Note: Descriptions are shown in the official language in which they were submitted.
~25S~
Title BA-B479-A-~
HERBICIDAL N-HYDROXY-N'-SU~FONYLGUANIDINES
Backqround of the Invention
This invention relates to certain novel
N-hydroxy-N'-sulfonylguanidine compounds, to compo-
s;tions containing ~uch compounds, and to a method of
use of such compo~itions to control the growth o~
undesired vegetation.
U.S. Patent 4,127,405 issued November 28, 1978
disclose~ substituted triazinyl arylsulfonylurea com-
pounds of the following formuia:
.. . .
W N
Rl-SO2-NH-C-NH~ O ~ '
while U.S. Patent 4,169,719 issued October 2, 1979
discloses substituted pyrimidinyl arylsulfonylurea
compounds of the following formula:
X ..
W N
Rl-SO2-NH-c N
Z
The triazine and pyrimidine compounds within the sco~e
of the ~405 and ~719 patents include those wherein W
can be oxygen or sulfur. .
U.S. Patent 4,310,346 issued January 12, 1982
discloses sulfonylisothiourea compounds of the formula
SO A X
2 S-B N ~
~502N=C-NH~OZ
~Z~i66~
wherein
B i~ Cl-C6 alkyl, CH2CH2OCH3,
CH2CH2OCH2CH3, CH~CH2CH2OCH3, CH2Q, CH-Q
CH3
where Q i~
O ~ CH3 O
CO~-Cl 3 alkyl, -CN , -CN(Cl_3 alkYl)2
OCH3
O O
10 -cNH(cl-c3 alkyl)- CN 2'
phenyl, phenyl substituted with chlorine, CN,
C2 4 alkenyl, C2 4 alkynyl. ORll, where
Rll is Cl-C4 alkyl, -CH2OCH2CH2OCH3
or -CH2cH2cH2cH2cH3
South African Patent No. 79/2657, published
June 30, 1980 discloses sulfonylisothiourea compounds
of the formula
X
Rl-SO2N=C-NH ~ ~ Z
Y , .
wherein
R2 is Cl-C20 alkyl; CH2CH2OCH3:
25 CH2cH2ocH2cH3; CH2CH2CH2 3
CH2OA~ where A' is C1-Cl2 alkyl.
-CH2CH~OCH3, -CH2CH OCH CH ,
phenyl or phenyl substituted with
1-2 NO2, 1-2 Cl,.or 1-2 CH3:
CH2A, CH-A where A is CO2(H, C1-C4 alkyl).
CH3
O ~ C1-C4 alkyl ~ C1-C4 alkyl
CN , CN
H \ Cl~Cq alkyl,
S6~i3l
, / 3 ,,
CN , CNH~ , phenyl, CN, C2-C4
\ OCH3
alkenyl, Cl-C4 alkynyl, phenyl substi-
tuted with 1-2 CH3, 1-2 N02, 1-2 OCH3,
1-2 chlorine or phenoxy.
U.S. 4,301,2~36 issued November 17, lg81 dis-
closes O-alkylsulfonylisoureas of the formula
RS02N=C-NHR
wherein
W is Cl, Br or OR12; and
R is Cl-C12 alkyl, C3-C4 alkenyl, CH2CH20CH3,
2CH20CH2CH3~ (CH2)30CH3~ benzyl,
CHR13Co2R14, where R13 is H or CH3 and
R14 is Cl-C4 alkyl.
The compounds taught in the above five refer-
ences are useful as general or selective herbicides
having both preemergent and postemergent-herbicidal
activity or plant growth regulant activity.
~2~S6~
Summar~ of the Invention
The novel sulfonylguanidine compound~ of the
present invention incorporating a guanidyloxyl moiety
are highly active herbicides in both preemergent and
postemergent applications. Certain compounds addi-
tionally exhibit selective herbicidal 6afety to wheat
and barley. Speci~ically, the i~vention relates to
novel compounds of formula I, agriculturally suitable
compositions containing them and their method of-use .
as pre-emergent and~or post-emergent hecbicides or
plant growth regulants.
N-OR'
L-S02NHCN-A
R
wherein
~ is H or CH3:
R' is H. C(O)Rl, C(O)NR2R3 or CO2R4;
Rl is Cl-C3 alkyl or CF3:
2 H~ CH3 or C2H5; .
R3 is Cl-C3 alkyl:
R4 is Cl-C3 alkyl;
L is ~ ; ~ ~ R8
L-l . L-2 L-3
~ R 9
L-4 L-5 L-6
q
~ZS;S~6~
s
R13
~ ~ E
L-7 L-8
14~ 5 N-E16 ~ O
L-9 L 10 L-ll
.. R13 R13
~ 5 ~ Cl ~ 5,N E16
L _ L-13 L-14
~ R17 ~ ~ ~ RlB ;
- O O
L-15 L 16 L-17
R5 is C1-C4 alkyl, Cl-C4 alkoxy, OCHzCH2OCH3,
F, Cl, Br, NO2, CF3, CO2Rlg, SO2NR20R21.
s~2N(ocH3)cH3~ 52R22~ 5()nR23 3
WCHF2, C3-C4 alkenyloxy. C3-Cg alkynyloxy.
Ci-C2 alkyl substituted wit~ OCH3 or
~SS6~
N-N N-N
OCH2CH3. C6H5~ ~ O ~ CH3 ' O
N-N r N
o,N ~ N~O , ~ S , ~ O
/~\ / =\ r N
-~`N,N-CH3 ' N~N ~ N`N >
. ~ , ~ or ~ ~ ;
R6 is H, F, Cl, Br, CF3, CH3, OCH3,
SCH3 or OCF2H:
R7 is H, CH3, OCH3, F, Cl, Br, 5O2N~CH3)2,
oso2cH3 Or s(o)ncH3;
R8 is CH3, CH2CH3, OCH3, OCH2CH3, F, Cl,
2 20R21' SO2N~OCH3)CH3 or S(O) R23
Rg is Cl-C3 alkyl, F, Cl, Br, NO2,
2 19 2 R20R21~ 52N(CH3)cH3 or S(O) R23;
Rlo is Cl, NO2, CO2CH3~ C2CH2CH3'
SO N(CH3)2' OS2CH3- S02CH3, SO2CH2C 3 3
OCH2CH3:
R11 is H, CH3 or CH2CH3:
R12 is H~ CH3 or CH2cH3
R13 is H or CH3:
R14 is H or CH3:
R15 is H or CH3:
R16 is CH3 or CH2CH3:
R17 is ~ or Cl-C4 al~y~;
RlB is H or CH3;
Rlg is Cl-C4 alkyl, CH2CH2OCH3,
CH2CH2Cl oc CH~CH=CH2:
~ZS5~
R20 is Cl-C3 alkyl
~21 i8 Cl-C3 alkyl
R22 i~ Cl-C3 alkyl or N(CH3)2:
R23 is Cl-C3 alkyl or CH2CH5CH2:
m i~ 0 or 1;
n is 0 or 2;
Ql is O~ S~ SO2 or ~R17
Q2 is O, S OL NR17 and
W is O, S or SO2:
N ~ N Xl ~ X
~ lC ~0~ ~ ~0~ ~
lS A-l A-2 A 3
Xl X2 OCH3
Y; 3 N ~
A-4 A-5 A-6
X is CH3, OCH3, OCH2CH3, Cl, F, ~r, OCF2H,
CH2F o~ CF3;
Y is H, CH3, OCH3, OCH2CH3, CH20CH3,
2 2 3' ( 3)2' Z 3' 3' 3'
OCH2CH=CH2, 0CH2C--CH. OCH2CF3, 0CH2CH20CH3,
/
CH2SCH3, OCF2H, SCF2H, CR24(QCH3~2 \2
Q
Q ~ Q ~,CH~
CR24 ~ ' \24J or CR24(QCH~cH3~2;
Q is O or S;
~Z5S6~ 3L
R24 is H or CH3; . -
Z is CH or N:
Yl is CH2 or O:
Xl is CH3, OCH3, OCH2CH3 or OCF2H;
Y2 is H o~ C~3:
2 i~ C~3, CH2CH3 or CH2CF3;
Y3 is OCH3. OCH2CH3. SCH3, CH3 o~
CH2CH3;
X3 is,CH3 or OCH3
provided that
1) the total numbe~ of carbon atoms of R20
and R21 is less than or equal to ~our;
2) when m is 1. ~hcn R13 is H; ~
3) when L is L-17, then R17 and R18 are not
simultaneously H; and
4) when X i6 Cl, F or Br, then Z is CH and Y is
OCH3. OCH2CH3, N(CH3)2 or OCF2H.
This invention also relates tO novel compounds
2~ of Formula II, suitable agricultural compositions ,
containing them and their method o use as genecal or
selective preemergent or postemergent h-erbicides or
plant growth regulants.
SR''
L-S02N=C-N-A
R
II
wherein
R~ is Cl-C3 alkyl;
R, L and A are defined for Formula I:
provided that
1) when L is L-l and A is A-l, R5 is C2-C4
alkyl, C2-C~ alkoxy, OCH2CH20CH3. 0502R22.
)n 23' WCF2. WCHF2, C3-C4 alkenyloxY.
5~ti1
C3-C4 alkynyloxy, Cl-C2 alkyl substituted
with OCH3 or OCH2~H3~ C6H5~
~ ~ CH3
~ o3 ~ ~N
~ o , ~ -CH3, _N~
~ , ~ or ~
2) when L is L-l and A is A-2 or A-3, then R5 is
Cl-C4 alkyl, C2-C4 alkoxy,
OCH2CH2OCH3, Br, OSO2R22, WCF3,
WCHF2, C3-C4 alkenyloxy, C3-C4
alkynyloxy, Cl-C2 alkyl substituted with
OCH3 or OCH2CH3~ C6H5~
~CH3
~ O~ ' . ~o~N ' ~N~ ' ~ S
N ~ ~N
, ~ ~ 3~ ~N~ N
~ or
3) when L is L-3 and A is A-l, A-2 or A-3, then R8
is So2NR2oR2l/ so2N(ocH3)cH3 or
SO2R23;
4) when L is L-4, L-5 or L-6 and A is A~1, A-2 and
A-3, then Rg is C1-C3 alXyl, F, Cl, Br,
NO2, So2NR2oR2l~ so2N(ocH3~cH3 or
S(O)nR23; and
5) when L is L2 then A is A5 or A6.
....
~ZS5~
Preferred for reason~ of their higher herbicidal
activi~y, greater plant growth regulant activi~y or
more favoeable ease of synthesis are:
1) Compounds o~ Formula I where R is H, R' is H
S and A i~ A-l.
2) Compounds of Preferred 1 where Y i~ C~3.
CH3~ CH2cH~' CH20CH~' ~CH2CF3 or CH(OCH3)2
and X is CH3. OCH3, Cl or CF3.
3) Compounds of Preferred 2 where L is ~-1.
L-2, L-3, L-5, L-8, L-10, L-ll, L-16 or L-17.
4) Compounds of Preferred 3 where L is L-l.
R5 is OCH3, OCH2CH3, Cl, N02, CF3, C02CH3.
C2CH2CH3' SOZN(CH3)2' S02N(OCH3~CH3'
2R22' S()nR23. 0CF2H, S(:F2H,
N-N
OCH2CH=CH2. OCH2C_CH. ~ O ~ CH
O-N N-O N-N
~ ' ~ or ~ \
R22 is Cl-C3 alkyl;
: R23 is CH3 and n is 2. -
5) Compounds of Preferred 3 where L is L-2 and
R7 is Cl, CH3, OCH3, SCH3 or Br.
6) Compounds of Preferred 3 where L is L-3 and
R8 is Cl, S02CH~ or 502N(CH332.
7) Compounds of Preferred 3 wheee L is L-5 and
Rg is C02CH3 or C02CH2CH3.
8) Compounds of Preferred 3 where L is L-8.
9) Compounds of Preferred 3 where L is L-10.
10) Compounds of Preferred 3 where L is L-ll.
11) Compounds of Preferred 3 where L is L-16.
12) Compounds of Preferred 3 where L is L-17.
13) Compounds of Formula II whe~e R is H and A
3s is A-l.
1~S566~
11
14) Compounds of Preferred 13 where Y is CH3,
3, 2CH3, H20CH3, OCH2CF3 or CH(OCH3)2
and X is CH3, OCH3, Cl or CF3:
15~ Compounds of Preferred 14 where L is L-l
and R5 i~ S2R22~ 52R23' CF2~' 2
N-N 0-N
OCH2CH-CH~. OCH2C--CH, "l~ ,~ . , ~ .
N-0 N=N
~ or ~ 5 ,
Specifically Preerred for reasons of their
highest herbicidal activity or grea~est plant growth
regulant activity or most favorable ease of synthesis
are:
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]aminosul~onyl]benzoic acid
- methyl ester:
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-
l-(hydroxyimino)methyl]aminosulfonyl~benzoic acid
methyl ester:
o N',N'-dimethyl-N-[[1-(4,6-dimethyl-1;3,5-triazin-
2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzene-
disulfonamide; and
. N',N'-dimethyl-N-[[1-(4-methoxy-6-methylpyrimidin-
2-yl)amino]-1-(hydroxyimino)methyl]-1,2-benzene-
disulfonamide.
~Z~566~L
1~
Detailed Descr iPt ion of the Invention
SYnthes i6
The compounds of Formula Ia may be prepared ~y
the reaction of hydroxylamine with an appropriately
substituted S-alkyl benzenesulfonyl isothioure~ of
Fo~mula II. as shown in Equation 1.
