IL39562A - Herbicidal substituted haloacetanilides - Google Patents

Description

395622 HERBICIDAL SUBSTITUTED HALOACET^ANILIDES na "* ®a ' ΌΛΡ omenta o^'^^aKos i'yn ! arylalkyl, aryl al kenyl', nitrnaryl, nitroaryl thi oal kyl , and ni troarylal kyl having at least 6 and not move than 24 carbon atoms 2-pyridyl, 3-pyridyl, 4-pyridyl, or 3,4-methylenedioxyphenyl ; amino or mono- and dial kyl amino carbamoyl, alKyl-substituted carbamoyl, monoarylamino, mono (haloaryl) amino, mono- (tri fhil uoromethyl aryl ) amino, and al ky 1 al koxyamino having a maximum of 10 carbon atoms, and is alkyl, alkenyl, aryl, or alkaryl having a maximum of 18 carbon atoms, or and R^ are combined to form an alkylene or alkenylene bridge having at least 2 and not more than 5 carbon atoms, when n = 1_ they form together a phenylene group, X is chlorine , u.romine 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 alko y" 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 R1 - hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, ri-mcwy isobutyl , secondary sobutyl , tertiary butyl, n-amyl, branched chain a yls, the normal and branched hexyls, heptyls, octyls, nonyls, and decyls, methoxy, ethoxy, propoxy , butoxy, pentyloxy, heptylo::y, nonyloxy; R2 - hydrogen, chlorine, bromine, fluorine, iodine, nitro and the alkyl and alkoxy groups of R and R .

R3 - hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary -jrtrebutyl , tertiary butyl, the normal and branched amyls, hexyls, heptyls, octyls, nonyls, decyl: dodecyls, tetradec ls, hexadecyls and octadecyls chloromethyl , - - 39562/4 bromopropyl, lodobutyl, fluorohexyl, hy droxye thy 1 , the alko^y, alkenyl, lower alkanoyl, alkowalkyl groups corresponding to the above enumerated alkyl groups; phenyl, tolyl, naphthyl, pheno y, benzyl, pheno ya1kyl, 2-pyr1dyl, 3-pyr1dyl, 4-pyr1dyl or plpepyl-oyl. 3,4-methylenedioxyphenyl. \ R4 - the alkyl, alkenyl, aryl and aralkyl groups 3 4 or R and R are combined to form an alkyl ene or alkenylene bridge having 2 and not more than 5 carbon atoms, when n»l they form together a phenyl ene group. 39562/2 These Include 2-pyrrol1d1non-1-yl or (2-oxo-tetramethylene 1m1no) , 2-p1per1d1non-l-yl or (2-oxo-pentamethylene 1m1no) and 2-oxo-hexamethylene 1m1no. When m 3 4 Is 1 , R and R can combine to form cycl ic 1m1c.es ncluding phthaHm des.

The preferred compounds of the present Invention are those In which both R and R1 are ethyl and more particularly the compounds 1n which they are 1n the ortho positions.

The novel compounds of the present Invention In which A Is NH and n 1s 1 are prepared by a carbonlum 1on type reaction of a 2-halo-N-(subst1tuted methyl )acetan111de with a n1tr1 le or an Inorganic cyanide under acid, conditions. The novel compounds of the present Invention in which n 1s 1 and A 1s oxygen or sulfur are prepared similarly by the reaction of a 2-halo-N-(subst1-tuted methyl ) acetanl llde with a monocarboxyHc add. The methyl substltuent can be any group that 1s capable of forming a carbonlum 1on and Is readily displaced under acidic conditions; Thus, the starting material can be a 2-halo- -methyl acetanlllde In which the methyl group Is substituted with a halo, alkoxy, alkylth o, hydroxy, mercapto, alkenoyloxy and simi lar leaving groups. It 1s particularly preferred, however, to uti lize a 2-halo-N-chloromethyl acetanl llde In the preparation of these compounds. A solvent can be used but In most Instances 1s not generally required. While the reaction can be conducted at temperatures as low as o°C, It Is generally preferred to accelerate the reaction by conducting 1t under reflux conditions at the boiling point of the nltrl le or solvent 1n the system. After the reaction is substantially completed the reaction mixture i quenched with water and filtered to recover the acetanlllde which may then be purified in any conventional manner.

The 2-halo-N-(substituted methyl)acetanlllde used as a starting material in these reactions is the adduct of a haloacetlc 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 formaldehyde. The 2-halo-N-halomethyl acetanilides that can be employed in preparing the present compounds are described and claimed in U. S. Patent 3,637,8 γ granted January 25, 1972.

The compounds of the present invention in which A is NH and m is 1 can also be prepared by reacting a nitrile with an alpha halo-disubstituted-N-(alkoxymethyl)acetanlllde of the type described and claimed in U. S. Patent 3,^2,9^5, granted May 6, 1969.

The novel compounds of the present invention in which A is N-(C»0)m-R^and m is 1 are prepared by the reaction of a substituted methylenearylamine with an appropriately substituted amide or imide to form the corresponding N-(anilinomethyl) 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 chloroacetylatlon of an N-(substituted phenyl)-N'-acyl-ethylenediamine. The novel com- 4 pounds of the present invention in which A is N-(C=0)m-R are prepared similarly by the halqacetylation of an N- (substituted -(C=Q) -R -phenyl)-N'-acyl-N,-h^_f'ee-aa?:byl-ethylenediamine. The ethylene-diamine 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-bromoethyl ) ph the 1 ami de chloroethy1) -alkylamide, N-2- (hydroxyethyl) -alkylaraide/ 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 chloro-acetylation of an W- (substituted phenyl) -ethyl ester of the formula wherein R, R1, 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 specification, 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 2 ' ,6 ' -di ethyl phenyl parts of /azomethine dissolved in benzene were slowly added to about 177 parts of chloroacetic anhydride dissolved 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 elemental analysis of this product yielded the following results: EXAMPLE 2 This example describes the preparation of 2-chloro-2'-61 -diethyl-N-^cetamidomethyl) acetanilide . About 80 parts of 2-chloro-N- (2 ,6-diethylphenyl) acetamidomethyl chloroacetate prepared in accordance with the general procedure of Example 1 was mixed 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 148-149°C.

