Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
.iLæ~
Title BA-8479-A
HERBICIDAL N-HYDROXY-N'-SULFONYLGUANIDINES
Backqround of the Invention
This invention relates ~o certain novel
N-hydroxy-N'-sul~onylguanidine compounds. to compo-
sitions containing such compounds, and to a method of
use of such compositions to control the growth of
undesired ~egetation.
U.S. Patent 4,127,405 issued November Z8, 1978
discloses substituted triazinyl arylsulfonylurea com-
pounds of the following formuia:
.. . . ..
W N~
R - S2 -NH-C-NE~O N
N~
Z
while U.S. Patent 4,169,719 issued October 2, 1979
discloses substituted pyrimidinyl arylsulfonylurea
compounds of the following formula:
X
W N~
Rl-502-NH-C-NH ~ O,_~
N
Z
The triazine and pyrimidine compounds within the scope
of the '405 and ~719 patents include those wherein W
can be oxygen or sulfur. .
U.S. Patent 4,310,346 issued Januacy 12, 1982
discloses sulfonylisothiourea compounds of the formula
.
SO A X
Z S-B N ~
~502N=C-NH~
Rl Y
,
/
.~ .
,
' ' ~ ,
:L~345'Ddl
wherein
B is Cl-C6 alkyl, CH2CH20CH3,
CH2CH2CH2CH3' CHZCH2CH20C~3' CH2Q' CH-Q
CH,~
where Q is
O / CH3 0
C02-C1 3 alkyl, -CN -CN(Cl 3 alkYl)2
OCH3
O O
ll ll
-cN~I(cl-c3 alkYl)' CNH2'
phenyl, phenyl substituted with chlorine, CN,
C2 4 alkenyl, C2 4 alkynyl, ORll, where
Rll is C}-C~ alkyl, -CH20CH2CH20CH3
or -CH20CH2CH20CH2CH3.
South African Patent No. 79/2657, published
June 30, 1980 discloses sulfonylisothiourea compounds
of the formula
X
SR2 N ~
Rl-S02N=C-NH ~ O Z
Y , .
wherein
~2 is Cl-C20 alkyl; CH2CH20CH3:
CH2CH20cH2cH3; CH2CH2CH2 3
CH20A' where A' is Cl-C12 alkyl,
-CH2CE~20CH3, -CH2CH20CH2CH3,
phenyl or phenyl substituted with
1-2 N02, 1-2 Cl, or 1-2 CH3:
CH2A, CH-A where A is C02tH, Cl-C4 alkyl),
O ~ Cl-C4 alkyl~ O / Cl-C~ alkyl
CN , CN
H \ Cl-C4 alkyl,
:
:: 2
, ~
.' ' :
~:3~
O / CH3 0
CN , CNHz , phenyl, CN, C2-C4
\ OCH3
alkenyl, Cl-C4 alkynyl, phenyl substi-
tuted with 1-2 CH3, 1-2 NOz, 1-2 OCH3,
1-2 chlorine or phenoxy.
U.S. 4,301,286 issued November 17, 1981 dis-
closes O-alkylsulfonylisoureas of the formula
W
RS02N=C-NHR
wherein
W is Cl, Br or OR12: and
R is Cl~C12 alkyl, C3-C4 alkenyl, CH2CH20CH3,
2 20CH2CH3, (CH2)30CH3, benzyl,
CHR C02Rl , where R1 is H or CH3 and
R 4 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.
'~
~ ,-
~ 3
. ~
~3~
Summary of the Invention
The novel sulfonylguanidine compounds 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 safety to wheat
and barley. Specifically, the invention relates to
novel compounds of formula ~, agriculturally suitable
compositions containing them and their method-of-use .
as pre-emergent and~or post-emergent herbicides or
plant growth regulants.
.. . .
N-OR'
L-502NHCN-A
I
wherein
R is H or CH3;
R' is H, C(O)Rl. Cto)NR2R3 or CO2R4;
Rl is Cl-C3 alkyl or CF3;
R2 is H- CH3 or C2H5
R3 is Cl-C3 alky};
R4 is Cl-C3 alkyl:
L is ~ , ~ ~ R8
L-l L-2 L-3
Rg
L-4 L-S L-6
~ -
.
.
, . .
.
:~3~
CRz- ~ Q~ R z
L-7 L-3
~ 2 ~)m
L-9 L-lO L-ll
~ ~ Cl
L-12 L-13 L-14
~ Rl7 ~ ~ 17 ~ R16
~ L-15 L-16 L l7
R5 is Cl-C4 alkyl, Cl-C4 alkoxy, OCH2CHzOCH3,
F. Cl, Br, NO2. CF3, C02Rl9, SO2NR20 21
S02N(OCH3)CH3, OS02R22, S(O)nR23, 3
WCHF2, C3-C4 alkenyloxy, C3~Cq alkynyloxy,
Ci-C2 alkyl substi~uted with OCH3 or
S
,
;
:
.
~3~
N-N N-N
OCHzC~3~ C6H5 ~ o ~ CH3 ' O
~N , ~ ~ ~ ~ S , ~ O
1~=\ /~=\ r--
N,N-CH3 ' `N ~ N`N~ -
~ , ~ or ~
R6 is H, F, Cl, Br, CF3, CH3, OCH3,
SCE~3 or OCF2H;
R7 is H, CH3, OCH3, F, Cl, Br, SO2N(CH3)2,
OSO2CH3 or S(O)nCH3:
~8 is CH3, CH2CH3, OCH3, OCH2CH3, F, Cl,
2 R20R21~ 52N~CH3)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~ C2CH3' C2CH2CH3'
SO N(CH3)~, OSO2CH3, 5O2CH3~ SOzC 2 3 3
OCH2CH3:
Rll is H, CH3 or CH2CH3
RI2 is H, CH3 or CH2 3
R13 is H or CH3;
Rl~ is H or CH3:
R15 is H or CH3:
R16 is CH3 or CH2CH3:
R17 is H or Cl-C4 alkyl;
R18 is H or CH3;
R19 is Cl-C4 alkyl, CH2CH2OCH3,
CH2CH2Cl or CH2CH-CH2;
. ~ 6
, . . .
.~34~7~
R20 is Cl-C3 alkyl;
R21 is C~-C alkyl;
R22 is Cl-C3 alkyl or NtCH3)2;
R23 is Cl-C3 alkyl or CH2CH_CHz:
5m is O or 1:
n is O or 2:
Ql is 0, S, S02 or NR17:
Q2 is 0, S or NR17: and
W is 0, S or S02:
N ~ N Xl N ~ 1
Y Y
A-l A-2 A-3
N Xl /X2 OCH3
~ O ~ ~N~ yH2 ~ O N
Y2 x3
A-4 A-5 A-6
X is CH3, OCH3, OCH2CH3, C1, F, Br, OCF2H,
CH2P or CF3;
Y is H, CH3, OCH3, OCH2CH3, CH20CH3,
2 2CH3, N(CH3)2 CHzCH3~ CF3, SCH3,
OCH2CH=CH2, 0CH2C--CH, OCH2CF3, OCH2CH20CH3,
:
CH25CH3, OCF2H, SCF2H~ CR24(QCH3)2~ \24
/Q ~ /Q ~ CH3
CR24 ~ , C\2qJ orCR24(QCH2C~3)2;
~Q ~ Q
35: Q is O or S;
:
:
:
~3~$~
~2~ is ~ or CH3;
Z is CH or N;
1 2
Xl is CH3, OCH3, OC~2CH3 oc OCF2H;
s Y2 is H or CH3;
X2 is CH3. CH2CH3 or CH2CF3;
Y3 is OC~3, OCH2CH3, SCH3, CH3 or
CH2CH3;
3 3 3
lo provided that
1) the total number of carbon atoms of R20
and R21 is les6 than or equal to four:
2) when m is 1. then R13 is H;
3) when L is L~17, then R17 and R18 are not
simultaneously H; and
q? when X i6 Cl, F or Br, then Z i6 CH and Y is
OCH3. OCH2CH3, N(CH3)2 or OCF2H.
This invention also relates to novel compounds
of Formula II, suitable agricultural compositions ,
containing them and their method of use as general or
selective preemergent or postemergent herbicides 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 tha~
1) when L is L-l and A is A-l, R5 is C2-C4
alkyl, C2-C4 alkoxy, OCH2CH20CH3. 05O2R22,
( )nR23' WCY2~ WC~IF2- C3-C4 alkenyloxy~
:.
:
9 ~;~3~57:~
C3-C4 alkynyloxy, Cl-C2 alkyl substituted
with OCH3 or OCH2CH3, C6H5,
~ O > ~,N , ~ ,O , ~ S
~N~ r~
~ ' ~N~N-CH 3 ' N~N ' -N`N J
~ ~ or ~
2) when L is L-l and A is A-2 or A-3, then
R5 is Cl-C4 alkyl, C2-C4 alkoxy,
lS OCH2CH2OCH3, Br, OSO~R22, WCF3, WCHF2,
C3-C4 alkenyloxy, C3-C4 alkynyloxy, Cl-C2
alkyl substituted with OCH3 or OCH2CH3,
O C~
N N ~ ~ N=NI
'o ~N ~N ' ,~S
r ~ ~ ~ rN
0 , N,N-CH3 , N~N ~N~
~ , ~ or ~
3) when L is L-3 and A is A-l, A-2 or A-3,
8 is S02NR2o~21, S02NtOCH3)CH3 or
S2R23;
4) when L lS L-4, L-5 or L-6 and A is A-l,
: A-2 and A-3, then R9 is C1-C3 ~lkyl, F,
Cl, Br, N02, sO2NR20R2l~ S02 ( 3 3
or S(O)nR23; and
5) when L is L2 then A is ~5 or A6.
,
'
Preferred fsr reasons of their higher herbicidal
activity, greater plant growth regulant activity or
more favorable ease of synthesis are:
1) Compounds of Formula I where R is H, R~ is H
s and A is A~l.
2) Compounds of Preferred 1 where Y is CH3,
3' 2 3~ H20CH3, OCH2CF3 or CH~OC 3)2
and X is CH3, OCH3, Cl or CF3.
3) Compounds of Preferred 2 where L is L-l,
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,
2 2 3' 2 (CH3)2~ 02N~OcH3)cH
2 22~ S()nR23, OCF2H, SCF2H,
N-N
O_H2CH=CH2, OCH2C_CH, ~ O ~ CH
O-N - N-O N-N
~ ' ~ or ~ \
R22 is Cl-C3 alkyl:
23 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, S02CH3 or S02N(CH3)2-
7) Compounds of Preferred 3 where L is L-5 and
Rg is C02CH3 or :CO~CH2CH3.
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 Preerred 3 where L~is L-16.
12): Compounds of Preferred 3 where L is L-17.
13) Compounds of Formula II where R is H and A
is A-l. :
: - :
: : ~
,
~:
,:
'
~23~
11
14) Compounds of Preferred 13 where Y is CH3,
3' 2 3' 2 3' 2 3 r ( 3)2
and X is CH3, OCH3, Cl or CF3;
15) Compounds of Preferred 14 where L is L-l
and R5 is S~R22~ 52R23' CF2 2
N-N O~N
OcH2cH=cH2~ OCH2~~CH' ~ O ~ CH
N-O N-N
,~ o~
.. . . .
Specifically Preferred for reasons of their
highest herbicidal activity or greatest plant growth
regulant activity or most favorable ease of synthesis
are:
2-~[1-(4,6-dimethyleyrimidin-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:
N',N'-dimethyl-N-t[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.
:
. ~ .
r ~
` ''' 1 1
'
- .