Equation 1
N-OH
SR'' ll
10LS2N-- NH2H L502N ~ \ N-A
. N A. R
R
II Ia
wherein
L, R, R'' and A are as previously defined.
The reaction of Equation 1 is conducted by con-
tacting 1-3 equivalents of hydroxylamine hydcochloride
and an equivalent amount of sodium acetate with a com-
pound of Formula II in a suitable solvent, e.g.
tetrahydrofuran, at 0-30 for 1-24 hours. The product
may be isolated by removal of solvent and trituration
of the residue with water.
The compounds of Formula II may be prepared by
the methods described in U.S. 4,301.286. Alternatively,
they may be prepared by the procedure outlined in
Equation 2.
Equation 2
SR''
LS2Cl ~ HN ~ N-A ~ II
III IV
wherein
L. R. R'' and A are as previously defined.
56~
i
13
~he reaction of Equation 2 may be carried out
by contacting a sulfonyl chloride of Formula III with
an appropriately substituted S-alkyl isothiourea of
Formula IV in an inert solvent, e.g., methylene
chloride or tetrahydrofuran, in the presence of an acid
scavenger, e.g~, aqueous sodium bicarbonate or a
tertiary amine, e.g., triethylamine, for 1-3 days at
20-40. The product is isolated by removal of solvent
and trituration of the residue with water, or by
10 extraction from water with an organic solvent,
concentration, and chromatography.
Reference to the following patents and patent
applications is sug~ested for details regarding the
preparation of the sulfonyl chlorides III: U.S. Patent
15 4,169,719 to G. Levitt issued October 2, 1979, U.S.
Patent 4,127,405 to G. Levitt, issued November 28,
1978; U.S. Patent 4,383,113 to G. Levitt issued May 10,
1983; U.S. Patent 4,394,506 to G. Levitt issued July
20 19, 1983; U.S. Patent 4,120,691 to G. Levitt, issued
October 17, 1978; U.S. Patent 4,238,621 issued December
9, 1980; European Patent Application Number 80304286.0
(E.I. du Pont de Nemours and Company) published June
10, 1981; European Patent Application Number 79302769.9
25 (E.I. du Pont de Nemours and Company) published July
23, 1980; Canadian Paten~ 1128042; European Patent
Application 82301500.3 IE.I. du Pont de Nemours and
Company) published November 17, 1982; European Patent
Application 81305160.4 (E.I. du Pont de Nemours and
30 Company) published May 12, 1982; and copending Canadian
Patent Applications Serial No. 413,400, to M.P. Rorer
filed October 14, 1982; Serial ~o. 413,385, to R.J.
Pasteris filed October 14, 1982; Serial No. 439829,
filed October 27, 1983 and Serial t~o. 419,031, to M.P.
35 Rorer filed January 06, 1983.
~;~SS6g~l
~. ~4
The preparatio~ of the compounds of Formula IV
i6 ~hown in Equation~ 3, 4 and 5.
(3a) S
ll
NC-N-A H25 ~ H2 N-A
pyridine R
V VI
'3b?
VI (~ )2S04 _ ~ IV
R''I
wherein
R, R'' and A are as previously defined.
The reaction of Equation 3a may be carried out
by saturation of a solution of a compound of Formula V
in pyridine with hydrogen sulfide, allowing to react
for 1 to 5 days at 25 to 40, removal o~ pyridine in
vacuo, and crystallization of the product with water
or an organic solvent e.g. ether or methylene
chloride. The resulting compound of Formula VI may be
reacted according to Equation 3b with one eguivalent
of a dialkyl sulfate or alkyl iodide at 20 to 80 for
1 to 3 days to provide the corresponding alkyl sulfate
or iodide salt of IV. The free base may be obtained
by extraction from aqueous ~odium bicarbonate with an
organic ~olvent, e.g. e~hyl acetate. An alterna-
tive synthesis of compounds o Formula VI is shown in
Equation 4.
3s .
15 ~ ~Ss 6~;
E~_ion 4
4a) ~ 5
HN'~`N-A
RNH-A J ~ NCS ~ ~ R
VII VIII
(4b)
. . H20
VIII NaOH or ~ VI
MgO
wherein
R and A are as previously defined: and
J is C6H5 or C6H5O.
The reaction of Equation 4a is carried out by
contacting a compound of Formula VII with l-1.5
equivalents of benzoyl- or phenoxycarbonylisothio-
cyanate at 30-80 for 1-24 hours in a suitable sol-
vent, e.g. acetonitrile or tetrahydrofuran. The
product may be isolated by cooling or concentration
and filtration. The reaction of Equation 4b may be
performed by heating the compound of Formula VIII in
an aqueous medium, with or without a cosolvent, in the
presence of 1 to 2 equivalents of an alkali metal
hydroxide or an alkali earth oxide at 30 to 80~ for
1-24 hours. The product is isolated by cooling,
neutralization to pH 8, and filtration in the case
where an alkali metal hydroxide is used, and in the
case where an alkali earth oxide is used, the reaction
mixture is filtered and the filtrate is concentrated,
cooled, and filtered.
~S5661
` 16
Heterocyclic amine~ of Formula VII and method6
for preparing them are known in the art. The synthe-
si of heterocyclic amines such a6 those of For~ula
VII ha~ been reviewed in "The Chemi~ry of Hete~ocyclic
Compounds~, a series published by Interscience Publ.,
New Yor~ and London. 2-Aminopyrimidine~ are de~cribed
by D. J. Brown in "The Pyrimidines~, Vol. XVI of this
series. 2-Amino-1,3,5-triazines can be prepared
accordin~ to methods described by E. M. S~olin and
L. Rapaport in "s-Triazines and Derivatives", Vol.
XIII of the same series. The synthesis of tciazines
is also described by F. C. Schaefer, U.S. 3,154,5~7
and by R. R. Huffman and F. C. Schaefer; J. Orq. Che~.,
28, 1816 (1963). See also copending C~dian Application N~r
416,863, filed ~r 02, 1982, ~pean Pabent Application N~r
80300505.7, published September 17, 1980 (Pub. ~o.
15,683), European Patent ~pplication Number 81303837.9,
published March 3, 1982 (Pub. No. 46,677): European
Patent Application Number 82306492.8, published
July 27, 1983 (Pub. No. 8q,22q); and European Patent
Application Numbec 82303611.6, published March 9, 1983
(Pub. No. 73,562), for description of met~ods for
preparing heterocyclic amine derivatives.
A third method by which certain compounds of
Formula IV may be obtained is shown in Equa~ion 5.
Equation S
.
X ..
~ SR
N N
~ N ~ R2NH~ ~NH _~ IV
Cl Y
IX
wherein
R, R'~. X and Y are as previously defined.
.
16
~Z~S6~
The reaction of Equation 5 may be carried out by
contacting a chlo~otriazine of Formula IX with an
S-alkyl isothiourea of Formula X in the same manner as
was described in the reaction of Equation 2.
Compounds of Formulae Ib and Ic may be obtained
from those of Formula Ia by the reactions of Equation
6.
Equation 6
(6a)
lo N-OR'
Ia R~Cl ~ LS02N N-A
Ib
(6b). o
N-o ~ NHR
R3NCO ~
Ia ~ ES02N N-A
H R
Ic
wherein
( ) 1~ C(O)NR2R3, or C02R4, and L, R, R
R2, R3, R4, and A are as previously defined.
The reaction of Equation 6a is carried out by
contacting Ia with 1-10 equivalents of the appropriate
carboxylic acid chloride .or anhydride, or alkyl chloro-
formate, or dialkyl carbamoyl chloride in the pre~ence
of an acid scavenger, e.g. pyridine or a ~ertiary
amine, at O to 40 for 2 to 24 hours, adding ice-
water, and filtering or extracting the product into an
organic solvent.
s~
18
The reaction of Equation 6b may be conducted by
treating a solution of Ia in an inert ~olvent e.g.
methylene chloride or acetonitrile with 1-1.5 equiva-
lents of an alkyl isocyanate at 20-aoo for 1 to 2~
hours. The product is isolated by concentrating the
reaction mixture and trituration with a solvent e.g.
ether or chlorobutane.
Agriculturally suitable salts of compounds of
Formulae I and II are also useful herbicides. Salts
of compounds of Formulae I and II can be prepared in a
number of ways known to the art. For example, metal
salts can be made by treating compounds of Formulae I
and II wi~h a solution of an alkali or alkaline earth
metal salt having a sufficiently basic anion (e.g.,
hydroxide, alkoxide, carbonate or hydride). Quater-
nary amine salts can be made by similar techniques.
Salts of compounds of Formulae I and II can also
be prepared by exchange of one cation for another.
Cationic exchange can be effected by direct treatment
of an aqueous solution of a salt of a co~pound of For-
mulae I and Il (e.g.. alkali metal or quaternary amine
salt) with a solution containing the cation to be ex-
changed.
This method is most effective when the desired
salt containing the exchanged cation is insoluble in
water, e.g., a copper salt, and can be separated by
filtration.
Exchange may also be effected by passing an
aqueous solution of a salt of a compound of Formulae I
and II (e.g., an alkali metal or quaternary amine
salt) through a column packed with a cation exchange
resin containing the cation to be exchanged. In this
method, the cation of the resin is exchanged for that
of the original salt and the desired product is eluted
from the column. This method is particularlv useful
18
~2S.S6~i1
19
when the de~ired ~alt iz water-soluble, e.g., a po~a6-
~ium, sodiu~ or calcium salt.
Acid addition salts, useful in this invention,
can be obtained by reacting a compound o~ Formulae I
and II with a ~uitable acid, e.g., ~-toluenesulfonic
acid, trichloroacetic acid or the like.
In the following examples, all parts are by
weight and temperatures in C unless otherwise
indicated.
ExamPle 1
2-Chloro-N-[[(4,6-dimethylpy~imidin-2-yl)a~ino]hydroxy-
iminomethYllbenzenesulfonamide
To a solution of 0.5 g of methyl N'-(2-chloro-
phenylsulfonyl)-N-(~,6-dimethylpycimdin-2-yl)carbam-
imidothioate in 10 ml of cetrahydrofuran was added 0.3
g of hydroxylamine hydrochloride and 0.3 g of sodium
acetate. The mixture was stirred at room temperature
for 2 hours, whereupon the product was precipitated
with ice-watec, filtered, washed with water, and dried
by suction to afford 0.3 g of the title compound, m.p.
165-167. NMR(CDC13/DMSO-d6) ~ 2.6 (s, 6), 6.S (~,
25 1), 7.4 (m, 3), 8.2 (m, 1), 10.2 (br, 1), 12.0 (br,
1). m/e: 355 (M ).
Example 2
N-(4,6-Dimethylpvrimidin-2-Yl)thiourea
A suspension of 10 g of 2-cyanoamino-4,6-di-
metbylpyrimidine in 50 ml of pyridine was saturated
with hydrogen sulfide and stored for 1 hour at 25.
The H2S treatment was repeated twice more. and the
mixture was allowed to stir at 25 for 16 houcs.
Methylene;-chloride was added. and the product was
S66~
~ 20
filtered and washed with methylene chloride to affo~d
8 g of 4,6-dimethylpyrimidin-2-yl ~hiourea, m.p.
~260. IR (Nu~ol* mineral oil) 3280, 3180, 3120~ 1610
cm
ExamPle 3
N-[(4-Methoxy-6-methylpyrimidin-2-yl~aminothioxo-
methYllbenzamide
To a hot solution of 1~ 9 of ammonium ~hiocya-
nate in 300 ml of ace~onitrile was added 24 ml of ben-
zoyl chloride. The mixture was heated on the steam
bath for 30 minu~es and filtered. The filtrate Wa6
heated with 21 g of 4-methoxy-6-me~hylpyrimidine-2-
amine for 30 minutes and cooled. The product was
collected by filtration and washed wi~h a little
acetonitrile to provide 28 g of N-[[(4-methoxy-6-
methylpyrimidin-2-yl)amino~hiocarbonyl]amino]benz-
amide, m.p. 193-195. IR (Nujol) ~290, 1720 cm 1.
Example 4
N-(4-MethoxY-6-methylpYrimidin-2-yl)thiourea
A mixture of 25 g of the compound ~rom Example 3
and 55 ml of 10% aqueous sodium hydroxide was heated
on the steam bath for 30 minutes, cooled, neutralized
with aqueous HCl to p~ 8, filtered, washed with water,
dried by suction, and washed with ether to aford 16 g
of the title compound, m.p. 220d.
Anal. Calc~d.: C: 42.4, H: 5.06, N: 28.2, S: 16.2
Found: C: 42.6, H: 4.~, N: 28.8~ S: 15.3
mJe 198 (M ).
~denotes t,rade mark.
~2~S~6~L
21
ExamPle 5
Methyl 2-~[1-(4-methoxy-6-me~hylpyrimidin-2-ylimino)-1-
(methYlthio~meth~llaminosulfonvllbenzoate
To 9 g of the compound from Example 4 and 100 ml
of tetrahydrofuran was added 7.6 g of dimethyl sulfate
and the mixture was stirred for 2 days at room temper-
ature. The product was filtered and washed with a
little tetrahydrofuran to give 22 g of crude product.
Five grams of this material was suspended in 150 ml of
methylene chloride and 1 ml of water, and 5 g of
sodium bicarbonate and 6 g of methyl 2-chlorosulfonyl
benzoate were added. The mixture was stirred for 24
hours, washed with dilute aqueous HCl, dried with
sodium sulfate, filtered, and chromatographed on
silica gel to afford 2.8 g of the title compound as
a crystalline solid, m.p. 143-144.