Calc'd for C15H21C1N202 : C, 60.7 H, 7.13 Found: C, 60.68 H, 7.22 EXAMPLE 3 This example describes the preparation of 2-chloro-2'- 61 -diethyl-N- (2 ,6-dichlorobenzamidomethyl) acetanilide . About 100 -2 ' ,6 ' -diethyl parts of 2-chloro-N-chloromethyl /acetanilide were added to about 350 parts of sulfuric acid in a suitable reaction vessel, cooled to about 0°C 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 75 °C 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 150.5-153°C.

Calc'd for C20H21Cl3 2O2 : C, 56.16 H, 4.95 Found: C, 55.69 II, 4.85 EXAMPLE 4 This example describes the preparation of 2-chloro-2 ' ,61 - 3-buten diethyl-N-aliylamidomethyl acetanilide. About 300 parts of sul parts of allyl nitrile, dissolved separately in glacial acetic_^ acid, were added to the sulfuric acid. After these reactants were added, the reaction mixture was heated to about 55°C 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°C.

Calc'd for C^I^Cl^^ : C, 63.25 H, 7.18 Found: C, 62.38 H, 6.95 EXAMPLE 5 This example describes the preparation of 2-chloro-21 ,- 6 ' -diethyl- -formylamidomethy1 acetanilide. About 200 parts of 2 ' ,6 ' -diethyl - 2-chloro-N-chloromethyl/ acetanilide were added to 400 parts of concentrated sulfuric acid. The mixture was cooled to about 10°C and 70 parts of sodium cyanide were then added and the reaction mixture heated to about 50°C. The reaction was exothermic and the temperature of the reaction mixture rose to about 85°C. 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. 85-89°C.

Calc'd for Ci H19Cl 202. C, 59.46 H, 6.77 Found: C, 59.64 II, 6.69 EXAMPLE 6 This example describes the preparation of 2-chloro-2 ' -61 -diethyl-K- (3-chloro-2-methylpropionamidomethyl) acetanilide . About -2 ' ,6 ' -di ethyl- 100 parts of 2-chloro-N-chlororaethyl /acetanilide were mixed with 26 parts of methacrylonitrile and added to about 350 parts sul-furic acid at a temperature of about 10°C in a suitable reaction vessel. The reaction mixture was heated to about 65°C for about The reaction mixture was poured into ice water and filtered to remove the precipitate which was then recrystallized from iso^-"""^ propanol.

Calc'd for C17H24C12N202 : C, 56.83 H, 6.73 Found: C, 56.85 H, 6.62 EXAMPLE 7 This example describes the preparation of 2-chloro-2 · 6 * -diethyl- -^crylamidomethy]^ 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 sulfuric acid were added. The reaction mixture was heated to about 55°C 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 174-175°C.

Calc'd for C16H21C1H202 : C, 62.23 H, 6.85 Found: C, 62.54 H, 7.05 EXAMPLE 8 This example describes the preparation of 2-chloro-21 -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 0°C while being -gthyl , 6 ' -methyl agitated. About 100 parts of 2-chloro-2 ' ,6I=^iefefeyl-N-chloro-raethyl acetanilide were slowly added and the mixture heated to about 25°C to expedite dissolution of the adduct. The mixture was again cooled to about 10°C 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 55°C for about 20 minutes and then poured into ice water. This resulted in the about 8 hours. The solid precipitate was separated by filtration, washed with water, filtered and recrystallized from isopropanol. This material melted at 154-156.5°C.

EXAMPLE 9 N- (2 ,6-Diethylanilinomethyl) -N-methylacetamide About 100 parts of N-methylacetamide were charged into a suitable reaction vessel and about 100 parts of 2% sodium methoxide suspension in dimethylformamide were added. The reaction was exothermic and the temperature of the reaction mixture rose from about 2 °C to about 30 °C. Then about 160 parts of 2 ,6-diethyl-N-methyleneaniline were added resulting in an additional rise in temperature to about 44 °C. 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 temperature over a period of about 16 hours . About 3 parts of acetic acid were added, then about 200 parts water and 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-diethylaminomethyl-W-methyl acetamide was obtained.

Calc'd for C, 71.75 H, 9.46 N, 11.95 Found: C, 71.90 H, 9.54 H, 12.05 About 72 parts of N- (2 , 6-dimethylanilinomethyl) -limethylacetamide obtained in accordance with the procedure of Example 9 were dissolved in about 100 grams of toluene and intro-duced into a suitable reaction 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 minute period with the temperature of the reaction mixture being maintained between -20 °C and -30 °C. 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 fraction was discarded and the oily fraction washed twice with 150 parts of water at a temperature of about 35°C. 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- cry tion. The product §y-rstallized from the solution upon standing and was removed from the liquid phase by filtration. The precipitate was washed with a mixture of methylcyclohexane and benzene and then air dried. After recrystallization from a benzene-hexane mixture, a cream colored product having a melting point of 82-83°C «04fl(? was obtained.

