Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
lZV3S34
x 1 BA-8396-A
Title
HERBICIDAL SULFONA~IIDES
Background of the Invention
This invention relates to hydroxymethylbenzene-
sulfonamide derivatives which are useful as agricul-
tural chemicals and in particl~lar as general herbi-
cides kaving both pre- and post-emergence activity.
Netherlands Patent 121,788, p~blished
September 15, 1966, discloses the preparation of com-
pounds of the following Formula and their use asgeneral or selective herbicides:
Cl
l; R3 R2
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.
U.S. Patent 3,637,366 discloses compounds
having the formula:
RlHN~ SO~-N~IR2
wherein
. Rl ~s hydrogen or lower saturated aliphatic
acyl and
R2 is hydrogen, 2-pyrimidinyl, pyridyl,
amidino, acetyl or carbamoyl.
~he d$sclosed compounds are said to provide control of
crabgrass, cress, endive, clover and Poa annua.
1203S34
X ,
~rench Patent No. 1,468,747 discloses the
following ~ara-substituted phenylsulfonamides as being
useful as antidiabetic agents:
~ ~ ~ N 3
wherein
R ~ H, halogen, CF3 or alXyl.
~ogemann et al. Chem Ab., 53, 18052 g tl959),
disc~ose a number of sulfonamides, including uracil
derivatives and those having the formula:
H3C ~ S02N~CNHR
wherein , N
R is butyl, phenyl, or -~ ~ and
Rl is hydrogen or methyl. -<~1
When tested for hypoglycemic effect in rats (oral
doses of 25 mg/100 g), the compounds in which R is
butyl and phenyl were most potent. The others were of
low potency or inactive.
Wo~ciechowski, J. Acta. Polon. Pharm 19,
p. 121-5 (1962) lChem. Ab., S9 1633 el describes the
~ynthesis of N-tt2,6-dimethoxypyrimidin-4-yl)amino-
carbonyll-4-methylbenzenesu~fonamide:
oc~3
3 o CH3 ~3so2N~-c-N~N
oc~3
3~
1203534
x 3
Based upon similarity to a known comround, the author
speculated that the foregoing compound might bave a
hypoglycemic act~v~ty.
Subst~tuted-pyrimidinyl sulfonylureas of the
5 following formula, which are also ~ara-substituted on
the phenyl ring, are disclosed in Farmco Ed. Sci., 12,
586 ~1957) lChem. Ab., 53, 18052 g (1959]:
c~3
1oCH3 ~ S02N~-C-NH ~/
whercin
15R ~ H or C~3.
The presence of undesired vegetation causes
substantial damage to useful crops, especially agri-
- cultural products that satisfy man's basic food and
fiber needs, such as cotton, rice, corn, wheat, and
the like. The current population explosion and con-
20 comitant world food and fiber shortage demand improve-
ments in the efficiency of producing these crops.
Preventing or minimizing loss of a portion of such
valuable crops by ~illing, or inhibiting the growth
of undesired vegetation is one way of improving this
25 efficiency. A wide variety of materials useful for kill-
ing or inhibiting (controlling) the growth of unde-
sired vegetation is available; such materials are
commonly referred to as herbicides. The need still
exists however, for more effective herbicides.
lZ03534
x 4
Summary of the Inventlon
This invention relates to novel compounds
of Formula I and their agriculturally suita~le salts,
suitable agricultural compositions containing them,
S and their method of use as general and selective pre-
emergence and post-emergence herbicides and as plant-
growth regulants.
R ~ O~-HCN-A
~I)
where~ n
L ~s OH, OC(O)Rll, OC(O)NHR12 or OC(O)OR13;
R is H, F, Cl, Br, NO2, CF3, Cl-C3 alkyl or Cl-C3
alkoxy;
Rl 1s H or Cl-C4 alkyl;
R2 is H or CH3;
R8 is H, CH3 or OCH3;
Rll is H, Cl-C5 alkyl, C2-C3 alkenyl, C2-C3
alkynyl, C3-C4 cycloalkyl,
~ 14 , Cl-C4 alkyl substi tuted with 1-4
substituents selected from 0-3 F, 0-3 Cl or 0-3 Br,
or C2-C3 alkenyl substi tuted with 1-3 Cl;
R12 is H, Cl-C6 al kyl, C3-C4 alkenyl, C5-C6 cycloalkyl,
~ R17 ~ R17 or
1203534
x 5
or C5-C6 cycloalkyl substituted w~th CH3;
R13 ls Cl-C6 alkyl or
~ R18 ;
R14 and R15 are independently H, N02, CH3, Cl or
CH3;
R16 is H, F, Cl, Br, Cl-C3 alkyl, N02, CN, 502CH3,
OCH3, SCH3 or CF3i
R17 is H~ Cl or Cl-C3 alkyl;
R18 is H, CH3 or Cl;
A is
~ ~ ~ ~ or
~ is O or S;
X 1s H, Cl, 8r, CH3, CH2CH3, Cl-C3 alkoxy, CF3, SCH3
or CH20CH3;
Z ~s N, CH9 CCl, CBr, CCN, CCH3, CCH2CH3, CCH2CH2Cl or
CCH2CH~CH2;
yl ~s H, CH3, OCH3 or OCH2CH3; and
Q ~s O or CH2;
25 and their agriculturally su~table salts;
prov~ded that when W ~s S, then R8 1s H.
12(~353~
x 6
Preferred ~ompounds:
Preferred for their higher activity and/or
more favorable ease of sytnthesis are:
5 (1) Compounds of the generic scope where Z ~s N, CH,
CCl, CBr or CCH3, w is o and R8 is H or CH3
(2) Compounds of the generic scope where L is OH, R is
H, Rl and R2 are CH3, R8 is H or CH3;
A is ~; Z ~s CH or N; X and Y are
independently CH3 or OCH3; and W is O;
(3) Compounds of Preferred (1) where Z ~s CH or N; X
~s CH3 or OCH3; and Rl ~s H or CH3;
(4) Compounds of Preferred (3) where R and R8 are H,
and A ~s
2G N
~N ~
(S) Compounds of Preferred (4) where Rll, R12 and
Rl 3 are Cl -C3 alkrl;
(6) Compounds of Preferred (4I where L ~s OH.
Specifically preferred for their highest
activity a~d/or most favorable ease of synthesis are:
12~3~34
x 7
N-r(4,6-Dimethoxypyrimid~n-2-yl)aminocarbonyl]-2-
(hydroxymethyl)benzenesulfon3mide, ~p 149-151-;
N-~4,6-D~methoxy-1,3,~-triazin-2-yl)aminocarbonyl~-2-
(hydrq~ymethyl)benzenesulfonamide, ~p 146-148-(d);
5 N-~(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl3-2-(hydroxy-
methyl)ben2enesulfonamide,
N-t(4-methoxy-6-methylpyrimidin-2-yl~aminocarbonyl]-2-
(hydroxymethyl)benzenesulfonamide;
N-t(4,6-Dimethy~-1,3,5-triazin-2-yl)aminocarbonyl3-2-
thydroxy~ethyl)benzenesulfonamide; and
N-~(4-Methoxy-6-me~hyl-1,3,5-triazin-2-yl)aminocarbonyl]-
2-(hydroxymethyl)benzenesulfonamide.
Detailed Description of the Invention
Synthesis
Many of the compounds of Formula I may be pre-
pared as shown in Equation 1 by reaction of an appro-
priately substituted o-hydroxymethylbenzenesulfonyl-
urea, II, with an appropriate acid chloride.
Equation 1
~ C/ O R Rl R2
2S O + RlICCl --_~ O
SO2N~JC~.2~ So2NllcN-A
R8 R8
_ III
The reaction of Equation 1 is best carried out
in inert aprotic solvents e.g. methylene chloride,
tetrahydrofuran or acetonitrile at 0-80C. An excess
of the acid chloride is used and at least one equiva-
3S
1203534
Xlent of a tertiary amine such as pyridine, triethyl-
amine or 4-dimethylaminopyridine. Isolation 's
achieved by evaporation of solvent and recrystalli-
zation from suitable solvents such as l-chlorobutane,
S ethyl acetate or ethyl ether or by column chroma-
tography over silica gel.
Other compounds of Formula I may be prepared
as shown in Equation 2 by reaction of an appropriately
substituted o-hydroxymethylbenzenesulfonylurea, II,0 with an appropriate isocyanate.
Equation 2
\C / , ~X c~o-cNHR l 2
15 ~ 12NCO----t O
SO2N~C~ A SO NUC
R8 R8
II TV
The reaction of Equation 2 is best carried out
in inert aprotic solvents e.g. methylene chloride,
tetrahydrofuran or acetonitrile at 0-80C. An excess
of the isocyanate is used and a catalyst such as
dibutyltindilaurate or 1,4-diazal2,2,2]bicyclo-
octane (DABCO). Isolation is achieved by evaporation
of solvent and recrystallization from 'suitable solvents
such as l-chlorobutane, ethyl acetate or ethyl ether
or by column chromatography over silica gel.
Other compounds of Formula I may be prepared
as shown in Equation 3 by reaction of an appropriately
substituted o-hydroxymethylbenzenesulfonylurea, II,
with an appropriate chloroformate.
1203534
X g
Equation 3
\C/ H O R Rl R2
5 ~ O + clCo-Rl3 ~ ~ O
S02N~ICN--A So2Nl~cN--A
R8 R8
II V
The reaction of Equation 3 is best carried out
in inert aprotic solvents e.g. methylene chloride,
tetrahydrofuran or acetonitrile at 0-80C. An excess
of the chlorocarbonate is used and at least one
equivalent of a tertiary amine e.g. pyridine,
lS triethylamine or 4-dimethylaminopyxidine. Isolation
is achieved by evaporation of solvent and recrystalli-
zation from suitable solvents e.g. l-chlorobutane,
ethyl acetate or diethyl ether or by column chroma-
tography over silica gel.
The preparation of compounds of Formula II
where Rl=R2=H may be prepared as shown in Equation 4.
Equation 4 R
25~ C2~ O BH3.THF ~ CH2H
S02NHCN_A ) S02NHCN'--A-
~8 VII 8
VI
The carboxylic acid, VI, may be converted to the
alcohol by reduction with 4-5 equivalents OL borane-THF
reagent in TH~ at ambient pressure and temperature
for 4 to 18 hours. Isolation is achieved by drowning
in dilute acid followed by extraction of the product
with a solvent e.g. methylene chloride, ethyl
acetate or ethyl ether. Evaporation of solvent
and crystalliztion or column chromatography on silica
gel affords the pure alcohol, VII.
;
12V3534
X 10
The carboxylic acids, VI, may be prepared by
hydrolysis of the corresponding methyl esters as
shown in Equation 5.
Equation 5
S02N}ICN--A ~ ~ 502N3CN-A
R8 R8
VIII VI
When A is a pyrimidine type structure, the
methyl esters are best hydrolyzed by dissolving in
a solution of 80 parts ethanol, 10 parts water and
10 parts potassium hydroxide. The mixture is
stirred at ambient temperature for 18 hours
followed by pouring into a large excess of water
and acidifying to a pH of 2Ø The pure acid, VI,
precipitates and is filtered and washed with water.
When A is a triazine and X or Y is alkoxy, the
2~ hydrolysis is best performed by dissolving the
ester in a solution of potassium t-butoxide in
dimethyl sulfoxide at ambient temperature for
two hours. Addition of a large volume of water
followed by acidification to a pH of 2.0 precipitates
the acid, VI.
The preparation of esters of Formula VIII is
described in European Patent Application 7687.
