Note: Descriptions are shown in the official language in which they were submitted.
~`' 09-21-0893
1048518
HE'RB'IC'IDAL AN'IL'IDES
.....
This invention relates to novel acetanilides which are
useful as herbicides and to methods of preparing them. The in-
vention also relates to herbicidal compounds and to methods of
inhibiting or preventing the growth of plant systems.
The term "plants" is used herein to include germinant
seeds, emerging seedlings and established vegetation, including
the roots and above-ground portions.
The novel compounds of the present invention are
represented by the formula
R o
~ C - CH2X ~ ~
C ~--N
~ \ 11 ,
2 11 (CH2)n - A - C - R
R R
wherein
A is NH, N-(C=O)m-R , oxygen or sulfur,
Y is oxygen or sulfur when A is oxygen or sulfur, and
is oxygen when A is N-(C~o)m-R4 or NH,
R and Rl are hydrogen, alkyl or alkoxy having at least
1 and not more than 10 carbon atoms and can be like or unlike~ ;
R2 is hydrogen, alkyl or alkoxy having at least 1 and
not more than 10 carbon atoms, NO2 or halogen,
R3 is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkyl-
thio, polyalkoxy, polyalkylthio, alkoxyalkyl, alkylhhioalkyl,polyalkoxyalkyl, ~olyalkylthioalkyl, haloalkyl, hydroxyalkyl,
mercaptoalkyl, haloalkenyl, oxoalkyl, alkenyloxyalkyl, alkenyl-
thioalkyl, each of a maximum of 18 carbon atoms; cycloalkyl having
at least 3 and a maximum of 6 carbon atoms; aryl, aryloxy, aryl-
oxyalkyl, arylthioalkyl, trifluoromethyl- and haloaryl, trifluoro-
methyl- and haloaryloxyalkyl, trifluoromethyl- and haloarylthioalkyl,
-2-
C: ,, .
1048S18
ar~lalkyl, arylalkenyl, nitroaryl, nitroarylthioalkyl, and
nitroarylalkyl having at least 6 and not more than 24 carbon
atoms; amino or mono- and dialkylamino, carbamoyl, alkyl-
substituted carbamoyl, monoarylamino, mono(haloaryl)amino,
mono(trifluoromethylaryl)amino, and alkylalkoxyamino having a
maximum of 10 carbon atoms, and
R4 is alkyl, alkenyl, aryl or alkaryl having a maxi-
mum of 18 carbon atoms, or n3 and R4 are combined to form an .
alkylene or alkenylene bridge having at least 2 and not more
than 5 carbon atoms or a phenylene group,
X is chlorine, bromine or iodine, and :
n is an integer of 1 or 2 and m is an integer of 0 to
2 inclusive.
Unless otherwise indicated, "alkyl" and "alkoxy" is
used generically to include primary, secondary, and tertiary
groups.
Representative compounds of the present invention
include those in which the groups of the above formula have
the following identities:
R and Rl - hydrogen, methyl, ethyl, propyl, isopropyl,
n-butyl, primary isobutyl, secondary isobutyl, tertiary butyl,
n-amyl, branch chain amyls, the normal and branched hexyls, ~:~
heptyls, octyls, nonyls, and decyls, methoxy, ethoxy, propoxy,
butoxy, pentyloxy, heptyloxy, nonyloxy;
R2 _ hydrogen, chlorine, bromine, fluorine, iodine,
nitro and the alkyl and alkoxy groups of R and Rl.
R3 - hydrogen, methyl, ethyl, propyl, isopropyl, n-
butyl, primary isobutyl, secondary isobutyl, tertiarybutyl, the
normal and branched amyls, hexyls, heptyls, octyls, nonyls, dec-
yls, dodecyls, tetradecyls, hexadecyls and octadecyls, chloro-
methyl, bromopropyl, iodobutyl, fluorohexyl, hydroxyethyl,dihy-
droxypropyl; the a~oxy, alkenyl, oxoalkyl, alkoxyalkyl and alky-
nyl groups corresponding ~ the above-enumerated alkyl groups;
phenyl, toly~ naphthyl, phenoxy, benzyl, phenoxyalkyl; 2-pyridyl,
3-pyridy~ 4-pyridyl, 3,4-methylenedioxyphenyl; ethylene, tri-
--3--
09-21-0893
,~
~ (~48S18
methylene, tetramethylene; and the like.
R4 - the alkyl, alkenyl, alkynyl, aryl and alkaryl
groups of R3.
When R3 and ~4 are combined as a polymethylene bridge
between the nitrogen atom and the carbonyl carbon atom and m is
0, lactamyl radicals are formed. These include 2-pyrrolidinon~
yl or (2-oxo-tetramethylene imino), 2-piperidinon-1-yl or (2-oxo-
pentamethylene imino) and 2-oxo-hexamethylene imino. I~hen m is
1, R3 and i~4 can combine to form cyclic imides including phthali-
mi~es.
The preferred compounds of the present invention arethose in which both R and Rl are ethyl and Illore particularly the
compounds in which they are in the ortho positions.
The novel compounds of the present invention in which
A is l~ll and n is 1 are prepared by a carbonium ion type reaction
of a 2-halo-N-(substituted methyl)acetanilide with a nitrile or
an inorganic cyanide under acid conditions. '~he novel compounds
of the present invention in which n is 1 and A is oxygen or sul-
fur are prepared similarly by the reaction of a 2-halo-I~-(substi-
tuted methyl)acetanilide with a monocarboxylic acid. The methylsubstituent can be any group that is capable of forming a car-
bonium ion and is readily displaced under acidic conditions.
'l~hus, the starting material can be a 2-halo-N-methyl acetanilide
in which the methyl group is substituted with a halo, alkoxy,
alkylthio, hydroxy, mercapto, alkenoyloxy and similar leaving
groups. It is particularly preferred, however, to utilize a 2-
halo-N-chloromethyl acetanilide in the preparation of these com-
pounds. A solvent can be used but in most instances is not
generally required. While the reaction can be conducted at
~0 temperatures as low as O~C, it is generally preferred to accel-
erate the reaction by conducting it under reflux conditions at
the boiling point of the nitrile or solvent in the system. After
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_ 09-21-0893
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~he reaction is substantially completed the reaction mixture is
quenched with water and filtered to recover the acetanilide which
may then be purified in any conventional manner.
The 2-halo-N-(substituted methyl)acetanilide used as a
starting material in these reactions is the adduct of a haloacetic
derivative such as the halide or anhydride with a substituted
azomethine or methylenearylamine. The azomethines are prepared
by the reaction of a suitably substituted aniline with formalde-
hyde. The 2-halo-N-halomethyl acetanilides that can be employed
in ~reparing the present compounds are described and claimed in
U. S. Patent 3,637,847 granted January 25, 1972.
The compounds of the present invention in which A is
NH and n is 1 can also be prepared by reacting a nitrile with an
alpha halo-disubstituted-N-(alkoxymethyl)acetanilide of the type
described and claimed in U. S. Patent 3,442,945 granted May 6,
1969.
The novel compounds of the present invention in which ;
A is N-(C=o~m-R4 and m and n are both 1 are prepared by the
reaction of a substituted methylenearylamine with an appropriate-
ly substituted amide or imide to form the corresponding N-(anilino-
methyl) amide or imide. The intermediate amide or imide is
then haloacetylated with a haloacetylhalide to provide the
compounds under consideration.
The novel compounds of the present invention in which
A is NH and n is 2 are readily prepared by the chloroacetylation
of an N-(substituted phenyl)-N'-acyl-ethylenediamine. The
novel compounds of the present invention in which A is N-(C=o)m-R4,
and m is 0 to 2, are prepared similarly by the haloacetylation
of an N-(substituted phenyl)-N'-acyl-N'-~C=O)m-R -ethylenediamine.