Calc'd for C16H23C1I202 : C, 61.83 H, 7.46 CI, 11.41 II, 9.01 EXAMPLE 11 2-chloro-2 ' ,6 '-diethyl-N- (succinimidoraethyl) acetanilide 0 A mixture of about 30 parts of 2 , 6-diethyl-N-methyl aniline, 20 parts of succinimide and 75 parts of dimethyl forma-mide were heated at a temperature of about 90-95 °C 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 -10 eC 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 -10 °C and 5°C. This resulted in the formation of a heavy precipitate. The reaction mixture was then cooled to about 0°C 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 dilute 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 146-147°C.

Calc'd for C^H^Cl^C^ : C, 60.62 H, 6.28 CI, 10.53 N, 8.32 EXAMPLE 12 chloro-21 ,6 ' -diethyl-N- [2-pyrrolidinon-l-yl) methyl] acetanilide 2-pyrrol i di none About 40 parts of N- (2 ,6-diethylanilinomethyl) -H-methyieceteirtide were dissolved in about 100 parts toluene and about 30 parts 2,6-lutidine were added to the solution contained in a suitable reaction vessel. The mixture was then cooled to about -30 °C 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 -30 °C. After the addition was complete, the reaction mixture 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 mixture of 100 parts of methyl-cyclohexane and 20 parts benzene. The product precipitated from this mixture on standing and upon recrystallization from a mixture of methylcyclohexane and benzene was obtained in the form of colorless granules having a melting point of 56-57°C.

Calc'd for C17H23C1 202 : C, 63.25 H, 7.18 CI, 10.98 Found: C, 63.36 H, 7.33 Cl, 11.02 EXAMPLE 13 N- (2 , 6-diethylanilinomethyl) - ,N * , N 1 -trimethyloxamide About 650 parts of Ν,Ν' ,N ' -trimethyloxaraide and about 4 parts of potassium hydroxide pellets were introduced into a suitable reaction vessel and about 800 parts of 2 , 6-diethylphenyl-azomethine 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 50 °C in 15 minutes, followed by a drop in temperature to about 45 °C. The mixture was subsequently heated to about 100 °C with continued stirring and allowed to cool to room temperature (about 23 °C) . 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 mixture, the product crystallized to form colorless granules which were filtered and washed twice with 1200 parts of methylcyclohexane. The product was finally washed 3 times with 1500 parts of water and air dried, The product thus obtained had a melting point of 73-73.3°C.

Calc'd for C16H25N302: C, 65.9 H, 8.6 N, 14.4 Found: C, 65.9 H, 8.6 , 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 EXAMPLE 14 " This example describes the preparation of 2-chloro-2 ' ,- 6 '-diethyl-N- (propionyloxymethyl) acetanilide . About 140 parts of - - 1 1 - - - and a solution of about 40 parts of propionic acid in tetrahydro-furan added. When 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 magnesium sulfate. The 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 64-65°C.

Calc'd for C^I^Cl Oj: C, 61.63 II , 7.11 Found: C, 61.94 H, 7.04 EXAMPLE 15 This example describes the preparation of 2-chloro-21 ,6 * diethyl-N- (formyloxymethyl) acetanilide . About 140 parts of 2-chloro 21 , 61 -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 cooled to room temperature. The tetrahydrofuran was stripped from the mixture by vacuum distillation. The residue was dissolved in diethyl ether and the ether solution washed first with aqueous sodium bicarbonate, then with water and finally dried over magnesium sulfate. The ether solution was vacuum distilled at 65°C under pressure of 5 mm. of mercury to provide a clear oily residual material.

Calc'd for C14H18C1 03 : 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 ' - hydrofuran 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 magnesium sulfate. The magnesium sulfate was removed by filtration and the solvent stripped by distillation at 60 °C and 1 mm. of mercury. The residue thus obtained is a red-orange oil.

Calc'd for C.-^H^T& O.j : C, 62.66 H, 7.42 17 Found: C, 63.01 H, 7.73 EXAMPLE 17 This example describes the preparation of 2-chloro-2 ' ,6 ' - acryl yl oxymethyl diethyl-N- (aG-s ioK me4i- l) acetanilide . About 200 parts of 2-chloro-2 ' ,61 -diethyl-IJ-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 91-96°C.

Calc'd for C16H20ClNO3: C, 62.03 II , 6.51 Found: C, 62.66 II , 6.59 EXAMPLE 18 In a substantial repetition of the procedure of the fore- aue carboxyl i c going examples, using cyclopropieaie acid as a reactant, 2-chloro- n 2 ' ,6 · -diethyl-N- (cyclopropanecarboxyloxymethyl) acetanilide , a solid product melting at 84-87 °C was obtained.

