IL27363A - Alpha-chloroacetamides and phytotoxic compositions - Google Patents

Description

g-CHLOROACETAMIDES AND PHYTOTOXIC COMPOSITIONS a-CHLOROACETAMIDES AND PHYTOTOXIC COMPOSITIONS This invention relates to novel N-(cycloalken-l-yl) a-chloroacetamides which are useful as biocides, particularly phytotoxicants, and to processes for making them. This invention further relates to phytotoxic compositions and methods of controlling or modifying the growth of plant systems therewith.

The term "phytotoxicant" as used herein and in the appended claims means materials having a modifying effect upon the growth of plant systems. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. In like manner, "phytotoxic" and "phytotoxicity" are used to identify the growth modifying activity of the compounds and compositions of this invention.

The term "plant system" as used herein and in the appended claims means germinant seeds, emerging seedlings and established vegetation including the roots and-above-ground portions.

The N-(cycloalken-l-yl) a-chloroacetamides of this in- vention are represented by the formula 0 II R-N-C-CHsCl I Y - wherein R is selected from the group consisting of alkyl having from 1 to 8 carbon atoms, cycloalkyl having from 3 to 8 carbon atoms, alkoxyalkyl having from 2 to 8 carbon atoms, alkenyl having from 2 to 8 carbon atoms and aryl having from 6 to 18 carbon atoms and Y is a cycloalkenyl having from 5 to 7 carbon atoms in the ring selected from the group consisting of wherein R* is alkyl having from 1 to carbon atoms and n is an integer from 0 to 3· The N-(cycloalken-l-yl) a-chloroacetamides of this invention contain unsaturation in the alkenyl ring at the ring carbon atom through which the ring is bonded to the nitrogen atom. When the cycloalkenyl is a six-membered ring the ring system can be conjugated, but one unsaturation must be at the ring carbon atom through which the ring is bonded to the nitrogen atom, i.e. the 1 or 6 position.

Representative R radicals for the a-chloroacetamides of this invention include alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the straight and branched chain amyIs, pentyls, hexyl's, heptyls and octyls; alkenyl, for. example, allyl, butenyl, pentenyl, hexenyl, heptenyl and octenylj alkoxyalkyl, for example, methoxymethyl, methoxy-ethyl, methoxypropyl, methoxybutyl, methoxyheptyl, propoxypropyl, ethoxyethyl and butoxybutyl; cycloalkyl, for example, cyclopropyl* cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and aryl, for example, phenyl, biphenyl, naphthyl and the like.

Representative Y cycloalkenyl radicals for the a-chloroacetamides of this invention include by way of example 1-cyclopentenyl, 3-methyl-l-cyclopentenyl, 5-methyl-l-cyclopentenyl, 2,5-dimethyl-l-cyclopentenyl, 5- dimethyl-1-cyclohexenyl, 3-methyl-6-cyclohexenyl, 3,4-dimethyl- 6-cyclohexenyl, 2,6-dimethyl-l-cyclohexenyl, 3,3-dimethyl-l- cyclohexenyl, 6-( er -but l)-1-cyclohexenyl, 1,3-cyclohexadienyl, -raethyl-l,5-cyclohexadienyl, 3*4-dimethyl-l,3-cyclohexadienyl, 6-methyl-l,3-cyclohexadienyl, 2, -dimethyl-l,5-cyclohexadienyl, 2-methyl-4,6-cyclohexadienyl, 3,4-d:ljnethyl-4,6-cyclohexadienyl, 2,6-d: nethyl-4,6-cyclohexadienyl, 5,5-dimethyl-l,3-cyclohexa- dienyl, 6-( ert-butyl)-1,3-cyclohexadienyl, 2>5i5-trimethyl-l,2-cyclohexadienyl, 1,4-cyclohexadienyl, 3-niethyl-l,4-cyclohexa-dienyl, 3,4-dimethy1-1,4-cyclohexadienyl, 6-methyl-l,4-cyclohexa-dienyl, 2,4-dimethyl-l,4-cyclohexadienyl, 2,6-dimethyl-l,4-cyclohexadienyl, 2,5-dimethyl-l,4-cyclohexadienyl, 6-(tert-butyl>-1,4-cyclohexadienyl, 3,6,6-trimethy1-1,4-cyclohexadienyl, limethyl- i6-cyclohexadienyl, 6-methyl-3,6-cyclohexadienyl, 2,6-dimethyl-3,6-cyclohexadienyl, 2,5*5- rimethyl-5,6-cyclohexadienyl, 35>5-trimethy1-3,6-cyclohexadienyl, 2,4-dimethy1-3,6-cyclohexa-dienyl, 6-(tert-butyl)-3, -cyclohexadienyl, 1,5-cyclohexadienyl, 3-methyl-l,5-cyclohexadienyl, 3,4-dimethyl-l,5-cyclohexadienyl, 6-isopropyl-l,5-cyclohexadienyl, 6-tert-butyl-l,5-cyclohexa-dienyl, 2,6-dimethy1-1,5-cyclohexadienyl, 3-methyl-2,6-cyclo- . hexadienyl, 2,5*5-trimethy1-2,6-cyclohexadienyl, 3,5,5-trimethyl-2,6-cyclohexadienyl, 6-(tert-butyl)-2,6-cyclohexadienyl, 6-methyl-2,6-cyclohexadienyl, 1-cycloheptyl, 3-methyl-l-cyclo-heptyl, 3,4-dimethyl-l-cycloheptyl, 7-methyl-1-cycloheptyl, 4,5-dimethyl-1-cycloheptyl, 2-methyl-1-cycloheptyl, 6-methyl-l-cycloheptyl, 7-methyl-7-cycloheptyl, 7-(tert-butyl)-1-cycloheptyl and 3,4-diisopropyl-1-cycloheptyl.

The present N-(cycloalken-l-yl) a-chloroacetamides are prepared by a process which comprises reacting a chloroacetyl consisting of wherein R1 and n are as defined above.

