table III (continued) m.p.
R R1 R2 R4 W R3 R8 Y' Q (C) 3-Cl H H CH3- 0 CH3- H C 3 4-Cl H H CH3- 0 CH3- H CH3 5-Cl H H CH3- 0 CH3- H CH30 H n-C3H7 CH3 0 CH3 H CH30 H n-c4H9 H CH3 0 CH3 H CH30 0 H H H CH3 3 CH30 C2HsOCH2 Table IV
C!S2NR3R4 Y ' R~ S0 2NH~C~N, ~0~
H H n-C4Hg CH3 0 H CH30 HH HH HH cHH 33 CH 3 CCH2H 50 HH C~. H CH3 ccH33 S0 HH ccH330 HH n ~,4H9 3 ccH33 oo HH CcHH3300 3-Cl N N CCCCNN33 CCNN333 O N CN ~0 3o HH HH HH CcHH33 CHH33 CH3 CH3 H H H CH3 CH3 C~30 CH30 Table V
R~ /R2 R ~ n ~<
So2NH-c-NH - ~o Z
N ~
Cl 10 R Rl R2 R3 R4 Z
15 H H H n-C4Hg CH3 CH
H H H i_C3H7 CH3 CH
20 H n-C4Hg H CH3 CH3 CH
3-Cl H H CH3 CH3 CH
4-Cl H H CH3 CH3 CH
5-Cl H H CH3 CH3 CH
25 6-Cl H H CH3 CH3 CH
H H H n-C4Hg CH3 N
3o H H H l-C3H7 CH3 N
H n-C4Hg H CH3 CH3 N
1;2~35~3~
Table V ~continued) R Rl R2 R3 R4 z 3-Cl H H CH3 CH3 N
4-Cl H H CH 3 CH3 N
5-Cl H H CH3 CH3 N
6-Cl H H CH3 CH3 N
Table VI
R~C-S02NR3R4 R Rl R2 R3 R4 15 H H H l-C3H7 CH3 H H H n-C4Hg CH3 o H n-C4Hg H CH3 CH3 3-Cl H H CH3 CH3 4-Cl H H CH3 CH3 5-Cl H H CH3 CH3 6-Cl H H CH3 CH3 5-Br H H CH3 CH3 5-i_C3H70 H B CH3 CH3 5-i_C3H7 H H CH3 CH3 Formulations Useful formulations of the compounds of Formula I
can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concen-trates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare.
High strength compositions are primarily used as intermediates for further formulation. The formula-tions, br~adly, contain about 0.1~ to 99% by weight of active ingredient(s) and at least one of a) about 0.1~ to 2~ surfactant(s) and b) about 1~ to 99.9 solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Table VII
Active*
Ingredient Diluent(s) Surfactant(s) Wettable Powders20-90 0-74 1-10 Oil Suspensions, Emulsions, Solu-tions (including Emulsifiable Concentrates 3-50 40-95 0-15 Aqueous Suspensions 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 3D Compositions 90-99 0-10 0-2 Active ingredient plus at least one Gf a surfactant or a diluent equals 100 weight percent.
~203535 Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.
Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey.
The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Sol-vents Guide", 2nd Ed., Interscience, New York, 1950.
Solubili~y under 0.1~ is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishi~g Co., Inc., New York 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, ~Agglomeration", Chemical Engineering, December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, ~ew York, 1973, pp. 8-57ff.
lZ03535 For further information regardin~ the art o~
formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5, line 43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 5B, 132, 13B-140, 162-164, 166, 167 and 169-182.
H. Gysin and E. Xnusli, U.S. Patent 2,891,855, June 23, 1959, Col. 5, line 66 thr~ugh Col. 5, line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wil~y ~ Sons, Inc., New York, 1~61, pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Hand~ook"j 5th Ed., Blackwell Scientific Publica-tions, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
Example 7 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-~(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyllbenzene-sulfonamide 80%
sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2~
synthetic amorphous silica 3%
kaolinite 134 The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns and then reblended.
Example 8 Wettable Powder 2-1(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl)-S benzenesulfonamide 50%
sodium alkylnaphthalenesulfonate 2%
low viscosity methyl cellulose 2%
diatomaceous earth 46~
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles of active essentially all below 10 microns in diameter.