Calc'd for C17H22C1N03: C, 63.05 H, 6.85 Found: C, 63.43 H, 7.00 EXAMPLES 19 THROUGH -1?9 165 The following compounds are also prepared by substantial repetition of the general procedures set forth in the foregoing 2- iromo-2 ' ,3* , 6 · - 1rimethyl-N- (acetamidomethy1)acetanilide -m.p. 131 - 132*0 2-iodo-2 ' ,6 ' -diethyl-4 · -methyl-N- (chloroacetamidomethyl) acetanilide 2-chloro-2 · ,6' -diethyl-N- (3-ethoxypropionamidomethyl)acet- anilide - m.p. 70.5eC 2-chloro-2 · ,6 ' -diethyl-N- (2-chloroacetamidomethyl)acet- anilide -m.p. 153-159*0 . 2-chloro-2 · ,6 '-diethyl-N-ttsobuty.»3rlamidomethyl) acetanilide -m.p. 130-133.5*0 7 2-chloro-21 ,61 -diethyl-N-caprylamidomethyl acetanilide 2-chloro-2 ' ,6 ' -diethyl-N- reidomethylJ acetanilide -m.p. 206eC j ' 2-chloro-21 ,6'-diethyl-N'(benzamidomethy¾ acetanilide -m.p. 132eC , 2-chloro-2 ' ,6 ' -diethyl-N-(phenylacetamidomethylJ acetanilide -m.p. 135-137*0 2-chloro-2 ' ,6 ' -diethyl-N-methacrylamidomethyl acetanilide -m.p. 106-108.5*0 2-chloro-2 ' ,6' -diethyl-N-(3-ethylthiopropionamidomethyl)acetanilide 2-chloro-2 ' ,6'-diethyl-N-laurylamidomethyl acetanilide 2-brorao-2 ' ,6 ' -dimethyl-N-methoxyformamidomethyl acetanilide 2-chloro-2 '-tert-butyl-N-valeramidomethyl acetanilide 2-chloro-21 -methyl-6 ' -ethyl-N- (acetamidomethyl)acetanilide white solid, m.p. 132-133*0 2-chloro-2 · ,6'-diethyl-N- (¾-?-dichloropropionamidomethyl)- acetanilide white solid, m.p. 154-156*0 acet 2-chloro-2 · -methyl-6 '-tertiary butyl-N- (me haeryiamidomethyl)- acetanilide -m.p. 158-160.5*0 2-chloro-2 ' -methoxy-6 '-tertiary butyl-N- (methacrylamido- methyl)acetanilide acet 2-chloro-2 ' ,6 '-dimethyl-N- (methacTylamidomethyl)acetanilide white solid, m.p. 159.5-l60.5*C 2-chloro-2 ' ,3' -dimethyl-6'-tertiary butyl-N- (acetamidomethyl)- acetanilide -m.p. 163-165*C (45) 2-bromo-2 '-methyl-6 '-tertiary butyl-N- (methacrylamidomethyl)- 09-21-0893 (46) 2-chloro-2»,6 '-diethyl-N- (cyclopropane carboxamidomethyl)- acetanilide -m.p. 179-l80*C ( γ) 2-chloro-2 ' ,6'-diethyl-N- (3-methoxypropionamidomethyl)acet- anilide white solid, m.p. 70.5-72.5*0 (48) 2-bromo-2» -ethyl-6 '-tertiary butyl-N-(acetamldomethyl)acetanilide -m.p. 157.5-159.5*0 (49) 2-chloro-2«,6'-diethyl-N-acetamidoethyl acetanilide -m.p. i9-l-50*e 83-86°C (50) 2-chloro-2 · ,6 «-diethyl-N- (2",6"-dichlorobenzamidoethyl)acetanilide (3-buten- (51) 2-chloro-2l ,6'-diethyl-N-¾drlylamidoethyl acetanilide (52) 2-chloro-2' ,6» -diethyl-N-formylamidoethyl 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- (cinniimidoethyl )acetanilide (57) 2-chloro-21 ,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. 89-92*0 (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 39562/2 2-chloro-2 · ,6 ' -die thyl-N- t2-pyrrolidinon-l-yl )ethyl7acet- anilide 2-chloro-2 · , 6 » -diethyl-N- T2-piperidinon-l-yl anilide 2-chloro-2 ' , 61 -diethyl-N- (2-piperidinon-l-yl-ethyl )acetani- lide 2-chloro-2 ' ,6 ' -diethyl-N- (2-oxo-hexamethyleneiminomethyl )~ acetanilide 2-chloro-2 ' , 6 ' -diethyl-N- (2-oxo-hexamethyleneiminoethyl)- acetanilide 2-chloro-N-(N-methylacetamido)-ethyl-2' ,6'-diethyl acetanilide 2-chloro-2 ' ,6 · -diethyl-N- (N-methyl-dichlorobenzaraido)methyl acetanilide 2-chloro-2 ' ,6 '-diethyl-N- (N-methyl-dichlorobenzamido ) ethyl acetanilide 2-chloro-21 , 6 ' -diethyl-N- (N-ethyl-3-buten-amidomethyl ) acetani - lide 2-chloro-2 ' ,6 * -diethyl-N- (N-methyl -3-buten-ami doethyl ) acetani - lide, 2-bromo-2 » ,6 '-dimethyl-N- (N-methylformamido methyl acetanilide 2-bromo- ' ,6 '-dimethyl-N- (N-methylformamido) ethyl acetanilide 2-chloro-21 , 6 ' -diethyl-N- (N-methylacrylamido )raethyl acetanilide ( 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-propionamidomet yl ) acetanilide (92) 2-chloro-2'-methyl-6,-ethyl-N-( N-ethyl -acetami doethyl ) acet- anilide 93) 2-chloro-N-(phthalimidomethyl)-2 ' ,6 '-acetoxylidide white powder, m.p. 209-212*C 94 ^ 2-chloro-2 ' ,6' -diethyl-N- ( isobutyryloxymethyl )acetanilide white solid, m.p. 40-42.5eC 2-chloro-2 ' , 6 · -diethyl-N- (methoxyacetoxymethyl )acetanilide white solid, m.p. 66-68.5*C 2-chloro-2 * , 6 ' -diethyl-N- (methacryHyl oxymethyl )acetani 1 i de white solid, m.p. 8-52'C 2-chloro-2 ' ,6 ' -diethyl-N- (cinnarayloxymethyl) acetanilide white solid, m.p. 68.5-72.5*C 2-chloro- ' ,6 ' -diisopropyl-N- (butyryloxymethyl )acetanilide 2-chloro-2» ,6'-diethyl-N-(3-ethoxypropionyloxyinethyl)acet- anilide brown viscous oil 2-chloro-21 ,6 diethyl-N- ( capryl jrkixymeth l )acetanilide 2-chloro-2 ' , 6' -diethyl-N- (beta-chloropropionyloxymethyl)- acetanilide 2-chloro-2 ' ,61 -dimethyl-N- (propionyloxymethyl)acetanilide -m.p. 6 -65*C 2-chloro-2 · ,6' -dimethyl-N- (butyryloxymethyl)acetanilide 2-chloro-2 '-tertiarybutyl-61 -methyl-N-acetoxymethyl acetanilide 2-chloro-2 ' ,6 ' -diethyl-N carbamyloxymethy¾acetanilide 2-chloro-2 ' ,6 '-diethyl-N- (phenylacetoxymethyl)acetanilide 2-chloro-2 ' ,6* -diisopropyl-N- (methacrylyl oxymethyl ) acetanilide . 