The synthesis of the present compounds can be set forth as follows: 0 0 II , R-N-C CHaCl wherein R is as defined above and X is CI, Br or I.

The reaction of the chloroacetyl halides with imines in accordance with this invention can be carried out in various ways. Normally it is desired for maximum yield th.t the imine be present in at least an equimolar amount to the chloroacetyl halide and preferably in excess of equimolar amount. The reaction is suitably carried out at room temperature, i.e. about 20-25°C. However, higher or lower temperatures can be used, the temperature not being critical. For example, temperatures above about 40°C. are generally employed when no acid acceptor is used.

The reaction is preferably carried out in the presence of an acid acceptor and an inert organic medium. The acid acceptor is generally present in at least equimolar amounts based on the amount of hydrogen halide formed in the reaction. quarternary ammonium hydroxides, N-ethylmorpholine and the like; inorganic bases such as sodium hydroxide and potassium hydroxide, sodium carbonate and the like. An excess of imine reactant also serves as an acid acceptor.

Inert organic media which can be used in the practice of this invention include by way of example hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-heptane, n-hexane and the like; ethers such as isopropyl ether, n-butyl ether, 1,4-dioxane, isobutyl ether, diethyl ether and the like; aliphatic and cycloaliphatic ketones such as methyl isopropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, diisopropyl ketone> cyclohexanone and the like; and organic halides such as carbon tetrachloride, n-butyl chloride, ethylene dichloride, tetrachloroethylene and the like.

The separation of the resulting reaction product from the reaction mixture is readily accomplished. Fcr example the salt, such as a tertiary amine hydrochloride salt formed during the reaction because of the presence of a tertiary amine compound therein as an acid acceptor, is separated from the product containing reaction mixture by simple means such as filtration and the solvent is removed from the resulting filtrate by stripping or distillation, preferably low temperature vacuum distillation. The product can be purified by any of the conventional means well known in the art, e.g. fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas or any suitable combination of these. If desired the product can be subjected to film distillation, recrystallization or a combination of both for further purification. such as alcohols, ketones, benzene, toluene, xylene, hexa e or the like.

While the present N-(cycloalken-l-yl) a-chloroacetamides are useful as fungicides, insecticides, nematocides, algaecides, bactericides, bacteriostats, and fungistats, their most outstanding characteristic is phytotoxicity. In accordance with this invention it has been found that tiie growth of germinant seeds, emerging seedlings and established vegetation can be controlled or modified by exposing the seeds, emerging seedlings or the roots or above-ground portions of established vegetation to the action of an effective amount of one or more of the N-(cycloalken-l-yl) a-chloroacetamides of the present invention. These compounds are effective as general phyto-toxicants, including post-emergent phytotoxic nts and pre-emergent phytotoxicants, but their most outstanding utility is as pre-emergent phytotoxicants. Furthermore, these compounds are characterized by broad spectrum herbicidal or phytotoxic activity; i.e. they modify the growth of a wide variety of plant systems including both broadleaf and grass plants.

For the sake of brevity and simplicity, the term "active ingredient" will be used hereinafter to describe the present N-(cycloalken-l-yl) a-chloroacetamides.

The phytotoxic compositions of this invention contain at least one active ingredient and a material referred to in the art as a phytotoxic 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 V agent, a dispersing agent, an emulsifying agent or any suitable combination of these.

Typical finely divided carriers and extenders or the phytotoxic compositions of this invention include by way of example the talcs, clays, pumice, silica, diatomaceous earth, walnut flour, chalk, quartz, Puller's earth, salt, sulfur, powdered cork, powdered wood, tobacco dust, volcanic ash and the like. Typical liquid diluents include kerosene, Stoddard solvent, hexane, toluene, benzene, acetone, ethylene dichlorid xylene, alcohols, Diesel oil, glycols and the lil.e.

The phytotoxic compositions of this invention, parti- cularly liquids and wettable particles, usually 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. By the term "surface-active agent" it is understood that wetting-agents, dispersing agents, suspending agents and emulsifying agents are included therein.

The term "phytotoxic composition" as used herein and in the appended claims is intended to mean not only compositions in a suitable form for application but also concentrated com-, positions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

In the following exSaples as well as in the specification and appended claims, parts and cent are by weight unless other- wise indicated.

P.A. 27363 II Similar compounds are known from U.S. Patents No.2, 863, 752; No.2,864, 683 and No.2,864, 679.

The compounds according to the present invention differ from these in that in the novel compounds there exists a cycloalken-l-yl substituent on the nitrogen atom, and this results in advantageous desired phytotoxic properties, both as regards pre-emergent phytotoxic activity and also as regards post-emergent phytotoxic activity which is absent or insignificant with most of the prior compounds.

The herbicidal activity of the compounds according to the present invention is better than that of the known compounds. Compounds according to U.S. Patent No* 2, 863, 752 are less active against wild oats and buckwheat; furthermore the novel compounds are less toxic towards crop plants, such as cotton. This applies also to the compounds of U.S. Patent No. 2,364, 679· The compounds according to the present invention a e of better activity against buckwheat at low rates of application, against wild oats and rye as compared with most compounds of U.S. Patent No. 2,864, 683 The advan tageous properties seem to be due to the cycloalken-l-yl substituent, as will be evident from the following Tables. A comparison of Table I, Example 76 and the first compound of Table II shows the significant difference between the compounds according to the invention and even as closely related compounds as those where there is present a cycloalken-2-yl substituent.

P.A. 27363/11 the following examples will illustrate the invention. In the following examples as well as in the Specification and appended Claims, parts and percent are by weight unless otherwise indicated.

Example i example describes the preparation of 0 II (C¾)2CHCH2-N-C CH2C1 ί N-(l-cyclohexen-l-yl) N-(isobutyl) α-chloroacetamide Into a solution of 33.9 parts of chloroacetyl chloride in 200 parts of benzene maintained at a temperature of about °C. are added slowly with stirring ^5- 9 parts of N-cyclohexyl-idene N-isobutyl amine. After stirring for an additional 20 minutes at about 5°C, 20.3 parts of triethyl amine are added.