The ethylenediamine derivatives used as starting materials for
such reactions can be readily prepared in conventional manners
by the alkylation of a substituted aniline with alkylating agents
-5-
~~ 09-21-0893
1048518
~such as an N-(2-chloroethyl)-alkylamide, N-2-(hydroxyethyl)-
alkylamide N-(2-bromoethyl)-phthalamide or an N-acyl aziridine.
The novel compounds of the present invention in which
A is oxygen or sulfur and n is 2 are readily prepared by the
S chloroacetylation of an N-(substituted phenyl)-ethyl ester of
the formula
R
NH-CH2-CH2-o-~-R3
R2 Rl
wherein R, Rl, R2 and R3 are as described above.
The ethyl ester derivatives used as starting materials
for such reactions can be readily prepared in conventional manners
by the alkylation of a substituted aniline with alkylating agents
such as an N-(2-chloroethyl)-ethyl ester or an N-2-(hydroxyethyl)-
ethyl ester.
The invention will be more clearly understood by
reference to the following detailed description of specific
examples thereof. In these examples and throughout the specifi-
cation, all proportions are expressed in parts by weight unless
otherwise indicated.
EXAMPLE 1
This example describes the preparation of 2-chloro-N- -
(2',6'-diethylphenyl)acetamidomethyl chloroacetate. About 168
parts of 2',6'-diethylphenyl azomethine dissolved in benzene were
slowly added to about 177 parts of chloroacetic anhydride dis-
solved in hot benzene. The reaction mixture was agitated until
the reaction was substantially completed, concentrated and then
chilled. A white solid melting at 57-58 C was obtained. An ele-
mental analysis of this product yielded the following results:
Calc d for C15H19NC123
Found: C, 54.19; H, 5.91
-6-
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1048518
EXAMPLE 2
This example describes the preparation of 2-chloro-2'-
6'-diethyl-N-(acetamidomethyl)acetanilide. About 80 parts of 2-
chloro-N-(2',6'-diethylphenyl)acetamidomethyl chloroacetate pre-
pared in accordance with the general procedure of Example 1 wasmixed with about 1000 parts of methyl cyanide and about 2 parts
of 10% sulfuric acid in a suitable reaction vessel. The reaction
mixture was refluxed for about 2 1/2 hours at atmospheric pressure
and then poured into a mixture of ice and water. The solid
material thus obtained was recrystallized from methanol and
melted at 148-149C.
Calc d for C15 21 2 2 C, 60.7 H, 7.13
Found: C, 60.68 H, 7.22
EXAMPLE 3
This example describes the preparation of 2-chloro-2'-
6'-diethyl-N-(2",6"-dichlorobenzamidomethyi)acetanilide. About
100 parts of 2-chloro-N-chloromethyl-2',6'-diethyl acetanilide
were added to about 350 parts of sulfuric acid in a suitable
reaction vessel, cooled to about 0C and agitated. To this
mixture was slowly added about 67 parts of 2,6-dichlorophenyl
nitrile. After the addition of the nitrile was completed, the
reaction mixture was heated to about 75C for about 1 1/2 hours
with constant stirring. The reaction mixture was then poured
into ice water and a light tan solid precipitated. The solid was
separated from the reaction mixture by filtration, washed with
water, filtered and recrystallized from toluene to yield a
material melting at 150.5-153C.
Calc'd for C20H21C13N22 C, 56.16 H, 4.95
Found: C, 55.69 H, 4.85
EX~MP~E 4
This example describes the preparation of 2-chloro-2',6'-
diethyl-N-(3-butenamidomethyl) acetanilide. About 300 parts of
sulfuric acid were charged into a suitable reaction vessel. About
100 parts of 2-chloro-N-chloromethyl-2',6'-diethylacetanilide and
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_ 09-21-0893
~048S~8
~out 26 parts of allyl nitrile, dissolved separately in glacial
acetic acid, were added to the sulfuric acid. After these react-
ants were addad, the reaction mixture was heated to about 55C for
about 15 minutes and then poured into ice water. The resultant
solid precipitate was filtered and washed with water. After re-
crystallization from isopropanol, the product had a melting point
of 121.5-123.5~.
17 23 2 2 C, 63.25 H, 7.18
Found: C, 62.38 H, 6.95
EXAMPLE 5
This example describes the preparation of 2-chloro-2',-
6'-diethyl-N-formamidomethyl acetanilide. About 200 parts of 2-
chloro-N-chloromethyl-2',6'-diethylacetanilide were added to 400
parts of concentrated sulfuric acid. The mixture was cooled to
about 10C and 70 parts of sodium cyanide were then added and the
reaction mixture heated to about 50C. The reaction was exother-
mic and the temperature of the reaction mixture rose to about
85C. The reaction mixture was cooled, poured into ice water,
extracted with methylene dichloride, washed with water and dried
over magnesium sulfate. The oily residue formed was crystallized
from ether and recrystallized with a methylcyclohexane-toluene
mixture, m.p. 85-89C.
Calc d for C14HlgC1 2 2 C, 59.46 H, 6.77
Fou~d: C, 59.64 H, 6.69
EXAMPLE 6
This example describes the preparation of 2-chloro-2'-6'-
diethyl-N-(3-chloro-2-methylpropionamidomethyl)acetanilide. About
100 parts of 2-chloro-N-chloromethyl-2',6'-diethylacetanilide were
mixed with 26 parts of methacrylonitrile and added to about 350
parts sulfuric acid at a temperature of about 10C in a suitable
reaction vessel. The reaction mixture was heated to about 65C
for about four hours while dry hydrogen chloride gas was bubbled
-8-
~. .
- 09-21-0893
1(~4~S18
~hrough it. The reaction mixture was poured into ice water and
filtered to remove the precipitate which was then recrystallized
from isopropanol.
Calc'd for C17H24C12N22 C, 56.83 H, 6.73
Found: C, 56.85 H, 6.62
EXAMPLE 7
This exampIe describes the preparation of 2-chloro-2',-
6'-diethyl-N-(acrylamidomethyl)acetanilide. About 135 parts of
2-chloro-2',6'-diethyl-N-methoxymethyl acetanilide were mixed
with about 27 parts of acrylonitrile and about 300 parts of sul-
furic acid were added. The reaction mixture was heated to about
55C and maintained at that temperature for about one hour. At
the end of that time the reaction mixture was poured into ice
water and yielded a solid granular precipitate. This material
was removed from the reaction mixture by filtration, washed with
water and recrystallized from isopropanol. The recrystallized
material melted at 174-175C.
Calc d for 16 21 2 2 C, 62.23 H, 6.85
Found: C, 62.54 H, 7.05
EXAMPLE 8
This example describes the preparation of 2-chloro-2'-
ethyl-6'-methyl-N-(cyclopropane carboxamidomethyl)acetanilide.
About 300 parts of concentrated sulfuric acid were charged into
a suitable reaction vessel and cooled to about 0C while being
~ ~e~y/-6/~ f~yJ
agitated. About 100 parts of 2-chloro-~',6'-diethyl-N-chloro-
~ methyl acetanilide were slowly added and the mixture heated to
about 25C to expedite dissolution of the adduct. The mixture
was again cooled to about 10C and about 28 parts of cyclopropyl
nitrile were slowly added. After the addition of the nitrile was
completed, the reaction mixture was heated to about 55C for about
20 minutes and then poured into ice water. This resulted in the
formation of a gummy precipitate which solidified upon standing
1,~ , ~,
--- 09-21-0893
1048S18
dbout 8 hours. The solid precipitate was separated by filtration,
washed with water, filtered and recrystallized from isopropanol.
This material melted at 154-156.5C.