2-chloro-21 ,6 '-diethyl-N- (3-ethylthiopropionyloxymethyl)- acetanilide 2-chloro-21 ,6 '-dimethyl-N- (lauryloxymethyl) acetanilide golden viscous liquid 2-bromo-2 ' ,6 ' -dimethyl-N- (methoxyformyloxyraethyl) acetanilide 2-chloro-2 ' -tert-butyl-N- (valeryloxymethyl)acetanilide 2-chloro-2 ' -methyl-6 ' -ethyl-N- (acetoxymethyl )acetanilide 2-chloro-2 · ,6 '-diethyl-N- (1, -dichloropropionyloxymethyl)- acetanilide 2-chloro- ' , 6 ' -dimethyl-N- (methacrylyloxymethyl ) acetani 1 de 2-chloro-2 '-methyl-6 '-tertiary butyl-N- (methacrylyl oxymethyl ) acetanilide (117) 2-chloro-21 -methoxy-6 ' -tertiary butyl-N- (methacry lyloxyt methyl)acetanilide (118) 2-chloro-2 · , 3 ' -dimethyl-6 » - ertiary butyl-N- (acetoxymethyl) acetanilide 019) 2-bromo-2'-methyl-6 ' -tertiary butyl-N- (methacrylyl oxymethyl ) acetanilide 020} 2-iodo-2 · , 6 ■ -diethyl-N- (cyclopropanecarbonyloxymethyl )acet- anilide (121 ) 2-chloro-2 ' , 6 '-diethyl-N- (3-methoxypropionyloxymethyl )acet- anilide (122) 2-chloro-2 1 , 6 ' -diethyl-N-^cetoxyethyljacetanili de (123) 2-chloro-2 » , 6 '-diethyl-N- (2 " , 6"-dichloroben20yl oxyethyl )acet- anilide (124) 2-chloro-2 1 , 6 ' -diethyl-N- ( acrylyl oxyethyl ) acetanilide (125) 2-chloro-2 » , 6 ' -diethyl-N-(formyloxyethyl) acetanilide (126) 2-chloro-2 « , 6 ' -diethyl-N- (3-chloro-2-methylpropionyloxy- ethyl jacetanilide (127) 2-bromo-2 1 , 6 ' -diethyl-N- ( acryJyl oxyethyl )acetani l i de (128) 2-chloro-2 ' -ethyl-6 ' -methyl-N- (cyclopropanecarbonyl oxyethyl)acetanilide (129) 2-chloro-2 ' , 6 '-diethyl-N- (cinnamyloxyethyl)acetanilide 03°) 2-chloro-2 ' , 6'-diisopropyl-N-(butyryloxyethyl)acetanilide (131 ) 2-chloro-2 ' , 6 ' -diethyl-N- ( tert-butylacetoxymeth.yl )acet- anilide -m.p. 64-69'C ( 132) 2-chloro-2 ' , 6 » -diethyl-N- (ethoxypropionyloxymethyl )acet- anilide liquid (133), 2-chloro-2 · , 6 · -diethyl-N- (ethoxyacetoxymethyl)acetanilide -m.p. 38-42eC - — — ··· (134) 2-chloro-2 ' , 6 ' -diethyl-N- (hydroc nnamyloxymethyl )acetanilide reddish viscous liquid (135) 2-chloro-2 ' , 6 '-diethyl-N- (lauryloxyraethyl)acetanilide golden viscous liquid (136) 2-chloro-2 ' , 6 ' -diethyl-N- (3-methylcrotonyloxyraethyl)acet- anilide reddish -viscous oil (137) 2-chloro-2 ' , 6 ' -diethyl-N- (acetoxymethyl)acetanilide white solid, m.p. -^5*C (138) 2-bromo-6*-tert-butyl-N-(hydroxymethyl)-o- acetotoluidide, (2 ,4-dichlorophenoxy)acetate -m.p. 106-108*C (139) 2-bromo-6'-tert-butyl-N-(hydroxymethyl)-o- acetotoluidide, 2 , 5-dichloro-3-nitrobenzoate -m.p. 13 . -13^ . 5eC nicotinate tan crystalline solid, m.p. 95- 5-96.5*0 2-chloro-2 » , 6 '-diethyl-N- (hydroxymethyl )acetanilide, a-nitro- benzoate -m.p. 123-124*0 2-chloro-2 ' ,6'-diethyl-N-(hydroxymethyl)acetanilide, m-nitro- benzoate -m.p. 90-91*0 2-chloro-2 ' , 6 '-diethyl-N- (hydroxymethyl )acetanilide, p-nitro- benzoate -m.p. 102-103*0 2-chloro-2 · , 6 '-diethyl-N- (hydroxymethyl )acetanillde, 5-nitrosalicylate -m.p. 109-111*0 2-chloro-2 ' , 6 '-diethyl-N- (hydroxymethyl)acetanilide, benzoate -m.p. 120-122*0 (162) 2-chloro-2 6,-diethyl-N-,(hydroxymethyl)acetanilide, p-±peTon laire 3,4-methyl erfecli oxy benzoate -m.p. 106- 108*C (163 ) 2-bromc~6 '-tert-butyl-N- (hydroxymethyl)-o-acetotoluidide, 5-chlorosalicylate -m.p. 105- 108*C (164) 2-bromo~6 > -tert-butyl-N- (hydroxymethyl )-o-acetotoluidide, benzoate -m.p. 98-99'C (165) 2-chloro-2 ' , 6'-diethyl-N-(hydroxymethyl)acetanllide, o- benzoylbenzoate -m.p. 126-127eC In order to illustrate the advantages of the present invention, the pre-emergence herbicidal ratings of representative 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 1 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 : 0 - 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 application rates in both surface and soil-incorporated applications.