;: ` :
`~
5~
Detailed DescriPtion of the Invention
Synthesis
The compounds of Formula Ia may be prepared by
the reaction of hydroxylamine with an appropriately
substituted S-alkyl benzenesulfonyl isothiourea o~
Formula II, as shown in Equation 1.
Equation 1
SR'' N-OH
10 LS2N-- NH2H L502NJI\N-A
N-A. R
... . .
II Ia
wherein
L, R, R'' and A are as previously defined.
The reaction of Equation 1 is conducted by con-
tactinq 1-3 equivalents of hydroxylamine hydrochloride
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''
- LS02Cl ~ HN ~ N-A ~ II
R
I r I IV
wherein
L, R, R'' and A are as previously deined.
12
.
: ~ :
~2~
The 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.~., 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
extraction from water with an organic solvent,
concentration, and chromatography.
Reference tc the following patents and patent
applications is sug~es~ed for details regarding the
preparation of the sulfonyl chlorides III: U.S. Patent
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; ~.S. Patent 4,394,506 to G. Levitt issued July
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
(E.I. du Pont de Nemours and Company) published July
23, 1980; Canadian Patent 1128042; European Patent
Application 82301500.3 (E.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 copendin~ Canadian
Patent Applications Serial No. 413,400, to ~.P. Rorer
filed October 14, 1982; Serial No. 413,385, to R.J.
Pasteris filed October 14, 1982; Serial No. 439829,
filed October 27, 1983 and Serial No. 419,031, to ~.P.
Rorer filed Janu:ry 06, 1983.
.
13
:: : ;
-
:
.
:
'
14
The preparation of the compounds of Formula IV
is ~hown in Equations 3, 4 and 5.
Equation 3
(3a)
NC-N-A H2 ~ ~2N N-A
, pyridine R
V VI
3b?
VI (R'')2S04 IV
- or
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 l to S days at 25 to 40, removal of 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 equivalent
of a dialkyl sulfate or alkyl iodide at 20 to 80 for
l to 3 days to provide the correspondiny alkyl sulfate
or iodide salt of IV. The free base may be obtained
by extraction from aqueous sodium bicarbonate with an
organic solvent, e.g. ethyl acetate. ~n alterna-
tive synthesis of compounds of Formula VI is shown in
Equation 4.
~
.. 14
~ 34L~L
Equation 4
(4a) s
~ ~IN'~`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 C6~I5
The reaction of Equation 4a is carried out by
contacting a compound of Formula VII with 1-1.5
equivalents of benzo~yl- or phenoxycarbonylisothio-
cyanate at 30-B0 for 1-24 hours in a suitable sol-
vent, e.g. acetonitrile or tetrahydrofuran. The
product may be i601ated 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 coollng,
neutralization to pH 8, and filtrat~on 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.
,
.
:
.
:, :
~:
16
Heterocyclic amines of Formula VII and methods
for preparing them are known in the art. The 6ynthe
sis of heterocyclic amines such as those of Formula
VII has been reviewed in ~The Chemistry of HeterocycliC
Compounds", a se~ies published by Interscience Publ.,
New York and London. Z-Aminopyrimidines are described
by D. J. Brown in ~The Pyrimidines~, Vol. XVI of this
series. 2-Amino-1,3,5-triazines can be prepared
according to methods described by E. M. Smolin and
L. Rapaport in "s-Triazines and Derivatives", Vol.
XIII of the same series. The synthesi6 of triazines
is also described by F. C. Schaefer, U.S. 3,154,547
and by K. R. Huffman and F. C. Schaefer J. Ora. Chem.,
28, 1816 (1963). See also copending Canadian Application N ~ er
15 416,863, filed ~ecem}:er 02, 1982, European Pa~ent Application N~nber
80300505.7, published Sep~ember 17, 1980 (Pub. No.
15,683), European Patent Application Number 81303837.9,
published March 3, 1982 (Pub. No. 46,677); European
Patent Application Number 82306492.8, published
July 27, 1983 (Pub. No. 84,224); and European Patent
Application Number 82303611.6, published March 9, 1983
~Pub. No. 73,562), for description of met-hods for
preparing heterocyclic amine decivative6.
A third method by which certain compounds of
Formula IV may be obtained is shown in Equation 5.
Equation 5
X "
N N ~
~ N ~ R2NH NH -~ IV
Cl Y
lX
wherein
R. R'', X and Y are as previously defined.
, 16
~ 3~
The reaction of Equation 5 may be carried out by
contacting a chlorotriazine 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)
N-OR'
Ia R'Cl ~LS02N ~ N-A
H R
Ib
(6b) 0
N-0/L~N~R
P~ NC0
3 -> LSO~N~ N~~
H R
Ic
wherein
R' is C()Rl' C()NR2Ri, or C02R4, and L, R, Rl,
R2 ~ R3, R4, and A are as previously defined.
.
The reacti~on of Equation 6a is carried out by
contacting Ia with 1-10 equivalen~s of the appropriate
carboxylic acid chloride or anhydride, or alkyl chloro-
formate, or dialkyl carbamoyl chloride in the presence
of an acid scavenger, e.cl. pyridine or a tertiary
amine, at O to 40 for 2 to 29 hour6, adding ice-
wat-er, and filtering or extracting the product into an
organic solvent.
.
. ~' .
7~
18
The reaction of Equation 6b may be conducted by
treating a solution of Ia in an inert solvent e.g.
methylene chloride or acetonitrile with l 1.5 equiva--
lents of an alkyl isocyanate at 20-80 for l to 2~
hours. The product is isolated by concentrating the
reaction mixture and trituration with a solvent e.g.
ether or chlorob~tane.
Agriculturally suitable salts of compounds of
Formulae I and II are also use~ul 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 al~aline earth
metal salt having a sufficiently basic anion (e.g.,
lS hydroxide, alkoxide, carbonate or hydride). Quater-
nary amine salts can be made by similar techniques.
Salts of compounds of Formulae I and Il 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 compound of For-
mulae I and II (e.g.. alkali metal or quaternary amine
salt) with a solution containing the cation to be ex-
changed.
This method is mos~ effecti~e 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 i6 el~ted
from the column~ This method is particularlv useful
18
. .
~3~
when the desired salt is water-soluble, e.g., a potas-
sium, sodium or calcium salt.
Acid addition salts, useful in this invention.
can be obtained by reacting a compound o Formulae I
and II with a suitable acid, e.g., P-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-dimethylpyrimidin-2-yl)amino]hydroxy-
iminomethyllbenzenesulfonamide
To a solution of O.S g of methyl N'-~2-chloro-
phenylsulfonyl)-N-t4,6-dimethylpyrimdin-2-yl)carbam-
imidothioate in 10 ml of tetLahydrofuran 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-water, filtered, washed with water, and dcied
by suction to afford 0.3 g of the title compound, m.p.
165-167. NMR(CDC13/DMSO-d6) ~ 2.6 (s, 6), 6-8 (~,
25 1), 7.g (m, 3), 8.2 (m, 1), 10.2 (br, 1), 12.0 (br,
1). m/e: 355 (M ).
Example 2
N-t4,6-Dimethylpyrimidin-Z-~l)thiourea
A suspension of 10 g of 2-cyanoamino-4,6-di-
methylpyrimidine in 50 ml of pyridine was saturated
with hydrogen sulfide and stored for 1 houc at 25.
The H2S treatment was repeated twice more, and the
mixture was allowed to stir at 25 fo~ 16 houLs.
Methylene-chloride was added, and the product was
19
. , ,
:
'`': ;. ~
, ' , ,
.
filte~ed and washed with methylene chloride to afford
8 q of 4,6-dimethylpyrimidirl-2-yl thiourea, m.p.
>260O. IR (Nujol* mineral oil) 3280, 3180, 8120, 1610
cm
ExamPle 3
N ~(4-Methoxy-6-methylpyrimidin-2-yl)aminothioxo-
methvllbenzamide
To a hot solution of 14 g of ammonium thiocya-
nate in 300 ml of acetonitrile was added 24 ml of ben-
zoyl chloride. The mixture was heated on the steam
bath for 30 minutes and filtered. The filtrate was
heated with 21 g of ~-methoxy-6-methylpy~imidine-2-
amine for 30 minutes and cooled. The product was
collected by filtration and washed with a little
acetonitrile to provide 28 g of N-[~(4-methoxy-6-
methylpyrimidin-2-yl)aminothiocarbonyl~amino]benz-
amide, m.p. 193-195. IR (Nujol) 3290, 1720 cm 1
~ ple_q
N-(q-Methoxy-6-methYlpvrimidin-2-vl)thiourea
A mixture of 25 g of the co~pound from Example 3
and 55 ml of 10% aqueous sodium hydroxide was heated
on the steam bat~ for 30 minutes, cooled, neutralized
with aqueou6 HCl to pH 8, filtered, washed with water,
dried by suction, and washed with ether to afford 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: q.B, N: 28.8, S: 15.3
m/e 198 (M+3.
*denotes t,rade mark.
`` 20
~3~
Zl
Example 5
Methyl 2-[[1-(4-methoxy-6-methylpyrimidin-2-ylimino)-1-
(methylthio)methyllamino6ulfonyllbenzoate
To g g of the compound frorn 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 s~rred for Z4
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. 143-149.
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) ~ 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-(g,6-dimethoxy-1,3,5-triazin-2-yl)carbamimi-
dothioate
A mixture of 20 g of 2-chloro-4,6-dimethoxy-s-
~riazine, 20 g of S-methyl isothiouronium sulfate, 16
g of sodium carbonate, and S0 ml of water wafi stirred
for 72 hours, concentrated at reduced pressure, and
extEacted with 300 ml of methylene chloride. The
organic layer was dried with Na2S04, fil~ered,
concentrated to dryness, and recrys~allized from
chlorobutane to afford 10 g of title compound, m.p.
94-100. NMR(CDC13) & 2.6 (s, 3), 4.0 (s, 6~, 8.2
(brs, 1).
21
~;~3~7~
Using the procedures and examples shown above,
the compounds in Tables 1-13 can be prepared.
.. . .
i'
., :
22
~3~57~L
Table la
R6~
10 _5 6 R'' R X Y m.p.(C)
SCH2CH=CH2 3-Cl CH3 3 3
SCH2CH=CH2 H C2H5 H OCH3 OC2H5
OS02-n-C3H7 H CH3 CH3 CH3 CH20CH3
OS02-n-C3H7 H C~13 H CH3 SCH3
OS02CH3 H CH3 H OCH3 CH3
2 3 H CH3 3 3
CH2CH3 5-Br CH3 H CH3 OCH3
CH2CH3 H CH3 3 3
n-C4Hg H n-C3H7 H 3 3
i_C3H7 H CH3 CH3 OCH3 CH3
OS02N(CH3)2 H CH3 H CH3 CH(CH2CH2)
OCH2CH3 H CH3 "
CH2cH3 H CH3 H CH3 OCH3
O-i-C3H7 H CH3 3 3
O_i_C3H7 H CH3 H OCH3 C2H5
O-n-C4H9 H CH3 H CH3 CH(OCH3)2
O-n-C4Hg H CH3 H CH3 OC2H5
S02CF2H 5-CH3 CH3 H OC~3 OCH3
S02CF2H H C2H5 ~ H OCH3 OC2H5
SCF2H 6-SCH3: CH3 CH3 CH3 CH20CH3
SCF2H H CH3 H CH3 SCH3
OCF3 H C~3 H OCH3 CH3
OCF3 H H3 CCH3 oCH3
2 3 H _ 3 7 OCH3 OCH3
`~ 35 i~ ~
~ 23
,. .. ~ -. .
: - .
`:
~34l5~7~
Table la (continued)
R5 R6 R'' R X Y m.p.(C~
CHzOCH3 H CH3 CH3 OCH3 CH~
CH2OCH2CH3 H 3 Cl OCH3
CH2OCH2CH3 H 3 Cl CH3
OCF2H H CH3 H H3 H3
OCF2H H CH3 H OCH3 OCH3
OCF2H H CH3 H CH3 CH(OCH2cH2O)
.. . . . .