EXAMPLE 9
N-(2,6-Diethylanilinomethyl)-N-methylacetamide
f2H5 f H3
NH - C~2 ~
C2H5 ~ OCH3
About 100 parts of N-methylacetamide were charged into a suitable
reaction vessel and about 100 parts of 2% sodium methoxide sus-
pension in dimethylformamide were added. The reaction was exo-
thermic and the temperature of the reaction mixture rose from
about 24C to about 30C. Then about 160 parts of 2,6-diethyl-N- -
methyleneaniline were added resulting in an additional rise in
temperature to about 44C. The reaction mixture was maintained
at this temperature with continued agitation for about 7 hours.
With continued stirring it was permitted to return to room temper-
ature over a period of about 16 hours. About 3 parts of acetic
acid were added, then about 200 parts water ahd the mixture
vigorously agitated. About 150 parts of benzene were added to
aid in the separation of the mixture into an oil layer and a water
layer. The water layer was discarded and the oil layer washed
with an additional 200 parts water containing one part acetic
acid, dried over magnesium sulfate and vacuum distilled. A straw
colored liquid identified as N-(2,6-diethylanilinomethyl)-N-
methylacetamide was obtained.
~, .,
~5Calc'd for C ~ 22N2 C, 71.75 H, 9.46 N, 11.95
Found: C, 71.90 H, 9.54 N, 12.05
EXAMPLE 10
2-chloro-N-(N-methylacetamidomethyl)-2',6'-diethylacetanilide
--10--
.
~ 09-21-0893
~04851~
CH3
~2H5 CH2 - N ~.
N \ COCH3
~ \ ,
C2H5 ~OCH2Cl
About 72 parts of N-(2,6-diethylanilinomethyl) -N-
methylacetamide obtained in accordance with the procedure of
Example 9 were dissolved in about 100 grams of toluene and intro-
duced into a suitable reacti~n vessel to which about 40 parts of
2,6-lutidine were added. The mixture was chilled with carbon
dioxide-acetone and while being vigorously agitated about 40 parts
of chloroacetyl chloride in 70 parts of benzene were added over a
15 minut~ period with the temperature of the reaction mixture be-
ing maintained between -20C and -30C. With continued agitation,
the reaction mixture was permitted to warm to room temperature.
About 100 parts,of water were then added and the mixture separated
into an oily fraction and an aqueous fraction. The aqueous frac-
tion was discarded and the oily fraction washed twice with 150
parts of water at a temperature of about 35C. The reaction
mixture was then vacuum evaporated to substantial dryness and about
100 parts methylcyclohexane added to the residue followed by the
addition of about 15 parts benzene to provide a homogenous solu-
tion. The product crystallized from the solution upon standing
and was removed from the liquid phase by filtration. The pre-
cipitate was washed with a mixture of methylcyclohexane and ben-
zene and then air dried. After recrystallization from a benzene-
hexane mixture, a cream colored product having a melting point of
82-83C was obtained.
r C16H23ClN22 C, 61-83 H, 7.46 Cl 11 41
N, 9'.01
Found: C, 61.68 H, 7.47 Cl, 11.48
N,'8.97
., --1 1--
;
'
._ 09-21-0893
1~48518
EXAMPLE 11
2-chloro-2',6'-diethyl-N-(succinimidomethyl)acetanilide
f 2H5 / 2 1 -
q \ I - 1~2
2H5 COCH2Cl ,~
A mixture of about 30 parts of 2,6-diethyl-N-methylene-
aniline, 20 parts of succinimide and 75 parts of dimethyl forma-
mide wsre heated at a temperature of about 90-95C for 18 hours ~ -
in a suitable reaction vessel. The reaction mixture was then
vacuum evaporated to provide a residue containing N-(2,6-diethyl-
anilinomethyl)succinimide. The residue was dissolved in about
150 parts of toluene and about 30 parts 2,6-lutidine were added.
The mixture was cooled to about -10C and about 23 parts of
chloroacetyl chloride were added incrementally over a period of
20 minutes while maintaining the temperature of the reaction
mixture between about -10C and 5C. This resulted in the forma-
tion of a heavy precipitate. The reaction mixture was then
cooled to about 0C and maintained at that temperature for about
one hour, at the end of which time the precipitate was removed
from the dark mother liquid. The precipitate was washed with
dilut0 hydrochloric~acid, water and then with toluene. The
precipitate was then recrystallized from a methylcyclohexane-
ethyl acetate mixture to obtain a gray powder having a melting
point of 146-147C.
Calc'd for C17H21C1~2O3: C, 60.62 H, 6.28 Cl, 10.53
N, 8.32
25Found: C, 60.90 H, 6.25 Cl, 10.53
N, 8.25
A -12-
~ 09-21-0893
1048S18
EXAMPLE 12
2-chloro-2',6'-diethyl-N-[(2-pyrrolidinon-1-yl)methyl]acetanilide
O'C CH2
2H5 / CH2- N \ f H2
N CH2
~ \
~2H5 COCH2Cl
About 40 parts of N-(2,6-diethylanilinomethyl)-2-pyrrolidinone
were dissolved in about 100 parts toluene and about 30 parts 2,6-
lutidine were added to the solution contained in a suitable re-
action vessel. The mixture was then cooled to about -30C with
continuous agitation. About 23 parts of chloroacetyl chloride
dissolved in about 80 parts toluene were added over a 15 minute
period while maintaining the temperature of the mixture between
-20 and -30C. After the addition was complete, the reaction mix-
ture was permitted to warm to room temperature and about 100 parts
of water were added. This resulted in the formation of an oily
fraction and an aqueous fraction. The aqueous fraction was dis-
carded and the remaining oil washed with water and vacuum stripped.
The oily residue was dissolved in a mix*ure of 100 parts of methyl-
cyclohexane and 20 parts benzene. The product precipitated from
this mixture on standing and upon recrystallization from a mix-
ture of methylcyclohexane and benzene was obtained in the form of
colorless granules having a melting point of 56-57C.
Calc'd for C17H23ClN2O2: C, 63.25 H, 7.18 Cl, 10.98
Found: C, 63.36 H, 7.33 Cl, 11~02
EXAMPLE 13
N-(2,6-diethylanilinomethyl)-N,N',N'-trimethyloxamide
-13-
1048S18
C2H5CH3 0 0
N - CH~ - N - C C - N
C 2H5
About 650 parts of N,N',N'-trimethyloxamide and about
4 parts of potassium hydroxide pellets were introduced into a
suitable reaction vessel and about 800 parts of 2,6-diethyl-
phenylazomethine were added, followed by the addition of about
5 parts of a 25~ solution of sodium methoxide in methanol. The
reaction started slowly and the temperature rose from room
temperature to about 50C in 15 minutes, followed by a drop in
temperature to about 45Co The mixture was subsequently heated -
to about 100C with continued stirring and allowed to cool to
room temperature tabout 23C). The resulting honey-like syrup
which contained some unreacted pellets of sodium hydroxide was
dissolved in 2500 parts of methylcyclohexane and acidified with
about 10 parts of acetic acid. Upon stirring the reaction mix-
ture, the product crystallized to form colorless granules which
were filtered and washed twice with 1200 parts of methylcyclo-
hexane. The product was finally washed 3 times with 1500 parts
of water and air dried. The product thus obtained had a melt-
ing point of 73-73.3C.
Calc~d for C16H25N302: C, 65~9 H, 8.6 N, 14~4
Found: C, 65.9 H, 8.6 N, 14~4
This compound and related compounds having 2 adjacent carbonyl
groups can be readily haloacetylated to form compounds of the
present invention in which n is 1.
