Note: Descriptions are shown in the official language in which they were submitted.
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:
4 5O2NHCW
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)
25S SO2NHCNHR
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.
1203S35
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
S 0 2NHCN - A
(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;
(4) Compounds of Preferred (3) wherein R3
is Cl-C3 alkyl or OCH3, and R4
is CH3; and
1203535
(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-
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 the5 preparation of the herbicidal compounds of Formula I.
R~ R2
305O2NHCONH
(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 ~ ;
02NC
(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
R S2 R8
o
III VIII
~ ~R2
"~" C-so2NR3R4
)\ ~
. R SO2NHCNA
R8
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,
1203535
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
:, ` ~
1203535
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
R S2 2
IV
Rl R2
~C/ 52NR3R4 COC12
RSO2NSO Pyridine catalyst
VI
Rl R2
,~ C--S02NR3R4
~1
R SO2
III
1203535
11
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
R2
25Rl-c-so2NR3R6 X
so2NH2 + O~C-N
IV VII
R2
Rl-c-so2~R3R4 x2
O N ~
) ~ ~ SO2NH ~ -~ NO~2
R ~II
12U3535
12
(5b)
Ri-c-so2NR3R4 N~~
~,SO2~HCNH--( C) Z
II R2
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
1203535
13
(5d)
R2
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-.
1203S3S
14
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
12U3535
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
16
(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
19
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
RS2NH2
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
23
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
R 52 2
IV XVI I
C-S2NR3R4
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
26
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) .
1203S35
28
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
29
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- CH3 2 H CH30 CH30
H H H CH3- 0 CH CH CH2- H CH30 CH30
H H H CH3- 0 (CH )2CH- H CH30 CH30
H H H CH3- 0 CH3(CH2)3- H CH30 CH30
H H H CH3CH2- 0 CH3CH2 H CH30 CH30
H H H CH3- 0 CH3 H CH30 CH30
H H CH3 CH3- CH3 H CH30 CH30
H CH CH CH - 0 CH3 H CH30 CH30
3 3 3 0 CH3 H CH30 CH30
5-F H H CH - 0 CH3 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-N0 H H CH3- 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
S-CH3 H H CH3- CH3 H 3 3
5-C2H5- H H CH3- o CH3 CH 0 CH 0
5 5- ~ H H CH3- o CH3 H 3 3
1203535
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 CH3CH2 3
H H H CH3 0 CH3 H CH3CH2o 3
H H H CH3 0 CH3 H ~~{~ CH3
H H H CH3 0 CH3 H CF3 CH30
H' H H CH3 0 CH3 H CH3S CH30
H H H CH3 0 CH3 H CH30CH2 3
H H H CH3 0 CH3 H CH30CH2 3
H H H CH3 0 CH3 H H CH3
H H H CH3 0 CH3 H H CH30
H H H CH3 S CH3 H CH30 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 CH3 0 CH3 3 3 CH30
H H H CH3 0 CH3 CH3 CH30 CH3
H H H CH3 0 CH3 CH3 CH3 CH3
H H H CH3 0 CH3 CH30 CH30 C~30
H H H CH3 0 CH3 CH30 CH3 CH30
H H H CH3 0 CH3 3 3 CH3
3 5
1203~;35
Table lI
R2
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 CH3- CH3C 2 H CH30 CH30 CH
B H H CH3- 0 CH3CH2CH2- 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 H CH3CH2- 0 CH3CH2 H CH30 CH30 CH
H H CH3- o CH3 H CH30 CH30 CH
HH H CH3 CH3- 0 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
5-N02 H H CH3- CH H CH30 CH30 CH
5-CF3 H H CH3 3 H CH30 CH30 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
1203535
33
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 CH3CH2 3
H C 3 0 CH3 H CH3CH20- CH3 CH
H H H CH3 0 CH3 H >-- ~ CH3 CH
H H H CH3 0 CH3 H CF3 CH3
H H H CH3 0 CH3 H CH3S CH30
H H H CH o CH3 H CH3~H2- CH3 CH
H H H CH3 0 CH3 H CH3 2 3
H H H CH3 0 CH3 H H CH3
H H H CH3 0 CH3 H H CH3
H H H CH3 0 CH3 H H CH3 C-Cl
H H H CH3 0 CH3 H CH3 CH3
H H H CH3 0 CH3 H CH3 CH C-CH3
H H ,H CH3 0 CH3 H H CH3 C-CH3
H H H CH3 0 CH3 H CH3 CH3 C-CH2CH3
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 CH3 CH3 C CH2C 2
H H H CH3 0 CH3 H H CH3 C~H2cH~cH2
H H H CH3 S CH3 H CH30 CH30
H C2H5 H CH3 3 3 CH3
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
34
Table II (continued)
R Rl R2 R4 W R3 R8 X Y Z (C)
3 0 CH3 CH3 CH3 CH3 CH
H H H CH3 0 CH3 CH30 CH30CH3
H H H CH3 0 CH3 CH30 CH30CH3
H H H CH3 0 CH3 CH30 CH3 3
~Z(~3~i3~i
Table III
R2
Rl-C-S02NR3R4 Y
S ¦ W N--
~S02NHCN--< 0 ~
m-P-
R RI R2 R4 W 3 R8_ Q (C)
H H H CH3- CH3 H C2H50
H H H CH3- CH3 H CH3
H H H CH3- CH3 H CH3
lS ~ 'H H CH3- CH30 H CH3
H H H CH3- 0 C~3 2 H CH30
H H H CH3- CH3CH2CH2- H CH30
H H H CH3- 0 (CH3) 2CH- H CH30
H H H CH3- o CH3(CH2)3- H CH30
H H H CH3CH2- 0 CH3CH2 H CH3
H H CH3 CH3 0 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-N0 H H CH3 CH3- H CH30 0
5_CF2 H H CH3 CH3- H CH30 0
3 0 5-CH 0 N H C 3 CH3- H CH30 0
3 a CB 3 CH3- H CH30 0
2 5 B CH3 CH3- H CH30 0
5-CH3 H H CH3 CH3- H CH30
5-C2H5- H H CH3 CH3- H CH30 0
5-)-- H H CH3 CH3- H CH30 0 `.