Anal. Calc'd.: C: 45.22, H: 4.55, N: 14.06, S: 16.1
Found: C: 46.8, H: 4.35, N: 13.2, S: 16
m/e 395 (M -CH3)
NMR(CDC13) o 2.35 (s, 3), 2.45 (s, 3), 3.90 (s,
3), 4.0 (s, 3) 6.35 (s, 1), 7.7 (m, 3), 8.2 (m, 1),
10.8 (brs, 1).
Example 6
25 Methyl N-(4,6-dimethoxy-1,3,5-triazin-2-yl)carbamimi-
dothioate
A mixture of 20 g of 2-chloro-4,6-dimethoxy-s-
triazine, 20 g of S-methyl isothiouronium sulfate, 16
g of sodium carbonate, and 50 ml of water was stirred
for 72 hours, concentrated at reduced pressure, and
extEacted with 300 ml of methylene chloride. The
organic layer was dried with Na2SO9, filtered,
concentrated to dryness, and recrystallized from
chlorobutane to afford 10 9 of title compound, m.p.
99-100. NMR(CDC13) ~ 2.6 (s, 3), 4.0 (s, 6), 8.2
(brs, 1).
~2~6~1
22
Using the procedure~ and exar~ple~ ~hown above,
the compounds in Tables 1-13 can be prepaeed.
.. . . . .
.
i.
~Z~6t~
23
Table la
R6
R
10 5 6 R'' jR X Y m.p.(C)
2 .2. CH3 3 3
5cH2cH=cH2 H C2H5 H OCH3 C2H5
OS02-n-C3H7 H CH3 CH3 CH3 CH20CH3
OS02-n-C3H7 H CH3 H CH3 SCH3
15 OS02CH3 H CH3 H OCH3 CH3
2 3 H CH3 ~ 3 3
CH2CH3 5-Br CH3 H CH3 OCH3
CH2CH3 H CH3 H CH3 CH3
n-C4Hg H n-c3H7 H OCH3 OCH3
20 ~-C3H7 H CH3 CH3 OCH3 CH3
OS02N(CH3)2 H CH3 H CH3 CH(CH2CH2)
OCH2CH3 H CH3 H CH CH
CH2cH3 H CH3 H CH3 OCH3
O-l-C3H7 H CH3 H OCH3 OCH3
25 O_i_C3H7 H CH3 3 C2 5
O-n-C4H9 H CH3 H CH3 CH(OCH3)2
O-n-C4H9 H CH3 H CH3 OC2H5
S02CF2H 5-CH3 CH3 ~3 CH3
S02CF2H H C2H5 H OCH3 C2~5
30 SCF2H 6-SCH3 CH3 CH3 CH3 CH20CH3
SCF2H H CH3 H CH3 SCH3
OCF3 H CH3 3 3
OCF3 H CH3 3 3
20C 3 H n-c3H7 H H3 OCH3
-
56~
24
Table la (continued?
R5 R6 P~' ' R X Y m.P.(C~
CH20CH3 H CH3 CH3 OCH3 CH3
CH20CH2CH3 H CH3 H Cl OCH3
CH20CH2CH3 H CH ~ H Cl CH3
CF2EI H CH3 H OCH3 CH3
OCF2EI H CH3 H OCH3 OCH3
OCF2H ~ 3 CH3 CH(OCH2CH20)
.. . . . . .
~2S56t;3L
Table lb
5O2N ~ N 1 N ~ y
R
.
10 R5 R6 R'' R X Y m.p. (C)
SO?CH2CH-CH2 H CH3 3 C 3
S2CH2CH CH2 H CH3 H OCH3 C2HS
OS02-n-C3H7 H CH3 CH3 C~3 CH2OCH3
OS02-n-C3H7 H CH3 H CH3 SCH3
15 OSO2CH3 H CH3 3 3
2 3 H CH3 H 3 3
CHzCH3 3-Br CH3 H CH3 OCH3
CH2CH3 H CH3 H CH3 CH3
n-C4H9 H n-c3H7 ~ OCH3 OCH3
20 1-C3H7 H CH3 CH3 OCH3 CH3
OSO2N(CH3)2 H CH3 H CH3 CH(OCH2CH2O)
CH2cH3 H CH3 H CH CH
OCHzCH3 H C~3 H CH3 OCH3
o-i-C3H7 H CH3 H CH3 3
25 O_i_C3H7 ~ CH3 H OCH3 C2H5
O-n-C4Hg H CH3 H CH3 CH(OCH3)2
O-n-C4Hg H CH3 H CH3 OC2H5
SO2CF2H 6-SCH3 CH3 H OCH3 OCH3
SO2CF2H H C2H5 H OCH3 OC2H5
30 SCF2H H CH3 CH3 CH3 CH2OCH3
SCF2H H CH3 H CH3 SCH3
OCF3 H CH3 3 3
OCF3 H CH3 H OCH3 OCH3
CH2OCH3 H n-c3H7 H OCH3 OCH3
.
~ss~
- 26
Table lb (continued2
R5 R6 R'' R X Y m P.(C)
CH20CH3 H C:H3 CH3 OCH3 CH3
CH20CH2CH3 H CE~3 H Cl OCH3
CH20CH2CH3 H CH3 H C 1 CH3
OCF2H H CH3 H OCH3 CH3
OCF2H H CH3 H OC 3 3
OCF2H H CH3 H CH3 CH3
2 2 2 5 3 H OCH3 C 3
.. . . ...
3 s i .
lZS5i6~
27
Table lc
X
a~ SR'
R
m.p.
10 R R S 6 X Y Z (~C)
CH3 . . .2 ? 3 CH3 H CH
C~i H OCH2CH=CH2 H CH3 CK3 N
CH3 HOCH2cH-cH 6-OCH3 CH3 CH3 CH
CH3 6 5 H CH3 CH3 N
15 CH3 H N-N~ H CH3 OCH3 CH
O CH3
CH H N-N 3 3 N
3 /1 ~\
~O~
CH3 ~3 H 3 2 N
S ,.
CH3 ~3 H 3 2 2 3 N
o
25CH3 2 5 H OCH3 OCF2H CH
CH3 H OCF3 3 2 CH
CH3 2 3 3-OCF2H OCH3 C(CH3)(0CH3)2 CH
CH3 N OCH2CH3 H 3 3 N
3 S02CH2CH3 H OCH3 N(CH3)2 CH
30CH3 CH3 S02C~2CH3 H OCH3 C(CH3)(~CH3)2 N
CH3 H S02CH2CH3 HOCF2H CH~SCH2CH2Si CH
S02CH2CH3 H CF3 CH2CH3 CH
CH3 H S02CH2CH3 H F OCH3 CH
CH3 H S02CH2CH3 HOC2H5 C(CH3)(0CH2CH20) CH
j.
27
~2SS~i6~
28
T~ble ld
SR''
LS2N ~ N ~
N~/ z
R N ~
: m.p.
10 R'' R ~ X Y Z ~C)
CH3 H L2:R7.-Cl, 3 CH
3 2 7 3 3 3 CH
CH3 ~ L2 R7=so2N~cH3~2 C 3 3 CH
CH3 H L3 ~8=S2N~CH3)2 3 3 CH
CH3 H L3:R8=S02CH3 CH3 OCH3 CH
CH3 CH3 L3:X8=S02cH2c 3 C1 OCH3 CH
i-C3H7 H L4:R9=Br 3 3 CH
CH3 H 5 9 2 5 OCH3 CH2cH=c~l2 CH
CH3 H L6:Rg=Cl OCH3 OCH2 _ N
CH3 H L7:Rlo=co2c 3 OCH3 OCH2CF3 N
CH3 8 Q1 ~ m 0~ R11=R12=R13=cH3 OCH3 CH2SCH3 CH
CH3 H L9:Q2=S~ R14 R15 ' H CH
CH3 H L1o:~=0~ ~13=H~ R16 3 OCH3 SCF2H CH
CH3 H Lll:m=O, R13=H OCH3 C(CH3)~0CH3)2 CH
CH3 H L12:m=1, R13 C 3 3 3 CH
CH3 H L13:m-0, R13-H OCH3 N~CH3)2 CH
CH3 CH3 L14 R16 CH2 3 OCH3 C(CH3)~SCH3)2 CH
CH3 H Ll~:R17 CH3 OCF2H CH(SCH2CH2S) CH
CH3 H L16:~17=H CF3 CH2CH3 CH
CH3 ~ L17 R17=R18 C 3 F OCH3 CH
CH3. H L17 R17 ~18 3 OC2H5 C~CH3~(0CH2CH20) CH
;,
.
28
-
Tabl~ le
SR''
LS02N~N-A
R
m.p.
L R'' R A (C)
Ll aS=C02CH3' a6=H CH3 H ~4:Xl=C~3. Y2
Ll R5=S2C~3' R6-H CH3 H A5:X2=CH2CH3, Y3=SCH3
Li:R5=N02, R6=H CH3 H A6:X3=OCH3
Ll:RS=Br, R6=H CH3 H A3:Xl=OCH3
Ll:RS=Cl, R6=H CH3 H As:x2=cH3~ Y3 2 5
Ll R5=C2H5' R6=H CH3 H A2:Xl=CH3~ 1
Ll:R5=SCF3, R6=H C2H5 H A3:Xl OC 2
L17:R17=H~ R18 CH3 CH3 H A2:~1=OCH3, Yl CH2
16 17 3 CH3 H A3:Xl=OCF2H
2 7 3 CH3 H A4:Xl=CH3~ Y2 3
L3:R8=F CH3 H A5:X2=CH2CH3~ Y3 3
L :R ~ C H CH3 H A5:X2=CH3~ Y3 CH2 3
L5:R9=S02CH3 CH H A :X --OCH
L6:R9=S02CH3 CH3 H A2:Xl=CH3~ Yl
L7:Rlo=OCH2CH3 CH3 H A3:~1 3
~8 Ql S'~Rll=R12=CH3~ m=1, R13=H CH3 H A6:~3=CH3
L9 Q2=o~ R14=R15 CH3 CH3 H A4:X1=0CH3. Y2 3
10 16 2 5' 13 3' CH3 H A5:~2=CH3. Y3 SC 3
Lll:m=l, R13=H CH3 H A2:Xl=CH3' Yl 2
L12:m=0~ R13 C 3 CH3 H ~2:Xl~ocH3~ Yl 2
30 L13:m=1, R13=H CH3 H A5:~2=CH2CF3' Y3 2 3
L14 R16=C~3 CH3 H A~:Xl=OCH3, Y2=H
L15 R17ScH3 CH3 H A4:Xl=0CH3. Y2
29
~L2~5~6~
Table 2a
H~ ll-OI~'
6 2~, ,
" R
10 R5 R6 R H CH3 3 1zl_167'~
Ccl H HH H OCH3 3 142-144
F H H H CE~3 CH3
15 F H H H CH3 3
B ~ H H H OCH 3 3
H H H OCH3 3
NO H H H CH3 CH(OC~2CH2O)
NO2 HH CH3 H oCH3 C2H5
CF3 H H H OCH j 3
oO,c,3H3 HH HH HH CH3 CH (OCH3 ) 2
OCH3 H U H Cl OCH3
O_~ c~H <I~ CII]
C~ H H ~U~ C
~s~
Table 2a (cont;nued)
R5 R6 R R' X Y m.P.(C)
2 H3 H H 3 2H5
S02N(CH3)2 H ~E 3 ~3
S02N(CH3)2 H H CH3 CH3
S02N(CH3~2 H H H CH3 OCH3 166-168
S02N(CH3)2 H H H OCH3 OCH2C~E3
SO2N(CH3)2 H H H CH3 CH~OCH2CH20)
2 ( 2 H3)2 H CH3 H CH3 C2H5
S02N(CH2CH3)2 H H OCH3 OC2H5
2 ( 2 3)2 H H 3 CH3
CO2CH2CH3 H H H CH3 OCH3
C02CH2CH3 H H H CH3 CH(OCH3)2
2 H3 H H H Cl CH3
2 H3 H H H Cl OCH3
C2CH3 H H H CH3 CH20CH3
C02-i-C3H7 H H H CH3 CH3
CO 1 C H H CH3 H 3 3
$02N(OC~13)CH3 ~I H 3 CH3
C02CH2CH20CH3 H H H CH3 OCH3 -
C2CH2CH=CH2 H H 3 CH3
2 2 H2Cl ~E H H OCH3 OCH3
CO2-n-C4Hg H H 3 CH3
Z5 SO2CH3 H H CH3 CH3
02CH3 H H H CH3 OCH3
~ 3 H H 3 2H5
2 3 H H 3 OCH3
z 2C CH2 H H 3 3
S2CH2CH=CH2 H H H CH3 OCH3
2 2 23 H H H 3 H3
SCH CH H H H OCH3 OCH3
SCF3 H H H CH3 CH(CH2CH2)