Compounds of Formula VIImay also be prepared
by treatment of the carboxylic acids, VI, or the
methyl esters, VIII, with lithium aluminum hydride
- by the procedures described by R. ~. Nystrom and
W. G. Brown, J. Am. Chem. Soc. 69, 2548 (1947) and
R. B. Moffett, Or~anic Synthesis, Coll. Vol. 4, 834
12~3S34
o 11
(1963). Reduction of the esters with sodium bi5-
(2-methoxyethQxy)aluminum hydride is described in
. Fieser and L. E. Fieser, Reagents for Or~anic
S~_thesis, John Wiley & Sons, New York, Vol. 5,
5p. 596 (1975~.
The preparation of compounds of Formula II
where Rl=H and R2=CH3 may be carried out as shown
in Equation 6.
Equation 6
O C~3
"_~_, CCH3 ~ CHOH
O LiAlH4 ~ o
S02NHCN--A ~ S02NHCN'--A
R~ R8
IX X
Compounds of Formula IX are treated with one
- equivalent of li ~ um al~num hydride (IAH) in a sol~t
e.g. ether, tetrahydrofuran or glyme at -20 to
2025C for 1 to 6 hours. Next there is a successive
dropwise addition of an equivalent number of ml
of water as grams of LAH followed by an equal number
of ml of 15% sodium hydroxide followed by 3 times
that number of ml of water. This produces a dry
25 granular precipitate of aluminum oxide which is
easy to filter. The aqueous phase is then acidi-
fied with dilute acid and the product extracted
with solvent such as methylene chloride, ethyl
acetate or ethyl ether. Evaporation of solvent
30 and crystallization or column chromatography on
silica gel affords the pure alcohol, X.
Compounds of Formula IX are prepared by tne
reaction, as shown in Equation 7, usinq an excess
of methyl lithium with a carboxylic acid deriva-
~ 35 tive of Formula VI.
1203534
x 1~
Equation 7 R
R SO2NHCN-ACU3Li SO2N~CN-A
~8 R8
Compounds of Formula VI are restricted to
structures in which the substituents R, Z, X and
Y contain no displaceable halogens, N~2 or CN.
An excess of methyl lithium in a suitable
solvent such as diethyl ether, hexane, pentane or
benzene is added to a solution or slurry of VI in
a similar solvent at temperatures between -100 and
0C. The mixture is allowed to warm to room tempera-
ture and stir for 30 minutes. Aqueous acid is then
added and the compound IX is extracted into a suitable
solvent to free it from salts,followed by evaporation
of the solvent. Purification is by chromatography on
silica gel.
Another procedure for ~he preparation of com-
pounds of Formula X is the reaction of excess methyl
lithium with the corresponding aldehyde XI as shown
in Equation 8.
Equation 8
O C~ * ~ 5O2N~CN-A
~ZV3534
x 13
Compounds of Formula XI are restricted to
structures in which the substituents R, Z, X and Y
contain no displaceable halogens; NO2 or CN.
An excess of methyl lithium in a suitable
5 solvent e.g. diethyl ether, hexane, pentane or
benzene is adde~ to a solution or slurry of XI in
a similar solvent at temperatures between -100 and
0C. The ~ixture is allowed to warm to room tempera-
ture and stir for 30 minutes. Aqueous acid is then
10 added and the compound X is extracted into a suitable
solvent to free it from salts followed by evaporation
of the solvent. Purification is by chromatography
on silica gel.
Aldehydes of Formula XI are prepared by the
15 procedure of Equation 9.
Equation 9
R C2CN3 NaAl(OcH2cH2oc~3)2(~J~
SO2NHCN-A
VIII
- R
~ ,CHO
~ O
S02NHCN-A
XI
Following the procedure of R. Xanayawa and
T. Tokoroyama, a solution of sodium bis(2-methoxy-
ethoxy)aluminum hydride in THF is reacted with one
equivalent of morpholine. To this solution at -40C
is added methyl ester of Formula VIII and the solu-
tion is allowed to warm to 25C. The product is
lZ03534
x 14
isolated by addition of aqueous acid and extraction
into ether or methylene chloride. Evaporation of
solvent and crystallization or column chromatography
on silica gel affords the pure aldehyde, XI.
Aldehydes of Formula XI may also be prepared
from the esters of Formula VIII by treatment with
diisobutylaluminum hydride according to procedures
of E. Winterfeldt, Synthesis, 617 (1975).
The preparation of compounds of Formula II
10 where Rl=R2=CH3 may be prepared as shown in Equation
10 .
Equatlon 10
R ~ R CH3
15 ~ CCH3 excess ~ 3 Q
SO2NHCN-A CH3Li SO2NHCNt-A
IX R8 . r~8
XII
Compounds of Formula XII are prepared by the
reaction of an excess of methyl lithium with aceto-
phenones of Formula IX.
Compounds of Formula IX are restricted to
structures in which the substituents R, Z, X and Y
contain no displaceable halogens, NO2 or CN.
An excess of methyl lithium in a suitable
solvent e.g. diethyl ether, hexane, pentane or
benzene is added to a solution or slurry of IX in
a similar solvent at temperatures between -100 and
0C. The mixture is allowed to warm to room tempera-
ture and stir for 30 minutes. Aqueous acid is then
added and the compound XII is extracted into a
suitable solvent to free it from salts followed by
evaporation of the solvent. Purification is by
chromatography on silica gel.
~Z(~3534
Some of the compounds of Formula I, where
Z is CH or N, can also be prepared by the method
described in Equation 11.
Equation 11
s
(lla) ~ C - L N ~ Cl
+ OCN ~ O z --~
t n S2NH2 Cl
XIII , XIV
1~ / 2
R ~ C - L Cl
., N ~
S02N~ICNH--~ C Z
N~
XV
(llb)
30 8~ ~ SOz~Ch'll--( ~z
XVI
XV '
12~:13534
(llc)
1 ~ 2 1 / 2
~C L ~C - L
5 R ~ " N ~ ~ " N ~
S02NHCNH ~ NO~Z S02N~ ~ O~z
XVI XVII
wherein
R, Rl and R2 are as described in Formula I,
X is Cl-C3 alkoxy and L is not OH.
Reaction Step (lla)
In Reaction Step (lla), an aromatic sulfon-
amide of Formula XIII is contacted with a heterocyclicisocyanate of Formula XIV to yield an N-(halohetero-
cyclicaminocarbonyl) aromatic sulfonamide of Formula
XV.
The heterocyclic isocyanates used in Reaction
(lla) 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 heterocylic
isocyanate are contacted in the presence of an inert
organic solvent, for example, acetonitrile, tetrahydro-
furan (THF), toluene, acetone or butanone. Optionally,
a catalytic amount of a base, e.g. 1,4-diazabicyclo
12.2.2] 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
12V3534
x 17
to 110~, 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 (llb) and (llc)
In Reaction Steps (llb) and (llc), one or two
of the halogen atoms on the heterocyclic ring of the
compound of Pormula XV is displaced by a nucleophilic
species. Generally, this may be done by contacting
the compound of Formula XV either with alkanol or
with alkoxide as described by X where X is ~1-3 alkox~.
Thus, in Reaction Step (llb), a compound of
Formula XV, substituted with one displaceable
group, can be contacted with at least one equiva-
lent of alkanol. This reaction is sluggish, however,
and it is preferred to contact the compound of
~ormula XV with at least two equivalents of
alkoxide. The alkoxide can be provided in a
- 20 number of ways.
(a) The compound of Formula XV can be
suspended or dissolved in an alkanol
solvent in the presence of at least
two equivalents of alkoxide. The
alkoxide can be added dixectly as
alkali metal or alkaline earth metal
alkoxide or can be generated by the
addition to the alkanol solvent of
at least two equivalents of a base
capable of generating alkoxide from
the solvent. Suitable bases include,
but are not limited to, the alkali
and alkaline earth metals, their
hydrides and tert-butoxides. For
example, when X is methoxy, the
lZ03534
x 18
compound of Formula XV could be
suspended or dissolved in methanol
in the presence of two equivalents
of sodium methoxide. Alternatively,
S two equivalents of sodium hydride
could be used in place of the sodium
methoxide.
(b) The compound of Formula XV can be
suspended or dissolved in an inert
solvent in the presence of at least
two equivalents of alkoxide. Suit-
able inert solvents include, but
are not limited to, acetonitrile, THF
and dimethylformamide. The alkoxide
may be added directly as alkali metal
or alkaline earth metal alkoxide or
may be ger~erated from alkanol and a
base as c.escribed in (a) above. ~or
example, when X is methoxy, the com-
pound of Formula XV could be suspended
or diss-~lved in THF in the presence of
two equivalents of sodium methoxide.
Alternatively, two equivalents each
of methanol and sodium hydride could
be used instead of sodium methoxide.
For reasons of economy and efficiency, proce-
dure (a) is the more preierred method.
lt should be noted that two equivalents of
alkoxide are required for Reaction Step (b) whereas
only one equivalent of alkanol is needed for the
same process. This difference is due to the reaction
which is believed to occur between the alkoxide and
the sulfonyl nitrogen of the sulfonamide of Formula
XV. When alkoxide is used, the first equivalent of
alkoxide removes a proton from the sulfonyl nitrogen,
and is only the second e~uivalent which effects dis-
1203534
x 19
placement of the halogen. As a result, two equiva-
lents of alXoxide are re~uired. The resulting salt
must be acidified, e.g., with sulfuric, hydrochloric
or acetic acid, to yield a compound of Formula XVI.
5 Applicant, of course, does not intend to be bound by
the mechanism described above.
In Reaction Step (llc) a compound of Formula
XV~, is contacted with either one equivalent of
methanol or with two equivalents of methoxide. When-
10 methoxide is used, it may be provided in either ofthe methods described above in connection with
Reaction Step (llb) and the resulting salt can be
acidified to yield a compound of Formula XVII.
When X~XX3, Reaction Steps (llb) and (llc)
15 may be combined. Thus, a compound of Formula XV
may be contacted either with at least two equiva-
lents of methanol or with at least three equivalents
of methoxide.
For a compound of Formula XV, certain reaction
conditions will favor displacement of only one of the
chlorine gL~s. mese oonditions are thel-c~ of low tempera-
tures and, when a~ide is used, the slcw addition of the stoi-
chiometric amount of alkoxide or alkoxide-generating
base to the medium containing the compound of
Formula XV.
When alkoxide is used, both Reaction Steps
(llb) and (llc) are preferably run at temperatures
- within the range of about -10 to 80C, the range
of about 0 to 25C being more preferred. Reaction
3C Steps (llb) and (llc) are more sluggish when alkanol
is used instead of alkoxide, and more drastic condi-
tions are required for the reaction to go to com-
lZ~353~
x 20
pletion. Thus, higher temperatures, up to and in-
cluding the boiling point of the alkanol itself,
are required.
Depending on the nature of L in the compounds
5 of Formula XIII, the conversion to compounds of
Formula XVII by the reactions described in Equation
11 is carried out without alteration of L. In other
cases, the reactions result in the hydrolysis of the
benzyl alcohol derivatives to give compounds of
Formula XVIII wherein L is OH. Other compounds of
Formula I may then be prepared by the methods
previously described.
Thus, the reaction sequence described in
Equation 12 shows a protected 2-hydroxymethylbenzene-
lS sulfonamide converted to a useful herbicide via
reaction with a heterocyclic isocyanate.
Equation 12
o
R ~ 52~h2 OC~--< ON
XVIII XIX
"
~ CH20CCH3 Cl CH OH
R ~ --
' XX
R ~ O N--
~_~
OCH3
1203534
0 21
As shown in Equation 13, compounds of
Formula I wherein W is S are prepared by the
reaction of an appropriately substituted benzene-
sulfonamide with the appropriate triazine or
pyrimidine isothiocyanate OL formula XXI.