The product is reblended before packagino.
Example g Granule ~
wettable powder of Example 85%
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 granules in a double-cone blender. The granules are dried and packaged.
Example 10 Extruded Pellet 2-l(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-ben-zenesulfonamide 25%
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium~magnesium bentonite 59~
The ingredients are blended, hammer-milled and then moistened with about 12~ water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
S Example ll Oil Sus ension p 2-[(Dimethylamino)sulfonylmethyl~-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 25 polyoxyethylene sorbitol hexaoleate 5 highly aliphatic hydrocarbon oil 70~
The ingrPdients are ground tcgether in a sand mill until the solid particles have been reduced to under ab~t 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
Example 12 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-l(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 20~
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3 attapulgite 69~
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce parti~les essen-tially all below 100 microns, the material is re-blended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
3~
lZ03535 Example 13 Low Strength Granule 2-l(Dimethylamino)sulfonylmethyl]-~-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide 1%
N,N-dimethylformamide 9%
attapulgite granules 904 (U.S.S. 20-40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
_ Example 14 Acueous Suspension 2-[(Dimethylamino)sulfonylmethyl]-N-t(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 40%
polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether 0.5 disodium phosphate 1 monosodium phosphate 0.5 polyvinyl alcohol 1.0~
Water 56.7%
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
Example 15 - 30 solution 2-[(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyll-benzenesulfonamide, sodium salt 5%
water 95%
lZ03535 The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
Example 16 Low Strength Granule 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 0.1%
attapulgite granules 99.9 (U.S.S. 20-40 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 ~as been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
Example 17 Granule 2-l(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-1,3,5-triazin-2~yl)aminocarbonyl]benzene-sulfonamide 80%
wetting agent 1%
crude ligninsulfonate salt (containing 5-20% of the natural sugars) 10~
attapulgite clay 9%
The ingredients are blended and milled o pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidiza-tion and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water constant is reduced to the desired level, generally less than 1%. The material is then discharged, w reened to the desi~ed size range, gener-ally 14-100 mesh (1410-149 microns), and packaged for use.
Example 18 High Strength Concentrate 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzene-sulfonamide 99 silica aerogel 0~5%
synthetic amorphous silica 0.5%
The ingredients are blended and ground in a ha~mer-mill to produce a material essentially all passing a ~.S.S. No. 50 screen (0.3 mm opening~.
The concé~trate may be formulated further if necessary.
Example 19 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-[(4-methoxy-6-methyl-lJ3,5-triazin-2-yl)aminocarbonyl]-0 benzenesulfonamide 90%dioctyl sodium sulfosuccinate O.lZ
synthetic fine silica 9~97O
The ingredients are blended and ground in a hammer-mill to produce particles essentially all be-low 100 microns. The material is sifted through a.S.S. No. 50 screen and then packaged.
Example 20 Wettable Powder 2-[(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
lZ03S35 Example 21 Oil Suspension 2-~(Dimethylamino)sulfonylmethyl]-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide 35 blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6 xylene 59%
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified i~ water.
Example 22 Dust 2-[(Dimethylamino)sulfonylmethyl]-N-1(4,6-dimethYl-pyrimidin-2-yl)aminocarbonyllbenzene-sulfonamide 10~
attapulgite 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 pyrophyllite until homogeneous.
so ~tility The compounds of the present invention are active herbicides. They have utility for broadspectrum pre-and/or post-emergence weed control in areas where com-5 plete control of all vegetation is desired, su~h asaround fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highway and railroad structures.
By properly selecting rate and time of application. Some compounds of this invention may be used to modify plant growth beneficially, and also selectively contrDl w~ in crop6 such as wheat and b~rley.
The precise amount of the compound of Formula I
to be used in any given ~ituation will vary accordins to the particular end result desired, the amount of foliage p~nt, the w~ bo be oontr~lled, the crop species involved, the soil type, the fonN~ation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.05 to 20 kg/ha with a preferred range of 0.1 to 10 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions or where extended persistence in soil is desired.