The reaction mixture is allowed to warm to about 25°C. and is stirred for one hour. The reaction mixture is then filtered to remove the amine salts and the filtrate is washed twice with water. The benzene is removed by evaporation and the residue is fractionally distilled to obtain the product fraction boiling in the range of 130°C. to 13½°C. , at a pressure of 3 mm. of mercury. The product amounts to 26.1 parts of oily liquid and the structure is confirmed by nuclear magnetic resonance (NMR) spectrum analysis.

Calc'd for CiaHaoNOCl: C, 62.0; H, 8.7^5 CI, 15- 50 Found: C, 63- 2 H, 8.85; CI, 15.2 Example 2 This example describes the preparation of 0 if CH3CH2CH2-N-C CHaCl I N-(l-cyclohexen-l-yl) N-(n-propyl) a-chloroacetamide cyclohex lidene N-(n-propyl) amine. After stirring for an additional 50 minutes at about 5°C, 50.5 parts of triethyl amine are added and the reaction mixture is allowed to warm to about 25°C. The reaction mixture is stirred for one hour at °C, filtered, washed twice with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain the product fraction boiling in the range of 125°C. to 126°C, at a pressure of 5 mm. of mercury. This fraction is dissolved in hexane and recrystallized to obtain 57· 8 parts of solid product having a m.p. of 45- 7°C. The structure is confirmed by NMR spectrum analysis.

Calc'd for CnHieNOCl: C, 6l.40; H, 8.57J CI, -16.50 Found: C, 6l.54; H, 8. 0; CI, I6.O8 Example 5 This example describes the preparation of 0 N-(l-cyclohexen-l-yl) N-(ethyl) a-chloroacetamide Into a solution of 55·9 parts of chloroacetyl chloride in 2 0 parts of benzene maintained at a temperature of about 5°C. are added slowly with stirring 57.5 parts of K-cyclohexylidene ethyl amine. After stirring for an additional 50 minutes at about 5°C., 50.5 parts of triethyl amine are added and the reaction mixture is allowed to warm to about °C The reaction mixture is stirred for one hour at 25°C, filtered, washed twice with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain product having a m.p. of 27-28°C. The structure is confirmed by KMR spectrum analysis.

Calc'd for CiOHieN0Cl: N, 6.98; CI, -17.65; m.w., 201 Found: N, 00; CI, 18.20; m.w., 200 Example 4 This example describes the preparation of N-(l-cyclohexen-l-yl) N-(2-methoxyisopropyl) a-chloroacetamide Into a solution of 22.4 parts of chloroacetyl chlo-ride in 150 parts of benzene maintained at a temperature of about 5°C. are added with stirring 3 parts of N-cyclohexyli-dene N-(2-methoxyisopropyl)amine. After stirring for an additional 30 minutes, 20.2 parts of triethyl amine are added and the reaction mixture is allowed to warm to about 2 °C. The reaction mixture is stirred for one hour at 25°C, filtered, washed twice with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain the product fraction boiling in the range of 146°C. to 150°C, at a pressure of 2 mm. of mercury. The product fraction amounts to 24.1 parts of an oily liquid and has the assigned structure.

Calc'd for Ci2Hi902NCl: CI, 14.4; N, 5·7 Found: CI, 14.19; N, 5.9 Example 5 This example describes the preparation of N-(l-cyclopenten-l-yl) N-(isopropyl) ct-chloroacetamide Into a solution of 22.6 parts of chloroacetyl chloride in benzene maintained at a temperature of about 5°C. are added with stirring 25 parts of N-cyclopentylidene N-isopropyl amine. After stirring for an additional 30 minutes, 20 pares of triethyl amine are added. The reaction mixture is filtered, washed with water and the filtrate dried over MgSO*. The residue is fractionally distilled to obtain the product fraction boiling in the range of 120°C. to 122°C, at a pressure of 2mm. of mercury. The product amounts to 12.5 parts and the assigned structure is confirmed by NMR spectrum analysis.

Calc'd for CloHi6N0Cl: CI, 17-7; N, 6.95 Pound: CI, 19.20; N, 7.0 Example 6 This example describes the preparation of 0 N-(l-cyclohexen-l-yl) N-(2-propen-l-yl) -chloroacetamide Into a solution of 35.9 parts of chloroacetyl chloride in 250 parts of benzene maintained at a temperature of about 5°C. are added with stirring l parts of N-(cyclohexyli-dene) N-(2-propen-l-yl) amine. After stirring for an additional 50 minutes, 30.3 parts of triethyl amine are added and the reaction mixture is allowed to warm to about 2 °C. The reaction mixture is stirred for one hour at 25°C, filtered, washed twice with water and the benzene removed by evaporation.

^ Calc'd for CnHieNOCl: C, 62.0; H, 7-52; CI, 16.65 Found: C, 61 ; H, 7·295 CI, 16.73 Example 7.

This example describes the preparation of 0 II CH3-N-C CHaCl N-(2-methyl-6-cyclohexen-l-yl) N-methyl -chloroacetamide Into a solution of 5.6 parts of chloroacetyl chloride in 250 parts of benzene maintained at a temperature of about 5°C. are added slowly with stirring 7.2 parts of N-(2-0 methylcyclohexylidene) N-methyl amine. After stirring for an additional JO minutes at about 5°C, 6.9 parts of triethyl amine are added and the reaction mixture is heated at reflux for about 1 hour. The reaction mixture is cooled, filtered, washed with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain the product fraction boiling in the range of 125°C to 130°C, at a pressure of 1 mm. of mercury. This fraction is dissolved in hexane and recrystallized to obtain a solid product having a m.p. of 56-58°C. The assigned structure is confirmed by NMR spectrum analysis.