'
:
i.
24
~: ` ' ' '`' '`` '` ' ~ '
.
. ~
Table lb
R 6~ ~ )"` N
5 R6 R' ~ E~ X Y m-p- (C~
SO2CH2CH.CHZ .H. CH3 H OCH3 OCH3
SO2CHZC~I=CH2 H CH3 H OCH3 C2H5
OSO2-n-C3H7 H CH3 3 C 3 CH20CH3
OSO2-n-C3H7 H CH3 H CH3 SCH3
15 OS02CH3 H CH3 3 3
S2CH3 H CH3 H OCH3 OCH3
CH2CH3 3-BL C~3 H CH3 OCH3
CH2CH3 H CH3 H CH3 CH3
n-C4Hg H n-c3H7 H CH3 CH3
20 1-C3H7 H CH3 CH3 OCH3 CH3
OSO2N(CH3)2 H CH3 H C~l3 CH(OCH2CHZO)
H2CH3 H CH3 H CH3 CH3
0CH2CH3 H CH3 H CH3 OCH3
0-1-C3H7 H CH3 H OCH3 OCH3
0-1-C3H7 H CH3 3 2 5
0-n-C4Hg H CH3 H CH3 CH(OCH3~ 2
0-n-C4Hg H CH3 H CH3 2 5
S02CF2H 6 SCH3 CH3 EI OCH3 OCH3
SO2CF2H H C2H5 H OCH3 C2H5
SCF2H H CH3 CH3 CH3 CH20CH3
SCF2H ~ H~ CH3 H CH3 SCH3
3~ H CH3 H3 3
OCF3 H CH3 H OC~I3 OC~3 :
CH20CH3~ H n-C3H7 H OCH3 OC~3
3~ i.
, ~ 25
:
:: '
.. :
,
- '~ . . : '
~;~3~
- 26
Table lb (continued_~
6 R ' ' _ X Y m P . ( C
CH20CH3 H CH3 CH3 OC~13 CH3
CH20CH2CH3 H CH3 E~ Cl OCH3
CH20CH2CH3 H CH3 H Cl CH3
OCF2H H CH3 H OCH3 CH3
OCF2H H CH3 H 3 3
CF2H ~ 3 C~3 CH3
2 2 2 5 3 OCH3 CH3
.. . . ...
i.
:
26
' ' ~ .
.
,
~z~
27
Table lc
SR'' R ~ Z
m.p.
10 R`' _ R5 R6 X Y Z (C)
CH3 H OCH2CH?OCH3 H c~3 H CH
CH H OCH2CH=CH2 H CH3CH3 N
CH~ H OCH2CH-CH 6-OCH3 CH3 CH3 CH
CH3 6 5 H CH3 CH3 N
15 CH3 H N-N~ H CH3 OCH3 CH
O CH3
CH3 H N-N H 33 N
,l~ o ~ .
CH3 H ~ . H 3 2 N
CH3 H ~ 3 2 2 3 N
CH3 2 5 H OCH3OCF2H CH
CH3 H OCF3 H 3 2 CH
CH3 2 3 3-OCF2H OCH3 C(CH3)(0CH3)2 CH
CH3 HOCH2CH3 3 3 N
CH3 2 2 3 ocH3 N~CH3)2 CH
CH3 CH3 S2C~2CH3 H OCH3 C(CH3)(SCH3)2 N
CH3 H SO2CH2CH3 H OCF?H CH(SCH2CH2S) CH
CH3 H SO2CH2CH3 H CF3 CH2CH3 CH
CH3 H S02CH2CH3 H F OCH3 CH
CH3 H SO2CH2CH3 HOC2H5 C(CH3)(0CH2CH20) CH
.. ~ 27
: ; ~ :,
" . ~ ` '
~3~7~
T~ble ld
~ N~
R N
y
m.p.
10 R'' R L X Y Z (C)
CH3 H L2 R7=C1 3 CH
CH3 2 7 3 3 3 CH
CH3 H L2:R7=S02N(CH3)2 3 3 CH
CH3 H L3 R8=S2N(CH3)2 3 3 CH
CH3 H L3:R8=S02CH3 CH3 OCH3 CH
CH3 CH3 L3:~8=S02C~2C 3 Cl OCH3 CH
l-c3H7 H L4:R9=8r 3 3 CH
CH3 5 9 2 S OCH3 CH2cH=cH2 CH
CH3 H L6:R9=C1 3 2 N
CH3 H L7:Rlo=co2 3 OCH3 OCH2CF3 N
C~3 8 Ql ~ m 0~ Rll=R12=R13=c~3 OCH3 CH2SCH3 CH
CH3 H L9:Q2=S~ R14 R15 ' H CH
CH3 H L10:m=O. R13=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 L15 Rl7=cH3 - OCF2H CH~SCH2CH2S) CH
CH3 H L16:R17=H CF3 CH2CH3 CH
CH3 H L17 R17=R18 3 F OCH3 CH
CH3 H L17 R17 18 3 OC2H5 C(CH3~(0CH2CH20) CH
~ ~ 28
:
` ' : , ~,
'
.: :
:
': ~ ' '
~3~5;7~
29
Table le
S LS02N~R_A
L R'' R A (C)
10 Ll RS=C2CH3' R6=H CH3 H A4:Xl=CH3~ 2
Ll R5=SO~CH3, R6=H CH3 H A5:X2=CH2CH3, Y3=SCH3
i S 2; 6 CH3 H A6:X3 OCH3
Ll:R5=Br, R6=H CH3 H A3:Xl=OCH3
Ll:R5=Cl, R6=H CH3 H A5:x2=cH3~ Y3 oC2 5
Ll R5=C2H5' R6=H CH3 H A2:Xl=CH3~ 1
Ll:RS=SCF3, R~=H C2HS H A3:Xl=OCF2H
L17 R17=H, R18 C 3 CH3 H A2:~1=CH3' Yl 2
16 17 3 CH3 H A3:Xl=OCF2H
L2:R7=SCH3 CH3 H A4 Xl=CH3- Y2 3
L3:R8=F CH3 H A5:X2=CH2CH3~ Y3~ 3
L :R i C H CH3 H A5:X2=CH3, Y3=CH2CH3
L5:R9=S02CH3 CH3 H A6:Xj-OCH3
; L6:R9=S02CH3 CH3 H A2:Xl=CH3~ Yl
L7:Rlo=OCH2CH3 CH3 H A3:Xl CH3
8 Ql S~ Rl}=R12=CH3~ m=l~ R13=H CH3 H A6:X3=CH3
L9 Q2=, R14=Rl5 CH3 CH3 H A4:~1=0CH3. Y2 3
10 16 2 5' 13 3' CH3 H AS:X2=CH3. Y3 S 3
Lll:m=l, R13=H CH3 H A2:Xl=CH3' Yl 2
L12:m=0~ R13 C 3 CH3 H A2 Xl-CH3' Yl 2
L13:m=1, R13=H CH3 H A5:x2=cH2cF3~ Y3 2 3
L14'al6=CH3 CH3 H A4:Xl=CH3~ 2
lS 17 3 CH3 H A4:Xl=OC~3~ 2
.
;,
. .
,
,
s~
Table 2a
~6 50Zll~
R R 6 R H X Y I z 1 - I 2 a o
Cl H El HH GCH3 C2H5 142-144
F H H H CE~3 CH3
15 F H H H CH3 oCH3
E~ L H H H OCH 3 3
NO HH HH H oCH3 oCH3
~2 HH CH3 El CH3 C2E15
CFF3 H H H oCE13 3
CooccH3 H HH HH CH CH (ocH3 ) 2
2 5 OCH3 H H HH Ccl CoHH3
oOCCcH3R5 H H HH CH CH2ocH3
o n r~U/ U ocu~ oi:t
Co~cH3 H H H ~H3 Cll3 M~ 395
, .
~ : , . : ,
.. : .
,
31
Table 2a ~continued~
R5 R6 R R~ X Y m.P~(oc)
2 3 H ~ 32 5
S02N(CH3)2 H H 3 3
S02N(CH3)2 H H 3 3
502N(CH3)2 H H HCH3 OCH3 166-168
S02N(CH3)2 H H H OCH3 OCH2CH3
S02N(CH3)2 H H H CH3 CH(CH2CH2)
S02N(CH2CH3)2 H CH3 H CH3 C2H5
S02N(CHz~H3)2 H - H H OCH3 OC2H5
S02N(CH2CH3)2 H H H 3 3
C02CH2CH3 H H H CH3 OCH3
Co2CH2CH3 H H H CH3 CH(OCH3)2
2CH3 H H H Cl CH3
2 H3 H H H Cl OCH3
2CH3 H H H CH3 CH20CH3
, C02-i-C3H7 H H H CH3 CH3
C02-i-C3H7 H CH3 H 3 OCH3
S02N(OCH3)CH3 H H H 3 CH3
Co2cH2cH2ocH3 H H H CH3 OCH3 -
C2CH2CH=CH2 H H 3 CH3
2 2 2Cl H H 3 OCH3
CO2-n-C4H H H 3 3
02CH3 H H CH3 CH3
2 3 H H H CH3 OCH3
S2CH3 H H H OCH3 OC2H5
2 H3 H H H OCH3 OCH3
S2CH2CH=CH2 H H 3 CH3
S2CH2CH=CH2 H H H CH3 OCH3
S2CH2CH2CH3 H H 3 3
SCH2CH3 H H CH3 OCH3
SCF~ H H H CH3 CH(CH2CH2)
2CHF2 ; H 3 CH~ C2H5
CH3 H H H OCH OC H
31
5~
32
Tnble 2a (continued)
S 6 R R~ X Y m p. (~C)
1-C3H7 H H 3 3
5 n-C H H H H CH3 OCH3
OS02N(CH3)2 H H H CH3 CH(OCH3)2
OS02N(CH3)2 H H H C1 CH3
OS02CH(CH3)2 H H H Cl OCH3
2 2 S H H H CH3 CH20CH3
2 3 H CH3 H OCH3 OCH3
- 2 3 H . H 3 3
CH20CH3 H H H CH3 OCH3
CH2CH20CH3 H H 3 3
OCF3 H H 3 3
S02-i-C3H7 H H 3 3
Cl H H CH3C0 3 3 131-136~d
Cl 5-CF3 H H CH3 OCH3
Cl H H CH30CO OCH3 OC2H5
Cl 6-SCH3 H 3 3
F 5-SCH3 H CH3C0 3 3
F 6-ocH3 H H CH3 OCH3
Br H H ~CH3)2NCO OCH3 CH3
Br 3-OCH3 H 3 3
N02 H H CH3NHCO CH3 CH(CH2CH2)
N2 3 3 H CH3 C2H5
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
OCH3 3-Cl H H C1 CH3
OCH3 H H c~i3co Cl OCH3
2 S 5-F H H 3 2 3
C2H5 5-F 2 3 3
2 S 3-8r 3 OCH3 OCH3
35 o_i_c3H7 H H EtOCOOCH3 CH3
32
:
: .
, ,: .. .
:...-. . .~:.
.~: . , :.