2 HF2 j, H 3 CH3 C2~5
CH3 H H H OCH OC H
3 1
31 2S~ii6~;~
32
~ble 2a ~continued~
6 B jR' X Y m D. (-C?
_C H H H 3 3
n-C4Hg H H ~ CH3 OCH3
OS02NSCH3)2 H H H CH3 CH(OCH3)2
OS02NtCH3)2 H H H Cl CH3
OS02CH~CH3)2 H H H Cl OCH3
2 2 5 H H H CH3 CH20CH3
OS02CH3 H 3 OCH3 ~CH3
OS02CH~ , ~ , H 3 CH3
CH20CH3 H H H CN3 O~H3
CH3 ~ H H 3 CH3
OCF3 H H 3 3
lS S02-~-C3H7 H ~l 3 3
Cl H H CH3C0 3 3 131-136d
Cl S-CF3 H H CH3 OCH3
Cl H H CH30COOCH3 OC2H5
Cl 6-SCH3 H H 3 3
F 5-SCH3 H CH3C03 CH3
F 6-OCH3 H H CH3 OCH3
Br H H (CH3)2NCO OCH3 CH3
B~ 3-OCH3 H 3 3
N02 H H CH3NHCO CH3 CH(CH2CH2)
N2 3 3 CH3 C2HS
CF3 5-CH3 H CF3CO OCH3 OC2H5
CF3 6-Cl H C2H5CO OCH3 CH3
OCH3 H H 2 5 CH3 OCH3
OCH3 5-Cl H H CH3 CH(OCH3)2
30 OCH3 3-Cl H H Cl CH3
OCH3 H H CH3CO Cl OCH3
OC?HS 5-F H H 3 2 3
2 5 S-F H Et2NC 3 H3
OC2H5 3-Br 3 3 3
o-i-C3H7 H H EtOCO 3 3
~25~66~l
33
TAblQ ?a ~continued)
R5 R6 R R~ X y ~ .~^C)
O-n-C H N H - 3 7 CH3 OCH3
O-n-C H 6-CH3 H 3 3
O-l-C H 3-CF3 H 3 CO 3 H3
O-~-C4H9 6-CF3 H H 3 H3
2 3 5-CF3 H 3 3
C2CH3 6-CF3 H H CH3 OCH3
C2CH3 H X CH30CO OCH3 OC2H5
S02N(CH3)i 6-SCH3 3 CH3
SOzN(CH3)2 5-SCH3 H CH3CO CH3 CH3
S02N(CH3)2 6-OCH3 H H CH3 OCH3
S02N(CH3)2 H H (CH3)2NCO OC~3 OCH3
S02N(CH3)2 3-OCH3 H H OCH3 OCH2CH3
S02N~CH3)2 H H CH3NHCO CH3 CH(CH2CH2)
So2N(cH2cH3)2 3-CH3 3 CH3 C2H5
S02N(CH2cH3)2 5-CH3 CF3CO OCH3 OC2H5
2 2 3 2 H C2H5C0 3 3
C02CH2CH3 H H C2H5CO CH3 OCH3
C02CH2CH3 5-Cl H H CH3 CH~OCH3)2
2 3 6-Cl H H Cl CH3
2 H3 H H CH30CO Cl OCH3
2 3 5-F H H 3 2 3
C02-i-C3H7 5-F H (C2H5)2Nc CH3 C~3
C02-i-C3H7 3-Br 3 3 3
So2N(ocH3)cH3 H _ 3 7 3 3
C02CH2CH20CH3 H H H CH3 OCH3
C2CH2CH=CN2 6-CH3 H 3 3
2 2 2 3-CF3 H 3 3
C02-n-C4H9 6-CF3 H H 3 3
2 3 5-CF3 H 3 3
2 3 3-CF3 H H CH3 OCH3
S2CH3 H 3 OCH3 OC2H5
2 3 6-SCH3 H H OCH3 OCH3
~Z5S6~L
34
T~ble ?a ~continued)
S 6 R R' X Y m P.~-C)
S2C~2CH'C~2 5-SCH3 H CH3C0 3 H3
S2CH2CH~CH2 6-OCH3 3 OCH3
S2C~12CH2CH3 H H (CH3)2NCO OCH3 CH3
2 3 3-OCH3 H 3 3
SCF3 H H CH3NHCO CH3 CH~OCH2CH20)
S02CHF2 3 3 CH3 C2Hs
CH3 5-CH3 H CF3CO OCH3 OC2HS
~-C3H7 . 6-C1 H 3 3
n~C4H9 H H C2H5CO CH3 OCH3
OS02N~CH3)2 6-Cl H H Cl CN3
OS02N(CH3)2 H H CH30CO Cl OCH3
OS02CN(CH3)2 5-F H CH3C0 3 2 3
2 3 3-Br 3 3 3
2 3 H H n-C3H70CO OCH3 CH3
2 3 H. H 3 7 CH3 OCH3
CH2CH20CH3 6-CH3 H 3 3
OCF3 3-CF3 H 3 3
S02-i-C3H7 S-CF3 H 3 H3
2 2 2 5 H H 3 3
~ DPt~ re~er to molecular ion in electron-impact m~ss
spectrum.
i'
34
~2~i~6~L
Table ?b
R ~ 5 N-OR'~ 1
10 Rs R6 R ~ X Y m.P.(C)
Cl H . H H3 CH3
Cl H H H CH3 OCH3
Cl H H CH3 OC2H5
Cl H H H3 OCH3 137-140
15 F H H H CH3 CH3
F H H H CH3 OC~3
Br H H 3 3
Br H H 3 CH3
NO2 H H H CH3 CH(CH2CH2)
20 NO2 H CH3 H CH3 C2H5
. CF3 H H H OCH3 OC2H5 .
: CF3 H H H OCH3 CH3
OCH3 H H H CH3 OCH3
OCH3 H H H CH~ CH(OCH3)2
25 OCH3 H H CH3 CH3
OCH3 H H OCH3 OCH3
C2H5 H H H CH3 CH2OCH3
C2H5 H H H CH3 CH3
C2H5 H CH3 H OCH3 OCH3
30 O-i-C3H7 H H 3 3
O-n-C3H H H H CH3 OCH3
O-l;l-C3H7 H H H CH3 CH3
O- i -C H H H H 3 OCH3
O_i_C4Hg H H 3 CH3
35 CO2CH3 H H H CH CH
lZ55~61
36
Table 2b tcontinued)
R5 6 R R' X Y m p (C)
,_ _ _ _ _
2CH3 H H H CH3 OCH3
2~H3 H H H3 OC2H5
SO2N(CH3)2 H H H OCH OCH ~ 3.0 and
S2N(CH3)2 H ~ 3 3 4.0 (1:1)*~
S02N~CH3)2 H H H CH3 OCH3
S02N(CH3)2 H H H OCH3 OCH2CH3
S02N(CH3)2 H H H CH3 CH(OC~2CH20
o-2N(CH2~H332 H CH3 ~ CH3 C2~5
02N(CH2CH3)2 H ~ H OCH3 OC2H5
2N(CH2CH3)2 H H OCH3 C~3
C02CH2CH~ H H H CH3 OCH3
C02CH2CH3 H H H CH3 CH(OCH3)2
C2CH3 H H H CH3 CH3
2CH3 H H H CH3 OCH3
2C~3 H H H CH3 CH20CH3
C02-i-C3H7 H H H CM3 CH3
C02-i-C3H7 H CH3 H OCH3 OCH3
S02N(OCH3~CH3 H H OCH3 CH3
C02CH2CH20CH3 H H H CH3 OCH3
C2CH2CH=CH2 H H H CH3 CH3
C2CH2CH2Cl H H 3 OCH3
CO2-n-C4H9 H H 3 3
2 3 H H 3 3
2CH3 H H H CH3 OCH3
2CH3 H H H OCH3 OC2H5
30 2CH3 H H 3 OCH3
So2cH2cH-cH2 H H H CH3 CH3
S2cH2cH=cH2 H H H CH3 OCH3
502CH2CH2CH3 H H H OCH3 CH3
z 3 H H 3 OCH3
SCF3 H H H CH3 CH(OC~2CHzO)
S02CHF2 H CH3 H CH3 C2H5
36
~2~S6~i~
37
T~ble 2b ~continued ?
R R6 a R X Y m ~.~ C)
CH3 H H 3 2 5
5 i_C ~ H ~ 3 3
n~G4H9 H H 3 H3
OS02N~CN3)2 H H H CH3 CH~OCH3)~
OS02N~CH3)2 H H 3 3
OS02CH~CH3)2 H H H CX3 OCH3
OS02C2H5 H H H CH3 CH20CH3
OS02CH3 . H . C 3 H3 OCH3
2 3 H H H3 CH3
CH20CH3 H H H CH3 OCH3
CH2CH20CH3 H H 3 3
OCF3 H H 3 3
S02-1-C3H7 H H 3 H3
Cl 3-CF3 H CH3 CH3
Cl S-CF3 H H CH3 OCH3
Cl H H CH30CO OCH3 OC2HS
20 Cl 6-SCH3 H H OCH3 OCH3
F 5-SCH3 H CH3C0 3 ~3
F 6-OCH3 H H CH3 OCH3
Br H H (CH3)2NCO OCH3 CH3
8r 3-OCH3 H 3 CH3
No2 H H CH3NHCO CH3 CH(CH2CH2)
N2 3 3 CH3 C2Hs
CF3 5-CH3 H CF3CO OCH3 OC2H5
CF3 6-Cl H C2H5CO OCH3 CH3
OCH3 H H 2 5 CH3 OCH3
~CH3 5-Cl H H CH3 CH(OCH3)2
OCH3 6-Cl H H 3 3
OCH3 H H ~ 3 7 CH3 OCH3
C2H5 5-F H H 3 2 3
C2HS 5-F 2 3 3
C2H5 3-Br 3 3 3
37
~L2556~
.
38
l~ble 2b (continued)
R R6 ~ R~ X Y m p.('C)
O-i-C3H~ H H EtOCO 3 3
O-n-C3H7 H H - 3 7COCH3 OCH3
: O-n-C3H 6-CH3 ~ 3 ~3
o-i-c h 3-CF3 H CH30C0 3 3
O-i-C4~9 5-CF3 H H 3 3
C2CN3 3-CF3 H H 3 3
2 3 5-CF3 N H CH3 OCH3
CO~C.H3 H H C~130CO OCH3 OC2N5
S02N(CH3)2 6-SCH3 H 3 H3
S02N(CH3)2 S-SCH3 H 3 CH3 CH3
502N~CH3)2 6-OCH3 H H CH3 OCH3
S02N(CH3~2 H H (CH3)2NCO OCH3 OCH3
S02N~CH3)2 3-OCH3 H H OCH3 OCH2CH3
S02N~CH3)2 H H CH3NHCO CH3 CH~OCH2CH20)
S02N~CH2cH3)2 3-CH3 3 CH3 C2HS
so2N~cH2cH3)2 S-CH3 H - 3 7 OCH3 OCzH5
2 2 3 2 H H 3 3
C02CH2CH3 H H CF3COCH3 OC~3
C02CH2CH3 S-Cl H C2H5CCH3 CH(OCH3)2
2 3 6-Cl H H 3 3
C2CH3 H H C2H5COCH3 OCH3
2 3 5-F H H 3 2 3
C02-i-C3H7 S-F H HCH3 CH3
C02-i-C3H7 3-8r 3 3 3
S02N(OCH3)CH3 H H Et2NC0 3 3
C02CH2CH20CH3 H H n-C3H70CO CH3 OCH3
C2CH2CH=CH2 6-CH3 H 3 3
C2CH2CH2Cl H H CH30C0 3 3
C02-n-C4Hg H H C2H5C0 3 3
2 3 3-CF3 H 3 3
2 3 " s-cF3 H H CH3 OCH3
2 3 H H CH30CO OCH3 OC2HS
38
~zss~
39
able 2b (continued)
S 6 R R' X Y m p. ( -C)
S2CH3 6-scH3 H 3 3
5 S2CH2CH=CH2 5-SCH3 H H 3 3
S2CH2CH=CH2 6-OCH3 H SCH3)2NCo CH3 OCH3
~2CH2cH2cH3 H H H 3 3
2 3 3-OCH3 H 3 3
SCF3 H H CH3NHCO CH3 CH~OCH2Ci320)
2 2 3 3 CH3 C2H5
CH3 5-CH3 h 2 5 OCH3 OC2H5
i-C3H7 6-Cl H H OCH3 3
n~C4H9 H H ~ 3 7 CH3 OCH3
OS02N~CH3)2 6-Cl H C2H5CO CH3 CH3
os02N(cH3)2 H H ~ 3 7 CH3 OCH3
OS02CH(CH3)2 S-F H H 3 2 3
2 3 3-Br CH3 C2H5NHCO 3 3
2 3 H H (C2H5)2NCO OCH3 CH3
CH20CH3 H H C~3COCH3 OCH3
CH2CH20CH3 6-CH3 H H 3 3
OCF3 H H 2 SOCH3 OCH3
S02-i-C3H7 H H n-C3H7N~CO oCH3 CH3
2 2 2 S H H H 3 3
X*Data refer to characteristic si~nals in NMR spectrwm
(CDC13) in ppm downfield from tetramethylsilane.