Calc'd for CiOHieN0Cl: C, 59-50; H, 7.95; CI, 17.70; N, 6.95 . Found: C, 59-50; H, 7.89; CI, 17.84; N, 7.06 Example 8 This example describes the preparation of N-( -methylcyclohexen-l-yl) N-isopropyl a-chloroacetamide Into a solution of 36.8 parts of chloroacetyl chloride in 250 parts of benzene are added with stirring 100 parts of N-(4-methylcyclohexylidene) N-isopropyl amine. The reaction mixture is allowed to warm to about 50°C. and is stirred for 5 hours. The reaction mixture is filtered, washed with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain the product fraction, 56.6 parts, having a boiling point of 150°C, at a pressure of 1.5 mm. of mercury. The assigned structure of the product oil is confirmed by NMR spectrum analysis.' Calc'd for Ci2H2iN0Cl: N, 6.09; CI, 1 .

Pound: N, 6.07; CI, 15.55 Example 9 This example describes the preparation of CH3 0 I II CHaCHg-N-C CH2CI N-(l,5-cyclohexadien-l-yl) N-isopropyl a-chloroacetamide Into a solution of 22.4 parts of chloroacetyl chlo-ride in 250 parts of benzene maintained at a temperature of about °C. are added slowl with stirrin 2 .6 arts of N~ 5- about 25°C. The reaction mixture is filtered, washed twice with water and the benzene removed by evaporation. The residue is fractionally distilled to obtain the product fraction boiling in the range of 125°C. to 129°C, at a pressure of 1 mm. of mercury. This fraction is dissolved in hexane and recrystallized to obtain the white solid product having a m.p. of 3 -26°C. The assigned structure is confirmed by K R spectrum analysis.

Calc'd for CXiHiTNOCl: N, 6.56; CI, 16.7 Found: N, 6.63 CI,.16.52 Example 10 This example describes the preparation of (a) CHaCHa C1 N-(5, $5-trimethyl-l,3-cyclohexadien-l-yl) N-(ethoxyethyl) a-chloroacetamide 0 C1 N-(3j5.i5-trimethyl-2,6-cyclohexadien-l-yl) N-ethoxyethyl a-chloroacetamide, and 0 II CHaCHsOCHaCHa-N-C CH2C1 N-( 3 $ 5 » 5- rime h 1-5 , 6-cyclohexadien-l-yl) N-ethoxyethyl -chloroacetamide.

Into a solution of 11.3 parts of chloroacetyl chloride in 150 parts of benzene maintained at a temperature of about 5°C. are added slowly with stirring 20.9 parts of N-( 3 , 5 i 5-trimethyl-^-cyclohexen-l-ylidene) N-ethoxyethyl amine. After stirring for an additional 30 minutes at about 5°C.j .3 parts of triethyl amine are added and the reaction mixture is allowed to warm to about 25°C. The reaction mixture is filtered, washed twice with water and the benzene removed by evaporation. NMR spectrum analysis shows that the residue contains the compounds represented by' the formulae (a), (b) and (c) above. The residue is fractionally distilled to obtain the product fraction, 12.7 parts, having a boiling point of 135°C, at a pressure of 6 mm. of mercury. NMR spectrum analysis shows that the product is composed primarily of the compound represented by formula (a) above.

Calc'd for Ci5H24N02Cl: C, 63.20; H, 8.42; N, 4.90; CI, 12.45 Found: C, 63.33; H, 8.35; N, 4.90; Cl, 12.42 Following the procedure of the foregoing examples and using chloroacetyl chloride and the appropriate imine compound the following N-(cycloalken-l-yl) a-chloroacetamides are prepared.