33
Table 2a (continued)
RS R6 R R' X Y m.P.(C)
O-n-C H H H ~ 3 7 CH3 OCH3
O-n-C H 6-CH3 H H 3 3
o-i-c H 3-CF3 3 3 3
O-i-C4H9 6-CF3 H H 3 3
2 3 S-CF~ H 3 H3
2 3 6-CF3 H H CH3 OCH3
2 3 H H CH30CO OCH3 OCzH5
S02N(CH3)i 6 S 3 3 3
S02N(CH3)2 5-SCH3 H CH3CO CH3 CH3
SO~N(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(CH2CH2)
So2N(cH2cH3)2 3-CH3 3 CH3 C2HS
so2N(cH2cH3)2 5 3 CF3CO OCH3 OC2HS
202 2 3 2 H C2H5CO 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 3 H H CH30CO Cl OCH3
2CH3 5-F H H 3 2 3
C02-i-C3H7 5-F H (C2H5)2Nc CH3 CH3
C02-i-C3H7 3-Sr H3 H H3 OCH3
So2N(ocH3)cH3 H _ 3 7 OCH3 CH3
C02CH2CH20CH3 H H H CH3 OCH3
C2CH2CH=CH2 6-CH3 H H CH3 CH3
C2CH2CH2C1 3-CF3 H H OCH3 OCH3
C02-n-C4H9 6-CF3 H H 3 3
2 3 5-CF3 H 3 3
2 3 3-CF3 H H CH3 OCH3
2 3 H 3 OCH3 OC2HS
2 3 6-SCH3 H H OCH3 OCH3
, ~
:
~L23~
34
Table ?a (continued)
R5 R6 R R~ X Y m p.(C)
S2CH2CH=CH2 S-SCH3 H CH3C0 3 3
5 S2CH2CH=CH2 6-OCH3 H H CH3 OCH3
S2CH2CH2CH3 H H (CH3)2NCO OCH3 CH3
2 3 3-OCH3 H 3 3
SCF3 H H CH3NHCO CH3 CH(CH2C~2)
So2cHF2 3 3 CH3 C2H5
10 CH3 S-CH3 H CF3COOCH3 OC2H5
l-C3H7 6-Cl H CH3 CH3
n~C4H9 H H C2H5COCH3 OCH3
OSO~N(CH3)2 6-Cl H H Cl CH3
OS02N(CH3)2 H H CH30CO Cl OCH3
15 OS02CH(CH3)2 S-F H CH3C 3 2 3
2 3 3-Br 3 3 3
2 3 H H _-C3H70CO OCH3 CH3
2 3 H. H 3 7 CH3 OCH3
CH2CH20CH3 ~-CH3 H 3 3
20 OCF3 3-CF3 H 3 3
S02-i-C3H7 S-CF3 HH OCH3 CH3
2 2 2 S H HH OCH3 CH3
~ Data refer to molecular ion in electron-impact mass
spectrum.
~5
: 34
,.:.
.:
,....;
.
Table 2b
_ .
H~SO NJJ\N
6 2H R
10 Rs R6 R R~ X Y m.p.(C)
Cl H . H 3 H3
Cl H H H CH3 OCH3
Cl H H OCH3 OC2H5
Cl H H 3 CH3 137-140
15 F H H H CH3 CH3
F H H H CH3 OCH3
Br H H 3 3
Br H H H OCH3 OCH3
N02 H H H CH3 CH(OCH2CH20
20 N02 H CH3 H CH3 C2H5
CF3 H H H OCH3 OC2H5
CF3 H H 3 3
O~H3 H H H CH3 OC~3
OCH3 H H H CH3 CH(OCH3)2
25 OCH3 H H H CH3 CH3
OCH3 H H H OCH3 OCH3
C2H5 H H 3 20CH3
C2H5 H H H CH3 3
C2H5 H CH3 3 H3
30 O_i_C3H7 H H C 3 CH3
O-n-C3H7 ~ H H CH3 OCH3
O-n-C H H H H CH3 CH3
o-i-c H H H H OC~I3 OCH3
O_l_C4Hg ~ ~ 3 3
35 C02CH3 H H ; H CH CH
.
:
. .
~ `
`~ ~
. .
~23~
36
Table 2b ~continued)
R5 R6 R R' X Y m.p.(C)
2 3 H H H CH3 OCH3
2CH3 H H 3 2 5
S02N(CH3)2 H H H OCH OCH ~ 3.0 and
S02N(CH3)2 H H 3 3 4.0 (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(OCH2CH20)
2 ( H2CH3)2 H CH3 H CH3 C2H5
2 ( H2CH3)2 H H H OCH3 OC2H5
2 (CH2cH3)2 H H OCH3 CH3
152CH2CH3 H H H CH3 OCH3
C02CH2CH3 H H H CH3 CH(OCH3)2
2 3 H H 3 C~13
2 H3 H H H CH3 OCH3
2CH3 H H 3 2 CH3
CO2-i-C3H7 H H H CH3 CH3
C02-i-C3H7 H CH3 H CH3 OCH3
S02N(OCH3)CH3 H H H OCH3 CH3 .-
Co2cH2cH2ocH3 H H H CH3 OCH3
C2CH2CH=CH2 H H H CH3 CH3
2CH2CH2Cl H H 3 H3
CO2-n-C4Hg H H 3 3
2 3 H H H CH3 CH3
SOzCH3 H H H CH3 OCH3
SO2CH3 H H H OCH3 OC2H5
30 2CH3 H H H OCH~ OCH3
SO2CH2CH=CH2 H H CH3 CH3
S2CH2CH=CH2 H H H CH3 OCH3
2 2 H2CH3 H H 3 H3
2CH3 H H 3 OCH3
35 3 ~ H CH3 CH(OCH2CH20
SO2CHF2 H CH3 H CH3 C2H5
36
;
~;~3~L5~
37
Table 2b (continued)
Rs R6 R R~ X Y m p. (C)
CH3 H H 3 2 S
i_C H H H 3 3
n-C H H H 3 3
OS02N(CH3)2 H H H CH3 CH(OCH3)2
OS02N~CH3)2 H H 3 3
OS02CH(CH3)2 H H H CH3 OCH3
OS02C2H5 H H H CH3 CH20CH3
S2cH3 H " 3 3 3
2 3 H H 3 3
CH20CH3 H H H CH3 OCH3
CH2CH20CH3 H H 3 3
OCF3 H H 3 3
S02-~-C3H7 H H H 3 3
Cl 3-CF3 H H 3 3
Cl S-CF3 H H CH3 OCH3
Cl H H CH30CO OCH3 OC2HS
20 Cl 6-SCH3 H ~ H OCH3 OCH3
' F S-SCH3 H CH3CO CH3 CH3
F 6-OCH3 H H CH3 OCH3
Br H H (CH3)2NCO OC~13 C 3
Br 3-OCH3 H 3 3
No2 H H CH3NHCO CH3 CHtoCH2CH2o)
N2 3 3 H CH3 C2HS
CF3 S-CH3 H CF3CO OCH3 OC2HS
CF3 6-Cl H C2H5CO OCH3 CH3
OCH3 H H 2 5 CH3 OCH3
30 OCH3 S-Cl H H CH3 CH~OCH3)2
OCH3 6-Cl H H 3 3
OCH,3 H H ~ 3 7 CH3 OCH3
C2HS S-F H H 3 ~ 3
C2HS S-F H 2 3 3
OC2H5 3-8r ~ CH3 H 3 3
37
.
.. ..
.
~;23~
38
Table 2b ~continued)
R5 R6 R R' ~ Y m.P. ~C)
O-i-C3H7 H H EtOCO 3 3
O-n-C H H H _ 3 7CH3 OCH3
O-n-C H 6-CH3 H 3 3
O-i-C4H9 3-CF3 3 3 3
O-i-C4~9 5-CF3 H 3 3
2 3 3-CF3 H 3 3
2 3 5-CF3 H H CH3 OCH3
CO~CH3 H H CH30CO OCH3 OC2H5
S02N(CH3)2 6-SCH3 H 3 3
S02N(CH3)2 5-SCH3 H 3 3 3
S02N(CH3)2 6-oCH3 H H CH3 OCH3
S02N(CH3)2 H H (C~3)2Nc OCH3 OCH3
S02N(CH3)2 3-OCH3 H H OCH3 OCH2CH3
S02N(CH3)2 H H CH3NHCO CH3 CH(CH2CH2)
S02N(CH2CH3)2 3-CH3 3 CH3 C2H5
S02N(CH2cH3~2 5-CH3 H _ 3 7 OCH3 OC2H5
So2N(cH2cH3)2 6-Cl H H 3 3
C02CH2CH3 H H CF3CO CH3 OC~3
C02CH2CH3 5-C1 2 5 CH3 CH(OCH3)2
2 3 6-Cl H H 3 3
C2CH3 H H C2H5CO CH3 OCH3
2 3 5-F H H 3 2 3
C02-~-C3H7 5-F H H CH3 CH3
C02-i-C3H7 3-Br 3 3 3
S02N(OCH3)CH3 H 2 3 3
C02CH2CH20CH3 H Hn-C3H70CO CH3 OCH3
C2CH2CH=CH2 6-CH3 H H 3 3
2 2 2 H H CH30C0 3 3
C02-n-C4Hç H H C2H5CO 3 3
2 3 3-CF3 H 3 3
S2CH3;, 5-CF3 H H CH3 OC~3
2 3 H H CH30CO 3 2 5
.
~8
39 ~3~i7~
Table 2b (continued)
R R6 R R~ X Y m p.~C)
2 3 6-SCH3 H 3 3
S2CH2CH=CH2 5-SCH3 H 3 3
S2CH2CH=CH2 6-OCH3 H(CH3)2NCO CH3 OC 3
2 2 2 3 H H OCH3 CH3
2 3 3-OCH3 H 3 3
SCF3 H H CH3NHCO CH3 CH(OCH2CH20
2 2 3 3 CH3 C2HS
CH3 . 5.-CH3 H 2 5 OCH3 OC2H5
l_C3H7 6-Cl H H 3 3
n-C4Hg H H _-C3H70CO CH3 OCH3
OS02N(CH3)2 6-C1 H C2H5C0 3 3
15 OS02N(CH3)2 H H - 3 7 CH3 OCH3
OS02CH(CH3)2 5-F H H 3 2 3
2 3 3-8r CH3 C2H5NHCO OCH3 ~CH3
2 3 H H (C2H5)2NCOOCH3 CH3
CH20CH3 H H C~3CO CH3 OCH3
20 CH2CH20CH3 6-CH3 H 3 3
OCF3 H H C2H5C OCH3 OCH3
S02-i-C3H7 H H n-C3H7NHCO OCH3 CH3
CH2CH2C2H5 H H 3 3
~Data refer to characteristic signals in NMR spectrum
(CDC13) in ppm downfield erom tetramethylsilane.
- . j....... . . . .. .
40 ~;~3~S~L
Table 2c
S R- ~ N-O~K
R' R Rs R6 X m p
H H 2 2 3 CH3 H CH
H OCH2CH=CH2 H CH3 CH3 N
H H OCH2CH_CH 6-OCH3 CH3 CH3 CH
15 H H C6H5 H CH3 3 N
H H 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 F H OCH3 SCF2H CH
H H F 3-OCF2H .OCH3 C~CH3)~0CH3~2 CH
H H F H 3 3 N
30 H H Br H OCH3 N(CH3~2 CH
H . 3 3 ( 3) 3 2 N
H 3 H OCF2H CH(SCH2CH2S) CH
H 3 H CF3 CH2CH3 CH
3 H F OCH3 CH
H CH3 B~ C2H5 C(CH3)(0CH2CH20) CH
.
:
~ .