The compounds of Formula I may be combined with other herbicides and are particularly useful in combi-nation with 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines such as 2-chloro-4-(ethyl-amino)-6-(isopropylamino)-s-triazine (atrazine); the uracils such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil); N-(phosponomethyl)glycine (glyphosate);
3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(lH,3~)-dione (hexazinone); N,N-dimethyl-2,2-12~3535 diphenylacetamide (diphenamide); 2,4-dichlorophenoxy-acetic acid (2,4-d) (and closely related compounds);
4-chloro-2-butynyl-3-chlorophenylcarbamate (barban);
S-(2,3-dichloroallyl)diisopropylthiocarbamate (diallate) S-(2,3,3-trichloroallyl)diisopropyl-thiocarbamate (triallate); 1,2-dimethyl-3,5-di-phenyl-l~-pyrazolium methyl sulfate (difenzoquat methyl sulfate); methyl 2-~4-(2,4-dichlorophenoxy)-phenoxylpropanoate (diclofop methyl); 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)one (metri-buzin); 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron); 3-isopropyl-lH-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide (bentazon); a,a,a-trifluoro-2,6-dini~ro-N,N-dipropyl-~-toluidine (trifluralin);
1,1'-dimethyl-4,4'-bipyridinium ion (paraquat);
monosodium methanearsonate (~SMA); 2-chloro-2',6'-diethyl (me~hoxymethyl)acetanilide (alachlor); 1,1-dimethyl-3-(a,a,a-trifluoro-_-tolyl)-urea (fluome-turon); and 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, methyl ester (acifluorfen-methyl).
-The activity of these compounds was discovered in greenhouse tests. The test procedure is described and the data obtained are shown below.
Test A
Seeds of crabgrass ~Digitaria spp.), barnyard-grass (Echinochloa crusqalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea sp.), cocklebur (Xanthium spp.), sorghum, corn, soy-bean, rice, wheat and nutsedge tubers (CYperus rotundus) were planted in a growth medium and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent solution of the compounds of Table A. At the same time, cotton having five leaves (in-cluding cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass, barnyardgrass and wild oats with two leaves, cassia with three leaves ~including cotyledonary ones), morningglory and cocklebur with four leaves (including the cotyledonary ones), sorghum and corn with four leaves, soybean with 20 two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three to five leaves were sprayed with a non-phytotoxic solvent solution of the compounds of Table A. Other containers of the above mentioned weeds and crops were treated pre- or 25 post-emergence with the same non-phytotoxic solvent so as to provide a solvent control. A set of untreated control plants was also included for comparison.
Pre-emergence and post-emergence treated plants and controls were maintained in a greenhouse for sixteen 30 days, then all treated plants were compared with their respective controls and rated visually for response to treatment utilizing the following rating system:
0 S no effect;
10 s maximum effect;
C = chlorosis or necrosis;
E = emergence inhibition;
. G growth retardation;
H = formative effects:
X 8 axillary stimulation and 6Y = abscised buds or flowers.
The data obtained are summarized in Table A.
ComPound 1 O N_~/
~ SO2NHCNH ~ O ~
CH2SO2N(cH3)2 OCH3 20 ComPound 2 ~ SO2NHCNH ~ O N
CH2So2N(cH3)2 OCH3 ComPound 3 ~ ~ ~
CH2so2N(cH3)2 CH3 .