Example N-(l-cyclopenten-l-yl) N-(ethoxyethyl) a-chloroacetamide N-(3-methylcyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(cycloheptyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(phenyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(methyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(heptyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(methoxybutyl) a-chloroacetamide N-(l-cyclohexen-l-yl) N-(2-buten-l-yl) a-chloroacetamide N-(l-cyclopenten-l-yl) N-(n-butyl) a-chloroacetamide N-(l-cyclopenten-l-yl) N-(2-propen-l-yl) a-chloroacetamide N-(l-cyclohepten-l-yl) N-(isopropyl) a-chloroacetamide N-(l,3-cyclohexadien-l-yl) N-(methyl) a-chloroacetamide N-(3-methyl-l-cyclopenten-l-yl) N-(methyl) a-chloroacetamide N-(3, 4-dimethyl-l-cyclopenten-l-yl) N-(methyl) a-chloroacetamide N-(3, -dimethyl-5-cyclopenten-l-yl) N-(isopropyl) a-chloroacetamide N-/"~ 5-(tert-butyl)-l-cyclopenten-l-yl 7 N-(isopropyl) a-chloroacetamide N-(3-methyl-5-cyclopenten-l-yl) N-methyl a-chloroacetamide N-(3, -dimethyl-l-cyclohexen-l-yl). N-(isopropyl) a-chloroacetamide N-( 5-methyl-l-cyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-(3, 4-dimethyl-6-cyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-( 2, 4-dimethyl-l-cyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-(2, i 6-trimethyl-l-cyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-(2,6-dimethyl-6-cyclohexen-l-yl) N-(isopropyl) a-chloroacetamide N-/~2 , 6-di( tert-butyl) -1-cyclohexen-l-yl 7 N-(isopropyl) N-( 6-methyl-l,3-cyclohexadien-l-yl) N-(isopropyl) α-chloroacetamide N-(5-meth 1-4, 6-cyclohexadien-l-yl) N-(isopropyl) a-chloroacetamide N-( 3-methy1- , 6-cyclohexadien-l-yl) N-(isopropyl) a-chloroacetamide N-( 3,5-dimethyl-l,3-cyclohexadien-l-yl) N-( isopropyl) a-chloroacetamide N- ~2 , 6-di(tert-butyl ) -1, 3-cyclohexadien-l-yl_7-N- methyl a-chloroacetamide N-(2-methyl-l, 3-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 4-methyl-l, 3-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-(3*5-dimethyl-l, 4-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-(2, 6-dimethyl-l, 4-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 3,5-dimethyl-l, -cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 6-tert-butyl-l, 4-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 4-isopropyl-l, 4-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 4-methyl-l, 4-cyclohexadien- 1-y 1 )-N-isopropy 1 a-chloroacetamide N-( 3-methyl-2 , 6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 3,5-diraethy1- , 6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 4 , 4-dimethyl-2 , 6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-( 6-tert-butyl-2 , 6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide N-(2 , 6-dimethy1-2 , 6-cyclohexadien-l-yl)-N-isopropyl a-chloroacetamide N-(2 , 4-dimethy1-2 , 6-cyclohexadien-l-yl)-N-ifopropyl a-chloroacetamide 60. N-(5-methy 1-1, -cyclohexadien-l-yl)-N-methyl a-chloroacetamide 61. N-( -methy 1-1, -cyclohexadien-l-yl)-N-methyl a-chloroacetamide 62. N-( 2 , 6-dimethyl-l,5-cyclohexadien-l-yl)-N-methyl a-chloroacetamide 65. N-( 2,4, -trimeth l-l,5-cyclohexadien-l-yl)-N-methyl a-chloroacetamide 64. N-( 6-ter -buty 1- 1,5-eyelohexadien-l-y 1)-N-methyl a-chloroacetamide 65. N-(3-methyl-3,6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide 66. N-( 2-meth 1-2, 6-cyclohexadieh-l-y3-N-methyl a-chloroacetamide 67. N-( 2,5-dimethyl-5, 6-cyclohexadien-l-yl)-N-methyl a-chloroacetamide 68. N-( 6 - 1ert-but 1-3, -eyelohexadien-l-y 1)-N-isopropyl a-chloroacetamide 69. N-(3,6-dimeth l-3,6-cyclohexadien-l-yi-N-isopropyl a-chloroacetamide 70. N-(3-methyl-l-cyclohepten-l-yl) N-(isopropyl) a-chloroacetamide 71. N-(3,4-dimethyl-l-cyclohepten-l-yl) N-(isopropyl) a-chloroacetamide 72. N-( 7- ert-butyl-l-cyclohepten-l-yl) N-(isopropyl) a-chloroacetamide 73· N-(2>4-diisopropyl-l-cyclohepten-l-yl) N-(isopropyl) a-chloroacetamide 74. N-(6-methyl-7-cyclohepten-l-yl) N-(lsopropyl) a-chloroacetamide 75. N-(3,5-dimethyl-l-cyclohepten-l-yl) N-.(isopropyl) a-chloroacetamide The pre-emergent phytotoxicity of illustrative N-(l-cycloalken-l-yO) a-chloroacetamides of this invention is demonstrated as follows: A good grade of top soil is placed in 9-1/2" x -3/4" x 2-3/4" aluminum pans and compacted to a depth of 2/8 tions are applied to the soil "by two methods: (l) application to the surface of the top soil layer and (2) admixture with or incorporation in the top soil layer.

In the surface application method the seeds are covered with a 2/8" layer of prepared soil and the pan leveled. The phytotoxic composition is applied by spraying the surface of the top layer of soil, prior to watering the seeds, with a solution containing a sufficient amount of active ingredient to obtain the desired rate per acre on the soil surface.

In the soil incorporation method, the soil required to fill the pans is weighed and admixed with a phytotoxic composition containing a known amount of active ingredient. The pans are then filled with the admixture and leveled. Watering is carried out by permitting the soil in the pans to absorb moisture through the apertured bottom of the pans.