~ L + SCN-A > R ~ \L S
S2NH2 XXI O2NHCNH-A
The reaction of Equation 13 is best carried out by
dissolving or suspending the sulfonamide and
isothiocyanate in a polar solvent e-g. acetone,
acetonitrile, ethyl acetate or methylethyl-
ketone, adding an equivalent of a base e-g-
potassium carbonate and stirring the mixture atambient temperature up to the reflux tem~erature
for 1 to 24 hours. In some cases, the product
precipitates from the reaction mixture and can
be removed by filtration. The product is stirred
in di7ute mineral acid, filtered and washed with
cold water. If the product does not precipitate
from the reaction mixture, it can be isolated by
evaporation of the solvent, trituration of the
residue with dilute mineral acid and filtering
off the insoluble product.
The heterocyclic isothiocyanates which are
used in the procedure of ~quation 13 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,
691-697 (1973).
lZV3534
x 22
From the above, it is seen that compounds of
Formula XX are useful intermediates in the preparation
of compounds of this invention.
Compounds of Formula XVIII can be prepared via
a series of standard functional group transformations
as (J. F. King, A. Hawson, B. L. Huston, L. J. Danks,
and J. Romery, Can. J. Chem. 49, 943 (1971) for
2-(chloromethyl)benzenesulfonyl chloride.
~ NaBH4 ~ PC15
CHO ) ~ 2 POCl
S03Na S03Na
5
r
So2cl
Conversion of sulfonyl chlorides to sulfon-
amides is well known, e.g., Crossley et al., J. Am.
Chem. Soc., 60, 2223 (1938).
For those examples containing reactive func-
tionality on the position ortho to the sulfonamide
moiety it is convenient to add the sulfonyl chloride
to a measured quantity of ammonia in an inert sol-
vent, e.g., tetrahydrofuran, ethyl acetate, etc.
at low temperatures (-78-0). Side reactions
such as ring formation, elimination or condensa-
tion are thereby substantially avoided.
2C ~~~~~~ ~ J2 2
12C~353~
x 2i
The ~-haloalkylbenzenesulfonamide may be con-
verted to other required intermediates for this in-
vention by treatment with appropriate nucleop~iles,
e.g., acetate ion as described in Example 4.
~ C - Cl KOA ~ C - OCCH3
S2NH2 S2NH2
XVIII
Thus, compounds of Formula XVIII are useful
- intermediates in the preparation of compounds of
this in~ention.
The synthesis of heterocyclic amines has been
reviewed in ~The Chemistry of Heterocyclic Compounds"
a series published by Interscience Publ., New York
and London. 2-Aminopyrimidines are described by
D. J. Brown in The Pyrimidines, Vol. XVI of this
series. The 2-amino-1,3,5-triazines are reviewed
by K. R. Huffman and in The Triazines of this same
series. The synthesis of triazines are also de-
scribed by F. C. Schaefer, U.S. Patent No. 3,154,547
and by K. R. Huffman and F. C. Schaeffer, J. Org.
Chem. 28, 1816-1821 tl963).
The preparation of the aminoheterocycles de-
scribed by the following formulae are prepared by
methods described in unexamined European Patent 15683.
Y
~2N--( 0~ E12N
12V3534
x 24
Agriculturally suitable salts of compounds of
Formula I are also useful herbicides and can be pre-
pared by a number of ways known to ~he art. For exam- .
ple, metal salts can be made by treating compounds of
S Formula I with a so~ution of 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.
Salts of compounds of Formula I can also be
prepared by exchange of one cation to another.
Cationic exchange can be effected by direct treatment
of an aqueous solution of a salt of a compound of
Formula I (e.g., alkali metal or quaternary amine
salt) with a solution containing the cation to be
exchanged. This method is most effective when the
desired salt containing the exchanged cation is in-
soluble in water, e.g., a copper salt, and can be
separated by filtration.
Exchange may also be effected by passing an
aqueous solution of a salt of a compound of Formula
I (e.g., an alXali metal or quaternary amine salt)
through a column packed with a cation exchange resin
containing the cation to be exchanged. In this method,
the cation of the resin is exchanged for that of the
original salt and the desired product is eluted from
the column. This method is particularly useful when
the desired salt is water soluble, e.g., a potassium,
sodium or calcium salt.
Acid addition salts, useful in this invention,
can be obtained by reacting a compound of Formula I
with a suitable acid, e.g., p-toluenesulfonic acid,
trichloroacetic acid or the like.
The compounds of this invention and their pre-
paration are further illustrated by the following
examples wherein temperat~res are given in degrees
centigrade and all parts are by weight unless other-
wise indicated.
lZV3534
X ~s
Example 1
N-1(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-
carboxybenzenesulfonamide
,
A mixture containing 5 g of N-1(4,6-aimethoxy-
pyrimidin-2-yl)aminocarbonyll-2-methoxycarbonylbenzene-
sulfonamide, 20 ~1 of ethanol, 2.5 ml of water and
2.5 g of potassium hydroxide was stirred at ambient
tempe~ature and pressure for 18 hours. The mixture
was then diluted with 250 ml of water and 20 ml of
concentrated hydrochloric acid was added with stirring.
The precipitate was filtered and washed with water and
dried to yield 4.85 g of the desired product, melting
at 161-2C. ~he infrared absorption peaks at 3500,
3400 and 1700 cm 1 are consistent with the desired
lS structure and the nuclear magnetic resonance absorp-
tion peaks at 3.95 ppm, S, 6H, OCH3 of pyrimidine;
5.8 ppm S, lH, pyrimidine proton at position 5; and
7.6-8.3 ppm, M, 4H, aromatic protons, are consistent
with-the desired structure.
Example 2
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-
(hydroxymethyl)benzenesulfonamide
.
To a solution of 3.9 g of N-[(4,6-dimethoxy-
pyrimidin-2-yl)aminocarbonyl]-2-carboxybenzenesul-
fonamide in 100 ml of tetrahydrofuran was added
50 ml of a lM solution of borane, THF complex at
25C. The mixture was stirred at 25C for 18 hours
followed by addition of water and HCl. The mixture
was extracted with methylene chloride and the de-
sired product crystallized from solution, 1.1 g
29% yield, m.p. 149-lS0C. The infrared absorption
peaks at 3300 cm 1 and 1720 cm 1 are consistent
with the desired structure and the nuclear magnetic
resonance absorption peaks at 3.95 ppm, S, 6H, OCH3
of pyrimidine: 4.9 ppm, S, 2H, benzyl protons;
~2g:~534
\
5.9 ppm, S, lH, pyrimidine proton at position 5;
and 7.4-8.3 ppm, Multiplet, 4H, aromatic protons are
consistent with the desired structure.
Example 3
N-l(4,5-Dimethoxypyrimidin-2-yl)aminocarbonyl~-2-
methylcarbonylben~enesulfonamide
A mixture containing 0.85 g of N-1(4,6-
dimethoxypyrimidin-2-yl)aminocarbonyl]-2-carboxybenzene-
sulfonamide in 50 ml of anhydrous tetrahydrofuran was
treated with 40 ml of 1.4 molar solution of methyl
lithium (low halide, available from Aldrich Chemical
Company) in ether at 25 under a nitrogen atmosphere. The
mixture was stirred for 4 hours at 25 and was then
poured into 500 ml of water containing 10 ml of
concentrated hydrochloric acid. Thè precipitated oil was
extracted into methylene chloride and the oil on
evaporation of solvent was purified by preparative thin
layer chromatography on silica gel (available from
Analtec Inc, 2000 micron, 20 x 20 plates) by elution with
ethyl acetate/hexane in a one to one ratio. The isolated
product was recrystallized from a l-chlorobutane and
hexane mixture to give 0.1 9, m.p. 126-8. The infrared
absorption showed a broadened carbonyl peak at 1710
cm~l, and the absence of the 3500 and 3400 cm~l
peaks of the starting material. The nuclear magnetic
resonance spectrum showed peaks
o
at 2.6 ppm S, 3H, CH3CAr; 4.0 ppm, S, 6H, CH30 of
pyrimidine; 5.7 ppm S, lH, pyrimidine proton at
position S; and 7.3-7.7 ppm and 8.0 ppm M, 4H,
aromatic, which are consistent with the desired
structure.
t
12V3534
x 27
Example 4
N-~(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-
(-hydr~ye~ l)benzenesulfonamide
~ mixture containing 1.0 g of N-[(4,6-dimethoxy-
pyrimidin-2-yl)aminocarbonyl]-2-methylcarbonylbenzene-
sulfonamide in 50 ml of anhydrous THF is treated with
0.1 g of lithium aluminum hydride at 25 under a
nitrogen atmosphere. The mixture is stirred for
4 hours at 25 and is then poured into 500 ml of
1~ water containing 10 ml of concentrated hydrochloric
acid. The precipitated oil is extracted into
methylene chloride and the solid on evaporation
is purified by column chromatography on silica
gel.
Example 5
2-(Acetoxymethyl)benzenesulfonamide
A mixture of 2-(chloromethyl)benzenesulfonamide
(2.00 g), potassium acetate (6.0 g) and water (75 ml)
was heated to reflux for 1.5 hour. The pH was ad-
justed to ca. 5.0 by addition of hydrochloric acidand the chilled mixture was filtered to give 1.05 of
of shiny white solid, m.p. 131-133. 'H ~ ~(CD3)2CO
8.00-7.83 (M), 7.60-7.25 (M), 6.55 (brd s), 5.47
(s), 2.97 (brd s), 2.10 (s), consistent with the
assigned structure.
. --
` ` 12~)3534
28
Example 6
2-~Acetoxymethyl)-N-[(4,6-dichloro-1,3,5-triazin-2-
yl)aminocarbonyl]benzenesulfonamide
A solution of 4,6-dichloro-1,3,5-triazin-2-yl
isocyanate (0.87 g, 4.5 mmol) in acetonitrile
(9 ml) was treated with 2-(acetoxymethyl)benzene-
sulfonamide (1.04 g, 4.5 mmol) and stirred for 16
hours. Volatiles were removed under vacuum to give
a residue whose 'H NMR showed ~(CD3)2CO, 8.05-7.80
(m, lH), 7.65-7.27 (m, 3H), 6.45 (brd s, lH), 5.50
(s, 2H), 2.10 (s, 3H), consistent with the
assigned structure.
Example 7
2-(Hydroxymethyl)-N-1(4,6-dimethoxy-1,3,5-triazin-
1; 2-yl)aminocarbonyl]benzenesulfonamide
The crude 2-(acetoxymethyl)-N-[(4,6-dichloro-
1,3,5-triazinyl)aminocarbonyl]benzenesulfonamide was
treated with methanol (10 ml) and then with a solution
of sodium methoxide (14 mmol) in methanol. The mixture
was stirred at room temperature for 1.5 hour and
evaported. The residue was taken up in water and
filtered. The filtrate was acidified and filtered to
give 0.45 g of gummy solid which was recrystallized
from a chloroform/acetone mixture to give 115 mg
of white solid, m.p. 146-148(dec.).
'H NMR ~ DMSO-d6 12.2(brd s, lH), 10.73 (s, lH),
8.00-7.15 (m,4H), 4.80 (s and ~4.9-4.2 (brd s), 3H)
3.90 (s, 6H), consistent with the assigned structure.