4, ~L~3~S~l
Table 2c (continued)
R' R S 6 X Y Z m p.(C)
H H ~ H CH3 H CH
~ N N-CH
H H -N~N ~ H CH3 c~,3 CH
H H r N H CH3 OCH3 CH
~N~
COCF3 H O-n-C3H7 H OCH3 OCH3 CH
H H O-n-C3H7 H OCH3 OCH2CH-CH2 CH
H H O-n-C3H7 H OCH3 OCH C-CH N
H OCH3 3 2 3 N
15 H H OCH3 H OCH3 OCH2CHzOCH3 N
H H OCH3 H OCH3 CH2SCH3 CH
H H N02 H OCH3 OCFzH CH
H H N2 3 2 CH
- H H N02 3 3 3 2 CH
20 H H CF3 3 3 CH
H H CF3 H OCH3 N(CH3)2 CH
H CH3 CF3 3 3) 3 2 CH
H CH3 C02CH3 H OCF2H CH(SCH2CH2S) CH
H CH3 C02CH3 H CF3 CH2CH3 CH
H CH3 C02CH3 H F OCH3 CH
H CH3 C02CH3 H OC2H5 C(CH3)(0CH2CH20) CH
H H ~ H CH3 H N
~0~
30 H ~ H CH3 CH3 N
O
H H ~ 3 3 : CH
S
~ ,C07CH2CH-CH2~H 3 3 : CH
H H~; C02CH2C~=cH2;H OCH3 OCHzCH=CH2 CH
4 1
:: : ` :
'
~`
, . ~ .
~2~i7~
42
Tnble 2c (con inued)
R' R S 6 X Y Z m p.(C)
5 H H co2CH2cH=cH2 H 3 2 N
H H S02N(CH3)2 HOCH3OCH2CF3 N
H H S02N(CH3)2 3 2 2 3 N
H H S02N(CH3)2 HOCH3CH2SCH3 N
H H S02N(OCH3)CH3 H OCH3 OCF2H CH
H S02N(CH3)C2H5 H OCH3 SCF2H CH
H H SCF3 H OCH3 C(CH3)(0CH3)2 CH
H H SO CHF 3 3 CH
H H C2CH2CH2Cl }I OCH3 N~CH3)2 CH
3 2 2 3 3 ( 3)( 3)2 CH
'H H C02CH2CH3 H OCF2H CH(SCH2CH2S) CH
H H C2CH2CH3 ~ CF3 CH2CH3 CH
H H S2CH3 H F OCH3 CH
CO-i-C3H7 H S2CH3 H OC2H5 C(CH3)(0CH2CH20) CH
,~ H ~ H CH3 H N
o,N
H H~ 3 3 N
~N~O
H HN=N5-OCF2H CH3 OCH3 CH
~ S
H Hr N 3 3 CH
~0
HH OCH3 3 2 ~ CH
HH OCH3 HOCH3 OCH2CF3 CH
30 HH OCH3 H3 2 2 3 CH
H .H OC2HS HOCH3 CH2SCH3 CH
H 2 5 3-FOCH3 OCF2H : CH
C02CH2CH3 n OC2H5 3 2 CH
H 3 OCH3 C(CH3~(0CH3)2 N
35 H ~ H'' CH3 H OCH3 CF3 N
.
`'' ~ 4Z
,
,.
~3~5~
43
Table 2c (continued)
R' R S R6 X Y Z m p.(C)
H H CH3 H OCH3 N(CH3)z N
H CH3 1_C3H7 3 3 3 2 CH
H H l-C3H7 H OCF2H CH(SCH2CH2S) CH
H H ~-C3H7 H CF3 CH2CH3 CH
H H l-C3H7 H F OCH3 CH
H H n-C4H9 H OC2H5 C(CH3)(0CH2CH20) N
:
.
i'
43
, ~_
,' . : `
. :
:.. ~
".
- :
. . . : .
~2;3~5i73L
4q
T~ble 3
N-OR'
S02NHJ~N-~/ Z
~ R7 R N
10 R
7 R R' X Y Z m.P.(C)
H H H CH3 CH3 CH
CH3 H CoN(cH3)2 3CH3 3
OCH3 H H Cl CH3 CH
H H CH3 CH3 CH
Cl H H OCH3 OCH3 CH
Br H H F OCH3 CH
S02N(CH3)2 H H CH3 OCH3 CH
2 3 H H OCF2H OCH3 CH
2 3 H H CH2F C2H5 CH
H CH3 H 2 3 2 3 N
CH3 H H CF3 N(CH3)2 .- CH
OCH3 H H OCH3 CF3 CH
F H C02CH2CH3 CH3 CH(OCH3)2 CH
H H OCH3 OCF2H N
8r 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 0 ~ CH
CH3 H H CH3 OCH3 N
H H H CH3 OCH3 N
-
.
44
. . - ~ , .
,'
'
~234~
4S
Table 4
N-OR ' N ._~
5 SO2NHJ~N~/ Z
~/ R N =:~
N '`R8
10 8 RR' X Y Z ( C)
.. O
. . . / ~
CH3 H CN(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 CH3 CH3 CH
Br H H OCF2H CH3 CH
20 S2N(CH2CH3)2 H H CH2F OCH3 CH
S02N(CH3)2 3 OCH2CH3 OCH3 N
S02N(OCH3)CH3 H H CF3 OCH3 ' CH
SCH2CH=CH2 H H OCH3 OCH3 CH
S02C2H5 2 2 3 3 OCH3 CH
25 S-n-C3H7 ,H H OCH3 C2HS N
Sa2CH3 H H OCH3 C2H5 N
SCH3 H H OCH3 SCF2H N
CH3 H H OCH3 C(CH3)tSCH3)2 CH
F H H OCH2CH3 OCF2H CH
30 Cl H H CH3 CHtC2H5)2 CH
Br H H CH3 CH3 N
OCH3 : H H CH3 CH3 N :
:
.
;' : . .
4S
:
.
46
Tabl~ S
N-OR' N X
LS02NHJ~N~/ Z
R N ~
m.p.
L 9 R R' X Y Z (C)
4 3 H H CH3 OCH3 CH
L4 F H CON(CH3)2 OCH3 OC~3 N
L4 NO2 H H Cl OCH3 CH
4 2 2 5 H H C~3 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 NtCH3)2 CH
L5 Cl H H OCFzH CH20CH3 CH
L5 Br H H CH2F CH20CH3 CH
L5 C2CH3 3 2 3 2 3 N
L5 SO2N(C~H5)2 H H CF3 Cff3 CH
L5 SO2N(OCH3)CH3 H H OCH3 CH3,. CH
5 2 2 5 2 2 3 3 CH3 CH
L5 SCH2CH-CH2 H H OCH3 CH3 N
25 S 52 3 H H OCH3 S ~ N
L6 F H H OCH3 CH(OCH3)2 CH
L CO ~ C H H H OCH2CH3 OCH3 CH
L6 SO2CH3 H H CH3 OCH3 CH
30 L6 S2N(CH3)2 H H CH3 OCH3 N
~ H ~ 8 CH3 ' OCH3 N
. ~
:
: ~
.
~.
~7~3~571
47
Table 6
~C;2S02NHJ~N~
R N ~
R m.p.
10 10 R R X Y Z (C~
Cl H H CH3 CH3 CH
2 H CON(CH3)2 OCH3 CH3 N
2 3 H H Cl CH3 CH
C02CH2CH3 H H CH3 CH3 CH
S02N(CH3~2 H H OCH3 CH3 CH
2 3 H H F OCH3 CH
S2CH3 H H CH3 OCH3 CH
S02CH2CH3 H H OC~`2H OCH3 CH
OCH3 H H CH2F OCH3 CH
CH2cH3 3 CH2cH3 OCH3 N
2 3 H H CF3 CH2SCH3 CH
2 3 H H OCH3 CF3 CH
OCH3 H C02CH2CH3 CH3 CH2CH3 CH
S02CH2CH3 H H OCH3 OCH3 N
25 S2CH3 H H OCH3 SCF2H N
2 3 H H : OC~3 CH3 N
C02CH2CH3 H H OCH3 CH3 CH
2 3 H H ~ CH2cH3 CH3 CH
2 3 H H CH3 C~13 CR
30 C2CH3 H H CH3 OCH3 N
N02 H H CH3 OC~13 N
;
: : 47
,. ~
~:~ ~ ' :` . '
- -' ,. ,
''
- 48
Table 7
12 ~ N-OR' N ~
S02NH ~/ Z
R N ~
y
Ql Rll . R12 R13 R R' m p
O H H H H H CH3 OCH3 CH
S H H H H CON(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
S2 CH3 CH3 H H H 2 3 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
2 CH2CH3 CH2CH3 H H CO2 2 3 3 OCF2H CH
NH CH2CH3 CH3 H H H OCH3 OCH3 N
NCH3 ~H2CH3 CH3 H H H OCH3 OCH3 N
O H CH3 H H H OCH3 OCH3 N
S H CH3 H H H OCH3 OC~3 CH
S2 H CH3 H H H OCH2CH3 OCH3 CH
NH H CH3 H H H CH3 C(CH3)~0CH3)2 CH
. H H H CH3 CH3 N
O CH3 CH3 ~ H H CH3 CH3 N
:
"
:
,
. ~ :
49 ~;~3a~
T~ble 8
S R14~3 ~R' N~
S2NH N~(/ Z
R N ~
m.p.
`2 14 15 _ R' ~ Y Z (C)
O H H H H CH3 CH3 CH
O H 3 3 2 3 3
O H H H H Cl CH3 CH
15 0 H CH3 H H CH3 CH3 CH
O CH3 H H 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
' ' : '" ` ' :
:
.. . . . .
so ~ 57~
Table 9
LSO NH ~ N 4 Z
R N ~
y
L m 13 16 R R' X Y Z ~C)
10 L-10 O H 3 H CH3 CH3 CH
L-10 1 H 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,H3 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
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 ~ H C2H5 H H CH3 CH3 N
3 L-10 O H 2 5 CH3 CH3 N
i ~ :
::~ S O
-: . - . , :
'"''
'
~3~
51
~able 10
LS02NH~N~/ z
Rl 7 Rl 8 R R ~ m p
H H CH3 CH3 CH
L15 H - H -CON(CH3)2 OCH3 CH3 N
H H Cl CH3 CH
H H CH3 CH3 CH
H H OCH3 CH(OCH3~2 CH
lS H H F OCH3 CH
lS H H CH3 OCH3 CH
LlS CH3 - H H OCF2H OCH3 CH
L15 CH3 - H H CH2F OCH3 CH
lS 3 3 OCH2CH3 CH2SCH3 N
L16 CH3 - H H .CF3 2 3 CH
L16 CH3 - H H OCH3 3 .- CH
L16 CH3 - 2 2 3 3 OCH3 CH
L16 CH3 - H H OCH3 OCH3 N
25 16 H H OCH3 OCH3 N
16 H H OCH3 OCH3 N
16 H H OCH3 OCH3 CH
L17 CH3 CH3 H H OCH2CH3 CH3 CH
L17 CH3 H H H .; CH3 CH3 CH
L17 CH3 CH3 H H CH3 CH3 N
17 CH3 CH3 H H Cll3 CH3 N
:
~ 51
:~
,:
, ~:
52
TQble 11
H ~ 5 N-OR'
R5 R6 R R' A
10 CH3 H H H A2: Yl=CH2; Xl=CH3
-C3H7 H ........... H A2: Yl=O; ~l=OCH3
2 5 H H 2 1 2 1 2
o-n-c4H9 H H 3 1 3
3-CF3 H C2CH3 A3: Xl=OCH2CH3
15 Cl H R C2CH3 A4: Xl=CH3; 2
N02 H CH3 C2CH3 A4: Xl CH3; 2 3
CF3 H H C2CH3 A5: X2=CH3; Y3 3
2 3 H H C2CH3 A5: X2=cH3; Y3 SC 3
C02CH2CH3 3-CH3 H C2CH3 A5: X2=cH3; Y3 C2 S
20 S02N(CH3)2 H H C2CH3 A6 X3 CH3
S02N~C2H5)2 H H C2CH3 A6 X3 OC 3
OS02CH2CH3 H CH3 C2CH3 A2: Yl=O; Xl 2 3
SCH3 6-Cl H C2CH3 A2: yl=CH2; Xl 0 3
2 3 H H H A2: Yl=O; Xl 3
25 OCHF2 H H COCH3 A3: Xl=OCF2H
OCH2CH=CH2 H H H A3 X13CH3
C6H5 : H ~ H A4: Xl=~c1~3; Y2 C 3
N-N~ H H H A4: Xl=OCF2H; 2
~9 ~
H H A5: X2=CH2CF3; Y3 3
0 ' ~ :
CH20CH3~ H H H A6: X3=0CH3
CH20CH3 H H H 6 3 3
;,
:
. :: 52
` `:
.