The seed containing pans are placed on a wet sand bench and maintained for 14 days under ordinary conditions of sunlight and watering. The plants are observed at the end of 14 days and the results recorded. The phytotoxic pre-emergent activity index is based on the average percent germination of-each seed lot. The activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the examples. The pre-emergent phytotoxic activity index used in the following examples is defined as follows: Average Percent Numerical Germination Scale Phytotoxic Activity 76 - 100 « 0 => No phytotoxicity . 51 - 75 = 1 = Slight phytotoxicity 26 - 50 «= 2 =» Moderate phytotoxicity - = = ingredients in both surface and soil-incorporation applications. The terms "SA" and "SI" in the Application Method column of Table I mean surface application method and soil incorporation method, respectively. In Table I, the various plant seeds are represented by letters as follows: A — General Grass K -- Foxtail B — General Broadleaf L -- Barnyard Grass C — Morning Glory M -- Crab Grass D — Wild Oats N -- Pigweed E — Brome Grass 0 -- Soybean F — Rye Grass P -- Wild Buckwheat G — Radish Q -- Tomato H — Sugar Beets R -- Sorghum I — Cotton s -- Rice J — Corn TABLE I Pre-Emergent Phytotoxlc Activity of Various N-(cycloalken-l- Rate Application Example Compound Lb. /Acre Method 76 N-( 1-cyclohexen-l-yl) -N-isopropyl- a-chloroacetamide 5 SA 3 2 2 1 SI 3 1 2 0.25 SI 3 0 0.05 SI 3 0 0. 01 SI 3 0 77 N-(1-cyclohexen-l-yl) -N-raethyl- a-chloroacetamide 5 SA 3 1 1 SI 3 1 0.25 SI 2 0 0.05 SI 0 0 0 78 N-(1-cyclohexen-l-yl) -N-ethy1- a-chloroacetamide 5 SA 3 2 2 1 SI 2 0 0.25 SI 2 0 0.05 SI 0 0 79 N-( 1-cyclohexen-l-yl)-N-n propyl- -chloroacetamide 5 SA 3 1 1 SI 3 0 0.25 SI 3 0 0.05 SI 1 0 TABLE I (Continued) Pre-Emergent Phytotoxlc Activity of Various N-(cycloalken-l- Rate Application Example Compound Lb. /Acre Method 80 N-(1-cyclohexen-1-yl)-N-isobuty1- a-chloroacetamide 5 SA 3 0 1 SI 3 1 0.25 SI 2 0 0.05 SI 0 0 81 N-(1-cyclohexen-1-y1) -N-ally1- a-chloroacetamide 10 SA 3 3 SI 3 3 1 SI 3 2 0.25 SI 3 0 0.05 SI 2 0 0.01 SI 0 0 82 N-(1-cyclohexen-l-yl) -N-ethoxy- ethyl-a-chloroacetamide 10 SA 3 2 SI 3 2 1 SI 3 0 83 N-(1-cyclohexen-1-yl) -N-methoxy- propyl-a-chloroacetamide 5 SA 3 0 1 SI 2 0 0.25 SI 0 0 8 N~(1-cyclohexen-1-yl) -N-methoxy- ethyl-cc-chloroacetamide 5 SA 3 2 1 SI 3 0 TABLE I (Continued) Pre-Emergent Phytotoxlc Activity of Various N-(cycloalken-l- Rate Application Example Compound 85 N-(1-cyclopenten-l-yl)-N- (isopropyl)-a-chloroacetamide 86 N-(1-cyclohexen-l-y1)-N-(2-methox isopropyl) -a-chloroacetamide 5 SA 2 1 1 SI 3 0 0.25 SI - - 0.05 SI - - 87 N-(l,3-cyclohexadien-l~yl)-N- ( isopropyl) a-chloroacetamide 10 SA 3 2 SI 3 1 ■ 1 SI 3 0 0.25 SI 2 0 0.05 SI - - 88 N-(l-cyclohepten-l~yl)-N- (isopropyl) a-chloroacetamide 5 SA 3 1 1 SI - - 0.25 SI - - 0.05 SI 1 0 TABLE I (Continued) Pre-Emergent Phytotoxic Activity of Various N-(cycloalken-l-yl Rate Application Example Compound Lb. /Acre Method 89 N-(2-methyl-6-c clohexen-1-y1) N-meth l a-chloroacetamide 5 SA 32 1 1 SI 3 0 O Ο.25 SI I O O The data in Table I illustrate the general phytotoxic activity as well as the selective phytotoxic activity of representative N-(cycloalken-l-yl) a-chloroacetamides of this invention. It will be noted that unusual grass specificity is obtained at extremely lo application rates, for example at 0.01 lb./acre with N-(l-cyclohexen-l-yl)-N-isopropyl a-chloro-acetamide and N-(l-cyclohexen-l-yl)-N-(n-propyl) a-chloro-acetamide. It will also be noted that the N-(cycloalken-l-yl) cc-chloroacetamide phytotoxicants of this invention are not limited to removing. grasses from broadleaf plants since their selective action is such that certain genera of grasses are removed from corn which is also a genus of grass.

The lack of phytotoxic activity of a-chloroacetamides which are similar to the N-(cycloallen-l-yl) a-chloroacetamides of this invention is demonstrated as follows. Pre-emergent greenhouse tests are used and the seed planting procedure and application of a-chloroacetamide are carried out in the same manner as in the above pre-emergent examples. Results and further details are given in Table II. The identification of seeds, the phytotoxic activity index and application method symbols are the same as those used above.

TABLE II Pre-Emergent Phytotoxic Activity of ct-chloroace Rate Application Compound . Lb. /Acre Method N- ( 2 -eye lohexen-l- 1 )-N-is opr opyl- a-chloroacetamide 1 SI 000 0.25 SI 000 N-cyclohexyl-N- ( 2-methylpropenyl ) acetamide 5 SA 2 00 1 SI 100 Γ Ο The post-emergent phytotoxic activity of various N-(cycloalken-l-yl) a-chloroacetamides of this invention is demonstrated as follows. The active ingredients are applied in spray form to 21-day old specimens of the same plants used in the above pre-emergent tests. The phytotoxic spray is an acetone-water solution containing 0.5$ active ingredient. The solution is applied to the plants in different sets of pans at a rate equal to approximately 10 pounds of active ingredient per acre. The treated plants are placed in a greenhouse and the effects are observed and recorded after 1 days.

The post-emergent phytotoxic activity index used in the following examples is based on the average percent injury of each plant species and is defined as follows: Average Percent Numerical Injury Scale Phytotoxic Activity 0 - 25 = 0 = No phytctoxicity 26 - 50 = 1 = Slight phytotoxicity ' 51 - 75 s 2 = Moderate phytotoxicity 76 - 99 «= 5 = Severe phytotoxicity · 100 1 = = Plants dead The identification of the plants used is the same as in the above pre-emergent tests. Results and further details are given in Table III.

TABLE III Post-Emergent Phytotoxlc Activity of Various N-(eyelohexen-1 Rate Example Compound Lb. /Acre 90 N-(1-cyclohexen-l-yl)-N-allyl- a-chloroacetamide 10 334 91 N-(1-cyclohexen-1- 1)-N-isobuty1- a-chloroacetamide " 10 222 9 N-(l-cyclohexen-l-yl)-N-(ethyl) a-chloroacetamide 10 2 11 As mentioned hereinbefore the phytotoxic compositions of this invention comprise an active ingredient and one or more phytotoxic adjuvants which can be solid or liquid extenders, carriers, diluents, conditioning agents and the like. Preferred phytotoxic compositions containing the active ingredients of this invention have been developed so that the active ingredients can be used to the greatest advantage to modify the growth of plant systems in soil. The preferred compositions comprise wettable powders, aqueous suspensions, dust formulations, granules, e ulsifiable oils and solutions in solvents. In general these preferred compositions can all contain one or more surface-active agents.

Surface-active agents which can be used in the phytotoxic compositions of this invention are set out, for example, in Searle U.S. Patent 2,426,417, Todd U.S. Patent 2,655, W , Jones U.S. Patent 2,412,510 and Lenher U.S. Patent 2,139, 276. A detailed list of such agents is also set forth by J. .