Using the procedures of Examples 1 to 7 and the
proper reactants or the methods described herein, the
compounds of Tables I-XII may be prepared.
lZQ35~
-29-
Table I
\ /
C -OH X
R ~ SO2NHCN ~ ~N
R Rl R2 W R8 X Y
H H H O H CH3 CH3
H H H O H OCH3 CH3
H H H O H OCH3 OCH3
H H CH3 O H CH3 OCH3
H H CH3 O H SCH3 OCH3
H CH3 CH3 O H CH3 OCH3
H CH3 CH3 O H OCH3 OCH3
5-F H H O H CH3 CH3
6-F H H O H OCH3 OCH3
5-Cl H H O H CH3 OCH3
3-Cl H H O H OCH3 CH3
5-NO2 H H O H CH3 OCH3
5-NO2 H H O H OCH3 OCH3
5-OCH3 H H O H CH3 OCH3
5-OCH3 H H O H OCH3 OCH3
4-CF3 H H O H CH3 OCH3
5-CF3 H H O H OCH3 OCH3
5-CH-(CH3)2 H H O H OCH3 CH3
-OCH2CH2CH3 H H O H CH3 OCH3
~2~3~
Table I (continued j
R Rl ~2 W R8 X Y
_
4-CH3 H H O H CH3 OCH3
5-CH H H O H OCH3 OCH3
H H H O H Cl Cl
5-CH3 H H O H Cl Br
H CH3 H O H Cl Cl
5-OC2H5 H H O H Cl Cl
5-CH3 H H O H CH30CH2 CH3
5-CH3 H H O H CH30CH2 Cl
" ,CH3
4-CH H H O H CH3 OCH3
CH3
H H H O H SCH3 OCH3
H H H O H Br OCH3
,CH3
H H CH3 O H -OCH OCH3
CH3
H H CH3 O H CF3 Cl
H H H O H OC2H5 Cl
H H H S H CH3 CH3
H H H S H CH3 OCH3
H H H S H OCH3 OCH3
H H H CH3 CH3 CH3
H H H CH3 CH3 OCH3
H H H CH3 OCH3 OCH3
H H H OCH3 CH3 CH3
H H H OCH3 CH3 OCH3
H H H OCH3 OCH3 OCH3
~ j.
1203~;34
x 31
Table II
/
C - OH
R ~ SO2NHCN ~ ~ Z
R8
y
R ~ R2 W _ X Y Z m.p.(C)
10 H H H O H CH3 CH3 CH
H H H O H CH3 OCH3 CH
H H H O H OCH3 OCH3 CH
H HCH3 ~ O H CH3 CH3 CH
H H3 CH3 OCH3 CH
15 H HCH3 H OCH3 OCH3 CH
H CH3 CH3 o H CH3 CH3 CH
H CH3 CH3 o H CH3 OCH3 CH
H CH3 CH3 o H OCH3 OCH3 CH
5-F H H O H CH3 CH3 CH
5-F H H O H CH3 OCH3 CH
5-F H H O H OCH3 OCH3 CH
5-Cl H H O H CH3 CH3 CH
6-Cl H H O H CH3 OCH3 CH
5-Cl H H O H OCH3 OCH3 CH
5-NO2 H H CH3 CH3 CH
5-NO2 H H 3 OCH3 CH
5-N02 H H O H OCH3 OCH3 CH
5-OCH3 a H O H CH3 CH3 CH
4-oCH3 H H O H CH3 OCH3 CH
5-OCH3 H H O H OCH3 OCH3 CH
5-CF3 H CH3 CH3 CH
5-CF3 H H O H CH3 OCH 3 CH
3-CF3 H H O H OCH3 OCH3 CH
H H H O H H CH3 CCl
3~ H H H O H CH3 CH3 C-CN
lZ03534
32
Table II (continued)
R 1 2 W R8 X Y Z m.~.(C)
H H H o H CH3 CH3 C CH3
S H . H H o H H CH3 C-CH3
H H H o H CH3 CH3 C-CH2CH3
H H H o H H CH3 C-CH2CH3
H H H . o H H CH3 C-CH2CH2Cl
H H H O H CH3 CH3 C-CH2CH2Cl
H H H o H CH3 CH3 C-CH2CH-CH2
H H H o H C~3 C CH2CH CH2
5-OCH2CH2CH3 H H O H CH3 CH3 CH
5-CH2CH2CH3 H H ' o H CH3 OCH3 CH
H~ CH3 H O H H CH3 C-C2H5
HCH3 CH3 O H H OCH3 C-Cl
H H H S H CH3 CH3 CH
H H H S H CH3 OCH3 CH
H H S H OCH3 OCH3 CH
H H H O CH3 CH3 CH3 CH
H H H CH3 CH3 OCH3 CH
H H H O CH3 OCH3 OCH3 CH
H H H O OCH3 CH3 CH3 CH
H H H O OCH3 CH3 OCH3 CH
H H H O OCH3 OCH3 OCH3 CH
1203S34
X 33
Table II (continued)
R _ 2 W 8 X Y Z m.P.(C)
5-CH3 H H O H C~3 OCH3 CH
4-CH H H O H OCH3 OCH3 CH
H H H O H Cl Cl CH
H CH3 H O H Cl Cl CH
5-OC2H5 H H O H Cl Cl CH
~ CH3
4-CH H H H -CH20CH3 CH3 CH
CH3
H H H O H ^CH20CH3 CH3 CH
H H H O H SCH3 OCH3 CH
H H H O H SCH3 CH3 CH
; H H H O H SCH3 Cl CH
H H H O H CF3 Cl CH
, CH3
H H H O H -OCH ~ OCH3 CH
CH3
H H CH3 O H OC2H5 OCH3 CH
H H H O H CF3 3 CH
i
1203S34
x 34
Table III
~C/ OH Y'
S R ~ R~ N ~
R Rl R2 W 8 Y' Q m.p.(C)
H H H O H CH3 O
H H H O H OCH3 O
H H CH3 H CH3 O
H H CH3 O H OCH3
H CH3 CH3 O H CH3 O
H CH3 CH3 O H OCH3 O
5-F H H ~ O H OCH3 O
5-Cl H H O H OCH3
5-CH3 H H O H OCH3 O
5-NO2 H H O H OCa3 O
2 0 5-OCH3 H H O H OCH3 O
5-Cl H H o H CH3 O
H H H H H ca2
H H H H Cl CH2
H H H o H CH3 2
H H H H OCH3 CH2
H H H H H O
-35
` ` 120353
x 35
Table III_(continued)
R _ 2 W R8 y' Q p.tC)
5-CH3 H H O H OCH3 O
CH3
4-CH / H H O H OCH3 O
CH3
5-OC2H5 H H O H CH3 O
4-CH3 H H O H Cl O
OCH2CH2CH3 H H O H OCH3 O
H H H ~ S H CH3 O
H H H S H CH3 CH2
H H H S H OCH3 O
H H H S H OCH3 CH2
~S H H H ! o CH3 CH3 o
H H CH3 CH3 CH2
H H CH3 OCH3 o
H H H O CH3 OCH3 CH2
H H H O H OC2H5 o
H H OC2~5 CH2
lZ03534
0 36
Table IIIa
Rl R2
R ~ R8 N ~
R 12 W _8 Y m.p.(C)
H H H O H CH3
H H H O H OCH3
H H CH3 O H CH3
H H H3 H OCH3
H CH3 CH3 o H CH3
H CH3 CH3 o H OCH3
5-F H H O H OCH3
5-Cl H H O H OCH3
5-CH3 H H O H OCH3
5-~2 H H O H OCH3
5-OCH3 H H O H OCH3
5-Cl H H o H CH3
H H H H
H H H H Cl
H H H H CH3
H H H H OCH3
H H H H H
lZ03534
0 37
Table IIIa (continued)
R _ 2 W 8 y' m. p. (C)
S-CH3 H H ~ OCH3
CH3
4-CH ~ H H O H OCH3
CH3
5-OC2H5 H H O H CH3
4-CH3 H H O H Cl
4-OCH2cH2cH3 H H O H OCH3
H H H S H CH3
H H H S H CH3
H H H S H OCH3
H H H S H OCH3
. H H H CH3 CH3
H H H CH3 CH3
H H H O CH3 OCH3
H H C 3 OCH3
H H H O H C2~5
H H H O H OC2R5
lZ~3534
38
Table IV
Rl R2 o
/ "
C--O-C-Rll X
R ~ SO2NHCN ~ ~ N
R8 N ~
X
R Rl R2 R11 W 8 X Y m.p.(C)
10 H H H H H3 CH3
H H H H O HCH3 OCH3
H H H H O HH3 OCH3
H H H -CH3 O H3 CH3
H H H -CH3 o HCH3 OCH3
15 H H H -CH3 o H3 OCH3
H H H -CH2CH3 o HCH3 OCH3
H H H -CH2CH3 o H3 OCH3
H H H CF3 O HCH3 OCH3
H H H CF3 O HCH3 OCH3
H H H CH2C1 O HCH3 OCH3
H H H CH2CH-CH2 O HCH3 OCH3
H H H ~ o HCH3 OCH3
H H H ~ o HOCH3 OCH3
C1
H H H ~ O H CH3 OCH3
Cl
H H H ~ 2 H 3 OCH3
H H CH3 CH3 o H OCH3 OCH3
H CH3 CH3 CH3 o H 3 OCH3
5-F H H CH3 o H 3 OCH3
6-Cl H H CH3 H -H3 OCH3
1203534
x 39
Table IV (continued)
R Rl R2 Rll W R8 X Y m.p.(C)
5-CH3 H H CH3 O H OCH3 OCH3
5 5-NO2 H H CH3 O H OCH3 OCH3
4-OCH3 H H CH3 O H OCH3 . OCH3
5-CF3 H H CH3 O H OCH3 OC~3
3-Cl H H CH3 H CH3 OCH3
6-Cl H H CH3 H CH3 OCH3
10 H H H CH3 O H Cl C1
H H H CH3 O H Cl OCH3
H H H CH3 O H Br OCH3
H H H CH3 O H CH2CH3 aCH3
H H H CH3 O H OCH2CH3 CH3
lS H H H CH3 O H CH(cH3)2 CH3
H H H CH3 O H CF3 OCH3
H H H CH3 O H SCH3 OCH3
H H H CH3 O H CH20CH3 CH3
H H H CH3 O H CH20CH3 OCH3
H H H CH3 O H H CH3
H H H CH3 O H H OCH3
H H H ~ ~ H Cl Cl
H H H ~ Q H OCH3 OCH3
H H H -CH-CH2 O H CH3 ~ OCH3
H H H -C~CH O H CH3 OCH3
H H H -C~CCH3 O H OCH3 CH3
~ H H ~n-C5~1) O H OCH3 CH3
H H H CH20CH3 o H OCH3 CH3
H H H ~ O H OCH3 OCH3
3; H H H ~ O H OCH3 CH3
1203534
X 40
Tab ~ ontinued)
R _ R~ Rll W 8 X y m.p.(C.)