~ '~ ' ` .
~3~5~
53
T~ble 12
N-OR'
LSOzNH ~ N-A
R
L RR~ A
L-2: R7=SO2N(CH3)2 Hli A2: Yl=CH2; Xl 3
7 2 3 H H A2: Yl=O; Xl=OCH3
L-2: R7=Cl . ., H H 2 1 CH2; ~1=O~F2H
L 2- R7=Br H H 3 1 3
8 3 H CO2CH3 A3: Xl=OCH2CH3
8 3 Hco2CH3 A4 Xl=OCH3; 2
L-3: R8=SO2CH2CH3 CH3 C02CH3 ~4 Xl=CH3; 2 3
L-4: R9=C02CH3 HC02CH3 A5: X2=CH3; Y3 OC 3
.. L-5: Rg=CO2-i-C3H7 2 3 5 2 3; 3 3
L-6: Rg=Cl HC02CH3A5 X2=CH3; Y3 2 5
L-4: R9=NO2 2 3 6 3 3
L-5: R9=SO2NtCH3~2 HCO2CH3A6 X3 OCH3
L-6 R9=C2H5 CH3C02CH3 A2 Yl=O; Xl 2 3
L-7 Rlo-C02CH3 H2 H3 2 1 2; 1 3
L-7: Rlo=so2N(cH3)2 H H A2: Yl=; Xl 3
L-7: Rlo=OS02CH3 H COCH3 A3: Xl=OCFzH
L-8: Rll=R12=R13-CH3; m ; Ql 3 1 3
L-9: R14=CH3; RlS=~; Q2 N 3 H H A4: Xl=OCH3; Y2 3
16 2 5; R13 ; m 1 H H A4: Xl=OCF2H; Y2=H
13 ; H H As X2=C2H5; Y3=C2HS
13 3; H H A5: ~z=cH2cF3; y3=CH3
13 3; H H A5: X2-CH3; Y3 C2H5
16 3 H H 6 3 3
L-l5: R17=H H H A2: Yl=CH2; Xl=CH3
L-15: R17=H. H H A2: Yl,=; Xl ~CH3
L-15: R17=H H H 2 1 2' 1 2
53
.
i7~
S4
T~ble 12 (continued)
R R' A
L-16 R17=CH3 H H 3 1 3
5 L-16: R17=CH3 H C02CH3 A3 ~1-ocH25 3
L-16 R17=CH3 H C02CH3 A4 xl=OcH3~ Yz
L-17: R17=H; R18 CH3 CH3C02CH3 A4xl=cH3; 2 3
L-17: R17=H; R13 CH3 HC02CH3 A5: g2=CH3; Y3 OCH3
L-ï7:R17=H; R18=CH3 HC02CH3 A5 X2 3; 3 3
L-8: Rll=R12=R13=H; m l; Ql 2 C02CH3 A5: x2=cH3; Y3 2 5
L-8: Rll=R12--R13=H;,m=l; Ql S2 C02CH3 A6 X3=CH3
L-3. 211=R12=R13=H; m=l; Ql 2 C02CH3 A6: X3 OC 3
L-9R14=R15=H; Q2 S 3 2 3 2 1 ; 1 2 3
L-9:R14=R15=H; Q2 H C02CH3 A2 Yl=C~2; 1 3
L-9: R14=Rl5 H; Q2 H H A2: Yl=O; Xl 3
13 16 3; H COCH3 A3 Xl=OCF2H
13 16 3; H H 3 1 3
13 16 3; H H A4: Xl=OCH3; Y2 C 3
13 3; H H A4: Xl=OCF2H; Y2=H
~L-ll R13=CH3; m=O H H A5 X2=C2H5; Y3 2 5
13 3; H H A5: X2=CH2CF3; Y3 CH3
13 ; H H AS:X2=CH3; Y3 2 5
13 ; H H 6 3 3
L-14: R16=H H H 6 3 3
: : ~ 54
: ' ' ; ;.
-: ; ' ,
~3~
Formulations
Useful formulations o~ the compounds of Formula
I can be prepared in conven~ional ways. l'hey include
dusts, granules, pellets, solu~ions, suspensions.
5 emulsions, wettable powders, emulsi~ia~le concentrates
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. ~igh strength
10 compositions are primarily used as intermediates for
further formulation. The formulations, broadly, con-
tain about 0.1% to 99% by weight of active ingre-
dientts) and at least one of (a) about 0.1% to 20%
surfactant(s) and (b) about 1~ to 99.9% solid or li-
15 quid diluent(s). More specifically, they will containthese ingredients in the following approximate propor~
tions:
Table 13
.
Weight Percent~
Active
Inqrediene Diluent(s~ SurfactanttsL
Wettable Powders 20-90 0-74 1-10
Oil Suspensions, 3-50 40-95 0-15
Emulsions, Solutions,
25 (including Emulsifiable
Concentrates)
Aqueous Suspension 10-50 40-3~ 1-20
Dusts 1-25 70-99 0-5
Granules and Pellets 0.1-95 5-99.9 0-lS
High Strength 90-99 0-10 0-2
Compositions
* A~tive ingredient plus at least one of a Surfactant
or a Diluent equals 100 weight percent.
~: : :
.:,. sS
,
:
56
Lower or higher levels of active ingcedient can.
of course, be present depending on the intended us
and the physical properties of the compound. Higher
ratios of surfac~ant to active ingredient are some
s times desirable. and are achieved by incorporation
into the formulation or by tank mixing.
Typical solid diluents are described in Watkins,
et al.. ~Handbook of Insecticide Dust Diluents and
Carriers~, 2nd Ed., Dorland Books, Caldwell, New
10 Jersey, but other solids, either mined or manufac-
tured, may be used. The more absorptive diluents are
preferred for wettable powders and the denser ones for
dusts. Typical liquid diluents and solvents are de-
scribed in Marsden, ~Solvents Guide," 2nd Ed., Inter-
15 sci~nce, New Vork, 1950. Solubility under 0.1% ispreferred for suspension concentra~es: solution con-
centrates are preferably stable against phase separa-
tion at 0C. ~McCutcheon~s Detergents and Emulsifiers
Annual~, MC Publishing Corp., Ridgewood, New Jersey.
20 as well as Sisely and Wood, ~'Encyclopedia of Surface
Active Agents'l, Chemical Publishing Co., Inc., New
York, 1964, 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 methods 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 hammer or
30 fluid energy mill. Suspensions are prepared by wet
milling (see, for exam~le, Littler, U.S. Pa~ent
3,060,064). Granules and pellets may be made by
spraying the active material upon preformed granular
carciers or by agglomeration techniques. See J. E.
35 Brownlng, "Agglomeration", Chemical Enqineerinq,
56
`
: ~ .
57
December 4, 1967, pp. 1~7~. and "Perry's Chemical
Engineer's Handbook", 5th Ed., McGraw-Hill, New York,
1973, pp. 8-57ff.
For further information regarding the art of
5 formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, Februa~y 15
1966, Col. 6, line 16 through Col. 7, line 19 and
Examples 10 through 41;
R. W. Luckenbaugh, U.S. Patent 3,309,19Z,
10 March 14, 1967, Col. 5, line 43 through Col. 7, line
62 and Examples 8! 12, 15, 39, 41, 52, 53, 58, 132,
13;3-140, 162-164, 166, 167 and 169-182:
H. Gysin and E. Knusli, U.S. Patent 2,891,855,
June 23, 1959, Col. 3, line 66 th~ough Col. 5, line 17
15 and Examples 1-4:
G. C. Klingman, "Weed Cont~ol 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", sth Ed., Blackwell Scientific Publications,Oxford, 1968, pp. 101-103.
In the following examples, all par~s ar0 by
weight unless otherwise indicated.
Example 7
25 Wettable Powder
2-[[1-~s,6-dimethylpyrimidin-Z-yl)amino]-l-(hydroxy-
imino)methyl]aminosulfonyl]benzoic acid, methyl
es~er 80~
sodium alkylnaphthaienesulfona~e2%
sodium ligninsulfonate 2
synthetic amorphous silica 3~
kaolinite 13%
The ingredients are blended, hammer-milled until
all the solids are essentially under 50 miccons, ce-
35 blended, and packaged.
- 57
. ~
~L~3~
s8
ExamDle 8
Wettable Powder
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]aminosulfonyl]benzoic acid,
methyl ester 50%
sodium alkylnaphthalenesulfona~e 2%
low viscosity methyl cellulose 2%
diatomaceous earth 4S%
The ingredients are blended, coarsely hammer-
10 milled and then air-milled to produce particles essen-
tially all below 10 microns in diameter. The product
is rebiended before packaging.
Example 9
G r anule
Wettable Powder of Example 8 5%
attapulgite granules 95%
(u.s.s. 20-40 mesh: 0.s4-0.42 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.
Example 10
Extruded Pellet
N',N'-dimethyl-N-r[1-(4,6-dimethyl-1,3,5-triazin-2 yl)-
amino]-1-(hydroxyimino)methyl]-1,2-benzenedisulfon-
amide 25~
anhydrous sodium sulfate 10%
crude calcium ligninsulfonates%
sodium alkylnaphthalenesulfonate 1%
caIcium/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
35 used directly after drying, or the dried pellets may
:`
-~ SR
:
~Z3a~
59
be crushed to pa~ a U.S.S. No. 20 ~ieve (0.B4 mm
opening~). The granule6 held on a U.S~S. No. 40 sieve
(0.42 mm openings) may be packaged for use and the
fines recycled.
S Example 11
Oil Suspension
N',N'-dimethyl-N-t~l-(4-methoxy-6-methylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a sand
mill until the solid particles have been reduced to
under about S microns. The resulting thick suspension
15 may be applied directly, but preferably after being
e~tended with oils or emulsiied 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 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3~
at~apulgite 69%
The ing~edients are thoroughly blended. After
grinding in a hammer-mill to produce particles essen-
tially all below 100 microns, ~he material is re-
blended and sifted through a U.S.S. No. 50 sieve (0.3
30 mm opening) and packaged.
59
: .
.
,
~3~S~
ExamPle 13
Low Strenqth Granule
N~,N'-dimethyl-N-[[1-(4,6-d;methyl 1,3,5 triazin-2-yl~-
amino]-l-(hydroxyimino~methyl]-1,2-benzenedisulfon-
amide 1%
N,N-dimethylformamide 9%
a~tapulgite granules 90%
(U.S.s. 20-40 sieve)
The active ingredient is dissolved in the sol-
10 vent and the solution is sprayed upon dedusted gran-
ules in a doub~e cone blender. After spraying of the
soiution has been completed, the blender is allowed to
run for a shor~ period and then the granules are pack-
aged.
ExamPle 14
Aaueous SusPensio_
N',N'-dimethyl-N-[[1-~4-methoxy 6-methylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 40%
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 together
in a sand mill to produce par~icles essentially all
under 5 microns in size.
~ .