EXAMPLE 14
This example describes thepreparation of 2-chloro-2'-
6'-diethyl-N-(propionyloxymethyl)acetanilide. About 140 parts of
2-chloro-2',6'-diethyl-N-chloromethylacetanilide dissolved in
tetrahydrofuran were introduced into a suitable reaction vessel
-14-
.
og-21-0893
104~S18
d a solution of about 40 parts of propionic acid in tetrahydro-
furan added. ~hen the mixture was substantially uniform, about
55 parts of triethylamine were added incrementally. The solution
was then heated to and maintained at reflux temperature for about
3 hours and cooled to room temperature. The resultant precipitate
was removed from the reaction mixture by filtration and taken up
in diethyl ether. The ether solution was washed with aqueous
sodium bicarbonate solution, then with water and dried over mag-
nesium sulfate. 'l'he solution was then vacuum stripped to obtain
an oily residue which subsequently solidified and was recrystal-
lized from hexane to yield a white solid having a melting point of
64-65C.
Calc d for C16H22ClN3 C, 61.63 I~, 7.11
Found; C, 61.94 H, 7.04
EXAMPLE; 15
This example describes the preparation of 2-chloro-2',6'
diethyl-~-(formyloxymethyl)acetanilide. About 140 parts of 2-chloro-
2',6'-diethyl-N-chloromethylacetanilide dissolved in tetrahydro-
furan were charged into a suitable reaction vessel and about 25
parts of 99+% formic acid and 50 parts of triethylamine were added.
The reaction mixture was then refluxed for about 3 hours and cool-
ed to room temperature. The tetrahydrofuran was stripped from the
mixture by vacuum distillation. The residue was dissolved in di-
ethyl ether and the ether solution washed first with aqueous sodium
bicarbonate, then with water and finally dried over magnesium sul-
fate. The ether solution was vacuum distilled at 65C under pres-
sure of 5 mm. of mercury to provide a clear oily residual material.
Calc'd for C14l~l8C1~3: C, 59.26 H, 6.39
Found`: C, 59.32 II, 6.47
EXAMPLE 16
This example describes the preparation of 2-chloro-2',6'-
diethyl-N-(butyryloxymethyl)acetanilide. About 200 parts of 2-
chloro-2',6'-diethyl-~-chloromethyl acetanilide dissolved in tetra-
.
lV4~518 ~
h~drofuran were introduced into a suitable reaction vessel and well
agitated. About 70 parts of n-butyric acid and about 80 parts of
triethylamine were added incrementally with continued agitation.
The reaction mixture was refluxed for about 3 hours, cooled to
room temperature, filtered and the filtrate stripped by vacuum
distillation. The residue was dissolved in diethyl ether, washed
with aqueous sodium bicarbonate, water and then dried over magne-
sium sulfate. The magnesium sulfate was removed by filtration
and the solvent stripped by distillation at 60C and 1 mm of
mercury. The residue thus obtained is a red-orange oil.
c 17 24 3 C,62.66 H, 7.42
Found: C, 63.01 H, 7.73 -
EXAMPLE 17
This example describes the preparation of 2-chloro-2',-
6'-diethyl-N-(acrylyloxymethyl)acetanilide. About 200 parts of
2-chloro-2',6'-diethyl-~-chloromethylacetanilide, 55 parts of
acrylic acid and about 80 parts of triethylamine were reacted in
substantially the same manner as in the preceding example to
provide an off-white solid material melting at 91-96C.
Ca c 16 20 3 C, 62.03 H, 6.51
Found: C, 62.66 H, 6.59
EXAMPLE 18
In a substantial repetition of the procedure of the
foregoing examples, using cyclopropane carboxylic acid as a
reactant, 2-chloro-2',6'-diethyl-~-~cyclopropanecarbonyloxymethyl)-
acetanilide, a solid product melting at 84-87C was obtained.
Calc d for C17H22C1~3 C, 63.p6 H, 6.85
Found: C, 63.43 H, 7.00
EXAMPLES 19 THROUGH 165
The following compounds are also prepared by substan-
tial repetition of the general procedures set forth in the fore-
going examples:
- 16 -
s~
09-21-0893
1048518
~19) 2-chloro-2',6'-Oiethyl-N-(cinnamamidomethyl)acetanilide
-m.p. 146 - 147 C
(20) 2-chloro-2',6'-diisopropyl-N-(butyramidomethyl)acetanilide
(21) 2-chloro-2',4',O'-trimethyl-N-(acetamidomethyl)acetanilide
-m.p. 131 - 132 C
(22) 2-iodo-2',6'-diethyl-4'-meth~l-N-(chloroacetamidomethyl)
acetanilide
(23) 2-chloro-2',6'-diethyl-N-(3-ethoxypropionamidomethyl)acet-
anilide
- m.p. 70.5C
(24) 2-chloro-2',6'-diethyl-N-(2-chloroacetamidomethyl)acet-
anilide
-m.p. 153-159C
(25) 2-chloro-2',6'-giethyl-N-(isobutyramidomethyl)acetanilide
-m.p. 130-133.5 C
(26) 2-chloro-2',6'-diethyl-N-(caprylamidomethyl)acetanilide
(27) 2-chloro-2',6'-diethyl-N-(beta-chloropropionamidomethyl)acet-
anilide
-m.p. 133-136.5C
(28) 2-chloro-2',6'-diethyl-N-(propionamidomethyl)acetanilide
-m.p. 144-146C
(29) 2-chloro-2',6'-dOiethyl-N-(butyramidomethyl)acetanilide
-m.p. 122-123.5 C
(30) 2-chloro-2',6'-diethyl-N-(oxamidomethyl)acetanilide
(3i) 2-chloro-2',6'-diethyl-N-(ureidomethyl)acetanilide
-m.p. 206C.
(32) 2-chloro-2',6'-diethyl-N-(benzamidomethyl)acetanilide
-m.p. 132C
(33) 2-chloro-2',6'-diethyl-N-(phenylacetamidomethyl)acetanilide
-m.p. 135-137C
(34) 2-chloro-2',6'-diethyl-N-(methacrylamidomethyl)acetanilide
-m.p. 106-108.5C
(35) 2-chloro-2',6'-diethyl-N-(3-ethylthiopropionamidomethyl)acet-
anilide
(36) 2-chloro-2',6'-diethyl-N-(lauramidomethyl)acetanilide
(37) 2-bromo-2',6'-dimethyl-N-(urethylanylmethyl)acetanilide
(38) 2-chloro-2'-tert-butyl-N-(valeramidomethyl)acetanilide
(39) 2-chloro-2'-methyl-6'-ethyl-N-(acetamidomethyl)acetanilide
white solid, m.p. 132-133C
(40) 2-chloro-2',6'-diethyl-N-(2,3-dichloropropionamidomethyl)
acetanilide
white solid, m.p. 154-156C
(41) 2-chloro-2'-methyl-6'-tertiary butyl-N-(acetamidomethyl)
acetanilide
-m.p. 158-160.5C
! (42) 2-chloro-2'-methoxy-6'-tertiary butyl-N-(methacrylamido-
methyl)acetanilide
(43) 2-chloro-2',6'-dimethyl-N-(acetamidomethyl)acetanilide
white solid, m.p. 1S9.5-160.5C
(44) 2-chloro-2',3'-dimethyl-6'-tertiary butyl-N-(acetamidomethyl)
acetanilide
-m.p. 163-165C
(45) 2-bromo-2'-methyl-6'-tertiary butyl-N-(methacrylamidomethyl)
acetanilide
SS white solid, m. p. 151.5-154C
-17-
. _ :
.... : - ,., : .. .. ~ ; . .