H H- H CH3 H SCH3 OCH3
H H H CH3 ~ CF3 OCH3
,CH3
5-CH H H CH3 O H OCH3 CH3
CH3
5-OC2H5 H H CH3 H OCH3 OCH3
H H H CH3 O H Br OCH3
H H H CH20CH3 o H SCH3 CH3
H H H ~ O H SCH3 OCH3
l; 'H H ~ O H SCH3 CH3
H H H CH3 H SCH3 CH3
H . H H CH3 O H CF3 OCH3
H H H CH3 O H CH2OCH3 OCH3
N02
H H H ~ Cl OCH3 CH3
H H H Cl OCH3 CH3
OCH3
H H H ~ O H OCH3 OCH3
OCH3
H H H CH3 S H CH3 CH3
H a H CH3 S H CH3 OCH3
H ~ a CH3 S H OCH3 OCH3
H H H ca3 CH3 CH3 CH3
~ :.H H CH3 O CH3 CH3 OCH3
H a H CH3 CH3 OCH3 OCH3
H H H CH3 O OCH3 CH3 CH3
a H H CH3 O OCH3 CH3 OCH3
H H H CH3 3 3 OCH3
lZ03534
x 41
Table V
Rl ~R2 o
C- O-C-Rll X
R ~ S02NHC~ ~ ~ Z
R Rl R2 Rll W 8 X Y Z ~ P.( C)
H H H 3 CH3 CH
H H H 3 OCH3 CH
H H H H O HOCH3 OCH3 ~H
a H H -CH3 O HCH3 CH3 CH
H H H CH3 O HCH3 OCH3 CH
H H H CH3 O H OCH3 OCH3 CH
H H H CH2CH3 O HCH3 OCH3 CH
H H H CH2CH3 o HOCH3 OCH3 CH
H H H CF3 O HOCH3 OCH3 CH
H H H CF3 3 OCH3 CH
H H H CH2Cl O HCa3 OCH3 CH
H H H Ca2CH.CH2 O HCH OCH CH
H, H H ~ ~ 3 OCH3 CH
H H H ~ O HOCH3 OCH3 CH
H H H ~ Cl o HCH3 OCH3 CH
H H H ~ No2 O HOCH3 OCH3 CH
H H CH3 CH3 o HOCH3 OCH3 CH
H CH3 CH3 CH3 O HOCH3 OCH3 CH
5-F H H Ca3 O HOCH3 OCH3 CH
3.5 6-ClH H CH3 HOCH3 OCH3 CH
H H H ~ O HOCH 3 OCH3 CH
Cl
;
~Z03534
x 42
Table V (continuet)
R _ 211 W 8 X Y Z (C)
5-CH3 H H CH3 0 H OCH3 OCH3 CH
55-No2 H H CH3 0 H OCH3 OCH3 CH
5-OCH3 H H CH3 0 H OCH3 OCH3
5-CF3 H H CH3 0 H OCH3 OCH3 CH
4-Cl H H CH3 0 H CH3 OCH3 CH
6-Cl H H CH3 0 H CH3 OCH3 CH
10 H H H CH3 0 ~ Cl Cl CH
H H H CH3 0 H Cl OCH3 CH
H H H CH3 0 H Br OCH3 CH
H H H CH3 0 H Q 2CH3 ~CH3
H H H CH3 0 H OCH2CH3 CH3 CH
15~ H H CH3 0 H OCH(cH3)2 cH3 CH
H H H CH3 0 H CF3 OCH3 CH
H H H C~3 0 H SCH3 OCH3 CH
H H H CH3 0 H CH20CH3 CH3 CH
H H H CH3 0 H CH2OCH3 0c 3 CH
20 H H H CH30 H H CH3 CH
H H H CH30 H H OCH3 CH
. H H H ~ O H C1 Cl CH
25H H H ~ O H OCH3 OCH3 CH
H H H CH3 0 H CH3 CCl
H H H CH3 0 H CH3 C 3 C CN
H H H CH3 0 H CH3 CH3 CCH3
H H C~3 0 H H CH -CCH
H H H CH3 0 H CH3 CH3 CCH2CH3
H H H CH3 O H H CH3 CCH2CH3
H H H CH3 0 H Cl Cl C-CH2CH2Cl
H H H CH3 0 H H CH3 c-cH2cH
H H CH3 0 H CH3 CH3 c-cH2cH~cl
H H H CH3 0 H CH3 3 H2CH CH2
H H H CH3 0 H H CH3 c-cH2cH-c~2
lZ~353
x 43
Table V (continued)
R 1 R2 Rll W R8 X Y Z m.~.(C)
H H H -CH~CH2 S H CH3 OCH3 CH
H H H -C~CCH3 S H CH3 OCH3 CH
H H H -C~CCH3 S H OCH3 CH3 CH
H H H -(n-C5Hll) S ~ OCH3 CH3 CH
H H H -C~2CH3 S H OCH3 CH3 CH
H H H ~ S H OCH3 OCH3 CH
H H H ~ S H OCH3 CH3 CH
H H H CH3 S H SCH3 OCH3 CH
~ H H CH3 S H CF3 OCH3 CH
/ CH3
5-CH H H CH3 S H OCH3 CH3 CH
CH3
5-C2H5 H H CH3 S H OCH3 OCH3 CH
H H H CH3 S H CH2OCH3 OCH3 CH
NO2
a H H ~ S H CH3 OCH3 CH
H H H ~ NO2 S H OCH3 OCH3 CH
Cl
H H H ~ S H CH3 OCH3 CH
Cl
H3CO
H H H ~ S H CH3 OCH3 CH
H3CO
H H H H3C ~ S H CH3 OCH3 CH
iZ03534
, Table V (continuet)
Rl R2 Rll W R8 X Y Z m.p.(C)
_
H H H CH3 S H CH3 CH3 CH
H H CH3 S H CH3 OCH3 CH
H H H CH3 S H OCH3 OCH3 CH
H H H CH3 O CH CH3 CH3 CH
H H H CH3 O CH CH3 OCH3 CH
H H H CH3 O CH OCH3 OCH3 CH
H a H CH3 O OCH CH3 CH3 CH
H H H CH3 0 OCH CH3 OCH3 CH
H H CH3 O OCH OCH3 OCH3 CH
~30
~203534
x 4s
Table VI
Rl ~R2 0
C O-C-R11 y~
R ~ SO2NH ~ O ~
R Rl R2 Rll W R8 Y' Q . m-P-(C)
H H H H O H CH3 O
H H H H O H OCH3 O
H H H CH3 O H CH3 o
H H H CH3 O H OCH3 O
H H H CH2CH3 O H CH3 O
H H CF3 O H CH3 O
H H H CF3 O H OCH3 O
H H H CH2Cl O H OCH3 O
H H CH2CH-CH2 O H OCH3 O
H H H ~ O H CH3 O
H H H ~ O H OCH3 O
Cl
H H H ~ O H OCH3 O
H H Q 3 CH3 O H OCH3 O
H CH3 CH3 CH3 O H OCH3 O
5-F H H CH3 H OCH3 O
5-Cl H H CH3 H OCH3 O
1203S34
X 46
Table VI (continued)
R Rl R2 11 W R8 Y' Q m.p.~ C)
5-CH3 H H CH3 O H OCH3 o
5-NO2 H H CH3 O H OCH3 o
5-OCH3 H H CH3 H 3
3-CF3 H H CH3 o H OCH3 O
5-Cl H H CH3 H CH3 o
6-Cl H H CH O H CH3 o
H H H CH3 O H H O
H H H CH3 O H H CH2
H H H CH3 O H Cl CH2
H H H CH3 O H CH3 CH2
H H H CH3 O H OCH3 CH2
H H H CH3 S H CH3 O
H H H CH3 S H OCH3 CH2
H H H CH3 S H CH3 O
H H H CH3 S H OCH3 CH2
H H H CH3 ~ CH3 CH3 O
H H 3 3 CH3 CH2
H H H CH3 CH3 OCH3 O
H H H CH, o OCH3 OCH3 CH2
H H H CP O H OC2H5 O
H H H Cl O H OC2H5 CH2
~ .
1203534
x 47
Table VI (continued~
R Rl R2 R 11 W R8Y' Q m.p. (C)
H H CH2OCH3 O H 3 -
S H H H ~ O HCH3 o
H H H -CH-CH2 O HCH3 o
H H H -C~CH O H CH3 O
H H H -(n-C5Hll) O HCH3 O
5-CH3 H H ~ O HCH3 o
4-OC2H5 H H -CH~CH2 O HCH3 o
4-CH3 H H CH3 O HCH3 CH2
~--~N02
H H H ~ O HCH3 O
N02
H H H 02N ~ O HCH3 o
Cl
H H H ~ O HCH3 o
Cl
OCH3
H H H ~ O HCH3 o
2 5 H H 3 ~ O HCH,~
Br Br
H H ~ ~ HOCH3 O
H H 2C 3 H
Cl Cl
3 0 H H -CH2CH-CH2 O HCH3 o
H H H -CHC12 O HOCH3 O
H H H CC13 O HOCH3 O
H H H CHBr2 O HOCH3 O
H H H CH2Cl O HOCH3 O
3 5 CH
--CH Cl Cl
H H H -CH2-CH-CH2 H 3 o
120353~
0 48
~able VIa
_
Rl R2 0
/ ............ .
C o-C-Rll y '
~SO2~
R Rl R2 Rll W R8 Y' m.p.(C)
H H H H o H CH3
H H H H O H OCH3
H H H CH3 O H CH3
H 'H H CH3 o H OCH3
H H H CH2CH3 H CH3
H H H CF3 H CH3
H H CF3 O H OCH3
H H H CH2Cl O H OCH3
H H H CH2cH~cH2 O H OCH3
H H H ~ O H CH3
H H H ~ O H OCH3
Cl
H H H ~ O H OCH3
H H CH3 CH3 o H OCH3
CH3 CH3 CH3 O H OCH3
5-F H H . CH3 o H OCH3
5-Cl H H CH3 o H OCH3
lZ03534
0 49
Table VIa (continued)
R Rl R2 R 1l W 8 Y' m.p.(C)
H H CH2OCH3 O H CH3
H H H ~ O H CH3
H H H -CH'CH O H CH3
H H H -C-CH O H CH3
H H H -(n-C5Hll) O H CH3
5-CH3 H H ~ O H CH3
4-OC2H5 H H -CHSCH2 O H CH3
4-CH,3 H H CH3 O H CH3
~--~N2
H H ~ NO2 CH3
H H H 2 ~ O H C~3
H H H ~ O H CH3
Cl
OCH3
H H . H ~ O H CH3
OCH3
25 H H 3 ~ O H CH4
Br Br
H H H -CH2CH-CH2 O H OC~3
H H H CH2CF3 O H OCH3
Cl Cl
H H -CH2CH-CH2 o H CH3
H H H -CHC12 O H OCH3
H H H CC13 O H OCH3
H H H CHBr2 O H OCH3
H H H CH2Cl O H OCH3
3S -
-CH Cl Cl
H H H -CH2-CH-CH 0 H OCH3 ,
~z~3~i3
o 50
Table VIatcontinued)
R Rl R2 Rll W R8 Y~
S S-CH3 H H CH3 o H OCH3
5-NO2 H H CH3 O H - OCH3
5-OCH3 H H CH3 O H OCH3
3-CF3 H H CH3 O H OCH3
5-Cl H H CH3 H CH3
6-Cl H H CH3 O a CH3
H H H CH3 o H , H
H H H CH3 O H
H H H CH3 o H Cl
H H H CH3 O H CH3
H H H CH3 ~ OCH3
H H H CH3 S H CH3
H H H CH3 S H OCH3
H -H H CH3 S H CH3
H H H CH3 S H OCH3
H H H CH3 O CH3 CH3
H H H CH3 O OCH3 CH3
H H H CH3 CH3 OCH3
H R H CH3 , OC~3 OCH3
H H 3 OC2H5
~ H H CH3 o H OC2H5
,
lZ03534
x 51
Table VII
-
/ ..