39
~;Z55~61
Table 2c
S R ~ ~I~ 1 N 1
H R
m p
H H 2 2 3 CH3 H CH
H H OCH2CH=CH2 H CH3 CH3 N
H OCH2CH_CH 6-OCH3 CH3CH3 CH
lS H H C6H5 H CH3 3 . N
H H ~N-N~ H CH3 OCH3 CH
O CH3
H ~N-N~ 3 3 N
H H Cl H OCH3 OCH2C-CH N
CONHCH3 H Cl H OCH3 CH2cF3 CH
H H Cl H 3 2 2 3 N
25 H H Cl H OCH3 CH2SCH3 CH
: H H F H OCH3 OCF2H CH
H H P 3 2 CH
H H F 3-OCF2H .OCH3 C(CH3~0CH3)2 CH
H H F H OCH3 CF3 N
30 H H Br H OCH3 N(CH3)2 CH
H . 3 H OCH3 C(CH3)(SCH3)2 N
H 3 OCF2H CH(SCH2CH2S) CH
3 H CF3 CH2CH3 CH
H 3 H F OCH3 CH
35 H 3 H OC2H5 C(CH3)(0CH2CH20) CH
~lZ~S6~
~ble 2c ~continued)
R' R S 6 ~ Y Z m p.~'C)
S H ~ H CH3 H CH
N N-CH3
-N ~ 3 3 CH
H Hr N H CH3 OCH3 CH
~N~
COCF HO-n-C H7 3 3 CH
H HO-n-C3H7 H OCH3 CH2cH=cH2 CH
H HO-n-C3H~ H OCH3 OCH2C-CH N
H H. OCH3 ~-Br OCH3 OCH2cF3 N
H HOCH3 3 2 H2 3 N
H HOCH3 H OCH3 CH2SCH3 CH
H H 2 OCH3 OCF2H CH
H H N2 3 2 CH
H H N2 3 3 3 2 CH
20 H H CF3 3 3 CH
H H CF3 3 .( 3)2 CH
33 H OCH3 C~CH3)~SCH3)2 CH
H CH3 CO2CH3 H OCF2H CH(SCH2CH2S) CH
H CH3 CO2CH3 H CF3 CH2CH3 CH
25 H CH3 CO2CH3 H F OCH3 CH
H CH3 CO2CH3 H OC2H5 C(CH3)(0CH2CH20) CH
H H ~ H CH3 H N
30 H H ~ 3 3 N
H H ~3 H CH3 OCH3 CH
S
.- 2 2 2 3 3 CH
HC02CH2CH=CH2 HOCH3 OCH2CH=CH2 CH
.
41
~2S~
42
Tdble 2c . ( cont ~ nu~d~
R' j~ 5 6 jX Y Z m p.('C)
H ~i CO2C112CH=CH2 H OCH3 OCH2C--CH N
H H S02N(CH3)2 H OCH3 OC112CF3 N
% H SO2N(CH3)2 3 2 2 3 N
H H SO2N(CH3)2 H OCH3 CH2SCH3 N
H H SO2N(OCH3)CH3 HOCH3 OCF2H CH
H SO2N(CH3)C2H5 H OCH3 SCF2H CH
H H SCF3 H OCH3 ~CH3) (CH3)2 CH
H H SO CHF 3 3 CH
2 2 2 OCN3 N ( CH3 ) 2 CH
H3 C 2 2C 3 H OCH3 C ( CH3 ) ( SCH3)2 CH
'H H CO2CH2CH3 H OCF2H CH(SCH2CH2S) CH
H H CO2CH2CH3 H CF3 CH2CH3 CH
H H S2CH3 H F OC.13 CH
CO-i-C3H7 H S2CH3 H OC2HS C(CH3) ~OCH2CH20) CH
' H H ~ H CH3 H N
o,N
H H ~ 3 3 N
,O
H H N=N~6-OCF2H CH3 OCH3 CH
25 ~ S
H H r N\ 3 3 CH
~o
H H OCH3 HOCH3 OCH2C - CH CH
H H OCH3 HOCH3 OCH2CF3 CH
H H OCH3 3 2 2 3 CH
H - H OC2H5 NOCH3 C~2SCH3 CH
H H OC2HS 3-F OCH3 OCF2H CH
CO2CH2CH3 H 2 5 3 2 CH
H H CH3 H oCH3 C(CH3)(0CH3)2 N
3 5 H Hi' CH3 H . OCH3 CF3 N
~S56~31
43
Tabl~ 2c (continued?
R' R Rs R6 X Y Z m D. (-C)
H H CH3 H OCH3 N ( CH3 ) 2 N
51 ~N3 i_C3H7 H OCH3 C(CH3)(SCH3j2 CH
H H l-C3H? H OCF2H CH(SCH2CH2S) CH
H H i-C3H7 H CF3 CH2~H3 CH
H H l_C3H7 H F OCH3 CH
10 H H n-C4Hg H OC2HS C(CH3) (OCH2CH20) N
.. . . ..
~3
~LZS~66~
44
T~ble 3
~-OR' ~
5SO NH ~ N ~/ Z
~ ~ R7 R N ~
lo R~ a R' ~ Y Z m.P. ~C)
H H H CH3 CH3 CH
CH3 H CN(~H3)2 OCH3 CH3 N
OCH3 N N Cl CH3 CH
H H CH3 CH3 CH
C1 H H OCH3 OCH3 CH
Br H H F OCH3 CH
SO2N(CH3)2 H H CH3 OCH3 CH
2 H3 H H OCF2H OCH3 CH
2 3 H H CH2F C2H5 CH
H 3 2 3 2 3 N
CH3 H H CF3 N~CH3)2 . CH
OCH3 H H OCH3 CF3 CH
F 2 2 3 3 CH(OCH3)2 CH
H H OCH3 OCF2H N
Br H H OCH3 CH2cH2cH3 N
2N(CH3)2 H H OCH3 CH2SCH3 N
2 3 H H OCH3 OCH C-CH CH
SCH3 H H OCH2CH3 ~O ~ CH
30 SCH3 H H 3 O J CH
CH3 - ~ H CH3 OCH3 N
H H H CH3 OCH3 N
~ 4
~2~566~L
4S
T~bls b
N-OR' N X
S02N~N-</ Z
R N ~
m p
10 8 R R' X Y Z ~gC)
.. O--\
CH3 H CON(CH3)2 OCH3 o ~ N
CH2CH3 H H Cl OCH3 CH
15 OCH3 H H CH3 CH20C2H5 CH
2 3 H H OCH3 CH3 CH
F H H F CH3 CH
Cl H H CH3 CH3 CH
Br H H OCF2H CH3 C~
20 So2N~cH2cH3)2 H H CH2F OCH3 CH
S02NtCH3)2 CH3 H OCH2CH3 OCH3 N
S02N~OCH3)CH3 H H CF3 OCH3 CH
SCH2CH=CH2 H H OCH3 OCH3 CH
S02C2HS 2 2 3 3 OCH3 CH
25 S-n-C3H7 .H H OCH3 C2H5 N
2 3 H H OCH3 C2H5 N
SCH3 H H OCH3 SCF2H N
CH3 H H OCH3 C(CH3)(SCH3)2 CH
F H H OCH~CH3 OCF2H CH
H H C~3 2 5 2 CH
Br H H CH3 CH3 N
OCH3 H H CH3 CH3 N
~Z551~61
'r~ble 5
N-OR~ _~
LS02NHJ~Ny Z
R N~
m.p.
; L 9 R R' ~ Y Z ~-C)
4 3 H H CH3 OCH3 CH
L4 F . . H CN~CH3)2 OCH3 OC~3 N
L4 NO2 H H Cl OCH3 CH
4 2 2 5 H H CH3 OCH3 CH
L4 SO2N(CH3)2 H H OCH3 C~.2SCH3 CH
L4 S-i-C3H7 H H F CH3 CH
L n-C H H H CH3 N~CH3)2 CH
L5 Cl H H OCF2H CH20CH3 CH
L5 Br H H CH2F CH20C~13 CH
L~ CO2CH3 3 2 3 2 3 N
L5 S02N~C~H5)2 H H CF3 CH3 CH
. L5 SO2N~OCH3)CH3 H H OCH3 CH3. CH
S 2 2 S 2 2 3 3CH3 CH
5 2 2 H H OCH3CH3 N
25 Ls SO2CH3 H H OCH3S ~ N
L6 F H H OCH3 CH~OCH3)2 CH
L6 C2~1~C3H7 H H OCH2CH3 OCH3 CH
L6 SO2CH3 H H CH3 OC~3 CH
L6 S2N(CH3)2 H H CH3 OCH3 t N
L6 Br R H CH3OCH3 N
~;~S~i~6~L
4~
T~bl~ 6
~ CH SO NH ~ N ~/
R N ~
R m.p.
10 10 ~ R' X y z
C1 H H CH3 CH3 CH
NO H CON(CH3)2 OCH3 CH3 N
2 3 H H Cl CH3 CH
C02CH2CH3 H H CH3 CH3 CH
S2N(CH3)2 H H OCH3 CH3 CH
: OSo2cH3 H H F OCH3 CH
2 3 H H CH3 OCH3 CH
S02CH2CH3 H H OCL`2H OCH3 CH
OCH3 H H CH2F OCH3 CH
CH2cH3 3 CH2cH3 OCH3 N
CH2cH3 H H CF3 CH2SCH3 CH
OCH2cH3 H H OC~I3 CF3 CH
OCH3 2 2 3 3 C~2CH3 CH
S02CH2CH3 H H OCH3 OCH3 N
2 3 H H OCH3 SCF2H N
2 3 H H OCH3 CH3 N
C02CH2CH3 H H 3 3 CH
2 3 H H OCH2CH3 CH3 CH
C02CH3 H H CH3 CH3 CH
30 CO~CH3 H H ~H3 OCH3 N
N02 H H CH3 OCH3 N
47
~ZS56~
48
Table 7
S H~1~503~NHJ~ Z
R N ~
y
,l.. Rll . R12 R13 R R~ ~ m p
O H H H ~ H CH3 OCH3 CH
S H H H H CN~CH3)2 OCH3 OCH3 N
S2 H .H H H H Cl OCH3 CH
NH H H H H H CH3 OCH3 CH
NCH3 H H H H H OCH3 CH3 CH
O CH3 CH3 H H H F CH3 CH
S CH3 CH3 H H H CH3 CH3 CH
2 3 c,l3 H H H CF2H CH3 CH
NH CH3 CH3 H H H CH2F 2 3 CH
3 3 CH3 CH3 CH3 H 2 3 2 3 N
O CH2CH3 CH3 H H H CF3 2 3 CH
S CH2CH3 CH3 H H H OCH3 CF3 CH
S2 CH2CH3 CH2CH3 H H C02 2 3 3 OCF2H CH
NH CH2CH3 CH3 H H H OCH3 OCH3 N
3 2 3 3 H H H OCH3 OCH3 N
O H CH3 H H H OCH3 OCH3 N
S H CH3 H H H OCH3 OCH3 CH
S2 H CH3 H H H OCH2CH3 OCH3 CH
NH H CH3 H H H CH3 C(CH3~0CH3)2 CH
3 .3 H H H CH3 CH3 N
O CH3 CH3 H H H CH3 CH3 N
48
49
Tflble 8
R1~3 N-OR' ~
S02NHJI~N <Y Z
R N =~
Y
Q2 R14 Rls % R~ ~ m.p
O H H H H CH3 CH3 CH
O H CH3 H 3 2 3 CH3 N
O H H H H Cl CH3 CH
15 0 H CH3 H H CH3 CH3 CH
O CH3 H U H OCH3 CH(OCH3)2 CH
O CH3 CH3 H H F OCH3 CH
O CH3 H H H CH3 OCH3 CH
S H CH3 H H OCF2H OCH3 CH
20 S H H H H CH2F OCH3 CH
S H CH3 CH3 H OCH2CH3 CH2SCH3 N
S H H H H CF3 2 3 CH
3 3 H OCH3 OCH3 CH
S 3 2 2 3 3 OCH3 CH
25 S CH3 CH3 H H OCH3 OCH3 N
NH H H H H OCH3 OCH3 N
NH CH3 CH3 H H OCH3 OCH3 N
NH H H H H OCH3 OCH3 CH
NCH3 H 3 H OCH2CH3 CH3 CH
30 NCH3 CH3 H H H CH3 CH3 CH
NCH3 CH3 CH3 H H CH3 CH3 N
3 3 H H CH3 CH3 N
'
49
~;~S5~
Tabl~
LS02NHJ~N~ Z
R N =~
y
L jm 13 16 B R i_
10 L-10 O H 3 H CH3 CH3 CH
L-10 1 ~ -CH3 H 3 2 3 CH3 N
L-10 O H 3 H Cl CH3 CH
L-ll O CH3 - H H CH3 CH3 CH
L-Il O CH3 - H H OCH3 CH(OCH3)2 CH
L-ll O CH3 - H H F OCH3 CH
L-ll O H - H H CH3 OCH3 CH
L-12 1 H - H H OCF2H OCH3 CH
L-12 O H - H- H CH2F OCH3 CH
L-12 1 H - 3 OCH2CH3 CH2SCH3 N
L-13 O CH3 - H H CF3 2 3 CH
L-13 1 H - H H OCH3 OC~3 CH
L-13 O H - 2 2 3 3 OCH3 CH
L-13 1 H - H H OCH3 OCH3 N
L-14 O H - H H OCH3 OCH3 N
25 L-14 1 H - H H OCH3 OCH3 N
L-14 O CH3 - H H OCH3 OCH3 CH
L-10 1 H 3 H OCH2CH3 CH3 CH
L-10 O H C2H5 H H CH3 CH3 CH
L-10 1 H C2HS H H CH3 CH3 N
L-10 O H C2N5 H H CH3 CH3 N
i-
~ZS5~
Sl
T~ble 10
N-OR'
LS02NH ~ N ~/ Z
R N ~
L R17 RlB R R' X Y Z ~C)
15H H CH3 CH3 CH
lS H, ~ -CON(CH3)2 OCH3 CH3 N
lS H H Cl CH3 CH
lS H H CH3 CH3 CH
H H OCH3 CH(OCH3)2 CH
LlS H H H F OCH3 CH.
lS H H CH3 OCH3 CH
LlS CH3 - H H OCF2H OCH3 CH
15 3 H H CH2F OCH3 CH
15 3 3 OCH2CH3 CH2SCH3 N
L16 CH3 - H H .CF3 2 3 CH
16 3 H H OCH3 OCH3 ..... CH
L16 CH3 _ H 2 2 3 3 OCH3 CH
16 3 H H OCH3 OCH3 N
25 16 H H OCH3 OCH3 N
16 H H OCH3 OCH3 N
16 H H OCH3 OCH3 CH
17 3 3 H OCH2CH3 CH3 CH
17 3 H H . CH3 CH3 CH
L17 CH3 CH3 H H CH3 CH3 N
17 3 3 CH3 CH3 N
51
i
~Z~;566~
S2
Table 11
H R
~ N-9R'
R~So2NHJ~N-A
R
R5 6 R a~ A
CH3 ~ H HA2: yl=C~2; X1 CH3
1-C3H7 H . HA2: Yl=O; Xl=OCH3
OC H H H H 2 1 2; 1 2
O-n-C4Hg N H H A3 1 3
F 3-CF3 H C2CH3 A3: Xi=CH2 3
15 Cl H H C2CH3 A4: X1-CH3; 2
N02 H CH3 C2CH3 A4: Xl CH3; 2 3
CF3 H H C2CH3 A5: X2=CH3; Y3 OCH3
C2CH3 H H C2CH3 A5: X2=CH3; Y3 SCH3
- C02CH2CH3 3-CH3 H C2CH3 A5: X2=CH3; Y3 C2HS
20 S02N(CH3)2 H H C2CH3 A6 X3 CH3
S02N(C2H5)2 H H C2CH3 A6: X3=OCH3
oSo2cH2cH3 3 C2CH3 A2 Y1=; Xl=CH2CH3
SCH3 6-C1 H C 2C 3 2 1 2; 1 3
2 3 H H H A2: Y~=; Xl=CH3
25 OCHF2 H H COCH3 A3 X1=OCF2H
OCH2CH=CH2 H H H A : X -OCH
6 5 H H H A4: Xl=OCH3; Y2=CH3
N-N\ H H H A4: ~1=OCF2H; Y~=H
~ .