McCutcheon in "Soap and Chemical Specialties", November 19^7 J page 8011 et seq. , entitled "Synthetic Detergents"; "Detergents and Emulsifiers - Up to Date" ( i960) , by J. W.

McCutcheon, Inc., and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the U.S.D.A* In general less than 10 parts by weight of the surface active agent is present per 100 parts by weight of phytotoxic composition.

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 orig'-n such as the natural clays, diatomaceous earth and synthetic minerals 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 and ditertiary acetylinic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalenesulfonate and sodium N-methy 1-N-(long chain acid) taurates.

The wettable powders compositions of this invention usually contain from about 25 to about 90 parts by weight of active ingredient, from about 0.25 to 3.0 part by weight of wetting agent, from about 0.25. to 7 parts by weight of disper-sant and from 9 · 5 to about 7^· 5 parts by weight of inert solid extender, all parts being by weight of the total composition. Where required from about 0.1 to 2.0 parts by weight of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.

Aqueous suspensions are prepared by mixing together" and sandgrinding 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.

Dusts are dense finely divided particulate compositions which are intended for application to the soil in dry form. Dusts are characterized by their free-flowing and rapid ticulate extender. However, their performance is sometimes aided by .the inclusion of a wetting agent such as those listed hereinbefore under wettable powder compositions and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. Suitable classes of grinding aids are natural clays, diatoraaceous earth and synthetic minerals derived from silica or silicate. Preferred, grinding aids include attapulgite clay, diatoraaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.

The inert finely-divided solid extender for the dusts can be either of vegetable or mineral origin. The solid extenders are characterized by possessing relatively low surface areas and are poor in liquid absorption. Suitable inert solid extenders for phytotoxic dusts include micaceous talcs, pyro-phyllite, dense kaolin clays, ground calcium phosphate rock and tobacco dust. The dusts usually contain from about 0.5 to 95 parts active ingredient, 0 to 0 parts grinding aid, 0 to 5 parts wetting agent and 5 to 99· parts dense solid extender, all parts being by weight and based on the total weight of the dust.

The v/ettable powders described above may also be used in the preparation of dusts. While such wettable powders could be used directly in dust form, it is more advantageous to dilute them by blending with, the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Emulsifiable oils are usually solutions of active ingredient in water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of this and alityl aryl polyether alcohols, polyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters, fatty alkyllol amide condensates, amine salts of fatty alcohol sulfates together with long chain alcohols and oil soluble petroleum sulfonates or mixtures thereof. The emulsifiable oil compositions generally contain from about 5 to 95 parts active ingredient, about 1 to 10 parts surfactant 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 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 surfactant such as those listed hereinbefore under wettable powders can be present in the composition. Natural clays, pyrophyllites 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 attapul-gite or heat expended, 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 phytotoxic granules.

The mineral particles which are used in the granular phytotoxic compositions of this invention usually have a size range of 10 to 100 mesh, but preferably such that a large majority of the particles have from 14 to 60 mesh with the optimum size being from 20 to 40 mesh. Clay having substantially all particles between 14 and 80 mesh and at least about The granular phytotoxic compositions of this invention generally contain from about 5 parts to about 0 parts by weight of N-(cycloalken-l-yl) a-chloroacetamide per 100 parts by weight of clay and 0 to about 5 parts by weight of wetting agent per 100 parts by weight of particulate clay. The preferred phytotoxic granular compositions contain from about 10 parts to about 25 parts by weight of active ingredient per 100 parts by weight of clay.

The phytotoxic compositions of this invention can also contain other additaments, for example fertilizers, other phytotoxicants, pesticides and the like used as adjuvant or in combination with any of the above-described adjuvants. Phyto- toxicants useful in combination with the above-described compounds include for example 2,4-dichlorophenoxyacetic acids, 2, 4, 5-trichlorophenoxyacetic acid, 2-meth l—ii—chlorophenoxy- acetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2, 4-bis(3-methoxypropylajnino) -6-methyl- thio-S-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S- triazine, and 2-ethylamino-1-isopropylamino-6-methylmercapto- S-triazine; urea derivatives, such as 3-{J> -dichlorophenyl)- ' 1, 1-dimethyl urea and 5-(p_-chlorophenyl)-l,l-dimethyl urea, acetanilides such as N-isopropyl-a-chloroacetanilide, and N-ethyl-a-chloro-2-methylacetanilide and 2-tert-butyl-2 1 - chloro-6-methylacetanilide, and acetamides such as N,N-diallyl-• a-chioroacetamide, N-(a-chloroacetyl)hexamethylene imine, and N,N-diethyl-a-bromoacetamide, and the like. Fertilizers useful in combination with the active ingredients include for example ammonium nitrate, urea and superphosphate. Other useful addi- timents include materials in which plant organisms take root α-chloroacetamides are dispersed in soil or plant growth media and applied to above ground surfaces of plants in any convenient fashion. Application to the soil or growth media can be carried out by simply admixing with the media, by applying to the surface of the soil and thereafter dragging or discing into the soil to the desired depth, or by employing a liquid carrier to accomplish the penetration and impregnation. The application of liquid and particulate solid phytotoxic compositions to the surface of soil or to above ground surfaces of plants 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. In a further method, the distribution of the active ingredients in soil can be carried out by admixture with the water employed to irrigate the soil. In such procedures, the amount of water can be varied with the porosity and water holding capacity of the soil to obtain the desired depth of distribution of the phytotoxicants.

The application of an effective or phytotoxic amount of the N-(cycloalken-l-yl) a-chloroacetamides of this invention to the soil or growth media or plant system is essential and critical for the practice of one embodiment of the present invention. The exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, the specific soil and depth at which the active ingredients are distributed in the soil and the amount of rainfall as well as the specific H-(cycloalken-l-yl) a-chloroacetamide em lo ed. In foliar treatment for the control cation of the growth of germinant seeds, emerging seedlings and established vegetation, the active ingredients are applied in amounts from about 0.01 to about 25 or more pounds per acre. In such soil applications, it is desirable that the active ingredients be distributed to a depth of at least 0.2 inches. In selective pre-emergence applications the active ingredients are usually applied in amounts from about 0.01 to 5 pounds per acre. It is believed that one skilled in the art can readily determine from this specification, including examples, the application rate for any specific situation.