, C OcNHRl2
S R ~ S02NHCN
R8 N
R Rl R2 R12 ~ 8 X Y m.p. (C)
H H H H O H 3 H3
H H H H o HCH3 OCH3
H H H H o HCH3 OCH3
H H H -CH3 o HCH3 CH3
H ~ H -CH3 o HCH3 OCH3
H H H -CH3 o HCH3 OCH3
H H H CH2CH3 o HCH3 OCH3
H H H H2CH3 o H 3 CH3
H H H CH(CH3)2o H 3 CH3
H H H CH(CH3)2o HCH3 OCH3
H H H ~ o HCH3 OCH3
H H H CH2CH-CH2O HCH3 OCH3
. H H H ~ ' O HCH3 OCH3
H H H ~ o HOCH3 OCH3
H H H CH2 ~ o HCH3 OCH3
H H H ~ No2 o HH3 OCH3
H H C~3 CH3 o HC 3 OCH3
H C~3 CH3 CH3 o HC 3 OCH3
5-F H H CH3 HCa3 OC~3
4-Cl H H CH3 o HOCH3 OCH3
\
12Q3534
x 52
Table VII (continued)
R ~ R2 R12 W 8 X Y (C)
S 5-CH3 H H CH3 ~ OCH3 OCH3
3-N02 H H CH3 o H CH3 CH3
5-OCH3 H H CH3 O H OCH3 OCH3
5-CF3 H H CH3 O H OCH3 OCH3
5-Cl H H CH3 H CH3 OCH3
6-Cl H H CH3 H CH3 OCH3
H H a CH3 O H Cl Cl
H H H CH3 O H Cl OCH3
H H H CH3 H Br OCH3
H H H CH3 O H CH2CH.3 OCH3
H H H CH3 O H C 2 3 CH3
H H H CH3 O H CH(CH3)2 CH3
H H H CH3 O H CF3 OCH3
H H H CH3 O H SCH3 OCH3
H H H CH3 O H CH20CH3 CH3
2 a H H H CH3 O H CH20CH3 OCH3
H H H CH3 O H H CH3
H H H CH3 O H H OCH3
H H H ~ O H Cl Cl
H H H ~ O H OCH3 OCH3
lZ03534
x ~3
Table VII (continued)
R 1 R2 R12 W R8
H H H CH2-(CH2)4CH3O H CH3 OCH3
H H H -CH2-CH~CH-CH3O H CH3 OCH3
H H H ~ CH3 OCH3
H H Cl F O H OCH3 CH3
H H H ~ C2H5 H OCH3 f OCH3
H H CH3 ~ No2O H OCH3 CH3
H H H ~ CN O H OCH3 CH3
Br _ ~CH3
H H H ~ CH3 OCH3
H H H ~ SO2CH3O H CH3 OCH3
OCH3_
2~ H H H ~ Cl O H CH3 OCH3
H H H ~ SCH3 OCH3 OCH3
H' H H ~ CF3 H CH3 OCH3
Cl
H H H ~ O H OCH3 OCH3
H H H H2C ~ H OCH3 OCH3
H H H H2C ~ H3 H OCH3 CH3
H H H H2C ~ / ~3 OCH3
12Q3534
X 54
Table VII tcontinued)
R R1 2 12 W R8 X Y m.p.(C)
5-oC2H5 H H CH3 H OCH3 OCH3
~ CH3
6-CH ~ H H CH3 O H OCH3 OCH3
CH3
3-CF3 H H CH3 H ~CH3 OCH3
H H 3 S H CH3 CH3
H H 3 S H CH3 OCH3
H H 3 S H 3 OCH3
H H H CH3 O CH3 CH3 CH3
H : H H CH3 O CH3 CH3 OCH3
; H H H CH3 O CH3 OCH oc~3
H H CH3 O OCH3 CH 3 CH3
H . H H CH3 O OCH3 CH3 OCH3
H H 3 3 OCH3 OCH3
2G
lZ03534
` x 5s
Table VIII
Rl ~ / 2 O X
`R ~ SO2NHCN ~ ~ Z
~8 N ~
R Rl R2 12 W R8 X Y Z (oCj _
10 H H H H 3 CH3 CH
H H H H ~ CH3 OCH3 CH
H H H H O H OCH3 OCH3 CH
H H H -CH3 O H 3 CH3 CH
H H H -CH3 3 OCH3 CH
H H H -CH3 3 CH3 CH
H H H -CH2CH3 H3 OCH3 CH
H H CH2CH3 CH3 OCH3 CH
H H H -CH(C~3)2 O H OCH3 OCH3 CH -
H H H -CH(cH3)2 H CH3 OCH3 C~
H H H ~ O H CH3 OCH3 CH
H H H CH2CH- Q 2 H CH3 OCH3 CH
H H H ~ O H CH3 OCH3 CH
H H H ~ O H OCH3 OCH3 CH
H H H -CH2 ~ 3 OCH3
~ H H ~ N2 H OCH3 OCH3 CH
H H CH3 CH3 H CH3 OCH3 CH
H CH3 CH3 CH3 ~ CH3 OCH3 CH
5-F H H CH3 H C 3 OCH3 CH
5-Cl H H CH3 H OCH3 OCH3 CH
H H H CH2 ~ O OCH3 OC 3 CH
` 1203539
x 56
Table VIlI (continued)
R Rl R2R 12W R8 ~ m.p
5-CH3 H HH3 O H oOcCHH3 H3 CH
5-OCH3 H HCH3 O H oCH333
4-CF3 H HHH3 o H coHc33 OCH3 CH
6-Cl H HH3 H CH3 3
10 H H HH3 O H C1 3
H H H 3 O H Cl OCH CH
H H H 3 O H Br 3
HH 'H HH3 o H 2CH3 3CH
15 H HH HH3 o H 3)2 CH3 CH
H H H H3 11 SCH3OCX3 CH
HH HH HH 3 O H CH2ocH3 OCH CHH
2 O H H H 3 o H H CH3 CH
H H H 3 O H H OCH3 CH
H H H ~3 o H C1 Cl CH
2 5 H H H ~) O HOCH3 3 CH
3 O ~ ~ C 13 o H E3 CH3 C~3
3 a 3 CH~ O Cl 3 ~CY3
35 H H H 3 O H CH3 CH3 C-cH2cH2cl
H H 3 o H CH3 3 H2CH CH2
3 O H H 3 CH2cH CH2
57
Table VIII (conelnued)
R _ R2 R 12 U R8
H H H CH2-(CH2)4CH3 O H CH3 OCH3 CH
H H H -CH2-CH-CH-CH3 0 H CH3 OCH3 CH
H H H ~ O H OCH3 OCH3 CH
H H Cl F o H OCH3 OCH3 CH
0 H H H ~ C2H5 H OCH3 CH3 CH
H H CH3 ~ No2 O H OCH3 CH3 CH
H H H ~ CN O H OCH3 CH3 CH
H H B ~ C!33 oc~3 CH
H H H ~ S2CH3 O H CH3 OCH3 CH
H H ~SCH3 OCH3 OCH3 CH
H H H ~ CF3 H .CH3 OCH3 CH
H H H ~ Cl O H OCH3 OCH3 CH
H H 2C ~ CH ~ OCH3 CH3 CH
~Z~353
58
Table VIII (continued)
R 1 2 12 W 8 X Y Z
5-C2 5 H H CH3 ~ H OCH3 CH3
~ CH H CH3 o H OCH3 CH3 CH
4-C2H5 H H CH3 H OCH3 OCH3 CH
s-CH3 CH3 H CH3 o H OCH3 OCH3 CH
H H HCH3 S H CH3 CH CH
H H HCH3 S H CH3 oCH3 CH
H H HCH3 S H OCH3 3
l; H H HCH3 O CH3 CH3 3
H H HCH3 O C 3 CH3 OCH CH
H H HCH3 CH3 OCH3 3
H H HCH3 o 3 CH3 3
H H - H CH3 o 3 CH3 OCH3 CH
H H HCH3 3 OCH3 OCH3 CH
!
'I' --
.. ~..
~2~353
` x 59
Table IX
~ / ..
C--OCNHR12 Y'
R ~ ~ N--<
~ R8 N ~
R 1 2 12 W 8 Y~ ~ m.p. (C)
H H H H O H CH3 O
H H H H O H OCH3 0
H H H -CH3 O H CH3 O
15 H H H -CH3 O H OCH3 0
H ~1 H -CH2CH3 0 H CH3 O
H H H -CH(CH3)2 0 H CH3 O
H H H -CH(CH3)2 0 H OCH3 0
H H H _0 0 H OCH3 0
20 H H H CH2CH.cH2 o H OCH3 0
H H H ~> O H Ca3 o
25 H H H ~> O H OCH3 0
H H H CH2 ~ O H OCH3 0
H H CH3 CH3 O H OCH3 0
30 H 3 3 CH3 o ~ OCH3 0
3-F H a CH3 H OCH3 0
5-Cl H a CH3 H OCH30
120353
x ~;n
Table IX (continued)
R Rl R2 R12 W ~8 Y Q m.p.(C)
5-CH3 H H CH3 O H OCH3 o
5-NO2 H H CH3 O H OCH3 o
4-OCH3 H H CH3 O H OCH3 o
5-CF3 H H CH3 O H OCH3 o
5-Cl H H CH3 H CH3 o
6-Cl H H CH3 H Q 3 o
H H H CH3 O H H O
H H H CH3 O H H CH2
H H H CH3 H Cl CH2
H H H CH3 O H CH3 CH2
H H H CH3 H OCH3 CH2
H H H CH3 S H CH3 CH2
H H H CH3 S H OCH3 O
H H H CH3 S H CH CH
H H a CH3 S H OCH3
H H H CH3 CH3 CH3 O
H H H CH3 CH3 CH3 CH2
H H H CH3 CH3 OCH3 O
H H H CH O CH3 OCH3 CH2
H H H CH3 OC 3 CH3 O
H H H CH3 OCH3 CH3 CH2
H H H CH3 OC 3 OCH3 O
H H H CH3 OCH3 OCH3 CH2
H H H CH3 ¦ O H OC2H5 O
H a H CH3 ~ H OC2H5 CH2
lZ~353~
Table IX (continuet)
R 1 2 R12 W R8 Y' Q
H H H -CH2-(CH2)4CH3 O a OCH3 O
a ~ H Ca2-CH-CH-CH3 H CH3 o
H H H ~ O H OCH3 o
H H H ~ F O H OCH3 o
H H H ~ CN O H OCH3 o
H H H ~ 3
H H H ~ SO2CH3 o H OCH3 O
H H H ~ SCH3 H CH3 O
. H a H ~ O H Cl O
H H a -CH2 ~ CH3 C H Cl O
H H H -CH2 ~ CH O a OCH3 O
2 5 5-OC2H5 a H CH3 H OCH3
~ CH3
4-CH ~ H ~ CH3 H OCH3
CH3
5-CF3 H H ~ ~2 H OCH3
.