~ H H H A5: X2=cH2cP3; Y3 3
CH20CH3 H H 6 3 3
CH20CH3 H H 6 3 3
: 52
~25566~
,
53
Tsble_12
~-OR'
Jl
LS02NH ~ `'N-A
R
L R R' A
L-2: R7=S02N(CH3)2 H H A2: yl=CH2; Xl 3
10 L-2: R -OSO CH H H ~2: Yl=O; Xl=OCH3
L-2: R7=Cl . . .. H H 2 1 C82; ~1=0CF2H
L i- R7=Br H H 3 1 3
L-3 R8=CH3 H C02CH3 A3: Xl=OCH2CH3
L 3 8 3 H CO~CH3 A4: ~1=OCH3; Y2
15 L-3: R8=S02CH2CH3 CH3 C02CH3 .A4: Xl=CH3; 2 3
L-4: R9=C02CH3 H C02CH3 ~S X2=CH3; Y3 OC 3
.. L-S: R9=C02-i-C3H7 2 3 S 2 3; 3 3
L-6: R9=Cl H C02CH3 A5 X2=CH3; Y3 2 5
L-4: Rg=NO2 H C02CH3 A6 ~3 CH3
20 L-S: R9-S02N~CH3)2 H C02CH3 A6 X3 OCH3
9 2 5 CH3 co2cH3 A2 Yl=O; Xl 2 3
10 2 3 H C02CH3 A2 Yl=CH2; 1 3
L-7: Rlo=S2N~CH3)2 H H A2: Yl=; Xl 3
L-7: Rlo=OS02CH3 H COCH3 A3 Xl=OCF2H
25 L-8: Rll=R12=R13-CH3; m ; Ql 3 1 3
L-9: R14=CH3; R15=H; Q2 3 H H A4: Xl=OCH3; Y2 3
L-10: R16=C2HS; R13=H; m=l H H A4: Xl=OCF2H; Y~=H
L-ll R13=H; m=O H H A5: ~2=CZHS; Y3=C2HS
13 3; H H S ~2=CH2cF3; Y3=cH3
30 L-13 R13=CH3; m=O H H A5: X2=CH3; Y3 C2HS
L-14 R16=CH3 H H 6 3 3
L-lS: R17=H H H A2: Yl=CH2; Xl=CH3
L-lS: R~7=H H H A2: Yl.=O; Xl=OCH3
L-lS: R17=H H H 2 1 2' 1 2
53
~2S5~
54
T~ble 12 ~contlnued)
L R R' A
17 3 3 1 3
L-16: R1~CH3 H C02C~3 A3 Xl~OCH2 3
1~ 3 H C02CH3 A4: ~l~OcH3; Y2
L-17: R17~H; al8=CH3 CH3 C02CH3 A4: Xl=CR3; Y2GCH3
L-17: R17=H; R18 CH3 H CO CH A5: ~2-C83; Y3=CH3
L-17: R17=H; R18 CH3 H C02CH3 AS: X2=CH3; Y3 SC 3
L-8: R11=R12-R13=H; m=l; Ql 2 C02CH3 AS: X2=Cff3i ~3 C2 5
L-8: Rll=R12.-Rl~=Hi m=1; Ql S 2 C2CH3 A6 ~3=CH3
L-8i Rll=al2=al3=H; m=l; Ql S2 C02cH3 A6 ~3 OCH3
L-9: R14'R15=H; Q2 CH3 C02CH3 A2 Y1=0; Xl 2 3
L-9: R14=R15=H; Q2 H C02CH3 A2 Y1=CH2; ~1 3
L-9: R14=R15 H; Q2 H H A2: Yl=O; Xl C 3
13 16 3; H COCH3 A3: Xl=OCF2H
L-lO: R13=R16=CH3; H H A3 X1 3
13 16 3; H H A4: X1=0CH3; Y2 3
L 11: R13 H3; H H A4: Xl=OCF2H; Y2
~L-ll R13=CH3; m~O H H A5: ~2=C2Hs; Y3 C2 5
13 3; H H A5: X2=CH2CF3; Y3 3
L-12 R13=H; m=l H H A5: Xz=CH3; Y3 C2 5
L-13 R13=H; m=1 H H 6 3 3
L-14: R16=H H H 6 3 3
s4
~56~
Formulation~
Useful fo~mulation~ of the compounds of Formula
I can be prepared in conventional way~. They include
du~ts, granule~, pellet~, solu~ions, suspensions,
5 emulsions, wettable powders, emulsifiable concentrates
and the like. Many of these may be applied directly.
Sp~ayable formulations can be extended in suitable
media and used at spray volumes of from a few liters
to several hundeed liters per hectare. High strength
10 compositions ace primarily used as intermediates for
further formulation. The formulations, broadly, con-
tain about 0.1% to 99% by weight of ac~ive ingre-
dient(s) and at least one of ~a) about 0.1% to 20%
surfactant(s) and (b) about 1% to 99.9S solid or li-
15 quid diluent(s). More specifically, they will containthese ingredients in the following approximate propor-
tions:
Table 13
Weight Percent*
Active
Inqredient Diluent(c~ Surfactant(s)
Wettable Powders20-90 0-74 1-10
Oil SuspensionsL3-50 40-95 0-15
Emulsions, Solutions,
25 (includiny Emulsifiable
Concentrates)
Aqueous Suspension 10-50 40-84 1-20
Dusts 1-25 70-99 0-5
Granules and Pellets 0.1-95 5-99.9 0-15
High Strength so-gg 0-10 0-2
Compositions
Active ingredient plus at least one of a Sucfactant
or a Diluent equals 100 weight percent.
~ZS5~6~
56
Lower or higher levels of active ~ngredient can,
of cour~e, be present depending on the intended use
and the physical properties o the compound. Higher
ratios of 6urfactant to active ingredient are 60me-
times de6irable, and are achieved by incorporatio~in~o the ~ormulation or by tank mixing.
Typical solid diluents are described in Watkins,
et al., "Handbook of Insecticide Dust Diluents and
Carriers", 2nd Ed., Dorland Books, Caldwell, New
10 Jersey, but other solids, either mined or manufac-
tured, may be used. The more absorptive diluents a~e
preferred for wettable powders and ~he denser ones for
dusts. Typical liquid diluents and solvents are de-
scribed in Marsden, "Solvents Guide," 2nd Ed., Inter-
15 science, New York, 1950. Solubility under 0.1~. ispreferred or suspension concentra~es: solution con-
centrates are preferably stable against phase separa-
tion at 0C. "McCutcheon's Detergents and Emulsifiers
Annual~l, MC Publi6hing Corp., Ridgewood, New Jersey,
20 as well as Sisely and Wood, ~'Encyclopedia of Surface
Active Agents~, Chemical Publishing Co., Inc., New
York, 1969, list surfactants and recommended uses.
All formulations can contain minor amounts of addi-
tives to reduce foaming, caking, corrosion, microbio-
25 logical growth, etc.
The me~hods of making such compositions are wellknown. Solutions are prepared by simply mixing the
ingredients. Fine solid compositions are made by
blending and, usually, grinding as in a ham~er or
30 fluid energy mill. Suspensions are prepared by wet
milling (see, for example, Littler, U.S. Patent
3,060,0a4)~ Granules and pellets may be made by
spraying the active material upon preformed granular
carriers or by agglomeration techniques. See J. E.
35 Browning, "Agglomeration~, Chemical Enqineerinq,
S6~
57
December 4, 1967, pp. 147ff. and 'IPer~y'~ Chemical
Engineer'~ Randbook", 5th Ed . ~ McGraw-Hill, New York,
1973, pp. 8-57ff.
For further information regarding the art of
5 formulation, ~ee ~or example:
H. M. Loux, U.S. Patent 3,235,361, February 15,
1966, Col. 6, line 16 ~hrouqh Col. 7, line 19 and
Examples 10 through 41;
R. ~. Luckenbaugh, U.S. Patent 3,309,192,
10 March 14, 1967, Col. 5, line 43 through Col. 7, line
62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,
138-140, 162-16~, 166, 167 and 169-182:
H. Gysin and E. Knusli, U.S. Patent 2,891,855,
June 23, l9S9, Col. 3, line 66 through Col. S, line 17
lS and Examples 1-4;
G. C. Klingman, "Weed Control as a Science",
John Wiley and Sons, Inc., New York, 1961, pp. 81-96;
and
J. D~ Fryer and S. A. Evans. "Weed Control Hand-
20 book", 5th Ed., Blackwell Scientific Publications.Oxford, 196B, pp. 101-103.
In the following examples, all parts are by
weight unless otherwise indicated.
ExamPle 7
25 Wettable Powder
2-t[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-
imino)methyl]aminosulfonyl]benzoic acid, methyl
ester 8~%
sodiu~ alkylnaphthalenesulfonate ~ 2%
sodium ligninsulfonate 2S
synthetic amorphous silica 3%
kaolinite 13%
The ingredients are blended. hammer-milled until
all the solids are essentially under 50 microns, re-
35 blended, and packaged.
~5Si~6:~
5~
Example 8Wettable Powder
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]aminosulfonyl3benzoic acid,
methyl e~ter 50%
sodium alkylnaphthalenesulfonate 2%
low viscosity methyl cellulose 2%
diatomaceous earth 46%
The inqredients are blended, coarsely hammel-
10 milled and then air-milled to produce paeticles essen-
tially all below 10 microns in diameter. The product
is rebiended before packaging.
ExamPle 9
Granule
Wettable Powder of Example 8 5%
attapulgite granules 95%
(U.S.S. 20-40 mesh: 0.84-0.42 mm)
A slurry of wettable powder containing ~25%
solids is sprayed on the surface of attapulgite
20 granules in a double-cone blender. The granules are
dried and packaged.
Examvle 10
Extruded Pellet
~',N'-dimethyl-N-r[1-(4,6-dimethyl-1,3,5-triazin-2-yl)-
amino]-1-~hydroxyimino)methyl]-1,2-benzenedi~ulfon-
amide 25%
anhydrous sodium sulfate 10~
crude calcium ligninsulfonate5%
sodium alkylnaphthaienesulfonate 1%
calcium/magnesium bentoni~e S9
. The ingredients are blended, hammer-milled and
then moistened with about 12~ water. The mixture is
extruded as cylinders abou~ 3 mm diameter which are
cut to produce pellets about 3 mm long. These may be
35 used directly after drying, or the dried pellets may
58
3L~5S6~i~
be crushed to pa~ a U.S.S. No. 20 sieve (O.B4 mm
opening~). The granules held on a U.S.S. No. 40 sieve
(0.42 mm openings) may be packaged for use and the
fines recycled.
ExamPle 11
Oil susPension
N',~'-dimethyl-N-[[1-(4-methoxy-6-me~hylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5~
highly aliphatic hydrocarbon oil 70S
The ingredients are ground together in a ~and
mill until the solid particles have been reduced to
under about 5 microns. The resulting thick suspension
15 may be applied directly, but preferably after being
e~tended with oils oc emulsified in water.
ExamPle_12
Wettable Powder
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-
imino)methyl]aminosulfonyl~benzoic acid, methyl
ester .- 20%
sodium alkylnaphthalenesulfonate ~%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3%
attapulgite 69%
The ing~edients are thoroughly blended. After
grinding in a hammer-mill to produce particles essen-
~ially all below 100 microns, ~he material is re-
blended and sifted through a U.S.S. No. 50 sievè ~0.3
30 mm opening) and packaged.
;566~
Exa~Ple 13
Low Strenqth Granule
N'~N'-dimethyl-N-[rl-(4,6~dimethyl-1,3,5-triazin-2-yl)-
amino~-l-(hydroxyimino)methyl]-1,2-benzenedisulfon-
amide 1%
N,N-dimethylformamide 9S
attapulgite granules 90%
(U.5.5. 20-40 sieve~
The active ingredien~ is dissolved in the sol-
10 vent and the solution is sprayed upon dedusted gran-
ules in a double cone blender. After spraying of the
soiution has been completed, ~he blender is allowed to
run for a short period and then the granules are pack-
aged.