- 09-21-0893
1048518
~46) 2-chloro-2',6'-diethyl-N-(e~lopropane carboxamidomethyl)-
acetanilide
-m.p. 179-180C
(47) 2-chloro-2',6'-diethyl-N-(3-methoxypropionamidomethyl)acet-
white solid, m.p. 70.5-72.5C
(48) 2-bromo-2'-ethyl-6'-tertiary butyl-N-(acetamidomethyl)acet-
anilide
-m.p. 157.5-159.5C
(49) 2-chloro-2',6'-diethyl-N-(acetamidoethyl)acetanilide
-m.p. 83-86C
(50) 2-chloro-2',6'-diethyl-N-(2",6"-dichlorobenzamidoethyl)acet-
~ anilide
(51) 2-chloro-2',6'-diethyl-N-(3-butenamidoethyl)acetanilide
(52) 2-chloro-2',6'-diethyl-N-(formamidoethyl)acetanilide
(53) 2-chloro-2',6'-diethyl-N-(3-chloro-2-methylpropionamido-
ethyl)acetanilide
(54) 2-chloro-2',6'-diethyl-N-(acrylamidoethyl)acetanilide
(55) 2-chloro-2'-ethyl-6'-methyl-N-(cyclopropane carboxamido-
ethyl)acetanilide
(56) 2-chloro-2',6'-diethyl-N-(cinnamamidoethyl)acetanilide
(57) 2-chloro-2',6'-diisopropyl-N-(butyramidoethyl)acetanilide
(58) 2-chloro-2',6'-dimethyl-N-(succinimidomethyl)acetanilide
(59) 2-chloro-2',6'-dimethyl-N-(succinimidoethyl)acetanilide
colorless granular solid, m.p. 89-92C
(60) 2-bromo-2'-ethyl-6'-methyl-N-(succinimidoethyl)acetanilide
(61) 2-iodo-2',6'-diethyl-N-(succinimidomethyl)acetanilide
(62) 2-bromo-2',6'-diethyl-N-(succinimidomethyl)acetanilide
(63) 2-chloro-2',6'-diethyl-N-(maleimidomethyl)acetanilide
(64) 2-chloro-2',6'-dimethyl-N-(maleimidomethyl)acetanilide
(65) 2-chloro-2',6'-dimethyl-N-(maleimidoethyl)acetanilide
(66) 2-bromo-2'-ethyl-6'-methyl-N-(maleimidoethyl)acetanilide
(67) 2-iodo-2',6'-diethyl-N-(maleimidomethyl)acetanilide
(68) 2-bromo-2',6'-diethyl-N-(maleimidomethyl)acetanilide
(69) 2-chloro-2',6'-diethyl-N-(citraconimidomethyl)acetanilide
(70) 2-chloro-2',6'-dimethyl-N-(citraconimidomethyl)acetanilide
(71) 2-chloro-2',6'-dimethyl-N-(citraconimidoethyl)acetanilide
(72) 2-bromo-2'-ethyl-6'-methyl-N-(citraconimidoethyl)acetanilide
(73) 2-iodo-2',6'-diethyl-N-(itaconimidomethyl)acetanilide
(74) 2-bromo-2',6'-diethyl-N-(itaconimidomethyl)acetanilide
(75) 1-(N-chloroacetyl-2',6'-diethylanilinoethyl)-2-pyrrolidinone
, ~ -18-
. : : .
-~ 09-21-0893
~1148S18
~76) 2-chloro-2',6'-diethyl-N-[(2-pyrrolidinon-1-yl)ethyl]acet-
anilide
(77) 2-chloro-2',6'-diethyl-N-[(2-piperidinon-1-yl)methyl]acet-
anilide
(78) 2-chloro-2',6'-diethyl-N-(2-piperidinon-1-yl-ethyl)acet-
anilide
(79) 2-chloro-2',6'-diethyl-N-(2-oxo-hexamethyleneiminomethyl)-
acetanilide
(80) 2-chloro-2',6'-diethyl-N-(2-oxo-hexamethyleneiminoethyl)-
acetanilide
(81) 2-chloro-N-(N-methylacetamidoethyl)-2',6'-diethyl acet-
anilide
(82) 2-chloro-2',6'-diethyl-N-(N-methyl-dichlorobenzamidomethyl)
acetanilide
(83) 2-chloro-2',6'-diethyl-N-(N-methyl-dichlorobenzamidoethyl)
acetanilide
(84) 2-chloro-2',6'-diethyl-N-(N-ethyl-3-butenamidomethyl)acet-
anilide
~85) 2-chloro-2',6'-diethyl-N-(N-methyl-3-butenamidoethyl)acet-
anilide
(86) 2-bromo-2',6'-dimethyl-N-(N-methylformamidomethyl)acetani-
(87) 2-bromo-2',6'-dimethyl-N-(N-methylformamido)ethyl acetani-
lide
(88) 2-chloro-2',6'-diethyl-N-(N-methylacrylamido)methyl acet-
anilide
(89) 2-chloro-2',6'-diethyl-N-(N-ethyl-3-ethoxy-propionamido-
methyl)acetanilide
(90) 2-chloro-2',6'-diethyl-N-(N-methyl-beta-chloro-propionamido-
methyl)acetanilide
(91) 2-chloro-2',6'-diethyl-N-(N-propyl-propionamidomethyl)acet-
anilide
(92) 2-chloro-2'-methyl-6'-ethyl-N-(N-ethyl-acetamidoethyl)acet-
anilide
(93) 2-chloro-N-(phthalimidomethyl)-2',6'-acetoxylidide
white powder, m.p. 209-212C
(94) 2-chloro-2',6'-diethyl-N-(isobutyryloxymethyl)acetanilide
white solid, m.p. 40-42.5C
(95) 2-chloro-2',6'-diethyl-N-(methoxyacetoxymethyl)acetanilide
white solid,m.p. 66-68.5C
_ (96) 2-chloro-2',6'-diethyl-N-(methacrylyloxymethyl)acetanilide
white solid, m.p. 48-52C
(97) 2-chloro-2',6'-diethyl-N-(cinnamyloxymethyl)acetanilide
white solid, m.p. 68.5-72.5C
(98) 2-chloro-2',6'-diisopropyl-N-(butyryloxymethyl)acetanilide
(99) 2-bromo-2',3',6'-trimethyl-N-(acetoxymethyl)acetanilide
, ,` -19-
.~, . . ~ .
.. .. . .. .
104~S18 09-21-0893
`~100) 2-chloro-2',6'-diethyl-N-(3-ethoxypropionyloxymethyl)acet-
anilide
brown viscous oil
(101) 2-chloro-2',6'-diethyl-N-(caprylyloxymethyl)acetanilide
(102) 2-chloro-2',6'-diethyl-N-(beta-chloropropionyloxymethyl)- - :
acetanilide
(103) 2-chloro-2',6'-dimethyl-N-(propionyloxymethyl)acetanilide
-m.p. 64-65C .:: . .:
(104) 2-chloro-2',6'-dimethyl-N-(butyryloxymethyl)acetanilide :.:
(105) 2-chloro-2'-tertiarybutyl-6'-methyl-N-(acetoxymethyl)acet-
anilide
(106) 2-chloro-2',6'-diethyl-N-(carbamyloxymethyl)acetanilide ;
(107) 2-chloro-2',6'-diethyl-N-(phenylacetoxymethyl)acetanilide
(108) 2-chloro-2',6'-diisopropyl-N-(methacrylyloxymethyl)acet- .
anilide .