Compound 4 oCH
~SO2NHCNH--~O<
CH2so2N (CH3) 2 C 3 10 ComPound 5 O N--~S02NHCNH--< O>
_~ N~
CH2SO2N (CH3) 2 CH3 ComPound 6 ~CH3 SO2NHCNH--~O N
CH2SO2N (CH3) 2 CH3 lZ03535 Table A
Compound 1 ~ Compound 2 5 Rate kg/ha 0.1 2 0.1 2 POS$-EMERGENCE
Bush bean 5C,9G,6Y 4C,9G,6Y lC,4G,6Y 4S,9G,6Y
Cotton 5C,9G 5C,8G lC 5C,8G
Morningglory 4C,9~ SC,9G 2C,5G 3C,6G
Cocklebur 3C,9G 4C,9G 0 lC
Cassia 3C,7H 3C,6G lC lC
Nutsed5e lC,9G lC,9G 0 lC,5G
Crabgrass lC,3G 8G 0 0 Barnyardgrass 3C,9H 9C 0 0 Wild Oats 0 0 0 0 Wheat 0 0 0 0 Corn 2C,7H 5U,9C 0 0 Soybean 3C,9G 4C,9G lC,lH 2C,4G
15 Rice lC,5G 8G 0 2G
Sorghum 5C,9G 9C 0 lC,2G
PRE-EMERGENCE
Morningglory 2C,5H 9G 0 3C,6G
Cocklebur lC,3H 9H 0 6G
Cassia 6C 3C,8G 0 2C
Nutsedge 10E 10E 0 3G
20 Crabgrass lC 2C,8G 0 0 Barnyardgrass 3C,8H 5C,9H 0 lC,2G
Wild Oats lC 3C,7G 0 3G
Wheat lC` 4G 0 4G
Corn 2C,9H 9H 0 3C,9H
Soybean 3C,5H 9H 0 2C,3G
Rice 2C,6G 10E 0 3G
Sorghum 2C,9G 5C,9H 0 3C,8G
Table A (continued) Compound ~ Compound 4 Rate kg/ha 0.1 2 0.1 2 Moc in~lo~y 3C,8E 6C,9G 2C,4H lC,4G
Cassl 2C,6G 3C,8G 2G
Barnyardgrass lC 6H 2C,9H 0 lC,4G
Rice 2C,8G,5X 2C,8G lC,3G 2C 4G
PRE-EMERGE~CS 3C,5H 9GH lC 4C,9G
C--b~ras~ 922CC 36G 108 12Cc . 8G
Barnyardgrass 2C,6H 54Cc,98HG lo 4G
Siybe~n 233Ccc,,686Gd lC 7G 211GC 64GG ~312bc 21Cc Sorghum 5C,8H 4C,9H lC,3G 9G,3C
Table A (continued) Compound 5 Compound 6 Rate kg/ha 0.1 2 2 POST-EMERGENCE
Bush bean 3G 2C,9G 0 Cotton lC 2C,lH 0 Morningglory lC,9H 2C 0 Cocklebur lC lC 0 Nutsedge 0 lC,5G 0 CrabgraSs Barnyardgrass 0 0 0 Wild Oats 0 0 0 Wheat 0 0 0 Corn 0 0 0 Soybean lC 0 0 15 Sorghum lC lC,3G 0 PRE-EMERGENCE
Morningglory lC 3C,8G 0 CCaCsksleabUr 9H 0 Nutsedge 0 5G 4G
Crabgrass 0 2C,6G lC,3G
Wild Oats 0 4G 0 WchOerant 21c 22Gc,8H 02c,4G
Sorghum 122CCc l3Hcc~7G 121Hc,5G
Claims (18)
1. A compound of the formula:
wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, C1-C3 alkyl or C1-C3 alkoxy;
R1 is H or C1-C4 alkyl;
R2 is H or CH3;
R3 is C1-C4 alkyl or OCH3;
R4 is C1-C4 alkyl;
R8 is H, CH3 or OCH3;
A is , or W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3~ SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH=CH2;
Y1 is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
provided that:
(1) when R3 is OCH3, then R4 is CH3;
(2) the total number of carbon atoms of R3 and R4 is five or less; and (3) when W is S, then R8 is H.
wherein L is SO2NR3R4;
R is H, F, Cl, Br, NO2, CF3, C1-C3 alkyl or C1-C3 alkoxy;
R1 is H or C1-C4 alkyl;
R2 is H or CH3;
R3 is C1-C4 alkyl or OCH3;
R4 is C1-C4 alkyl;
R8 is H, CH3 or OCH3;
A is , or W is O or S;
X is H, Cl, Br, CH3, CH2CH3, C1-C3 alkoxy, CF3~ SCH3 or CH2OCH3;
Y is CH3 or OCH3;
Z is N, CH, CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or CCH2CH=CH2;
Y1 is H, CH3, OCH3 or OCH2CH3;
and Q is O or CH2;
and their agriculturally suitable salts;
provided that:
(1) when R3 is OCH3, then R4 is CH3;
(2) the total number of carbon atoms of R3 and R4 is five or less; and (3) when W is S, then R8 is H.