62
o
Table IXa
Rl ~R2 o
C--OCN8R12 Y
R ~ SO2N~CN, ~ ~
R Rl R2 R12 W R8 y~ m p.(C)
H H H H O H CH3
H H H H O H OCH3
lS ~ H H -CH3 H .CH3
H ~ H -CH3 O H OCH3
H H H -CH2CH3 O H CH3
H H H -CH(CH3)2 H CH3
H H H -CH(CH3)2 O H OCH3
20 H H H ~ ' ~ OCH3
H H H CH2CH~CH2 O H OCH3
H H H ~ O a CH3
25 H H H ~ O H OCH3
H H H C~2 ~ O H OCH3
30 H H CH3 3 O H OCH3
H C~3 CH3 CH3 . O H oocHa3
3-F H H CH3 H 3
5-Cl H H c~3 H OCH3
1203534
0 ~3
Table IXa(contin ~d)
R Rl R2 R 12 W ~8 Y' m p.(C)
S-C~ H ~ C~3 0 H 3
5-Cl H H CH3 H 3
- 10 6-Cl H H CH3 H C 3
H H H CH3 0 H HH
H H H CH3 0 H
H H H CH3 0 H CH
lS HH H CH3 o H OCH3
H H H CH3 S H CH3
H H H CH3 S HH OcHH3
HH HK H CH3 oc33
H H H CH3 CH3 C 3
H H H CH3 CH3 C 3
H H H CH O CH3 3
H a H CH C 3 OC 3
~ H H CH33 OCH3 CH3
H H H CH OCH3 C~3
H H H CH3 OC 3 OC 3
H H H CH33 OCH3 OCH3
H HH HH ccH33 oo HH OC2 5
1,Z0353~
. ~
0 64
Tabl _IX ~
R Rl R2 R12 W R8 y- m p.(C)
H H H -cH2-tcH2)4cH3 O H OCH3
H H H CH2-CH'CH-CH3 H CH3
H H H ~ .............. O H OCH3
H ~ H ~ F O H OCH3
H H H ~ CN O H OCH3
8r ,CH3
H H N ~
H H H ~ S2CH3 0 H OCH3
H H H ~ SCc~3 H CH3
H H H ~ O H Cl
H H B -CH2 ~ 3 O H Cl
H H H -CH2 ~ CH o H OCH3
2'
5-OC2H5 H H CH3 O H OCH3
4 CH ~ H H CH3 H OGH3
C~
30 5-CF3 3 - H H ~ ~2 H OCH3
~353~
X 65
Table X
Rl R2 0
C--o-C-Rl3 g
R ~ S02NHC~
R~ X ~
R Rl R2 R13 W R8 X Y m.p.t~C)
H H H -CH3 o H 3 3
H ~ H -CH3 o HCH3 OCH3
H H H -CH3 HC 3 OCH3
H H H CH2CH3 H CH3 OCH3
H H H CH2CH3 H C 3 OCH3
H H H ~ o HC~3 OCH3
H H H ~ O H C 3 OCH3
H H H ~ Cl O H C~3 OCH3
H H ~ Cl o H 3 0CH3
H H CH3 CH3 O H CH3 0CH3
3 33 ~ CH3 OCH3
5-F H H CH3 O H 3 0CH3
5-Cl H H CH3 H CH3 OCH3
1203534
x 66
Table X ~continued)
R _ 2 ~ 13 W R8 X Y m-p
5-CH H HCH3 H OCH3 OCH3
5 3-N2 H HCH3 o H OCH3 OCH3
5-OCH3 H HCH3 O R OCH3 OCH3
5-CF3 R HCH3 o H OCH3 OCH3
5-Cl H H3 O H CH3 OCH3
6-Cl H H3 o H CH3 OCH3
10 H H - H3 O H Cl Cl
H H HCH3 O R Cl OCH3
H H HCH3 O ~ Br OCH3
H H H3 o ~ CH2CH3 OCH3
H ~ 3 ~ H2CH3 CH3
l; H H H3 0 R ( 3)2 CH3
H H HX3 0 H CF3 OCH3
H H HCH3 O H SCH3 OCH3
R H HCH3 o H CH2OCH3 CH3
H H H3 o H CH2C~3 OCH3
H H H3 O H H CH3
H H HCH3 O H H OCH3
H H H~ O ~ Cl Cl
2; H H H ~ ~ OCH3 OCX3
s
l;~V3534
x 67
Table X ~continued)
R Rl R2 R13 W R8 X Y ~.p.(C)
4-CH3 H H CH3 o H 3 3
5-OC2H5 H H CH3 H OCH3 3
CH3
4-CH / H H CH3 O H OCH3 3
\ CH3
H H H CH2(CH2)4CH3 O H OCH3 3
H H H CH2CH2CH3 O H 3 3
4-CF3 a H CH3 H OCH3 3
H H H CH3 H Cl OCH3
6-C2H5 H H CH3 H Cl Cl
l; H a H ~ CH3 O H OCH3 3
H H CH3 S H C 3 3
H H H CH3 S H CH3 OCH3
H H H CH3 S H OCH3 3
H a H CH3 S CH3 CH3 CH3
H H H CH3 S CH3 CH3 OCH3
H H H CH3 S CH3 OCH3 OCH3
H H H C~3 S OCH3 CH3 M 3
H H ~ CH3 S OCH3 CH3 OCH3
H H H CH3 S OCH3 OCH3 OCH3
3i
..
1203~34
x 68
Table XI
Rl R2 o
COC-OR13 X
R ~ S02NHCN ~ O
R8 ~--~
R Rl R2 ~ 3W R8 X y Z m.p.(C)
H H H -CH3 CH3 3 CH
H ~ H -CH3 CH3 C 3 CH
H a H -CH3 H OCH3 OCH3 CH
H H H -CH2CH3 H CH3 gCH3 CH
H H H -CH2CH3 H OCH3 OCH3 CH
H H H ~ C1 H CH3 CH3 CH
H H ~ CH3 C 3 CH
H H H ~ O H OCH3 OCH3 CH
H H ~ Cl o H CH3 OCH3 CH
H H H ~ C1 0 H OCH3 OCH3 CH
H H CH3 Ca3 o H OCH3 3 CH
H C~3 CH3 ~3 H 3 3 CH
S-F H a CH3 H OCH3 3 CH
4-Cl H H C~3 H OCH3 OCH3 CH
lZQ35~'~
x 69
Table XI (continued)
l R2 13 W R8 ~ y Z (C)
5-CH3 H H CH3 H OCH3 OCH3 CH
5 5-~2 H H CH3 O H OCH3 OCH3 CH
5-OCH3 H H CH3 H OCH3 OCH3 CH
5-CF3 H H CH3 O H OCH3 OCH3 CH
5-Cl H H CH3 H CH3 OCH3 CH
6-Cl H H CH3 H Ca3 OCH3 CH
10 ~ H H CH3 a Cl Cl CH
H H H CH3 O H Cl OCH3 CH
H H H CH3 O H Br OCH3 CH
H H H CH3 O H CH2CH3 ~ca3
H H H CH3 O H CH2cH3 Q 3 CH
15 H H H CH3 a OCH(CH3)2 CH3 CH
H H H CH3 H CF3 OCH3 CH
H H H CH3 -O H SCH3 OCH3 CH
H H H CH3 O H CH2OCH3 CH3 CH
H H H CH3 O H CH2OCH3 OCH3 CH
20 H H H CH3 H H CH3 CH
H H H C~3 O H H OCH3 CH
H H a ~ O H Cl Cl . CH
25 ~ H H ~ O H OCa3 OCH3 CH
H H H CH3 O H H Ca3 CCl
H H H Ca3 O H CH3 CH3 C-CN
H H H CH3 H CH3 CH3 CCH3
H H H Ca3 O H H CH3 3
H H H CH3 H CH3 CH3 CCH2CH3
H H H CH3 O H H CH3 CCa2CH3
H H H CH3 O B Cl Cl C`CH2CH2
H a H Ca3 0 H H CH3 C-Ca2CH2Cl
H H H CH3 H ca3 ca3 C-CH2CH2Cl
H H a CH3 ~ CH3 CH3 C C 2C 2
H H H CH3 O H a CH3 C-CH2CH-CH2
120353~
X 70
Table XI (continued)
R Rl R2 R13 W R8 X Y Z m.p.(C)
5-OC2H5 H H CH3 HOCH3 OCH3 CH
/ CH3
5-CH H H CH3 HOCH3 OCH3 CH
CH3
4-CF3 H H CH3 HOCH3 OCH3 CH
H H H CH2(CH2)4C~3 O HOCH3 OCH3 CH
H H H CH2CH2CH3 O HOCH3 CH3 CH
H H H CH3 H Cl Cl CH
6-C2H5 H H CH3 H Cl Cl CH
1~ H H H ~ CH3 HOCH3 OCH3 CH
H H H CH3 S HCH3 CH3 CH2
H H H CH3 S HCH3 OCH3 CH2
H H H CH3 S HOCH3 OCH3 CH2
H H H CH3 CH3 C 3 C 3 2
H H H CH3 O CH3 C 3 3 2
H H H CH3 CH3 3 3 2
H H H CH3 OCH3 CH3 CH3 CH2
H H H CH3 OCH3 CH3 OCH3 CH2
H H H CH3 O OCH3 OC 3 OCH3 C 2
~203534
x 71
Table XII
Rl R2 0
~C OCORL3 y
R ~ .. ~ ~O ~
R Rl 2 ~3 W _ Y' Q m.p.(C)
H a H -CH3 O H CH3
H H H -CH3 O H OCH3 O
H H H CH2CH3 O H CH3
lS H H H ~ O H CH3 O
H H H ~ O H OCH3 O
H H H ~ Cl O H OCH3 O
H H C 3 3 H OCH3 o
H CH CH CH3 H OCH3 O
5-F 3 3 O H OCH3
5-Cl H H ca3 H OCH3 O
3-CH3 H H CH3 O H OCH3 o
5-NO2 H H CH3 O H OCH3 o
5-OCH3 H ~ CH3 H OCa3 o
4-CF3 H H CH3 H OCH3 o
5-Cl H H CH3 H Ca3 o
6-Cl H H CH3 H CH3 o
H H H Ca3 ~ H O
H H H CH3 O H H CH2
H H H CH3 o H Cl CH2
H H H CH3 CH3 CH2
H H H C~3 O H OCH3 CH2
1203534
X 72
Table XII (continue~?
R 1 2 13 W 8 Y Q ~.P.( C)
5-OC2H5 H H CH3 H OCH3
S / C~3
4-CH H H CH3 H OCH3
~ CH3
6-CH3 H H CH3 H OCH3
4-CF3 H H CH3 OCH3
H H H CH2(CH2)4CH3 O H OCH3
H H H CH2CH2 3 O H OCH3
H H H ~ CH3 H OCH3
; Cl C1 O H CH3
H H H ~ O H OCH3
H H H CH3 S H CH3
H H H CH3 S H OCH3
H H H CH3 S H CH3 CH2
H H H CH3 S H OCH3 CH2
H H H CH3 o CH3 3
H H H CH3 O C 3 3 CH2
H H H CH3 CH3 OCH3
H H H CH3 o CH3 3 CH2
H H H CH3 OCH3 3
H H H CH3 OCX3 CH3 CH2
H H H CX3 o OCa3 3
H H H CH3 OCH3 3 CH2
H X H CH3 O H C2H5
H H H CX3 H OC2H5 CH2
lZ0353.~.
Table XIIa
Rl ~R2 0
R ~--So2~lc~ ~
R Rl R2 R~ 3 W R8 y ~ m p . ~ C)
H H HH -CCHH33 H HH Ccc333
H H H CH2C 3 O H
H H H ~3 0 H CH3
H H H ~> O H OCH3
2 0 H H H ~} Cl O H OCH3
S-F Q3 C~3 C113 O ~ OC~3
5-Cl a ~ ca3 0 a OCH3
3-CH3 H aH ccaH33 O 8 OC 3
S-OCI13 ~ 3 CH3 OCI!3
6-Cl H H CH3 a c~3
H ~ H CH3 H H
H H H CH3 o H H
H H H Ca3 o H Cl
H ' a a ca3 o a ca3
H B a ca3 o H OCH3
1203534
0 74
T~ble XIIa(continuedj
R 1 2 13 W R8 Y' m p.(C)
5-OC2H5 H H CH3 H OCH3
c~3
4-CH / H R CH3 H OCH3
CH3
6-CH3 H H CH3 H OCH3
4-CF3 H H CH3 OCH3
H H H CH2(CH2)4CH3 O H OCH3
H H H CH2C 2 3 O H OCH3
H H H ~ CH3 OCH3
H H ~ Cl O H CH3
Cl
H H H ~ o H OCH3
H H H CH3 S H CH3
- H H H CH3 S H oc~3
H a H CH3 S H CX3
H H H ca3 S H OCH3
H H H CH3 o CH3 3
a H H CH3 O C 3 3
H H H CH3 CH3 OCH3
H H H C~3 O C 3 3
H H a CH3 OCH3 CH3
H H H C~3 O OCH3 CH3
30 H H H CX3 O 0C 3 3
H H H CH3 OCH3 OC 3
H H H CH3 O H OC2H5
H H H CH3 O H OC2H5
1203534
Formulations
Useful formulations of the compounds of Formula I
can be prepared in conventional ways. They include
dusts, granules, pellets, so,lutions, 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.
lG High strength compositions are primarily used as
intermediates for further formulation. The formula-
tions, broadly, contain about 0.1% to 99% by weight
of active ingredient(s) and at least one of a) about
0.1% to ~ surfactant(s) and b) zbout 1~ to 99.9%
solid or liquid diluent~s). More specifically,
they ~ill contain these ingredients in the following
approximate proportions:
Table XIII
-
Active*
2G Ingredient Diluent(s) Surfactant(s)
Wettable Powders20-90 0-74 1-10
Oil Suspensions,
Emulsions, Solu-
tions (including
~mulsifiable
Concentrates 3_50 40-95 0-lS
Aqueous Suspensions 10-50 40-84 1-20
Dusts 1-25 70-99 0-S
Granules and
Pellets 0.1-95 5-99.9 0-li
High Strength
Compositions gO-99 0-lG 0-2
Active ingredient plus at least one of a surfactant
or a diluent eguals 10~ weight percent.