(109) 2-chloro-2',6'-diethyl-N-(3-ethylthiopropionyloxymethyl)-
acetanilide :
(110) 2-chloro-2',6'-dimethyl-N-(lauryloxymethyl)acetanilide
golden viscous liquid
(111) 2-bromo-2',6'-dimethyl-N-(methoxyformyloxymethyl)acetanilide
(112) 2-chloro-2'-tert-butyl-N-(valeryloxymethyl)acetanilide
(113) 2-chloro-2'-methyl-6'-ethyl-N-(acetoxymethyl)acetanilide
~ 3~ ~ d~ o~o~pro~o ~o~ /o)~y~n e~Ay/
~;; (114) 2-chloro-2',6'-diethyl-N-(1,3-diahloropropionyloxym~thy.l)-
acetanilide
(115) 2-chloro-2',6'-dimethyl-N-(methacrylyloxymethyl)acetanilide
(116) 2-chloro-2'-methyl-6'-tertiary butyl-N-(methacrylyloxy-
methyl)acetanilide
(117) 2-chloro-2'-methoxy-6'-tertiary butyl-N-(methacrylyloxy-
methyl)acetanilide
(118) 2-chloro-2',3'-dimethyl-6'-tertiary butyl-N-(acetoxymethyl)
acetanilide
(119) 2-bromo-2'-methyl-6'-tertiary butyl-N-(methacrylyloxymethyl)
acet~nilide
(120) 2-iodo-2',6'-diethyl-N-(cyclopropanecarbonyloxymethyl)acet-
anilide
(121) 2-chloro-2',6'-diethyl-N-(3-methoxypropionyloxymethyl)acet-
~ anilide
(122) 2-chloro-2',6'-diethyl-N-(acetoxyethyl)acetanilide
(123) 2-chloro-2',6'-diethyl-N-(2",.6"-dichlorobenzoyloxyethyl)acet-
anilide
(124) 2-chloro-2',6'-diethyl-N-(.acrylyloxyethyl)acetanilide
(125) 2-chloro-2',6'-diethyl-N-(formyloxyethyl)acetanilide
(126) 2-chloro-2',6'-diethyl-N-(3-chloro-2-methyl-propionyloxy-
-20-
.. . . .
. . . .. .
_ 09-21-0893
1048518
ethyl)acetanilide
(127) 2-bromo-2',6'-diethyl-N-(acrylyloxyethyl)acetanilide
(128) 2-chloro-2'-ethyl-6'-methyl-N-(cyclopropanecarbonyloxy-
ethyl)acetanilide
(129) 2-chloro-2',6'-diethyl-N-(cinnamyloxyethyl)ac~tanilide
(130) 2-chloro-2',6'-diisopropyl-N-(butyryloxyethyl)acetanilide
(131) 2-chloro-2',6'-diethyl-N-(tert-butylacetoxymethyl)acet-
anilide
-m.p. 64-69C
(132) 2-chloro-2',6'-diethyl-N-(ethoxypropionyloxymethyl)acet-
anilide
liquid
(133) 2-chloro-2',6'-diethyl-N-(ethoxyacetoxymethyl)acetanilide
-m.p. 38-42 C
(134) 2-chloro-2',6'-diethyl-N-(hydrocinnamyloxymethyl)acetani-
lide
reddish viscous liquid
(135) 2-chloro-2',6'-diethyl-N-(lauryloxymethyl)acetanilide
golden viscous liquid
(136) 2-chloro-2',6'-diethyl-N-(3-methylcrotonyloxymethyi)acet-
anilide
reddish viscous oil
(137) 2-chloro-2',6'-diethyl-N-(acetoxymethyl)acetanilide
white solid, m.p. 44-45C
(138) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
(2,4-dichlorophenoxy)acetate
-m.p. 106-108C
(139) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
2,5-dichloro-3-nitrobenzoate
-m.p. 133.5-134.5C
(140) 2-bromo-6'-tert-butyl-N-(hydroxymethyi)-o-acetotoluidide,
3-amino-2,5-dichlorobenzoate
-m.p. 126-129C
(141) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
(2,-4,5-trichlorophenoxy)acetate
-m.p. 132-135C
(142) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
2,6-dichlorobenzoate
-m.p. 133-139C
(143) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
(2-naphthylox~)acetate
-m.p. 113-114 C
(144) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
piperonylate O
-m.p. 156.5-157.5 C
(145) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
5-nitrosalicylate
-m.p. 142-145C
(146) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
l-naphthaleneacetate
resinous liquid
(147) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
5-chloro-2-hydroxy-3-biphenylcarboxylate
-m.p. 138-140C
(148) 6'-tert-butyl-2-chloro-N-(hydroxymethyl)-o-acetotoluidide,
t2,4-dichlorophenoxy)acetate
-m.p. 93-94C
(149) 2-bromo-2'-tert-butyl~6l-ethyl-N-(hydroxymethyl)acetanilide,
(2,4-dichlorophenoxy)acetate
-m.p. 82.7-83.0C
-21-
,
~`~ 09-21-0893
1~4~518
~150) 6'-tert-butyl-N-(hydroxymethyl)-2-iodo-o-acetotoluidide, ;~
(2,4-dichlorophenoxy)acetate
-m.p. 110.5-111.5C
(151) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
salicylate
-m.p. 139-140C
(152) 2-chloro-2',6'-diethyl-N-(mercaptomethyl)acetanilide di-
methyldithiocarbamate
-m.p. 86-87C
(153) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide,
picolinate O
pale tan solid, m.p. 106-108 C
(154) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide,
nicotinate
peach colored solid, m.p. 95-96 C
(155) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, iso-
nicotinate
tan crystalline solid, m.p. 95.5-96.5C
(156) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, o-
nitrobenzoate
-m.p. 123-124C
(157) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, m-
nitrobenzoate
-m.p. 90-91C
(158) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, p-
nitrobenzoate
-m.p. 102-103C
(159) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, 5-
nitrosalicylate
-m.p. 109-111C
(160) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide,
benzoate
-m.p. 120-122C
(161) 2-bromo-6'-tert-butyl-N (hydroxymethyl)-o-acetotoluidide,
2,3,6-trichlorobenzoate
syrup
(162) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide,
piperonylate
-m.p. 106-108C
(163) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
5-chlorosalicylate
-m.p. 105-108C
~164) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o-acetotoluidide,
benzoate
-m.p. 98-99C
(165) 2-chloro-2',6'-diethyl-N-(hydroxymethyl)acetanilide, o-
benzoylbenzoate
-m.p. 126-127C
-22-
- ~ iO48S18 0g-21-0893
, :
In order to illustrate the advantages of the present
invention, the pre-emergence herbicidal ratings of representat-
ive 2-haloacetanilides were determined in greenhouse tests
in which a specific number of seeds of a number of different
plants, each representing a principal botanical type, were
planted in greenhouse flats.
A good grade of top soil was placed in aluminum
pans and compacted to a depth of 3/8 to 1/2 inch from the top
of the pan~ On the top of the soil was placed a predetermined
number of seeds of various plant species. The soil required
to level fill pans after seeding was weighed into a pan, a
known amount of the chemical applied in a solvent or as a
wettable powder, the soil thoroughly mixed, and used as a
cover layer for seeded pans. After treatment the pans were
moved into a greenhouse bench where they were watered from
below as needed to give adequate moisture for germination and
growth.
Approximately 14 days after seeding and treating,
the plants were observed and the results recorded. The
herbicidal rating was obtained by means of a fixed scale
based on the average percent germination of each seed lot.
The ratings are defined as follows:
-23-
P~
~9~21-0893
1~4~S18 :
O - No herbicidal activity
1 - Slight herbicidal activity
2 - Moderate herbicidal activity
3 - Severe herbicidal activity
The pre-emergence herbicidal activity of the alpha-halo-
acetanilides are recorded in the following table for various appli-
cation rates in both surface and soil-incorporated applications.
In the table, the letter "M" following the rate of appli-
cation indicates that the herbicide was incorporated in the soil
and the various seeds are represented by letters as follows:
A - Soybean I - Hemp sesbania
B - Sugar Beet J - Lambsquarters
C - Wheat ~ - Velvetleaf
D - Rice L - Bromus Tectorum
E - Sorghum ~q - Panicum spp.