ExamPle 15
Solution
2-[[1-(4-methoxy-6-methylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]amino~ul~onyl]benzolc dcid~
methyl esteL 5%
water 95%
The salt is added directly to the water with
stirring to produce the solution, which may then be
packaged ~or 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. 20-40 mesh)
The active ingredient is dissolved in a solvent
and the solution is sprayed upon dedusted granules in
a double-cone blender. After spraying of the solution
20 has been completed, the mate-rial is warmed to evapor-
ate the solvent. The material is allowed to cool and
then packaged.
ExamPle 17
Granule
25 2-[[1-(4-methoxy'6-methylpyrimidin-2 yl)amino]-l-
(hydroxyimino)methyl]aminosulfonyl]benzoic acid,
methyl ester 80%
wetting agent 1%
crude ligninsul;fonate salt (containing 10%
5-20~ of the natural sugars)
attapulgite clay 9%
The ingredients are blended and milled to pass
through a 100 mesh ~creen. This material is then
added to a fluid bed granulator, the ai. flow is ad-
justed to gently fluidize the material, and a fine
61
:
,
~3~
62spray of water is sprayed onto the fluidized ma-
terial. The fluidization and ~praying are continued
until granules of the desired size range are made.
The spraying is stopped, but fluidiza~ion is con-
~inued, optionally with heat, until the water contentis reduced to the desired level, generally less than
1%. The material is then discharged, screened to the
desired size ranqe, generally 14-100 mesh (1410-1~9
microns), and packaged for use.
~xample 18
Hiqh Strenqth Concentrate
N',N'-dimethyl-N-t[l-(4-methoxy-6-methylpyrimidin-2-
yl)amino]-l-(hydroxyimino)methyl]-1,2-benzenedi-
sulfonamide 99%
15 silica aerogel 0.5%
synthetic amorphous silica 0.5%
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
20 concentrate may be formu-lated further if necessary.
Example 19
Wettable Powder
N',N'-dimethyl-N-t[l-(4,6-dimethyl-1,3,5-triazin-2-yl)-
amino]-l-(hydroxyimino)methyl]-1,2-benzenedisulfon-
amide ' 90%dioctyl sodium sulfosuccinate 0.1%
synthetic fine silica 9.9
The ingredients are blended and ground in a
hammer-mill to produce particles essentially all below
30 100 microns. The material is sifted through a U.S.S.
No. 50 screen and then pa~kaged.
3s .
- 62
.
'' ~' :,
~2;~ 7~
63
Example 20
We~table Powder
2-[[1-(4,6-dimethylpyrimidin-2-yl)amino]-1-(hydroxy-
imino)methyl]aminosulfonyl]benzoic acid, methyl
ester 40%
sodium ligninsulfonate 20%
montmorillonite clay 40%
The ingredients are thoroughly blended, coarsely
hamme~-milled and then air-milled to produce particles
10 essentially all below 10 microns in size. The
material is replended and then packaged.
ExamPle 21
Oil 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
sulfonates
20 , xylene 59~
The ingredients 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 waee~.
Exam~le 22
Dust
2-[~1-(q-methoxy-6-methylpyrimidin-2-yl)amino]-1-
(hydroxyimino)methyl]aminosulfonyl~benzoic acid,
methyl ester 10%
attapulgite 10
. Pyrophyllite 80
The active ingredient is blended with attapul-
gite and then passed through a hammec-mill to produce
particles substantially all below 200 microns. The
ground concentrate is then blended with powdered pyco-
phylIite until homogeneous.
63
... . -
,
.
i7~L
6~
~xample ?3
Emulsif iable C~n~en~rate
N' .N'-dimethyl-N-t tl-(4-methoxy-6-methylpyrimidin-2-
yl)amino~-l-(hydroxyimino)methyl~-1,2-benzenedi-
sulfonamide Z0%chlorobenzene 74%
sorbitan monostearate and polyoxyethylene
condensates thereof 6~o
The ingredients are combined and stirred to pro-
10 duce a solution which can be emulsified in water forapplication.
.. . .
Utilit~
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 vegetation is de-
sired, such as around fuel storage tanks, ammunition
depo~s, industrial storage areas, parking lots, drive-
20 in theaters, around billboards, highway and railroadstructures. Alternatively, 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, the types of weeds
to be controlled, weather and climate, formulations
selected, mode of application, amount of foliage pre-
30 sent, etc. In general terms, the subject compoundsshould be applied at levels of around 0.03 to S kg/ha,
the lower rates being suggested ~or use on lighter
soils and/or those having a low organic matter con-
tent, ~or selective weed control or for situations
35 where only short-term persistence is required.
6~
,
The compounds of the invention may be used in
combination with any other commercial herbicide exam-
ples of which are those of the triazine, triazole,
uracil, urea, amide, diphenylether, carbamate and
5 bipyridylium types.
The herbicidal properties of the subject
compounds were discovered in a number of greenhouse
tests. The test procedures and results follow.
.. . . .
~, '
: 65
~ ~ :
: :
~3~
Test A
Seeds of crabgrass (Diqitar_a ~pp.), barnyard-
grass (Echinochloa crusqalli), wild oats (Avena fa~ua),
sicklepod (Cassia obtusifolia), morningglory (IPomoe_
5 spp.), cocklebur (Xanthium PensY-l-v--an--cum)~ sorghu~,
corn, soybean, sugar beet, rice, wheat, and purple
nutsedge (CYPerus rotundus) tubers were planted and
treated preemergence with the test chemicals dissolved
in a non-phytotoxic solvent. At the same time, these
10 crop and weed species. along with cotton and bush
bean, were treated with a soil/~oliage application.
At the ~ime 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 ex~ending from 0 = no injury, to
10 = complete kill. The accompanying descriptive
20 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 compounds tested are highly active
herbicides at the low rates of application selected
for this test.
'.
66
~3~
67
Compounds~
Compound 1
CH
NOH N~ 3
(~502-NH-C-NH -<0~
Cl CH3
10 compound ? CH
NOH N~ 3
''' ' ~S02-NH-C-NH-~O~
Cl OCH3
Compound 3
OCH3
NOH N~
~S02-NH-C-NH~ 0
\~ N
Cl or H3
.
Compound ~
OCH
~ NOH N ~ 3
~S02-NH-~-NH~ON
Cl OCH3
30 Compound 5
n CH
S 2 - N H - C - NH ~
N
3 5 . ! C 1 C ~1 3
67
:,
': ' '
,
~3~
Compounds (continued~
Compound 6
NOH N--( 3
~S02-NH-C-NH <0~
COOCH3 CH3
Compound 7
OCH
NOH N ~ 3
< ~ 502-NH-C-NH-< 0~
COOCH3 CH3
ComPound 8
OCH3
NOH N_~
~ 502-NH-C-NH ~ O~
50 2N ( C H 3 ) 2 C H 3
, .
Compound 9
~ 502-NH-C-NH ~ O N
SO2N (CH3 ) 2 OCH3
3 O
, 5
68
~39~5~
69
Table A
Cmpd. 1 Cmpd. 1 Cmpd. 2 Cmpd. 3
5 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
Cocklebur 3G 8G 3C,9G 3C,8H
Sicklepod 2C 3C,8G 2C,8G ~C,9G
Nutsedge 2C,6G lOC 4C,9G 9C
Crabgrass 0 2C,8G lC,3H 2C,3G
Barnyardgrass 2C,6H 9C 5C,9H 2C,9H
Wild Oats lC lC,7G O 2C,4G
Wheat lC lC,9G O 3G
Corn 2U,8H 5U,9G 3U,9G 2U,9G
Soybean lC,3H 4C,9G 2C,9H 3C,9H
Rice 2C,8H 5C,9G 3C,9G 4C,9G
Sorghum lU,9G 5U,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,8G 9G
Nutsedye 5G 3C,9G 2C,5G lOE
Crabgrass 0 3C lC,3G lC,5G
Barnyardgrass 3C,6H 3C,9H 5C,9H 9H
Wild Oats Q 2C,7G 5C,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,8~ 7H
Rice 4C,6G lOE 5C,9G lOE
Sorghum 2C,7H 3C,9H 4C,9G lC,9H
Sugar beet
. ~ 69
~, ~
" ,
. , :.. ~.. ...
~ .
,
~ 23~S 71
Table A (continued)
Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7
S Rate kg~ha .05 .05 .05 .05
POST-EMERGENCE
Bush bean lC SC,9G,6Y 3C,6H,6Y 9C
Cotton 4C,BG 4C,8H 2C,SG 6C,9G
Morningglory 3C,8G 3C,SG 3G 2C,7G
10 Cocklebur 2C SG 4G 4C,9H
Sicklepod 5C,9G lC 3G 9C
Nutsedge 0 3C,8G 7C,9G lOC
Cr~bgrass 3C 2H lOC 4C,9G
Barnyardgrass 2C,SH 3C,~H 4E~ 9C
Wild Oats 0 2C O SC,9H
Wheat O lC o SC,9G
Corn 2G 3C,8H 2C,8H SC,9G
Soybean 3C,BG 2C,7H 2C,2H SC,9G
Rice ~ 3G 3C,9H 2C,8H SC,9G
Sorghum 3G 3C,9G 2C,9H 4U,9G
Sugar beet - - 2C lOC
PRE-EMERGENCE
Morningglory 9G 3C 2C,4G 8H
20 Cocklebur 9H 9H 9H 8H
Sicklepod 9G 3C,8H 2C,SG 2C,9G
Nutsedge 9G 3C,8G 2C,SG lOE
Crabgrass 3G 2C lC 2C
Barnyardgrass 2C,SG SC,9H 2H 4C 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 SC,9H 3C,8H lOE
Sorghum 2C.SG 4C,9H 2C,9H 2C,9G
Sugar beet - - 2C,9G 9C
:. : 70
` :-
.
, ' ':
: ,:
~Z3~;7~
Table A (continued~
Cmpd. 8 Cmpd. 9
5 Rate kg/ha .05 .05
POST-EMERGENCE
Bush bean 5C,9G,6Y 5C,9G,6Y
Cotton sC
Morningglory 5C,9G 5C,9G
10 Cocklebur 4C,9G 4C,9G
Sicklepod 3C,8G 4C,3H
Nutsedge ZC,7G SG
Crabgrass 2C,9G 2C,8G
Barnyardgrass 2C,9H 5C,9H
Wild Oats 2C,8G 0
Wheat 5C,9G o
Corn 3U,9H 9C
15 Soybean 2C,9H 9C
Rice 5C,9G 5C,9G
Sorghum 2C,9G 9C
Sugar beet 3C,9G 9C
PRE-EMERGENCE
Morningglory 9C 9C
20 Cocklebur 9H
Sicklepod 5C,9G 2C,9G
Nu~sedge 10E 6G
Crabgrass 3C,9G ZC,6G
Barnyardgrass 4C,9H 3C,9H
Wild Oats 3C.9G 3C,9G
Wheat : 10C lC,6G
Corn 9G 5C,9H
25 Soybean 3C,9H 9H
Rice 10E 10E
Sorghum 5C,9H 5C,9H
Sugar beet SC,9G 9C
~5 ~ : ~
`''` :
.
,.
: , .
~z~
Test B
Two plastic bulb pans were filled with ferti-
lized and limed ~oodstown sandy loam. One pan was
planted with corn, sorghum, Kentucky bluegrass and
several grass weeds. The other pan was planted with
cotton, soybeans, purple nutsedge (CYPerUS rotundus),
and several broadlea~ weeds. The following grass and
broadleaf weeds were planted: crabgrass (Diqitaria
sanquinalis), barnyardgrass (Echinochloa crusqalli),
10 wild oats (Avena fatua), johnsongrass (Sorqhum hale-
pense), dallisgrass (Paspalum dilatatum~, giant fox-
taii (Setaria faberii), cheatgrass (Bromus secalinus),
mustard (Brassica arvensis), cocklebur (Xanthiu_ pen-
svlvanicum), 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 we~e treated preemergence with
several test compounds within the scope of the inven-
tion.