In the table, the letter "M" following the rate of application indicates that the herbicide was incorporated in the soil and the various seeds are represented by letters as follows : A - Soybean Hemp sesbania B - Sugar Beet Lambsquarters C - Wheat Velvetleaf D - Rice Bromus Tectorum E - Sorghum Panicum spp.

F - Cocklebur Barnyardgrass (common) Crabgrass G - Wild Buckwheat H - Morningglory PRE-EMERGENCE HERBICIDAL ACTIVITY PLANT SPECIES Compound of Rate Example No. lb./A A B c D E F G H I J L M N 0 2 1M 1 0 2 2 3 0 0 0 0 0 1 3 3 3 3 4 1 0 1 2 0 2 0 1 0 2 0 0 3 2 3 3 5 1M 1 0 3 3 3 0 1 0 1 2 1 3 3 3 3 6 1 0 0 0 0 0 1 0 0 0 0 0 0 2 3 1 7 1 0 2 0 2 3 1 0 0 2 1 0 2 3 3 2 8 1/4 0 0 0 0 3 0 1 1 0 0 0 2 3 3 3 0.05 0 0 0 0 0 2 0 1 0 0 0 0 2 3 0 23 1 0 2 2 3 2 0 0 0 3 2 0 3 3 3 3 1/4M 0 0 2 3 2 0 0 0 1 2 0 3 3 3 3 25 1 0 0 0 1 1 0 0 0 1 0 0 1 2 3 2 27 1 0 0 0 3 3 0 0 0 1 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 3 0 1 0 1 2 0 3 3 3 3 31 1M 0 1 0 0 0 0 0 0 1 0 0 0 0 3 3 39 1 0 2 1 3 3 0 1 0 2 3 0 3 3 3 3 40 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 1 0 0 0 0 1 0 0 3 3 3 3 42 1M 0 1 0 0 2 0 1 2 1 0 0 2 3 3 3 43 1M 1 0 0 0 1 0 0 1 0 0 1 0 2 3 3 44 1M 1 1 1 1 3 0 0 2 1 0 1 3 2 3 3 45 1M 1 0 0 0 1 0 0 1 0 0 0 0 1 3 2 46 1M 1 1 1 1 3 0 0 2 1 0 0 1 3 3 3 47 1 0 0 0 2 1 0 1 1 1 0 0 2 3 3 3 48 1M 0 0 1 1 3 0 1 0 1 0 0 3 3 3 3 1/4 0 0 0 0 3 0 0 0 2 1 0 1 3 3 3 49 1H 0 0 0 1 0 0 0 0 0 1 0 1 1 3 3 1/4 0 0 0 0 1 0 0 0 0 0 0 0 1 3 3 0 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 1 0 0 0 1 2 2 1M 0 0 1 3 2 0 0 0 1 0 0 2 3 3 3 PRE-EMERGENCE IIERBICIDAL ACTIVITY PLANT SPECIES Compound of Rate Example Uo. lb. /A A B C D E F G K I J K L M N 0 14 1 0 0 0 0 1 0 0 1 0 0 0 2 2 3 3 15 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 2 2 1 2 0 1 1 2 2 0 2 2 3 3 1 1 1 0 0 1 0 2 0 1 3 2 2 2 3 2 1 0 3 0 1 0 0 2 0 1 2 0 0 2 3 2 lei 1 0 0 0 0 1 0 2 0 0 1 1 2 2 3 3 1 0 0 0 0 0 0 0 0 0 1 0 3 2 3 2 5 0 1 0 2 3 0 0 1 0 0 1 3 3 3 3 1 2 2 0 0 2 0 1 1 3 3 0 2 1 2 2 1 0 1 0 0 0 1 0 0 0 1 0 0 3 3 1 1 0 1 0 0 0 0 0 0 0 1 0 0 3 3 1 <±5T 1 0 2 1 1 1 0 1 0 2 1 0 2 2 3 3 ±5* 1 1 0 2 3 2 0 0 0 1 0 3 3 3 3 The data set forth in the foregoing table clearly illustrates 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 compounds 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 containing active ingredient and a surfactant (35 parts butylamine 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 observed and recorded after approximately 14 days.