F - Cocklebur N - Barnyardgrass
(common) O - Crabgrass
G - Wild Buckwheat
~l - Morningglory
-24-
- ` 09 -21-0893
1048518
' P'RE-EMER'GENCE' HERB'IC'IDAL' ACT`IVITY
'PLANT' SPE'CIES
Compound of Rate
EXample- No . 'lb' . /A ' A ' B 'C' D' ' E' ' F ' G' H ' I' J K L M ' N O
2 lM 102230000013333
4 1 0 l 2 0 2 0 1 0 2 0 0 3 2 3 3
lM 103330101213333
6 1 000001000000231
7 1 0 2 0 2 3 1 0 0 2 1 0 2 3 3 2
8 l/4 0 0 0 0 30110002333
0.05 0 0 0 0 0 2 0 1 0 0 0 0 2 3 0
23 1 0 2232000 3 20 3 3 3 3
1/4M 0 0 2 3 2 0 0 0 1 2 0 3333
l 0 0 0 1 1 0 0 0 1 0 -0 l 2 3 2
27 1 000 3 3 0 0 0 l 0 0 3 3 3 3
28 1 0 3 3 3 3 0 0 1 2 3 0 3 3 3 3
29 1 1 1 3 2 30101 2 0 33 3 3
31 lM 0 1 0 0 0 0 0 0 1 0 0 0 0 3 3
39 1 0 2 l 3 3 0 l 0 2 3 0 3333
1 0 1 0 2 2 0 0 0 1 2 0 2 3 3 3
41 1 0 2 0 1 1 0 2 0 0 1 0 2 2 3 3
1/4 0 0 1 l 0 0 0 0 l 0 0 3 3 3 3
42 lM ' 0100 2 0 1 2 1 0 02 3 :3 3
43 lM 1 0 0 0 1 0 0 1 0 0 l 0 2 3 3
44 lM 1111 3 0 0 2 1 0 1 3 2 3 3
lM 1 0 0 0 1 0 0 1 0 0 0 0 1 3 2
46 lM 1111300 2 l 0 0 l 333
47 lM 0 0 0 2 1 0 1 1 1 0 0 2 3 3 3
48 lM 0 0 1 1 3 0 l 0 1 0 0 33 3 3
3 0 1/4 0 0 0 0 3 0 0 0 2 1 0 1 3 3 3
49 lM 0 0 0 l 0 0 0 0 0 1 0 1 l 3 3
1/4 0 0 0 0 1 0 0 0 0 0 0 0 1 3 3
1 1 - 1 1 0 0 0 0 0 2 0 1 1 3 3
1/4 0 1 0 0 0 0 0 0 l 0 0 0 l 2 2
12 lM 0 0 1 3 2 0 0 0 1 0 0 2 3 3 3
~/4 0 0 1 0 0 0 0 0 2 1 0 0 3 3 3
0.05 0 0 0 0 0 0 0 0 1 0 0 0 3 3 2
25-
--: 09 21-0893
1048518
PRE-EMERGENCE HERsIcIDAI- ACTIVITY
PLANT SPECIES
Compound of Rate :
Example No. lb./A A B C D E F G H I J K L M N O
14 1 0 0 0 0 1 0 0 1 0 0 0 2 2 3 3
1 0 1 0 0 2 3 2 0 0 1 0 1 1 3 1
16 1 1 1 0 1 1 0 2 0 1 3 1 1 2 3 3
17 1 0 0 0 0 0 0 2 0 2 3 0 0 1 2 2 ~ :
18 1 0 221 2 0 1 1 2 2 0 2 2 3 3
96 1 1 1 0 0 1 0 2 0 1 3 2 2 2 3 2
97 1 0 3 0 1 0 0 201 2 0 0 2 3 2
98 1 0 0 0 0 1 0 200112 2 3 3
99 1 0 0 0 0 0 ~ 0 0 0 1 0 3 2 3 2
0102 3 0 0 1 0 0 1 3 3 3 3
134 1 2200 2 0 1 1 3 3 0 2 1 2 2
136 1 0 1 0 0 0 1 0 0 0 1 0 0 3 3 1
137 1 0 1 0 0 0 0 0 0 0 1 0 0 3 3 1
139 1 0 211101021022 3 3
140 1 102 3 20001 - 0 3 3 3 3
--2 6--
. .
.
0~-21-089~
. .
1~)48S18
The data set forth in the foregoing table clearly illus-
trates that the compounds of the present invention are effective
herbicides and are particularly useful in the control of narrow
leaf or grass weeds, even in the presence of grass crops.
The post-emergence herbicidal activity of various com-
pounds of this invention is demonstrated as follows. The active
ingredients are applied in spray form to 28 day old specimens of
various plant species. The spray, an acetone-water solution con-
taining active ingredient and a surfactant (35 parts butyla~ine
salt of dodecylbenzenesulfonic acid and 65 parts tall oil condensed
with ethylene oxide in the ratio of 11 moles ethylene oxide to 1
mole tall oil), is applied to the plants in different sets of pans
at several rates (pounds per acre) of active ingredient. The
treated plants are placed in a greenhouse and the effects are ob-
5 served and recorded after approximately 14 days.The post-er,lergence herbicidal activity index used in
the following table is as follows:
PL~T RESPO~E I~DEX
No injury 0
Slight injury
Moderate injury 2
Severe injury 3
l~illed 4
The plant species utilized in these tests are identified
5 by letter in accordance Wit}l the following legend;
A - Morningglory J - Barnyardgrass
B - Wild oat X - Crabgrass
C - Brome L - Pigweed
D - Rye Grass M - Soybean
E - Radish 1l - Wild Buckwheat
F - Sugar Beet 0 - Tomato
G - Cotton P - Sorghum
~1 - Corn Q - Rice
I - Foxtail
-27-
. . .
,
- 09-21-0893 ,,
~048S18 ~ -
POST'-EME'~GENCE' HE~RBICIDAL ACTI~TY
PLANT 'SPEC'IES
Cpd . o f Rate
Ex. No . lb . /A A B C D E F G H I J ~ L M N O P Q
141 0 . 4 4 1 0 0 4 4 4 2 1 3 3 4 4 4 4 2 2 '
144 0 . 4 4 2 1 1 4 4 4 2 3 3 3 4 4 3 4 2 2
151 1 . 0 3 0 0 0 4 4 - - 1 - 1 4 4 4 4 0 - ,. . .
153 1.0 4 1 0 1 4 4 3 3 2 2 2 4 3 4 4 1 1
--28--
, ~ ,,
09-21-0893
f
lV48518
The herbicidal compositions of this invention including ~;
concentrates which require dilution prior to application contain at
least one active ingredient and an adjuvant in liquid or solid form. `
'l~he compositions are prepared by admixing the active ingredient
with an adjuvant including diluents, extenders, carriers and con-
ditioning agents to provide compositions in the form of finely-
divided particulate solids, granules, pellets, solutions, disper-
sions or emulsions. ~hus the active ingredient can be used with
an adjuvant such as a finely-divided solid, a liquid of organic
origin, water, a wetting agent, a dispersing agent, an emulsifying
agent or any suitable combination of these.
The compositions of this invention, particularly liquids
and wettable powders, preferably contain as a conditioning agent
one or more surface-active agents in amounts sufficient to render
a given composition readily dispersible in water or in oil. ~he
incorporation of a surface-active agent into the compositions
greatly enhances their efficacy. By the term "surface-active
agent" it is understood that wetting agents, dispersing agents,
suspendin~ agents and emulsifying agents are included therein.
Anionic, cationic and non-ionic agents can be used with equal
facility.
Preferred wetting agents are alkyl benzene and alkyl
naphthalene sulfonates, sulfated fatty alcohols, amines or acid
amides, long chain acid esters of sodium isethionate, esters of
sodium sulfosuccinate, sulfated or sulfonated fatty acid esters,
petroleum sulfonates, sulfonated vegetable oils, ditertiary
acetylenic glycols, polyoxyethylene derivatives of alkylphenols
(particularly isooctylphenol and nonylphenol) and polyoxyethylene
derivatives of the mono-higher fatty acid esters of hexitol an-
hydrides (e.g. sorbitan). Preferred dispersants are methyl cellu-
lose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl
naphthalene sulfonates, sodium naphthalene sulfonate, and poly-
., .