~20353~
x 76
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 s~rfactant to active ingredient are
S 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 n ~ 2nd Ed., Dorland Books, Caldwell, New Jersey.
lG The more absorptive diluents are preferred for wettable
powders and the denser ones for dusts. Typical liquid
diluents and solvents are described in ~arsden, "Sol-
vents ~uide", 2nd Ed., Interscience, New York, l9S0.
Solubili~y under 0.1% is preferred for suspension
l; 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
2G Publishing Co., ~nc., New York 1964, list surfactants
and recommended uses. All formulations can contain
minor amounts of additives to reduce foam, caking,
corrosion, microbiological growth, et~.
The methods of making such compositions are
2; well known. Solutions are prepared by simply mixing
the ingredients. Fine solid composi-tions 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. ~rowning, HAgglomeration~, Chemical Engineering,
December 4, 1967, pp. 147ff and_"Perry's Chemical
Engineer's Handbook", 5th Ed., McGraw-~ill, New York,
1973, pp. 8-57ff.
. lza3s3~
x 77
For further information regarding the art of
formulAtion, see for example:
H. M. Loux, U.S. Patent 3,235,361, February lS,
1966, Co~. 6, line 16 through Col. 7, line 19 and
5 Examples 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192,
~iarch 14, 1967, Col. 5, line 43 through Col. 1,
line 62 ana Examples 8, 12, 15, 39, 41, 52, 53,
~8, 132, 138-140, 162-164, 166, 167 and 163-182.
H. Gysin and E. Knusli, U.S. Patent 2,891,855,
June 23, lgS9, Col. 5, line 66 through Col. 5, line
17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", -
John Wil~y & sons, Inc., New York, 1961, pp. 81-96.
1~ J. D. Fryer and S. A. Evans, "Weed Control
Handbook", 5th Ed., Blackwell Scientific Publica-
tions, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by
weight unless otherwise indicated.
2G ~xample
Wettable Powder
~-r(4,6-~imethQxypyrimidin-2-yl2~mino-
carbonyl]-2-(hydroxymethyl2-
benzenesulfonamide 80%
2~ sodium alkylnaphthalenesulfonate 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended, ham~er-milled
until all the solids are essentially under 50 microns
and then reblended and packaged.
3~
lZ0353
,~ 78
Example 9
Wettable Powder
N-1(4-6-Dimethoxy-1,3,5-triazin-2-yl)amino-
~ carbonyl]-2-~hydroxymethyl)- .
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
essentially all below 10 microns in diameter. The
product is reblended before packaging.
Example I0
Granule ~
wettable powder of Example 9 5%
attapulgite granules 95
(U.S.S. 20-40 mesh; 0.84-0.42 mm)
A slurry of wettable powder containing ~25%
solids is sprayed on the surface of attapulgite
granules in a double-cone blender. The granules
are dried and packaged.
_xamole il
Extruded Pellet
N-[~4,6-Dimethoxypyrimidin-2-yl)amino-
carbonyll-2-~hydroxymethyl)-
benzenesulfonamide 25%
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate1%
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
lZ03534
x 7q
may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm
openings). The granules held on a U.S.S. No. 40 sieve
(0.42 mm openings) may be packaged for use and the
fines recycled.
Example 12
Oil Sus~ension
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)amino-
carbonyl~-2-(hydroxymethyl)-
benzenesulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70~
The ingredients are ground together in a sand
mill until the solid particles hav.e been reduced to
under about 5 microns. The resulting thick suspension
l; may be applied directly, but preferably a ter being
extended with oils or emulsified in water.
Example 13
h'ettable Powder
-
N-[(4,5-Dimethoxypyrimidin-2-yl)amino-
2C carbonyl]-2-(hydroxymethyl)-
benzenesulfonamide 20%
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose3%
2~ attapulgite 69%
The ingredients are thoroughly blended. After
grinding in a hammer-mill to produce particles 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.
3s
:1203534
Example 14
Low Strength Granule
N-t(4,6-Dimethoxy-1,3,5-~riazin-2-yl)-
àminocarbonyl]-2-(hydroxymethyl)-
benzenesulfonamide 1%
N,N-dimethylformamide 9%
attapulgite granules 90%
~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 ~lender. 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 15
Aqueous Suspension
N-[(4,6-Dimethoxypyrimidin-2-yl)-
aminocarbonyl~-2-(hydroxymethyl)-
benzenesulfonamide 40
polyacrylic acid thickener0.3%
dodecylphenol polyethylene qlycol
ether 0.5%
disodium phosphate lS
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 16
Solution
N-[(4,6-Dimethoxypyrimidin-2-yl)-
aminoca_bonyl~-2-(hydroxymethyl)-
benzenesulfonamide, sodium salt 5%
water 95%
1203534
x 81
The salt is added directly to the water with
stirring to produce the solution, which may then be
packaged for use.
Example 17
S Low Strength Granule
N-~(4,6-Dimethoxypyrimidin-2-yl)-
aminocarbonyl]-2-~hydroxy~ethyl)-
benzenesulfonamide 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 b~ender. After spraying of the solution
has been'~ompleted, the material is warmed to evaporate
the solvent. The material is allowed to cool and then
packaged.
Example 18
Granule
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-
2G aminocarbonyl]-2-(hydroxymethyl)-
benzenesulfonamide 80%
~etting agent lS
crude ligninsulfonate salt (containing
5-20~ of the natural sugars) 10~
attapulgite clay 9%
The ingredients are blended and milled to 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
leYel, generally less than 1~. The material is then
120353
,~ 82
discharged, screened to the desired size range, gener-
ally 14-100 mesh (1410-149 microns), and packaged for
use.
Example 19
High Strength Concentrate
N-[~4,6-Dimethoxypyrimidin-2-yll-
aminocarbonyl]-2-(hydroxymethyl)-
benzenesulfonamide 99%
silica aerogel o 5%
synthetic amorphous silica0.5%
The ingredients are blended and ground in a
hammer-mill to produce a material essentially all
passing a U.S.S. No. 50 screen (0.3 mm opening).
The concéntrate may be formulated further if
necessary.
Example 20
Wettable Powder
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-
aminocarbonyl~-2-~hydroxymethyl)-
benzenesulfonamide 90%
dioctyl sodium sulfosuccinate 0.1%
synthetic fine silica 9.9%
The ingredients ase blended and ground in a
hammer-mill to produce particles essentially all be-
low 100 microns. The material is sifted through a
U.S.S. No. 50 screen and then packaged.
Example 21
Wettable Powder
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)-
aminocarbonyl~-2-(hydroxymethyl)-
benzenesulfonamide 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ~ngredients 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.
1203534
x 83
Example 22
Oil Suspension
N-t(4,6-Dimethoxy-1,3,5-triazin-2-yl)-
aminocarbonyl~-2-(hydroxymethyl)-
S benzenesulfonamideblend 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
belo~ 5 microns. The product can be used dire~tly,
extended with oils, or emulsified in water.
lZ03534
x 84
Utility
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, such as
around 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,
compounds of this invention may be used to modify
plant growth beneficially, and also selectively
control weeds in crops such as wheat.
The precise amount of the compound of Formula I
to be used in any given situation will vary according
to the particular end result desired, the amount o~
foliage present, the weeds to he controlled, the soil
type, the formulation 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 use ul in combi-
nation with 3-(3,4-dichlorophenyl)-1,1-dimethylurea
(diuron); the triazines such as 2-chloro-4-(ethyl-
2mino)-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(1~,3~)-dione (hexazinone); N,N-dimethyl-2,2-
1203~3~
x 85
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
S (diallate); S-(2,3,3-trichloroallyl)diisopropyl-
thiocarbamate (triallate); 1,2-dimethyl-3,5-di-
phenyl-lH-pyrazolium methyl sulfate (difenzoquat
methyl sulfate); methyl 2-t4-(2,4-dichlorophenoxy)-
phenoxy~propanoate (diclofop methyl) 4-amino-6-tert-
10 butyl-3-(methylthio)-l~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); ~,,~-trifluoro-
2,6-dini~'ro-N,N-dipropyl-~-toluidine (trifluralin);
15 1,1'-dimethyl-4,4'-bipyridinium ion (paraquat);
2-chloro-2',6'-diethyl(methoxymethyl)acetanilide
talachlor); l,l-dimethyl-3-(a,~,~-trifluoro-_-
tolyl)urea ~fluometuron); S-(4-chlorobenzyl)N,N-
diethylthiolcarbamate (benthiocarb); N-(butoxy-
20 methyl)-2-chloro-2l~6l-diethylacetanilide
(butachlor); and 5-[2-chloro-5-(trifluoromethyl)-
phenoxy]-2-nitrobenzoic acid, methyl ester
. (acifluorfen-methyl).
lZ0353~
x 86
Test Procedure A
Seeds of crabgrass (Digitaria spp.), barnyard-
grass ~Echinochloa crusgalli), wild oats (Avena fatua),
cassia ~Cassia tora), morninsglory (Ipomoea spp.),
5 cocklebur ~Xanthium spp.), sorghum, corn, soy~ean,
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. At the same time, cotton having
five leaves ~including cotyledonary ones), bush
beans with the third trifoliolate leaf expanding,
crabgrass with two leaves, barnyardgrass with two
leaves, wild oats with one leaf, cassia with three
leaves (including cotyledonary ones), morningglory
with four leaves ~including the cotyledonary ones),
- cocklebur with four leaves (including the coty-
ledonary ones), sorghum with three leaves, corn with
three leaves, soybean with two cotyledonary leaves,
rice with two leaves, wheat with one leaf, and nut-
sedge with three to five leaves were sprayed.
Treated plants and controls were maintained in a
- greenhouse for 16 days, then all species were com~ared
to controls and visually rated for response to treat-
ment.
Ratings for compounds tested by this pro-
cedure are recorded in Table XIV.
O = no effect
10 = maximum effect
C 5 chlorosis or necrosis
D = defoliation
E S emergence inhibition
G = growth retardation
H = formative effects
6Y = abscised buds or flowers.
3;
120353~l
87
Table XIV
~ CH20
lo I I ~ s02N~C~H ~ o$
kglha O. 05
POSI-EMERGE~CE
BUSH BEA~ 5C, 10D, 6Y
COTIO~ 3C, 4H, 8G
MORNI~GGLORY 2G
COCKLEB~.~R 5C, 9
CASSIA 5C, 9G
N~'TSEDGE lC, 9G
CBRAB~G.ARDGRA5s 3C, 9H
WILD OATS lC, 3G
W~EAT 0
COR~ 2C, 9H _
SOYBE~ 9C
RICE ZC, 9G~ -~~
SORGHUM ZC, YH ~-
PRE-EMERGEXCE
MORNI'~GGLORY 8G
COCXLEB~~R 9H
CASSIA lC, 8G
NUTSEDGE _ lOE
CRABGRASS ~
BARNYARDGRASS 2C, 9H
WILD OATS 8G, O
WH~AI 6G, O
COR~ lC, 9H
SOY~EAN ZC, 8H
RICE I0E
SORGHE.-~ C, G
lZ03534
88
Table ~rv
s
~ CH2
S02NHCNH--< 0
0~
.
kg/ha 1 0 05
POST-EMERGE~CE
BUSHBF~ 2 7 6Y
COTIO~
MORNINGGLORY lC
C0CRLEBUR 0
CASSIA lC
NUTSEDGE O
CRABGRASS 2G
BA~ARDGRASS
WILD OAIS O
_~HEAI O
CO~N 2C, 9H
SOYBE~ lC, 6H
RICE lC, 4G
SORGHU~ 2C, 9H
PRE-EMERGENCE
MOR~ GGLORY 2
~OCKLEBUR
CASSIA lC
NUTSEDGE O
CRABGRASS O
BARNYARDGRASS 2C, 7H
WILD OATS O
WHEAT O
CORN 9H
SOYBEA~ 2C, 3H
RICE lC
SORGH~.I 2C, 9H