The post-emergence herbicidal activity index used in the following table is as follows : PLANT RESPONSE INDEX No injury 0 Slight injury 1 Moderate injury 2 Severe injury 3 Killed 4 The plant species utilized in these tests are identified by letter in accordance with the following legend; A - Morningglory J - Barnyardgrass B - Wild oat K - Crabgrass C - Brome L - Pigweed D - Rye Grass M - Soybean E - Radish W - Wild Buckwheat F - Sugar Beet 0 - Tomato G - Cotton P - Sorghum H - Corn Q - Rice I - Foxtail POST-EMERGENCE HERBICIDAL ACTIVITY PLANT SPECIES Cpd. of Rate Ex. No. lb. /A A B C D E F G H I J K L M N O P Q 141 0.4 4 1 0 0 4 4 4 2 1 3 3 4 4 4 4 2 144 0.4 4 2 1 1 4 4 4 2 3 3 3 4 4 3 4 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 The herbicidal compositions of this invention includSsn-concentrates which require dilution prior to application contain at least one active ingredient and an adjuvant in liquid or solid form. The compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emulsions . Thus 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. The 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, suspending 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 cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl methylene bisnaphthalenesulfonate . ,r^, Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender 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. Examples 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 95 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 00.1 to 2.0 parts of the solid inert 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 ingredient in the presence of dispersing agents to obtain a concentrated slurry of very finely-divided particles . The resulting concentrated 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 ingredient 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. The emulsifiable oil compositions generally contain from about 5 to 95 parts active 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 comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender". In order to aid leaching of the active ingredient from the particulate, 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 5 parts by weight of surface active agent per 100 parts by weight of particulate 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 3-amino-l,2,4-triazole 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-N , -diallylacetamide 2-chloroallyl diethyldithiocarbamate ' - (4-chlorophenoxy) phenyl-N,N-dimethylurea 1,1' -dimethyl-4 , 41 -bipyridinium dichloride isopropyl Jfi- (3-chlorophenyl) carbamate 2 , 2-dichloropropionic acid S-2 , 3-dichloroallyl N,N-diisopropylthiolcarbamate 2-methoxy-3 , 6-dichlorobenzoic acid 2.6-dichlorobenzonitrile N,W-dimethyl-2 ,2-diphenylacetamide 6.7-dihydrodipyrido(l,2-a:2' , 1 ' -c) -pyrazidiinium salt 3- ( 3 , 4-dichloropheny1 ) -1 , 1-dimethylurea 4 , 6-dinitro-o-sec-butylphenol 2-methyl-4 , 6-dinitrophenol ethyl ,N-dipropylthiolcarbamate 2 , 3 , 6-trichlorophenylacetic acid 5-bromo-3-isopropyl-6-methyluracil 3- (3 , 4-dichlorophenyl) -1-methoxy-l-methylurea 2-methyl-4-chlorophenoxyacetic acid 3- (p_-chlorophenyl) -1 , 1-dimethylurea 1-butyl-3- (3, 4-dichlorophenyl) -1-methylurea -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, -dipropyl-p_-toluidine S-propyl dipropylthiolcarbamate 2 , 4-dichlorophenoxyacetic acid N-isopropyl-2-chloroacetanilide 2' , 6 '-diethyl-N-methoxymethyl-2-chloroacetanilide monosodium acid methanearsonate disodium methanearsonate N- (1,1-dimethylpropynyl) -3 ,5-dichlorobenzamide Fertilizers useful in combination with the active ingredients 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 .

When operating in accordance with the present invention, effective amounts of the acetanilides are applied to the plants, or to soil containing the plants, or are incorporated into aquatic media in any convenient fashion. The 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 dosages. 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 ingredient to be employed is dependent upon various factors , including 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 usually applied at an approximate rate of from 1 to 25 pounds per acre. In selective pre-emergence application to the plants or to the soil containing a instances . 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 "soils" 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 compost, 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 (3)

1. WHAT IS CLAIMED IS: wherein A la NH, N-(C«0) -R , oxygen or sulfur, m Y Is oxygen or sulfur when A is oxygen or sulfur, and Is oxygen when A Is N-(OO) -R^ or NH, 1 m R and R are hydrogen* alkyl or alkox having at least 1 and not more than 1© carbon atoms and can be like or unlike* R Is hydrogen, alkyl or alkoxy having at least 1 and not more than 10 carbon atoms, N©g or halogen, R3 is hydrogen, alkyl, alkenyl, alkoxy, alkylthlo, alkoxyalkyl, alkylthloalkyl, haloalkyl, hydroxyalkyl, mercaptoalkyl lower al kanoyl haloalkenyl, -o-xeal-kyl, alkenyloxyalkyl, alkenylthloalkyl, each of a maxlnum of 13 carbon atoms; cycloalkyl havin at least 3 and a maximum of 6 carbon atoms; aryl-, aryloxy, aryloxyalkyl, arylthloalkyl, trifluor©methyl* and haloraryl, trlfluoromethyl-and haloaryloxyalkyl, trifluoromethyl- and haloarylthloalkyl, arylalkyl, arylalkenyl, nltroaryl, nltroarylthloalkyl, and nltroarylalkyl having at least 6 and not more than 24 carbon atoms; 2-pyrldyl, 3-pyridyl, 4-pyrldyl or 3*4-raethylenIifioxyphenyl amino or mono* and dlalkylamlno^ carbamoyl, alkyl-substltuted carbamoyl raonoarylamino, mono(haloaryl)aralno, mono-(trifluoromethyl aryl) amino, and alkylalkoxyamlno having a maximum of 1© carbon atoms, 4 R Is alk l alken l ar l or alkar l havin a 39562/2 maximum of 18 carbon atoms* or 3 and R4 are combined to form an al kenyl ene al kyiene or -al-kyl-ene bridge having at least 2 and not more than 5 carbon atoms when nsl they form together a phenyl ene group, 39562/2 X is chlorine, bromine or iodine, and n is an integer of 1 or 2 and m is an integer of 0 to 2.