- ~ . . . . .................... , . ; . ~ ~ . -
.. .~
og-21-0893
1048S1~
n ~ylene bisnaphthalenesulfonate.
Wettable powders are water-dispersible compositions -
containing one or more active ingredients, an inert solid extend-
er and one or more wetting and dispersing agents. The inert
solid extenders are usually of mineral origin such as the natural
clays, diatomaceous earth and synthetic minerals derived from
silica and the like. Lxamples of such extenders include kaolin-
ites, attapulgite clay and synthetic magnesium silicate. The
wettable powders compositions of this invention usually contain
from about 5 to about 9S parts of active ingredient, from about
0.25 to 25 parts of wetting agent, from about 0.25 to 25 parts
of dispersant and from 4.5 to about 94.5 parts of inert solid
extender, all parts being by weight of the total composition.
~, .
; Where required, from about ~0.1 to 2.0 parts of the solid inert
,j ................................................................. .. .
15 extender can be replaced by a corrosion inhibitor or anti-foaming ;
agent or both.
Aqueous suspensions can be prepared by mixing together
and grinding an aqueous slurry of water-insoluble active ingred-
ient in the presence of dispersing agents to obtain a concentrated
slurry of very finely-divided particles. The resulting concen-
trated aqueous suspension is characterized by its extremely small `
particle size, so that when diluted and sprayed, coverage is
very uniform.
Emulsifiable oils are usually solutions of active in- -`
gredient in water-immiscible or partially water-immiscible solvents
together with a surface active agent. Suitable solvents for the
active ingredient of this invention include hydrocarbons and
water~immiscible ethers, esters or ketones. 'rhe emulsifiable oil
compositions generally contain from about 5 to 95 parts active
~O ingredient, about 1 to 50 parts surface active agent and about 4 to
94 parts solvent, all parts being by weight based on the total
weight of emulsifiable oil.
Granules are physically stable particulate compositions
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09-21-0893
0~8S18
comprising active insredient adhering to or distributed through
~ asic ~atrix of an inert, finely-divided particulate extender.
In order to aid leaching of the active ingredient from the par-
ticulate, a surface active agent such as those listed herein-
before can be present in the composition. Natural clays,pyrophyllites, illite and vermiculite are examples of operable
classes of particulate mineral extenders. The preferred extenders
are the porous, absorptive, preformed particles such as preformed
and screened particulate attapulgite or heat expanded, particulate
vermiculite, and the finely-divided clays such as kaolin clays,
hydrated attapulgite or bentonitic clays. These extenders are
sprayed or blended with the active ingredient to form the herbi-
cidal granules.
The granular compositions of this invention generally
contain from about 5 parts to about 30 parts by weight of active
ingredient per 100 parts by weight of clay and 0 to about S parts
by weight of surface active agent per 100 parts by weight of par-
ticulate clay. The preferred granular compositions contain from
about 10 parts to about 25 parts by weight of active ingredient
per 100 parts by weight of clay.
The compositions of this invention can also contain other
additaments, for example fertilizers, herbicides, other pesticides
and the like used as adjuvants or in combination with any of the
above-described adjuvants. Chemicals useful in combination with
the active ingredients of this invention include for example tria-
zines, ureas, carbamates, acetamides, acetanilides, uracils, acetic
acids, phenols, thiolcarbamates, triazoles, benzoic acids, nitriles
and the like such as:
3-amino-2,5-dichlorobenzoic acid
~0 3-amino-1,2,4-triazole
2-methoxy-4-ethylamino-6-isopropylamino-s-triazine
2-chloro-4-ethylamino-6-isopropylamino-s-triazine
- 31 -
~ ` 09-21-0893
~4851~
2-chloro-N,N-diallylacetamide
2-chloroallyl diethyldithiocarbamate
N'-(4-chlorophenoxy) phenyl-N,N-dimethylurea
1,1'-dimethyl-4,4'-bipyridinium dichloride
isopropyl N-(3-chlorophenyl)carbamate
2,2-dichloropropionic acid
S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate
2-methoxy-3,6-dichlorobenzoic acid
2,6-dichlorobenzonitrile
N,N-dimethyl-2,2-diphenylacetamide
6,7-dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt
3-(3,4-dichlorophenyl)-1,1-dimethylurea
4,6-dinitro-o-sec-butylphenol
2-methyl-4,6-dinitrophenol
ethyl N,N-dipropylthiolcarbamate
2,3,6-trichlorophenylacetic acid :
5-bromo-3-isopropyl-6-methyluracil
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea
2-methyl-4-chlorophenoxyacetic acid
3-(p-chlorophenyl)-1,1-dimethylurea
l-butyl-3-(3,4-dichlorophenyl)-1-methylurea
N-l-naphthylphthalamic acid
1,1'-dimethyl-4,4'-bipyridinium salt
2-chloro-4,6-bis(isopropylamino)-s-triazine
2-chloro-4,6-bis(ethylamino)-s-triazine
2,4-dichlorophenyl-4-nitrophenyl ether
alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-
- _-toluidine
S-propyl dipropylthiolcarbamate
2,4-dichlorophenoxyacetic acid
N-isopropyl-2-chloroacetanilide
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. ~ ' - .
og-21~0893
,. . .
~048S18
2~,6'-diethyl-N-methoxymethyl-2-chloroacetanilide
monosodium acid methanearsonate
disodium methanearsonate
N-(l,l-dimethylpropynyl)-3,5-dichlorobenzamide
Fertilizers useful in combination with the active in-
gredients include for example ammonium nitrate, urea, potash,
and superphosphate. Other useful additaments include materials
in which plant organisms take root and grow such as compost,
manure, humus, sand and the like.
r~hen operating in accordance with the present invention,
effective ~nounts of the acetanilides are applied to the plants,
or to soil containing tlle plants, or are incorporated into aquatic
media in any convenient fashion. '~he application of liquid and
particulate solid compositions to plants or soil can be carried
out by conventional methods, e.g. power dusters, boom and hand
sprayers and spray dusters. The compositions can also be applied
from airplanes as a dust or a spray because of their effectiveness
at low dosases. The application of herbicidal compositions to
aquatic plants is usually carried out by adding the compositions
to the aquatic media in the area where control of the aquatic plants
is desired~
The application of an effective amount of the compounds
of this invention to the plant is essential and critical for the
practice of the present invention. The exact amount of active in-
gredient to be employed is dependent upon various factors, in-
cluding the plant species and stage of development thereof, the
type and condition of soil, the amount of rainfall and the specific
acetanilide employed. In non-selective pre-emergence treatments,
the compounds of this invention are u~ually applied at an approxi-
~0 mate rate of from 1 to 25 pounds per acre. In selective pre-
emergence application to the plants or to the 80il containing a
dosage of from 0.05 to about S pounds of acetanilide per acre is
usually employed. Lower or higher rates may be required in some
~33~
og-21-0893
.
1~48S18
il.dtances. One skilled in the art can readily determine from this
specification, including the examples, the optimum rate to be
applied in any particular case.
The term "soil" is employed in its broadest sense to
be inclusive of all conventional "80ils" as defined in Webster's
New International Dictionary, Second Edition, Unabridged (1961).
Thus the term refers to any substance or media in which vegetation
may take root and grow, and includes not only earth but also com-
post, manure, muck, humus, sand and the like, adapted to support
plant growth.
Although the invention is described with respect to
specific modifications, the details thereof are not to be construed
as limitations except to the extent indicated in the following
claims.
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