The terms "soil" and "growth media" are employed in the present specification and claims in their broadest sense to be inclusive of all conventional "soils" as defined in Webster's New International Dictionary, Second Edition, Unabridged (l96l). Thus the terms refer to any substance or media in which vegetation may take root and grow, and are intended to include not only earth but also compost, manure, muck, humus, sand and the like, adapted to support plant growth.

Claims (2)

1. iiAVING NOW particularly descrioed and ascer- tk tained the nature of our said invention and in what ^ manner the same is to be performed, we declare that what we claim is : 1. Phytotc ic composition comprising an adjuvant and an effective amount of an K-(cycloalken-l-yl) a-chloroacetamide of the formula 0 II RN-C-CHaCl i wherein R is selected from the group, consisting of alkyi having from 1 to 8 carbon atoms-, cycloalkyl having from 3 to 8 c£._-bon atoms, alkoxyalkyl having from 2 to 8 carbon atoms, alkenyl having from 2 to 8 carbon atoms and aryl having from 6 to 1δ carbon atoms, and Y is selected from the group consisting of wherein R» is alkyl having from 1 to carbon atoms and n is an integer from 0 to >.

2. Phytotoxic composition of Claim 1 wherein n is 0. j5. A phytotoxic composition of Claim 1 wherein the a-chloroacetamide is N-(l-cyclohexen-l-yl)-N-isopropyl a-chloro-acetamide. 4. A phytotoxic composition of Claim 1 wherein the a-chloroacetamide is N-(l-cyclo exen-l-yl)-N-methyl a-c lcrc- AG-90 5. A phytotoxic composition of Claim 1 wherein 'ZS'XL a-c loroacetamide is N-( l-cyclohexen-l-yl)-N-ethyl a-ehloro- aceta ide. 6. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is W-(l-cyclohexen-l-yl)-N-(n-propyl) a-chloroacetamide. 7. A phytotoxic composition- of Claim 1 wherein the α-chloroacetamide is N-(l-cyclohexen-l-yl)-N-isobutyl a-chloroacetamide. 8. A phytotoxic composition of Claim 1 wherein the a-chloroacetamide is N-(l-cyclohexen-l-yl)-N-allyl a-chloroacetamide. 9. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is N-(l-cyclohexen-l-yl)-N-ethoxyethyl α-chloroacetamide. 10. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is. N-(l-cyclohexen-l-yl)-N-methoxypropyl a-chloroacetamide. 11. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is N-(l-cyclohexen-l-yl)-Di-methoxyethyl a-chloroacetamide. 12. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is N-(l-cyclopenten-l-yl)-N-(isopropyl) a-chloroacetamide. 15. A phytotoxic composition of Claim 1 wherein the lA. A phytotoxic composition of Claim 1 wherein the a-chloroacetamide is N-(l53-cyclohexadien-l-yl)-N-(isopropyl) a-chloroacetamide. 15. ' A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is li-(l-cyclohepten-l-yl)-N-(isopropyl) α-chloroacetamide. 16. A phytotoxic composition of Claim 1 wherein the α-chloroacetamide is N-(2-methyl-6-cyclohexen-l-yl) N-met yl α-chlorcacetamide. 17. Method of applying to plant systems in soil an effective amount of an a-chloroacetamide of the formula 0 !i RN-C-CH2C1 I Y wherein R is selected from the group consisting of alkyl having from 1 to 8 carbon atoms, cycloalkyl having from 3 to 8 carbon atoms, alkoxyalkyl having from 2 to 8 carbon atoms, alkenyl having from 2 to 8 carbon atoms and aryl having from 6 to l8 carbon atoms, and Y is selected from the group consisting of wherein R' is alkyl havin from 1 to 4 carbon atoms and n is an integer from 0 to 3· 18. Process for the preparation of an a-chloro- acetamide of the formula 0 11 RN-C-CHaCl Y wherein R is selected from the group consisting of alkyl having from 1 to 8 carbon atoms, cycloalkyl having from 5 to 8 carbon atoms, alkoxyalkyl having from 2 to 8 carbon atoms, alkenyl having from 2 to 8 carbon atoms and aryl having from 6 to l8 carbon atoms and Y is selected from the group consisting of wherein R1 is alkyl having from 1 to carbon atoms and n is an integer from 0 to 5 which comprises reacting a chloroacetyl halide with an imine of the formula R-N=A, wherein R is as defined above and A is selected from the group consisting of E'n wherein Rf and n are as defined above. 19. α-Chloroacet mide of the formula 0 II R -C-CHaCl I Y wherein R is selected from the group consisting of alkyl having from 1 to 8 carbon atoms, cycloalkyl having from 5 to 8 carbon atoms, alkoxyalkyl having from 2 to 8 carbon atoms, alkenyl having from 2 to 8 carbon atoms and aryl having from 6 to 18 carbon atoms, and Y is selected from the group consisting of wherein R" is alkyl having from 1 to 4 carbon atoms and n integer from 0 to 5. 20. a-Chloroacetamide of Claim 19 wherein Y is 1-cyclohexenyl. 21. a-Chloroacetamide of Claim 20 wherein R is isopropyl. 22. a-Chloroacetamide of Claim 20 wherein R is n-propyl. 2J. a-Chloroacetamide of Claim 20 wherein R is allyl. 24. α-Chloroacetamide of Claim 20 wherein R is ethox eth l. 26. Phytotoxic compositions, their application to plant systems, alpha-chloroacetaraides of the formula defined in Claim 19 , and process for the · preparation of same, substantially as hereinbefore described and with reference to any of the examples. DATED THIS 29th day of December, 1966" Attorneys for Applicants.