2. A compound of Claim 1 wherein R and R1 are alkyl and are in the 2 and 6 position.

3. A compound of Claim 2 wherein R and R1 are ethyl. . A compound of Claim 1 which is 2-chloro- ' ,6 '-diethyl- acetanilide, 2-chloro-2 ' ,6 '-diethyl-N- (cyclo propane carboxamidoraethyl) acetanilide, 2-chloro-2 '-methyl-6'-ethyl-N-(acetamidomethyl) acetanilide, 2-chloro-2 ' ,6 '-diethyl-N-(beta-chloropropionamidomethyl) acetanilide, 2-chloro-N- (N-methyl-acetamido roet yl ) 21 ,6 '-diethylacetanilide, 2-chloro-2 ' ,6 '-diethyl-N-(succinimidomethyl) acetanilide, 1- (N-chloroacetyl- ' ,6'-diethyl-anilino methyl ) ^-pyrrolidinone, 2-chloro-2 ' ,6' -diethyl-N- (propion-yloxymethyl) -acetanilide, 2-chloro-N- (cinnamyloxymethy] )2',6'-diethyl) acetanilide, 2-chloro-2 » ,6' -diethyl-N- (hydrocinnamyloxy-methyl) acetanilide, 2-chloro-2' ,6' -diethyl-N- (acetoxymethyl) acetanilide, or 2-chloro-21 ,6 ' -diethyl- (N-methacryl yl oxymethyl ) acet-anilide. 5. A herbicidal composition comprising an adjuvant and an effective amount of a compound of the formul wherein A is NH, N-(C=0)m-R4, oxygen oV sulfur, Y is oxygen or sulfur when A is oxygen or sulfur, and is oxygen when A is N-(C=0)m-R* or N¾ 1 2 . . . r R is hydrogen, alkyl or alkoxy having at least 1 and not ^ more than 10 carbon atoms, NOg or halogen, 3 R Is hydrogen, alkyl, alkenyl, alkoxy, alkyl thlo, alkylthloa kyl, haloalkyl, hydroxyalkyl, mercaptoalkyl , haloalkenyl, lower alkanoyl, alkenyl oxyalkyl , alkenyl thloalkyl , each of a maximum of 18 carbon atoms, cycloalkyl having lat least 3 and a maximum of 6 carbon atoms; aryl, aryloxy, aryl oxyalkyl, arylthloalkyl , trlfluoromethyl- and haloaryl, trlfluoromethyl- and haloaryl oxyalkyl , trifluoromethyl- and haloaryithioalkyl, aryl alkyl, arylalkenyl, nitroaryl, nitroaryl thloalkyl, and nitroaryl alkyl having- at least 6 and not more than 24 carbon atoms; 2 pyridyl, 3-arylalkenyl-pyridyl , 4-pyr1dyl or 3,4-methylened1oxy- phenyl amino or mono- and dlalkylamino, carbamoyl, alkyl -substituted carbamoyl, monoaryl ami no, mono(haloaryl)amino, mono- (trifluoromethyl aryl) amino, and alkylalkoxyamino having a maximum of 10 carbon atoms, and R is alkyl, alkenyl, aryl or alkaryl having a maximum of 3 4 18 carbon atoms, or R and R are combined to form an a kyl ene or alkenylene ibrldge having at least 2 and not more than 5 carbon atoms or a phenyl ene group, X Is chlorine, bromine or iodine, and . n 1s an Integer of 1 or 2, and m is an Integer of 0 to 2 inclusive. 6. A herbiddal composition of Claim 5 wherein R and R^ are alkyl and are In the 2 and 6 positions. 7. A composition of Claim 5 wherein R and R1 are ethyl. 8. A composition of Claim 5 wherein the compound 1s 2- chl oro-2 ' ,6 ' -d1 ethyl -M acetaml domethyl ) ace tan i 11 de , 2-chloro-2' ,6'- dlethyl -N-(cycl opropane carboxaml domethyl ) acetanl 11de, 2-chloro- 2' -methyl -6' -ethyl -N- (acetaml domethyl) acetanlHde, 2-chloro-2' ,6' diethyl -N-(beta-chloroprop|cinam1 domethyl) acetanlHde, 2-chloro-, N- (N-methyl acetaml do )methyl -2 · ,6 ' -diethyl acetanlHde, 2-chl oro-2 ' ,- 6 ' -diethyl -N-(succ1n1m1 domethyl ) acetanlHde, l-(N-chloroacetyl- 39562/2 \ . v. ethylUH-(propionyloxymethyl) acetanilide, 2-chloro-N-cinnamyloxy-" methyl )2', 6' -diethyl acetanilide, 2-chloro-2' ^'-diethyl-N-ihydro-* cinnamyloxyraethyl) acetanilide, 2-chloro-2 ' ,6 '-diethyl-N^iacetoxy- 09 -21- 089 ^ 39562-2 ^-'- 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 o 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. 10. A method of Claim 9 wherein R and R1 are alkyl. 11. A method of Claim 10 wherein R and R1 are ethyl. 12. A method of Claim 9 wherein the compound is 2- chloro-2 ' ,6'-diethyl-N^cetamidomethyl) 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-chloropropionamidoraethyl) acetanilide, 2-chloro-N- (N-methylacetamido methyl ) ·21 ,6'-diethylacetanilide, 2-chloro-2 ' ,6'- diethyl-N-(succinimidomethyl) acetanilide, 1- (N-chloroacetyl-2 ' ,6'- diethylanilinomethy ) 2-pyrrolidinone, 2-chloro-2 » , 6 ' -diethyl-N-(propionyloxymethy )acetanilide, 2-chloro-N-cinnamyloxymethyl- · ,6'- diethyl acetanilide, 2-chloro-2 ' ,6'-diethyl-N-(hydrocinnamyloxy- methy3 } acetanilide, 2-chloro-2 · ,6 '-diethyl-N-acetoxymethyl )acet- anilide or 2-chloro-21 ,6 '-rdiethyl-N^-methacrylyloxymethyl ) acetanilide. Attorneys for Applicant