ExamPle 14
Aqueous SusPension
N',N'-dimethyl-N-t[1-(4-methoxy 6-methylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 40S
20 polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether 0.5%
disodium phosphate 1%
monosodium phosphate 0.5%
polyvinyl alcohol 1.0%
25 water ' 56.7%
The ingredients are blended and ground toge~her
in a sand mill to produce particles essentially all
under 5 microns in size.
~L~Z556~L
61
Example 15
olution
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino~-1-
(hydroxyimino)methyl]aminosulfonyl]benzoic acid,
methyl ester 5
water 95
The salt is added directly to the water with
stirring to produce the solution, which may then be
packaged for use.
Example 16
Low Strenqth Granule
2-[[1-(9,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-
imino)methyl]aminosulfonyl]benzoic acid, methyl
ester ~ 0.1~
attapulgite granules 99.9%
(U.S.S. 20-~0 mesh)
The active ingredient is dissolved in a solvent
and the solution is sprayed upon dedusted granules in
a double-cone blender. After spraying of the solution
20 has been completed, the material is warmed to evapor-
ate the solvent. The material is allowed to cool and
then package~.
E~
Granule
2-[[1-(4-methoxy'6-methylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]aminosulfonyl]benzoic acid,
methyl es~er 80%
wetting agent 1%
crude ligninsulfonate sal~ (containing 10%
5-20% of the natural sugars)
attapulgite clay 9%
The ingredients are blended and milled to pass
through a 100 mesh screen. This material is t~en
added to a fluid bed granulator, the air flow is ad-
justed to gently fluidize the material, and a fine
62
spcay of water i~ sprayed onto the fluidized ma-
terial. The fluidizatisn and speaying are continued
until granules of the desired size range are made.
The spraying is stopped, but fluidization is con-
S tinued, optionally wi~h heat, until the water contentis eeduced ~o the desired level, generally less than
1~. The ma~erial is then discharged, screened to the
desi~ed size range, generally 14-100 mesh (1410-149
microns), and packaged for use.
ExamPle 18
Hiqh Strenqth Concentrate
. . .
N' ,N' -dimethyl-N-t[1-(4-methoxy-6-methylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 99%
silica aerogel 0.5%
synthetic amorphous silica 0.5s
The ingredients are blended and ground in a
hammer-mill to p~oduce a material essentially all
passing a U.S.S. No. 50 screen (0.3 mm opening). The0 concentcate may be ~ormu~ated further if necessary.
ExamPle 19
Wettable Powder
N',N~-dimethyl-N-[tl-(4,6-dimethyl-1,3,5-triazin-2-yl)-
amino]-l-(hydroxyimino)methyl]-1,2-benzenedisulfon-
amide 90Sdioctyl sodium sulfosuccinate 0.1%
6ynthetic fine silica 9.9%
The ingredien~s are blended and ground in a
hammer-mill to produce particles essentially all below
30 100 microns. The material is sif~ed ~hrough a U.S.S.
No. 50 screen and then packaged.
62
~SS66gL
ExamPle 20
Wettable Powder
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-
imino)methyl]aminosulfonyl~benzoic acidO methyl
es~er ~0%
sodium lign;nsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely
hammer-milled and then air-milled to produce particles
10 essentially all below 10 microns in size. ~he
material is replended and then packaged.
Example 21
oi 1 SusPension
N',N'-dimethyl-N-[~l-(dimethyl-1,3,5-triazin-2-yl)-
amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-
amide 35%
blend of polyalcohol carboxylic 6%
esters and oil soluble petroleum
sul~onates
20 ~ xylene 59%
The ingredient~ are combined and ground togetherin a sand mill to produce particles essentially all
below 5 microns. The product can be used directly,
extended with oils~ or emulsified in water.
Example 22
Dust
2-t[1-(4-me~hoxy-6-methylpyrimidin-2-yl)amino~-1-
(hydroxyimino)methyl]aminosulfonyl]benzoic acid,
methyl ester 10%
attaQulgi~e 10~
. Pyrophyllite 80%
The active ingredient is blended with attapul-
gite and then passed through a hammer-mill to produce
particles substantially all below 200 microns. The
ground concentrate is then blended with powdered pyro-
phyllite until homogeneous.
~3
~2~S~
64
Exam~le 23
Emulsifiable Concentrate
N',N' -dimethyl-N-[ tl-(4-methoxY-6-1nethylpyrimidin-2-
yl)amino]-l-(hydroxyimino)~ethyl]-1,2-benzenedi-
sulfonamide 20Schlorobenzene 74%
sorbitan monostearate and polyoxyethylene
condensates thereof 6~
The ingredients are combined and stirred to pro-
10 duce a solution which can be emulsified in water foeapplication.
. . .
_tilitY
The compounds of the present invention are
15 active herbicides. They have utiiity for broad-
spectrum pre-and/or post-emergence weed control in
areas where complete control of all vege~ation is de-
sired, such as around fuel storage tanks, ammunition
depots, industrial storage areas, parking lots, drive-
20 in theaters, around billboards, highway and railroad
structuces. Alte~natively, the subject compounds are
useful for the selective pre- or post-emergence weed
control in crops, such as wheat and barley.
The rates of application for the compounds of
25 the invention are determined by a number of factors,
including their use as selective or general herbi-
cides, the crop species involved, ~he types of weeds
to be controlled, weather and climate, formulations
selected, mode of application, amount o~ foliage pre-
30 sent, etc. In general terms, the su~ject compounds
should be applied at levels of around 0.03 to 5 kg/ha,
the lower rates being sùggested for use on lighter
soils and/or those having a low organic mattec con-
tent, for selective weed control or for situations
35 where only short-term persis~ence is required.
64
~2S56~
The compounds of the invention may be used in
combination with any other commercial herbicide exa~-
ples of which are tho~e of the triazine, triazole.
uracil, urea, amide, diphenylether, carbamate and
5 bipyridylium ~ypes.
The herbicidal properties of the subject
compounds were discovered in a number oÇ greenhouse
test~. The test procedures and results follow.
.
.. . .
~2~5~
66
est ~
Seeds of crabgrass (Di~itacia 6pp. ), barnyard-
grass (Echinochloa crus~alli), wild oats (Avena ~ L,
sicklepod (Cassia obtusi~olia~, morningqlory (IPomoea
5 spp.), cocklebur (Xanthium pens~lvanicum), sorghu~,
corn, soybean, sugar beet, rice, w~eat, and purple
nutsedge (CYperus rotunduY) tuber were planted and
treated preemergence with the test chemi~als dissolved
in a non-phyto~oxic solvent. At the same time, these
10 crop and weed species, along with cotton and bush
bean, were treated with a soil~foliage application.
.
At the time of treatment, the plants ranged in height
from 2 to 18 cm. Treated plants and controls were
maintained in a greenhouse for sixteen days, after
15 which all species were compared to controls and
visually rated for response to treatment. The
ratings, summarized in Table A, are based on a
numerical scale extending from 0 = no injury, to
10 = complete kill. The accompanying descriptive0 symbols have the following meanings:
C = chlorosis/necrosis;
E = emergence inhibition:
G = growth retardation;
H = formative effect;
U = unusual pigmentation; and
6Y= abscised buds or flowers.
Note that co~pounds tested are highly ac~ive
herbicides at the low rates of application selected
for this tes~.
66
~ z556~
67
Compounds
Compound 1
NOH N~ 3
~ S 2 ~ N H - C - NH -< .0~>
Cl CH3
10 Compound 2
NOH Nl 3
~S02-NH-C-NH -< ,0~
Cl OCH3
Compound
N O H N
'. ~Sb2-NH-C-NH~O~
N
Cl orH3
Compound g
OCH3
, ~ NCH N ~
<~ S 2- N H- C -N H~O N
: Cl OC H3
3 0 Compound 5
CH3
N OC C H~
N
3 5 .. Cl CH3
67
~Z~ 6~
6a
Compounds (con~tinued)
Compound 6 CH
NOH N--~ 3
~ n ~O~
COOI:H3 CH3
CmPOUnd 7 OCH3
NOH N~
~S02-NH-C-NH <O~
COOCH3 CH3
Compound 8
OCH
NOH N l 3
~S02-NH-C-NH~O~
5o2NtcH3)2 CH3
.. ..
Compound 9
OCH
~_ NOH N~ ~
502NtCH3)2 OCH3
68
566~
69
Table A
Cmpd. 1 Cmpd. 1 Cmpd. 2 Cmpd. 3
S Rate kg/ha .05 0.4 .05 .05
POST-EMERGENCE
Bush bean 3C,7H,6Y 9C 9C 9C
Cotton 5C,7H 6C,9G 4C,9G 3C,9G
Morningglory 3C 4C,8G 2C,9G 3C,8H
10 Cocklebur 3G 8G 3C,9G 3C,8H
Sicklepod 2C 3C,8G 2C,8G 4C,9G
Nutsedge 2C,6G 10C 4C,9G 9C
Crabgcass 0 2C,8G lC,3H 2C,3G
Barnyardgrass 2C,6H 9C 5C,9H 2C,9H
Wild Oats lC lC,7G 0 2C,4G
Wheat lC lC,9G 0 3G
Corn 2U,BH 6U,9G 3U,9G 2U,9G
15 Soybean lC,3H 4C,9G 2C,9H 3C,9H
Rice 2C,8H 5C,9G 3C,9G 4C,9G
Sorghum lU,9G SU,9G . 2C.9G 2C,9G
Sugar beet - - - -
PRE-EMERGENCE
Morningglory 3C 8G 9G 9G
20 Cocklebur 2C,7H 8H 9H
Sicklepod 2C,5G 3C,9G 2C,BG 9G
Nut~edge SG 3C,9G 2C,5G 10E
Crabg~ass 0 3C lC,3G lC,SG
Barnyardgrass 3C,6H 3C,9H SC,9H 9H
Wild Oats 0 2C,7G SC,9G 8G
Wheat 3G 2C,8G 4C,9G 2C,8G
Corn 2C,6G lC,9G 2C,9G 2C,9H
25 Soybean 2C 3C,6G 3C,8H 7H
~ice 4C,6G 10E SC,9G 10E
Sorghum 2C,7H 3C,9H 4C,9G lC,9H
Sugar beet - - - -
69
Table A (conti~ L
Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7
5 Rate kg/ha .05 .05 .05 .05
POST-EMERGENCE
Bush bean lC 5C,9G,6Y 3C,6H,6Y 9C
Cotton 4C,8G ~C,8H ZC, SG 6C, 9G
Morningglory 3C,8G 3C,5G 3G 2C,7G
10 Cocklebur 2C 5G 4G ~C, 9H
Sicklepod 5C,9G lC 3G 9C
Nut~edge 0 3C,8G 7C,9G lOC
Cfabgras~ 3C 2H lOC 4C,9G
Barnyardgrass 2C,5H 3C,8H 4H 9C
Wild Oat~ 0 2C O 5C,9H
Wheat O lC O 5C,gG
Corn 2G 3C 8H 2C 8H 5C 9G
lS Soybean 3C,8G 2C 7H 2C 2H 5C 9G
Rice ~ 3G 3C,9H 2C,8H 5C,9G
Sorghum 3G 3C,9G 2C,9H 4U,9G
Sugar beet - - 2C lOC
PRE-EMERGENCE
Morningglory 9G 3C 2C,~G 8H
20 Cocklebur 9H 9H 9H 8H
Sicklepod 9G 3C,8~ 2C,5G 2C,9G
Nutsedge 9G 3C,8G 2C,5G lOE
Crabgrass 3G 2C lC 2C
Barnyardgrass 2C,5G 5C,9H 2H ~C,9H
Wild Oats lC 2C,8G 2C, 8G 3C,9G
Wheat lC 3C,9G 9G 2C,9H
Corn 2C,8G 4C.9H 9G 3C,9H
25 Soybean 8H 3C,SH 4C,7G 3C,7H
Rice 6G 5C,9H 3C,8H lOE
Sorghum 2C,5G 4C,9H 2C,9~ 2C,9G
Sugar beet - - 2C,9G 9C
~i5~
Table A (cont;nued~
Cmpd. 8 Cmpd. 9
5 Rate kg~ha .05 .05
POST~EMERGENCE
Bush bean 5C,9G,6Y 5C,9G,6Y
Cotton 9C
Morningglory 5C,9G 5C,9G
Cocklebur ~C,9G 4C,9G
10 Sicklepod 3C,8G 4C,3H
Nu~sedge 2C,7G 5G
Cr~bgrasfi 2C,9G 2C,8G
Barnyardgrass 2C,9H 5C,9H
Wild Oats 2C,8G O
Wheat 5C,9G 0
Corn 3U,9H 9C
15 Soybean 2C,9H 9C
Rice SC,9G SC,9G
Sorghum 2C,9G 9C
Sugar beet 3C,9G ~C
PRE-EMERGENCE
Morningglory 9C 9C
Cocklebur 9H
20 Scklepod 5C,9G 2C,9G
Nutsedge 10E 6G
Crabgrass 3C,9G 2C,6G
Barnyardgrass 9C,9H 3C,9H
Wild Oats 3C,9G 3C,9G
Wheat 10C lC,6G
Corn 9G SC,9H
25 Soybean 3C,9H 9H
Rice 10E 10E
Sorghum 5C,9H 5C,9H
Sugar beet 5C,9G 9C
.
