CA1048518A - Herbicidal anilides, herbicidal-n-(acyl-tertiary-amidoalkyl) anilides, and herbicidal acyloxyalkyl anilides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A compound of the formula wherein A is NH, N-(C=O)n-R4, oxygen or sulfur, Y is oxygen or sulfur when A is oxygen or sulfur, and is oxygen when A is N-(C=))n-R4 or NH, R and R1 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, alkylthioalkyl, polyalkoxyalkyl, polyalkylthioalkyl, 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 haloarylthio-alkyl, arylalkyl, arylalkenyl, nitroaryl, nitroarylthioalkyl, and nitroarylalkyl having at least 6 and not more than 24 carbon atoms;
2-pyridyl, 3-pyridyl, 4-pyridyl, 3,4-methylenedioxyphenyl, amino or mono- and dialkylamino, carbamoyl, alkyl-substituted carbamoyl, monoarylamino, mono(haloaryl)amino, mono(trifluoromethylaryl)amino, and alkyalkoxyamino having a maximum of 10 carbon atoms, R4 is alkyl, alkenyl, aryl or alkaryl having a maximum of 18 carbon atoms, or R3 and R4 are combined to form an alkylene or alkenylene bridge having at least 2 and not more than 5 carbon atoms, X is chlorine, bromine or iodine, and n is an integer of 1 or 2 and m is an integer of 0 to 2.

There is also disclosed a method and herbicidal compositions of the above compounds.

Description

~`' 09-21-0893 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, C: ,, .

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-,~

~ (~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

-4-_ 09-21-0893 ~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 ~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.

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-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 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

-7-_ 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 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 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-~. .

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 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 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,~ , ~, 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.

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 2-chloro-N-(N-methylacetamidomethyl)-2',6'-diethylacetanilide .

~ 09-21-0893 ~04851~

~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 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 ~ 09-21-0893 2-chloro-2',6'-diethyl-N-[(2-pyrrolidinon-1-yl)methyl]acetanilide O'C CH2 2H5 / CH2- N \ f H2 ~ \
~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 N-(2,6-diethylanilinomethyl)-N,N',N'-trimethyloxamide N - CH~ - N - C C - N

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.

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 .

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 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 -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 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 The following compounds are also prepared by substan-tial repetition of the general procedures set forth in the fore-going examples:

s~

~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

. _ :
.... : - ,., : .. .. ~ ; . .

~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-.. . . .
. . . .. .

_ 09-21-0893 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

, ~`~ 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

- ~ 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:

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 - ` 09 -21-0893 ' 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 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 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 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 1/4 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 49 lM 0 0 0 l 0 0 0 0 0 1 0 1 l 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 --: 09 21-0893 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

17 1 0 0 0 0 0 0 2 0 2 3 0 0 1 2 2 ~ :

99 1 0 0 0 0 0 ~ 0 0 0 1 0 3 2 3 2 . .
.

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 . . .
, - 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 , ~ ,, 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 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 ~ ` 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 . ~ ' - .

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.

Claims (8)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A compound of the formula wherein A is NH, N-(C=O)m-R4, 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 R1 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, alkylthio, polyalkoxy, polyalkylthio, alkoxyalkyl, alkylthio-alkyl, polyalkoxyalkyl, polyalkylthioalkyl, haloalkyl, hydroxy-alkyl, mercaptoalkyl, haloalkenyl, oxoalkyl, alkenyloxyalkyl, alkenylthioalkyl, each of a maximum of 18 carbon atoms; cyclo-alkyl having at least 3 and a maximum of 6 carbon atoms; aryl, aryloxy, aryloxyalkyl, arylthioalkyl, trifluoromethyl- and haloaryl, trifluoromethyl- and haloaryloxyalkyl, trifluoro-methyl- and haloarylthioalkyl, arylalkyl, arylalkenyl, nitro-aryl, nitroarylthioalkyl, and nitroarylalkyl having at least 6 and not more than 24 carbon atoms; 2-pyridyl, 3-pyridyl, 4-pyridyl, 3,4-methylenedioxyphenyl, amino or mono- and dialkylamino, carbamoyl, alkyl-substituted carbamoyl, mono-arylamino, mono(haloaryl)amino, mono(trifluoromethylaryl)amino, and alkylalkoxyamino having a maximum of 10 carbon atoms, R4 is alkyl, alkenyl, aryl or alkaryl having a maximum of 18 carbon atoms, or R3 and R4 are combined to form an alkylene or alkenylene bridge having at least 2 and not more than 5 carbon atoms, X is chlorine, bromine or iodine, and n is an integer of 1 or 2 and m is an integer of o to 2.