lZ03535
36
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 H H CH3 S CH3- H CH30 0
H H H CH3 0 CH3 H H 0
H H H CH3 0 CH3CH2 H CH3 0
H H H CH3 0 CH3 H H CH2
H H H CH3 0 CH3 H C2 5 2
H H H CH3 0 CH3 H CH3CH2
H H H CH3 0 CH3 H CH30CH2
H H H CH3 0 CH3CH2 H CH30 CH2
H C2H5 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 CH3 0 CH3 CH3 CH30 0
H H H CH3 0 C 3 CH3 CH3 0
H H H CH3 0 CH3 CH3 C2H50
H H H CH3 0 CH3 CH30 CH30 2
H H H CH3 0 CH3 CH30 CH3CH2
H H H CH3 3 CH30 C2HsOCH2
37
Table IV
C!S2NR3R4 Y '
R~ S0 2NH~C~N, ~0~
R R R4 W R8 Y
H H H CH 3 CH 3 H CH 3
H H CH30 CH3 H CH3
H H H C2H5 CE13 H CH3
H H n-C4Hg CH3 0 H CH30
HH HH HH cHH 33 CH 3 CCH2H 50
H H H CH3 CH3 0 H H
HH C~. H CH3 ccH33 S0 HH ccH330
H CH3 H CH3 CH3 H CH30
HH n ~,4H9 3 ccH33 oo HH CcHH3300
3-Cl N N CCCCNN33 CCNN333 O N CN ~0
H H H CH 3 CH 3 CH 3 CH 3
3o HH HH HH CcHH33 CHH33 CH3 CH3
H H H CH3 CH3 C~30 CH30
120353S
38
Table V
R~ /R2
R ~ n ~<
So2NH-c-NH - ~o Z
N ~
Cl
10 R Rl R2 R3 R4 Z
H H H CH3 CH3 CH
H H H CH3O CH3 CH
H H H C2HS CH3 CH
15 H H H n-C4Hg CH3 CH
H H H i_C3H7 CH3 CH
H H H C2 5 C2H5 CH
H CH3 H CH3 CH3 CH
H C2HS H CH3 CH3 CH
20 H n-C4Hg H CH3 CH3 CH
H CH3 CH3 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 CH3 CH3 N
H H H CH3O CH3 N
H H H C2H5 CH3 N
H H H n-C4Hg CH3 N
3o H H H l-C3H7 CH3 N
H H H C2HS C2H5 N
H CH3 H CH3 CH3 N
H C2 5 H CH3 CH3 N
H n-C4Hg H CH3 CH3 N
35 H CH3 CB3 CH3 CH3 N
1;2~35~3~
39
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
1203535
Table VI
R~C-S02NR3R4
S02NC
R Rl R2 R3 R4
H H H CH3 CH3
H H H CH30 CH3
H H H C2H5 CH3
15 H H H l-C3H7 CH3
H H H n-C4Hg CH3
H CH3 H CH3 CH3
H C2H5 H CH3 CH3
o H n-C4Hg H CH3 CH3
2 H CH3 CH3 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-F H H CH3 CH3
5-Br H H CH3 CH3
5-N02 H H CH3 CH3
5-CF3 H H CH3 CH3
5-CH30 H H CH3 CH3
5-CH3 H H CH3 CH3
5-i_C3H70 H B CH3 CH3
5-i_C3H7 H H CH3 CH3
1203535
41
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
42
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.
1203S35
44
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
1203535
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
46
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
47
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
1203535
48
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
49
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.
1203535
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).
-
1203S35
52
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:
1203535
53
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
OCH3
O N_~/
~ SO2NHCNH ~ O ~
CH2SO2N(cH3)2 OCH3
20 ComPound 2
OCH3
~ SO2NHCNH ~ O N
CH2So2N(cH3)2 OCH3
ComPound 3
OCH3
~ ~ ~
CH2so2N(cH3)2 CH3
.
1203535
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
1203535
56
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
3S
1203535
57
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