Twenty-eight days after treatment, the plants
25 were evaluated and visually 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.
72
. :
':
.
'
~3~
73
Table B
PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM
Compound 1 Compound 2
Rate kg/ha 0.120 0.500 0.030 0.120
Crabgrass 2G SG 2G ~G
Barnyardgrass 8G,3H lOC 7G,3H 9G,5H
Sorghum - - 7G,SH 9G,5H
Wild Oats 2G SG 4G 5G
Johnsongrass 5G,3H 8G,3H 4G,3H 6G,2H
Dallisgrass 6G 8G,SH 2G 4G
Giant foxtaii 6G,SH 8G,5H 9G 6G,3H
Ky. bluegrass 8G,8C lOC 6G 7G
Cheatgrass 6G,3C lOC 8G,8C 8G,9C
Sugar beets 8G,8C lOC 8G,8C lOC
Corn 7G,5H 9G,8C 6G,3H 7G,3H
Mustard 9G,9C lOC 9G.8C 9G,9C
Cocklebur 6G 7G,3H 6G 5G
20 Pigweed 8G lOC
Nutsedge 7G lOE 7G 7G
Cotton 3G 8G 3G 5G,3H
Morningglory 0 6G,5H 4G 9G,5C
Sicklepod 6G 7G 7G 8G,3H
Teaweed SG 8G,3H 5G lOC
Velvetleaf 6G,5H sG,gC SG,5H 8G,9C
Jimsonweed 6G 7G 7G 8G,8C
25 Soybean 3G 6G,5H 3G,3H 6G,5H
Rice 9G,9C lOC 7G,8C lOC
Wheat 4G 6G O 4G
: .
35
:. 73
,
.
~23~
74
Table B (continued
PRE-EMERGENCE ON
WOODSTOWN_ SANDY LOAM
s
Compound 3 Compound 4
Rate kg~ha 0.030 0.120 0.007 0.030
Crabgrass 0 6G O O
Barnyardgrass 6G,2H 8G.5H O 3G
Sorghum 6G,3H 9G,5H O O
Wild Oats 3G 6G O O
Johnsongrass 4G,2H 7G,5H O O
Dallisgrass O SG o O
15 Giant foxtail 3G 7G,3H O O
Ky. bluegrass 5G,3H 7G,3H 4G O
Cheatgrass 8G,8C 8G,9C O O
Sugar beets lOC lOC 6G 8G
Corn 5G,3H 7G,3H 2G 3G
Mustard 9G,SH 9G,9C 9G 9G,9C
Cocklebur 0 3G O 2G
20 Pigweed 10~ lOE
Nutsedge 9G,9E lOE O SG
Cot~on 2G 4G. 2G SG
Morningglory 3G 3G O 7G
Sicklepod 8G 8G SG 6G
Teaweed 7G 8G 6G 9G
Velvetlea~ 7G,SH 9G,8C 5G,SH 8G
Jimsonweed 5G 6G O 4G
25 Soybean 3G 6G,5H 5G 8G
Rice 8G,8C lOE O SG
Wheat 2G 4G O O
74
~3~
Table B (Contlnued
PRE-EMERGENCE ON
Y~c~o~
Compound 5
Rate kg/ha 0.030 0.120
Crabgras6 , o O
Barnyardgras~ 2G 3H,8G
Sorghum 2G 3H,8G
Wild Oats 0 2G
Johnsongrass 0 2H,4G
Dallisglass 4G 8G
lS Giant foxtail 3H,4G SH,8G
Ky. bluegrass 6G lOE
Cheatgrass SG 8G
Sugar beets SG ~G
Corn 3G 3H,7G
Mustard 9G,9C 9G,9C
Cocklebur 2G 2G
20 Pigweed
Nutsedge 2G ; 6G
Cotton 3G ~5G
Morningglory 2G 2G
Sicklepod 2G SG
Teaweed O O
Velvetleaf 0 5G
Jimsonweed 0 4G
25 Soybean 3G 3G
Rice 8G 9G,9C
Wheat 2G 3G
~ :
: 75
:
. :
,
~3~57~
76
Test C
The test chemicals, dissolved in a non-phyto-
toxic solvent, were applied in an ove~all 6pray ~o the
foliage and surrounding soil of selected plant spe-
S cies. One day after treatment, plants were checkedfor rapid burn injury. Approximately fourteen days
after treatment 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 Woodstown 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 theophrasti), sesbania (Sesbania exaltata),
sicklepod (Cassia obtusifolia), morningglory (IPomoea
hederacea), jimsonweed (Datura stramonium), cocklebur
(Xanthium pensylvanicum), crabgrass tDiaitaria spp.),
nutsedge (Cyperus rotundus), barnyardgrass (Echino-
chloa crusqalli), giant foxtail (Setaria faberii), and
wild oats (Avena fatua). The following species were
grown in soil in a paper cup (12 cm diameter by 13 cm
deep): sunflower, sugar beets, and rape. All plants
were sprayed approximately 14 days after planting.
Additional plant species, such as johnsongrass and
- field bindweed, are sometimes added to this test in
order to evaluate unusual selectivity.
76
3~57~
77
Table C
Over-the-Top Soil~Foliage Treatment
Compound 2 Compound 5
Rate, kg/ha 0.015 0.00~ 0.06 0.015
Soybeans 8G,6C 6G 3G 0
10 Velvetleaf 0 0 4G O
Sesbania 0 -
Sicklepod - 0 0 0
Cotton 3G 3G 3G 3G
Morningglory 2G C 4G 3G
Alfalfa 7G 5G 4G 3G
Jimsonweed 3G 0 0 0
Cocklebur 0 - 2G 3G
Sunflower 2G 0 3G lG
Rape 2G 0 5G 0
Sugar beets 2G 0
Corn 2G 0 lC O
Crabgrass 4G 0 0 0
Rice 6G 2G 6G 6G
Nutsedge 0 0
Barnyardqrass 0 3G 0 0
Wheat 0 0 0
Giant Foxtail 2G 4G 0 0
Wild Oats 0 0 0
Sorghum 3G 5G 8G 6G
Johnsongrass 0 0 0 0
Field Bindweed 3G 0 0 0
:
7 7
:
. .
~L23~
7Q
Test D
Two ten-inch in diameter plastic pans lined with
polyethylene liners were filled with prepared Woods
town sandy loam soil. One pan was planted with seeds
5 of wheat (Triticum aestivum), barley (Hordeum _1-
qare), wild oats (Avena fatua), downy brome (Bromus
tectorum), cheatgrass (Bromus secalinus), blackgrass
(Alopecurus mYosuroides), annual bluegrass (Poa
annua)~ green ~oxtail (Setaria viridis), quackgrass
10 (AqroPyron rePenS), Italian ryegrass (Lolium multi-
florum) and ripgut brome ~Bromus riqidus). The other
pan was planted with seeds of Russian thistle (Salsola
kali), tansy mustard (Descuraina Dinnata), cleavers
~Galium aparine), tumble mustard (SisYmbrium altis-
15 sium), kochia ~Kochia scoparia), shepherd~s purse
(CaPsella bursa-pastoris), Ma~ricaria inodora, blac~
nightshade (Solanum niqrum), yellow eocket (Barbarea
vulqaris), rapeseed (Brassica 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 untreated control and a solvent-alone con-
trol were included for comparison. All treatments
were maintained in the greenhouse for 19-21 days at
30 which time the treatments were compared to the con-
trols and the e~fects visually rated. The recorded
data are presented in Table D. Some of the compounds
tested have utility for selective weed control in
cereal crops such as wheat and barley.
7 8
':
. ,
. ~ ' ' ;
: '
.
~23~i71
79
Table D
Compound 2
Pre-Emergence Post-Emergence
Rate kgtha 0. 060 0 . 015 0 . 060 0 . 015
wheat 7G 2G 6G 3G
barley lC, 7G 2G 6G 3G
10 wild oats lC, 7G SG 5G 2G
downy brome 2C, 9G 8G BG 7G
cheatgrass lC, 9G 8G 8G 7G
blackgrass 2C, 8G 7G 5G 3G
annual bluegrass 8G 7G 7G 3G
green foxtail 2C, 8G 2C, 4G 2C, 8G 4G
quackgrass 9G 8G 3G 6G
Italian ryegrass lC, 8G 7G 4C, 8G 7G
ripgut brome 8G 8G 2C, 8G 7G
Russian thistle 2C, 3G 2G 8C, 8G 4C, 5G
tansy mustard 2C, 9G 9G 8C, 8G SC, 7G
Galium aparine 6G 8G 7G 4G
tumble mustard lC, 8G 9G lOC 7G
kochia 7G 5G 3C, 8G 4G
shepherd's purse ~C, 9G 9G 4C, 9G 7G
Matricaria inodora 7G 7G 8C, 8G 2C, 7G
bla~ck 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
3 5
:. : 7 9
.
s~
Table D (continued~
Compound 3
Pre-Emergence Post-Emergence
Rate kg/ha 0.060 O.OlS 0.060 0.015
wheat 3G 0 3G 0
barley 3G 0 5G 0
10 wild oats 5G 0 4G 0
downy brome sG 8G 9G 7G
cheatgrass 2C,9G 7G 8G 6G
blackgrass 7G 6G 6G 3G
annual bluegrass 7G 6G 2C,8G 3G
green foxtail 2C,6G ~G 2C,6G 6G
quackgrass 9G 8G 8G 7G
Italian ryegrass 8G 8G 2C,8G 6G
15 ripgut brome 8G 6G 7G 6G
~ussian thistle lC,ZG 0 8C,8G 0
tansy mustard 9G 9G lOC 9G
Galium aparine lOE 8G 6G 5G
tumble mustard 2C,9G 9G lOC 9G
kochia 8G 2C,5G ZC,8G 5G
shepherd's purse 9C,9G 9C,9G lOC 2C,8G
20 ~Satricaria inodora 8G 9G 8C,8G 8C,8G
black nightshade 6G 3G 7G 6G
yellow rocket 9G 7G 8C,8G 8C,~G
rapeseed 3C,9G 9G lOC lOC
wild buckwheat 6G 4G 2C,8G 7G
.: :
: 80
: : :
- : .
- .
,
, , ~` , ~ ,
~: ~
8~ 5~
Table D (continued3
Compound S
Pre-Emergence Post-Emergence
~ate kg/ha 0.060 0.250 0.0~0 0.250
wheat lC,2G 5G 2G 7G
barley 6G 2C,~G 3G 7G
10 wild oats 5G 7G 3G 5G
downy brome 5G 8G 5G 6G
cheatgrass 6G 8G 5G 7G
blackgrass 5G lC,7G 6G 2C,7G
annual bluegrass 6G lC,~G ~G 3C,8G
green foxtail 0 2C,6G 0 2C,SG
quackgrass 4G 8G 2G 6G
Italian ryegrass 8G 2C,9G 2C,6G 2C,8G
15 ripgut brome 6G lC,8G 5G 7G
Russian thistle 0 2C,5G 0 lOC
tansy mustard 8G 2C,sG sG 8G
Galium aparine sG lOE 0 3G
tumble mustard 7G 9G 0 6G
kochia - - - 0
shepherd's pucse 2C,9G lOC 5G lOC
20 Matricaria inodora 8G 9G 3G 9G
black nightshade 0 5G 0 4G
yellow rocket 8G 9G 0 6G
rapeseed 2C,8G 9G 7G 9C,9G
wild buckwheat 0 6G 0 3G
~his application is a division of copending
Canadlan Appl}catlon Serlal No. 443,738 flled
1983 December 20.
35 ~ i
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