2. A compound of claim 1, wherein R and R1 are alkyl and are in the 2 and 6 positions.

3. A compound of claim 2, wherein R and R1 are ethyl.

4. A compound of claim 1, which is 2-chloro-2',6'-diethyl-N-(acetamidomethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(cyclopropane carboxamidomethyl) acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(acetamidomethyl) acetanilide, 2-chloro-2',6'-diethyl-N-(beta-chloropropionamidometthyl) acetanilide, 2-chloro-N-(N-methylacetamidomethyl) 2',6'-diethylacetanilide, 2-chloro-2',6'-diethyl-N-(succinimidomethyl) acetanilide, 1-(N-chloroacetyl-2',6'-diethylanilinomethyl) 2-pyrrolidinone, 2-chloro-2',6'-diethyl-N-(propionyloxymethyl) acetanilide, 2-chloro-N-(cinnamyloxymethyl-2',6'-diethyl) acetanilide, 2-chloro-2',6'-diethyl-N-(hydrocinnamyloxymethyl) acetanilide, 2-chloro-2',6'-diethyl-N-(acetoxymethyl) acetani-lide, or 2-chloro-2',6'-diethyl-(N-methacrylyloxymethyl) acetanilide.

5. A herbicidal method which comprises applying to plants or to soil an effective amount of a compound of the formula wherein A is NH, N-(C=O)m-R4, 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 R1 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, alkylthio, polyalkoxy, polyalkylthio, alkoxyalkyl, allcylthio-alkyl, polyalkoxyalkyl, polyalkylthioalkyl, haloalkyl, hydroxy-alkyl, mercaptoalkyl, haloalkenyl, oxoalkyl, alkenyloxyalkyl, alkenylthioalkyl, each of a maximum of 18 carbon atoms;
cycloalkyl having at least 3 and a maximum of 6 carbon atoms, aryl aryloxy, aryloxyalkyl, arylthioalkyl, trifluoromethyl-and haloaryl, trifluoromethyl- and haloaryloxyalkyl, trifluoro-methyl- and haloarylthioalkyl, arylalkyl, arylalkenyl, nitroaryl, nitroarylthioalkyl, and nitroarylalkyl having at least 6 and not more than 24 carbon atoms; 2-pyridyl, 3-pyridyl, 4-pyridyl, 3,4-methylenedioxyphenyl; amino or mono- and dialkyl-amino, carbamoyl, alkyl-substituted carbamoyl, monoarylamino, mono(haloaryl)amino, mono(trifluoromethylaryl)amino, and alkyl-alkoxyamino having a maximum of 10 carbon atoms, and R4 is alkyl, alkenyl, aryl or alkaryl having a maximum of 18 carbon atoms, or R3 and R4 are combined to form an alkylene or alkenylene bridge having at least 2 and not more than 5 carbon atoms or a phenyl 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.

6. A method of Claim 5 wherein R and R1 are alkyl.

7. A method of Claim 6 wherein R and R1 are ethyl.

8. A method of Claim 5 wherein the compound is 2-chloro-2',6'-diethyl-N-(acetamidomethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(cyclopropane carboxamidomethyl)acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(acetamidomethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(beta-chloropropionamidomethyl) acetanilide, 2-chlor-N-(N-methylacetamidomethyl) 2',6'-diethyl-acetanilide, 2-chloro-2',6'-diethyl-N-(succinimidomethyl) acetanilide, 1-(N-chloroacetyl-2',6'-diethylanilinomethyl) 2-pyrrolidinone, 2-chloro-2',6'-diethyl-N-(propionyloxymethyl) acetanilide, 2-chloro-N-cinnamyloxymethyl-2',6'-diethyl acetanilide, 2-chloro-2',6'-diethyl-N-(hydrocinnamyloxymethyl) acetanilide, 2-chloro-2',6'-diethyl-N-(acetoxymethyl)acetani-lide or 2-chloro-2',6'-diethyl-N-(methacrylyloxymethyl) acetanilide.