12SS66~
Test B
Two plastic bulb pans were filled with ferti-
lized and limed Woodstown sandy loam. One pan was
planted with corn, sorghum, Kentucky bluegrass and
several grass weeds. The other pan was planted with
cotton, soybeans, purple nuts~!dge (CYPerus rotundus),
and several broadleaf weeds. The following grass and
broadleaf weeds were planted: crabqrass (Diqitaria
sanquinalis), barnyardgrass (Echinochloa crusqalli),
~0 wild oats (Avena fatua), johnei;ongrass (Sorqhum hale-
pense), dallisgrass (PasPalum dilatatum), giant fox-
tail (Setaria faberii), cheatgra~s (~romus secalinus),
mustard (Brassica arvensis), cocklebur (Xanthium Pen
sylvanicum), pigweed (Amaranthus retroflexus), morn-
ingglory (Ipomoea hederacea), sicklepod (Cassia obtu-
sifolia), teaweed, (Sida sPinosa), velvetleaf (Abu-
tilon theophrasti), and jimsonweed (Datura stramo-
nium). A 12.5 cm diameter plastic pot was also filled
with prepared soil and planted with rice and wheat.
20 Another 12.5 cm pot was planted with sugar beets. The
above four containers were treated preemergence with
several test compounds within the scope o~ the inven-
tion.
Twenty-eight days after treatment, the plants
25 were eva~uated and visual}y rated for response to the
chemical treatments utilizing the rating system de-
scribed previously for Test A. The data are sum-
marized in Table B.
5~6~L
73
Table ~
PRE-EMERGENCE ON
WOODSTO'~N S~NDY_LOAM
Compound 1 Compound 2
Rate kg/ha 0.120 0.500 0.030 0.120
lo
Crabgra~s 2G 5G 2G 4G
Barnyardgrass 8G,3H 10C 7G,3H 9G,SH
Sorghum - - 7G,5H 9G,5H
Wild Oats 2G 5G 4G SG
Johnsongrass SG,3~ 8G,3H 4G,3H 6G,2H
Dallisgrass 6G 8G,5H 2G 4G
Giant ~oxtail 6G,SH 8G,5H 4G 6G,3H
Ky~ bluegrass 8G,8C 10C 6G 7G
Cheatgrass 6G,3C 10C 8G,8C 8G,9C
Sugar beets 8G,8C 10C 8G,8C 10C
Corn 7G,SH 9G,8C 6G,3H 7G,3H
Mustard 9G,9C 10C 9G,8C 9G,9C
Cocklebur 6G 7G,3H ~G SG
20 Pigweed 8G 10C
Nutsedge 7G 10E 7G 7G
Cotton 3G 8G 3G SG,3H
Morningglory 0 6G,SH 4G 9G,5C
Sicklepod 6G 7G 7G 8G,3H
Teaweed 5G 8G,3H 5G lOC
Velvetleaf 6G,SH 9G,9C SG,5H aG,9C
Jimsonweed 6G 7G 7G BG,8C
2S Soybean 3G 6G,SH 3G,3H 6G,SH
Rice 9G,9C 10C 7G,8C 10C
Wheat 4G 6G 0 4G
35
~L~5S6~L
Table B (continued~
PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM
Compound 3 Compound 4
Rate kg/ha 0.030 0.120 0.007 0.030
Crabgrass 0 6G 0 0
Barnyardgrass 6G,2H 8G,SH 0 3G
Sorghum 6G,3H 9G,SH 0 0
Wild Oats 3G 6~ 0 0
Johnsongrass ~G,2H 7G,5H 0 0
Dallisgrass 0 SG 0 0
Giant oxtail 3G 7G,3H 0 0
Ky. blueg~ass SG,3H 7G,3H 4G O
Cheatgrass 8G,8C 8G,9C 0 0
Sugar beets 10C 10C 6G 8G
Corn 5G,3H 7G,3H 2G 3G
Mustard 9G,SH 9G,9C 9G gG,9C
Cocklebur 0 3G 0 ZG
20 Pigweed 10E 10E - -
Nutsedge 9G,9E 10E 0 5G
Cotton 2G 4G 2G 5G
Morningglory 3G 3G 0 7G
Sicklepod 8G 8G 5G 6G
Teaweed 7G 8G 6G 9G
Velvetleaf 7G,5H 9G,8C SG,5H 8G
Jimsonweed 5G 6G 0 4G
Soybean 3G 6G,5H 5G 8G
Rice 8G,8C 10E 0 SG
Wheat 2G 4G 0 0
74
~25SG61
Table 8 (continued2
PRE-EMERGENCE ON
WOODSTOWN_SANDY LOAM
Compound 5
Rate kg/ha 0.030 0.120
Crabgras6 ~ o
Barnyardg~ass 2G 3H,BG
Sorghum 2G ~H.8G
Wild Oa~s 0 2G
Johnsongrass 0 2H,4G
Dallisg~ass 4G 8G
15 Giant foxtail 3H,4G 5H,8G
Ky. bluegrass 6G lOE
Cheatgrass SG 8G
Sugar beets 5G 8G
Corn 3G 3H,7G
Mustard 9G,9C 9G,9C
Cocklebur 2G 2G
Pigweed - -
20 Nutsedge 2G 6G
Cotton 3G SG
Morningglory 2G 2G -
Sicklepod 2G SG
Teaweed O O
Velvetleaf O SG
Jimsonweed 0 4G
25 Soybean 3G 3G
Rice 8G 9G,9C
Wheat 2G 3G
~L~5~
76
Test C
The test chemicals, dissolved in a non-phyto-
toxic solvent, were applied in an overall spray to the
oliage and surrounding soil ~f selected plant spe-
S cies. One day after trea~ment, piants were checkedfor rapid burn inju~y. Approximately fourteen days
after treatmen~ all species were visually compared to
untreated controls and rated for response to treat-
ment. The rating system was as described previously
for Test A. The data are presented in Table C.
All plant species were seeded in Woodseown sandy
loam soil and grown in a greenhouse. The following
species were grown in soil contained in plastic pots
(25 cm diameter by 13 cm deep): soybeans, cotton,
alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abu-
tilon theoPhcasti), sesbania (Sesbania exaltata),
sicklepod (Cassia obtusifolia), morningglory (IPomoea
hederacea~, jimsonweed (Datura stramonium), cocklebur
( _nthium pens~lvanicum), crabgrass (Diaitaria spp.),
nutsedge (C~perus ~otundus), bacnyardgcass (Echino-
chloa crus~alli), giant foxtail (Setaria faberii), and
wild oats (Avena fatua). The following species were
grown in soil in a paper cup tl2 cm diameter by 13 cm
deep): sunflower, sugar beets, and rape. All plants
were sprayed approximately 14 days aftec planting.
Additional plant species, such as johnsongrass and
field bindweed, are sometimes added to this test in
order to evaluate unusual selectivity.
76
~566~
77
Table C
Over-the-Top Soil~Foliage Treatment
Gompound 2 Compound 5
Rate, kg/ha 0.015 0.004 0.06 0.015
: Soybeans 8G,6C 6G 3G O
10 Velvetleaf O O 4G O
Sesbania O - O
Sicklepod- O O O O
Cotton 3G 3G 3G 3G
Morningglory 2G C 4G 3G
Alfalfa 7G 5G 4G 3G
Jimsonweed 3G O O O
Cocklebur O - 2G 3G
Sunflower 2G O 3G lG
Rape 2G O SG O
Sugar beets 2G O
Corn 2G O lC O
Crabgrass 4G O O O
Rice 6G 2G 6G 6G
Nutsedge O O O O
Barnyardgrass 0 3G O O
Wheat O O O O
Giant Foxtail 2G 4G O O
Wild Oats O O O O
Sorghum 3G 5G 8G 6G
Johnsongrass O O O O
Field Bindweed 3G O O O
.
66~
78
Test D
Two ten-inch in diameter plastic pans lined with
polyethyleae liners were filled with ptepa~ed Wood~-
town sandy loam soil. One pan was planted with seeds
5 of wheat (Triticum aestivum), barley (Hordeum vul-
qare), wild Odts (Avena fatua3, downy beome (_romus
tectorum), cheatgrass (Bromus secalinus)~ blackgrass
(AloPecurus mvosuroides), annual bluegrass (Poa
annua), green foxtail (Setaria viridis), quackgrass
10 (AqroPyron rePens), Italian ryegrass (Lolium multi-
florum) and ripg~t brome (Bromus riqidus), The other
pan was planted with seeds of Russian thistle (Salsola
kali), tansy mustard tDescuraina pinnata), cleavers
(Galium ~ ), tumble mustard (SisYmbrium altis-
15 sium), kochia (Kochia scoparia), shepherd~s purse(Capsella bursa-pastoris) Matricaria inodora, black
nightshade (Solanum niqrum), yellow rocket (8arbarea
vulqaris), rapeseed (~rassica naPus), and wild buck-
wheat (PolYqonum convolvulus). The above two pans
20 were treated preemergence. At the same time, two pans
in which the above plant species were growing were
treated postemergence. Plant height at the time of
treatment ranged from 1-15 cm depending on plant
species.
The compound~ applied were diluted with a non-
phytotoxic solvent and sprayed over the top of the
pans. An untrea~ed control and a solvent-alone con-
trol were included for comparison. All ~reatments
were maintained in the green~louse for 19-21 days at
30 which time Che treatments were compared to the con-
trols and the efects visually rated. The recorded
data are presented in Table D. Some o~ the compounds
tested have utility for selective weed control in
cereal crops such as wheat and barley.
78
~5~6~
79
Table D
Compound 2
S Pre-Eme~gence Post-Emergence
Rate kg/ha 0.060 0.015 0.060 0.015
whea~ 7G 2G 6G 3G
barley lC,7G 2G 6G 3G
10 wild oats lC,7G 5G 5G 2G
downy brome 2C,9G 8G BG 7G
cheatgrasfi lC,9G 8G 8G 7G
b~ackgrass 2C,8G 7G SG 3G
annual bluegrass 8G 7G 7G 3G
green Soxtail 2C,8G 2C,4~ 2C,8G 4G
quackgrass 9G 8G 8G 6G
Italian ryegrass lC,aG 7G 4C,8G 7G
lS cipgut brome 8G 8G 2C,8G 7G
Russian thistle 2C,3G 2G 8C,8G 4C,5G
tansy mustard 2C,9G 9G BC,8G SC,7G
Galium aparine 6G 8G 7G 4G
tumble mustard lC,8G 9G lOC 7G
kochia 7G SG 3C,8G 4G
shepherd's purse 2C,9G 9G 4C,9G 7G
20 Matricaria inodora 7G 7G 8C,8G 2C,7G
bla~k nightshade 8G 5G 6G 6G
yellow rocket 9G 8G 7G SG
rapeseed 2C,9G 9G l~C 2C,8G
wild buckwheat 7G 6G 7G 4G
.
79
~L ~2 LJ~ ~i 6 6 31.
Table D (continued)
Compound 3
S Pre-Emergence Post-Emergence
Rate kg/ha 0.060 O.OlS 0.060 0.015
wheat 3G 0 3G 0
barley 3G 0 5~ 0
wild oats 5G 3 4G 0
downy brome gG ~G 9G 7G
cheatgrass 2C,9G 7G 8G 6G
blackgrass 7G 6G 6G 3G
annual bluegrass 7G 6G 2C,8G 3G
green foxtail 2C,6G 3G 2C,6G 6G
quackgrass 9G 8G RG 7G
Italian ryegrass ~G 8G 2C,BG 6G
15 ripgut brome 8G 6G 7G 6G
Russian thistle lC,2G 0 ~C,8G
tansy mustard 9G 9G lOC 9G
Galium aparine lOE 8G 6G SG
tumble mustard 2C,9G 9G lOC 9G
kochia 8G 2C,5G 2C,8G 5G
shepherd's purse 9C,9G 9C,9G lOC 2C,8G
20 Matricaria inodoea 8G 9G 8C,8G 8C,8G
black nightshade 6G 3G 7G 6G
yellow rocket sG 7G 8C,8G 8C,8G
rapeseed 3C,9G 9G lOC lOC
wild buckwheat 6G 4G 2C,8G 7G
~Z~56~
81
Table D (continued)
Compound 5
Pre-Emergence Pos~-EmergenCe
Rate kg/ha 0.060 0.250 0.060 0.250
wheat lC,2G SG 2G 7G
barley 6G 2C.8G 3G 7G
10 wild oats SG 7G 3G 5G
downy brome SG 8G 5G 6G
cheatgras~ 6G 8G 5G 7G
blackgras6 SG lC,7G 6G 2C.7G
annual bluegrass 6G lC,8G 4G 3C,8G
green foxtail 0 2C,6G 0 2C,SG
quackgrass 45 8G 2G 6G
Italian ryegrass 8G 2C,9G 2C,6G 2C,8G
15 ripgut brome 6G lC.8G SG 7G
Russian thistle 0 2C,5G 0 lOC
tansy mustard 8G 2C,9G SG 8G
Galium aparine 9G lOE 0 3G
tumble mustard 7G 9G 0 6G
kochia - - - o
shepherd's purse 2C,9G lOC SG lOC
20 Matricarla inodora 8G 9G 3G 9G
black nightshade 0 5G 0 4G
yellow rocke~ 8G 9G o 6G
rapeseed 2C,8G 9G 7G- 9C,9G
wild buckwheat 0 6G 0 3G
This application is a division of copending
Canadian Application Serial No. 443,738 filed
1983 December 20.
81