2. A compound of Claim 1 wherein Z is N, CH, CCl, CBr or CCH3, W is O, and R8 is H or CH3.
3. A compound of Claim 2 wherein Z is CH or N, X is CH3 or OCH3, and R1 and R2 are H.
4. A compound of Claim 3 wherein A is and R and R8 are H.
5. A compound of Claim 4 wherein R3 is C1-C3 alkyl or OCH3, and R4 is CH3.
6. A compound of Claim 5 wherein R3 is OCH3 or CH3.
7. The compound of Claim 1, 2-[(dimethylamino)-sulfonylmethyl]-N-[(4,6-dimethylpyrimidin-2-yl)amino-carbonyl]benzenesulfonamide.
8. The compound of Claim 1, 2-1(dimethylamino)-sulfonylmethyl]-N-l(4,6-dimethoxypyrimidin-2-yl)amino-carbonyl]benzenesulfonamide.
9. The compound of Claim 1, 2-[(dimethylamino)-sulfonylmethyl]-N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]benzenesulfonamide.
10. The compound of Claim 1, 2-[(dimethylamino)-sulfonylmethyl]-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide.
11. The compound of Claim 1, 2-[(dimethylamino)-sulfonylmethyl]-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]benzenesulfonamide.
12. The compound of Claim 1, 2-[(dimethyl-amino)-sulfonylmethyl]-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide.
13. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be proteted an effective amount of a compound of Claim 1.
14. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 2.
15. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 3.
16. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 4.
17. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 5.
18. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected and effective amount of a compound of Claim 6.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16834980A | 1980-07-11 | 1980-07-11 | |
| US168,349 | 1980-07-11 | ||
| US253,407 | 1981-04-27 | ||
| US06/253,407 US4397679A (en) | 1980-07-11 | 1981-04-27 | Herbicidal o-sulfamylmethylbenzenesulfonamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1203535A true CA1203535A (en) | 1986-04-22 |
Family
ID=26864031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381468A Expired CA1203535A (en) | 1980-07-11 | 1981-07-09 | Herbicidal o-sulfamylmethylbenzenesulfonamides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1203535A (en) |
-
1981
- 1981-07-09 CA CA000381468A patent/CA1203535A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4435206A (en) | Agricultural pyridinesulfonamides | |
| CA1094067A (en) | Herbicidal sulfonamides | |
| EP0045196B1 (en) | Herbicidal benzothiophene and benzofuran sulfonamides | |
| CA1159066A (en) | Herbicidal sulfonamides | |
| CA1204112A (en) | Herbicidal sulfonamides | |
| EP0030142A2 (en) | Herbicidal ureas, preparation, compositions and use thereof | |
| US4348219A (en) | Herbicidal sulfonamides | |
| IE51706B1 (en) | Herbicidal sulfonamides | |
| EP0094260B1 (en) | Herbicidal heterocyclic alkylaminocarbonylsulfonamides | |
| EP0044209B1 (en) | Herbicidal sulfonamides | |
| EP0125864A1 (en) | Herbicidal sulfonamides | |
| NZ198341A (en) | N-(heterocyclic aminocarbonyl)-aryl-sulphonamides and herbicidal compositions | |
| CA1157021A (en) | Agricultural ureas and isoureas | |
| EP0057546A2 (en) | Sulfonylurea N-oxides | |
| EP0164269B1 (en) | Herbicidal sulfonamides | |
| CA1144923A (en) | Herbicidal sulfonamides | |
| US4522645A (en) | Agricultural pyridinesulfonamides | |
| CA1198108A (en) | Herbicidal sulfamates | |
| GB2088362A (en) | Herbicidal sulfonamides | |
| US4515624A (en) | Herbicidal sulfonamides | |
| EP0135332A1 (en) | Herbicidal benzenesulfonamides, benzylsulfonamides and benzenesulfamates | |
| NZ201849A (en) | Heterocyclic urea derivatives,and herbicidal compositions containing such | |
| CA1203535A (en) | Herbicidal o-sulfamylmethylbenzenesulfonamides | |
| US4521241A (en) | Herbicidal benzenesulfonamides | |
| US4397679A (en) | Herbicidal o-sulfamylmethylbenzenesulfonamides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |