NO166647B - ANALOGY PROCEDURE FOR THE PREPARATION OF THERAPEUTICALLY ACTIVE SUBSTITUTED DIPEPTIDES. - Google Patents

Description

Phytotoxic preparations containing d-chloroacetamides.

The present invention relates to phytotoxic preparations which.

consists of or contains new N-(1-cycloalken-1-yl)-OUchloroacetamides.

The term "phytotoxic preparations" is used here <p>g in the subsequent requirements for materials which have a modifying effect on the growth of plant systems. Such modifying effects include all deviations from natural development, e.g. killing, inhibiting, killing, drying out, regulating, crippling, stimulating and the like. In the same way, "phytotoxic" and "phytotoxicity" are used to identify a growth modifying effect of the compounds and preparations according to the invention.

The term "plant system" is used here in the sense of "germinating seeds, shooting cuttings and established vegetation including roots and plant parts above ground".

The N-(1-cycloalken-1-yl) B-chloroacetamides used in the preparations according to the present invention are represented by the formula

where R denotes alkyl with 1-8 carbon atoms, alkoxyalkyl with 2-8 carbon atoms, alkenyl with 2-8 carbon atoms or phenyl, and Y is selected from the group consisting of

where R<1> is alkyl with 1-4 carbon atoms, and n is an index from 0 to 3.

The N-(1-cycloalken-1-yl) O-chloroacetamides used according to the present invention are unsaturated in the ring at the ring carbon atom above which the ring is bound to the nitrogen atom. When the cycloalkenyl is a 6-membered ring, the ring system may be conjugated but must be unsaturated at the ring carbon atom above which the ring is attached to the nitrogen atom, i.e.

in 1 or 6 position.

Representative R radicals in the ct-chloroacetamides include alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl straight and branched amyls, pentyls, hexyls, heptyls and octyls; alkenyl, e.g. allyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl; alkoxyalkyl, e.g. methoxymethyl, methoxyethyl, methyxypropyl, methoxybutyl, methoxyheptyl, propoxypropyl, ethoxyethyl and butoxybutyl, <p>g phenyl.

Representative Y cycloalkenyl radicals for the O -chloroacetamides include e.g. 1-cyclopentenyl, 3-methyl-1-cyclopentenyl, 5-methyl-1-cyclopentenyl, 3, 4-dimethyl-1-cyclopentenyl, 2, 5-dimethyl-1-cyclopentenyl, 5-methyl-5-cyclopentenyl, 3, 4-dimethyl-5-cyclopentenyl, 5-(tert-butyl)-l-cyclopentenyl, 1-cyclohexenyl, 3-methyl-1-cyclohexenyl, 3,4-dimethyl-1-cyclohexenyl, 6-methyl-1-cyclohexenyl, 2, 4-dimethyl-1 -cyclohexenyl, 3-methyl-6-cyclohexenyl, 3,4-dimethyl-6-cyclohexenyl, 2, 6-dimethyl-1 - cyclohexenyl, 3,3-dimethyl-1 - cyclohexenyl, 6- (tert-butyl)-1 - cyclohexenyl, 1, 3-cyclohexadienyl, 3-methyl-1, 3-cyclohexadienyl, 3, 4-dimethyl-1, 3-cyclohexadienyl, 6-methyl-1, 3-cyclohexadienyl, 2, 4-dimethyl-1, 3-cyclo - 'hexadienyl, 3 -methyl-4, 6- cyclohexadienyl, 3 , 4-dimethyl-4, 6-cyclohexadienyl , 2, 6-dimethyl-4, 6-cyclohexadienyl, 5,5 -dimethyl-1,3-cyclohexadienyl,6-(tert-butyl)-1,3-cyclohexadienyl,3,5,5-trimethyl-1,3-cyclohexadienyl,1,4-cyclohexadienyl,3-methyl-1 , 4-cyclohexadienyl, 3,4-dimethyl-1 , 4-cyclohexadienyl, 6-methyl -1, 4-cyclohexadienyl, 2,4-dimethyl -1, 4-cyclohexadienyl, 2,6-dimethyl-1, 4-cyclohexadienyl, 2,5-dimethyl-1, 4-cyclohexadienyl, 6-(tert-butyl) -1, 4-cyclohexadienyl, 3,6, 6-tri-methyl-1, 4-cyclohexadienyl, 3-methyl-3, 6-cyclohexadienyl, 6-methyl-3, 6-cyclohexadienyl, 2, 6-dimethyl-3 , 6 -cyclohexadienyl, 2,5,5 -trimethyl - 3 , 6 - cyclohexadienyl, 3,5,5 -trimethyl-3 , 6 - cyclohexadienyl, 2, 4-dimethyl - 3 , 6 - cyclohexadienyl, 6-(tert- butyl) -3, 6-cyclohexadienyl, 1, 5-cyclohexa- ,-- dienyl, 3 -methyl - 1 , 5 - cyclohexadienyl, 3 , 4-dimethyl -1 , 5 - cyclohexadienyl, 6-isopropyl-1 , 5 - cyclohexadienyl, 6 -tert-butyl -1 , 5 - cyclohexadienyl, 2 ,6-dimethyl- 1, 5 - cyclohexadienyl, 3 - methyl-2 , 6 - cyclohexadienyl, 2, 5 , 5 -tri - methyl-2, 6- cyclohexadienyl, 3,5,5 -trimethyl-2, 6 - cyclohexadienyl , 6-(tert-butyl)-2, 6-cyclohexadienyl, 6-methyl-2, 6-cyclohexadienyl, 1-cycloheptenyl, 3-methyl-1-cycloheptenyl, 3, 4-dimethyl-1-cycloheptenyl, 7-methyl -1-cycloheptenyl, 4, 5-dimethyl-1-cycloheptenyl, 2-methyl-1-cycloheptenyl, 6-methyl-1-cycloheptenyl, 7-methyl-7-cycloheptenyl, 7-(tert-butyl)-1-cycloheptenyl and 3,4-diisopropyl-1-cycloheptenyl.

The present N-(1-cycloalken-1-yl) CC-chloroacetamides are prepared by a method which consists in reacting a chloro acetyl halide with an imine of the formula

where R is as defined above and A is selected from the group

where R' and n are as defined above.

The synthesis of the present compounds can be stated as follows:

where R is as defined above and X is Cl, Br or J.

The reaction of chloroacetyl halide with imines can be carried out in different ways. Normally it is desired for maximum yield that the imine is present in at least an equimolar amount to the chloroacetyl halide and preferably in excess of the equimolar amount. The reaction is conveniently carried out at room temperature, i.e. about. 20 - 25°C. However, a higher or lower temperature can be used and the temperature is not critical. For example temperatures above approx. 4o°C when no acid acceptor is used.

The reaction is preferably carried out in the presence of an acid acceptor and

an inert organic medium. Acid acceptor is usually present in at least equimolar amounts based on the amount of hydrogen halide formed in the reaction. Suitable acid acceptors, e.g. alkaline-acting or basic materials with the ability to bind the acid that develops in the reaction are tertiary amines such as trimethylamine, triethylamine, pyridine, quaternary ammonium hydroxides, N-ethylmorpholine and the like. , inorganic bases such as sodium hydroxide and calcium hydroxide, sodium carbonate etc. An excess of imine reaction components also serves as an acid acceptor.

Inert organic media that can be used in the execution of the invention include e.g. 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 methylisopropylketone, methylisobutylketone, methylisoamylketone, diisopropylketone, cyclohexanone etc. 1.; and organic halides such as carbon tetrachloride, n-butyl chloride, ethylene dichloride, tetrachloroethylene, etc.

The separation of the resulting reaction product from the reaction mixture is easily accomplished. For example the salt is separated as a tertiary amine hydrochloride salt which is formed during the reaction due to the presence of a tertiary amine compound at this as an acid acceptor from the product which. contains the reaction mixture by simple means such as filtration, and the solvent is removed from the resulting filtrate by stripping or distillation, preferably vacuum distillation at low temperature. The product can be cleaned in any of the usual ways known in the field, e.g. fractional distillation at reduced pressure, selective extraction, fractional distillation using a carrier gas or a suitable combination of these. If desired, the product can be subjected to film distillation, recrystallization or a combination of both for further purification.

The N-(1-cycloalken-1-yl) α-chloroacetamides used in the preparations according to the present invention are liquid or crystalline solid materials which are insoluble in water, but somewhat soluble in many organic solvents such as alcohols, ketones, benzene, toluene , xylene, hexane etc.

According to the present invention, it has been found that the growth of germinating seeds, shoot cuttings and established vegetation can be controlled or modified by exposing the seeds, cuttings or roots or aboveground plant part of established vegetation to the action of an effective amount of one or more N-( 1-cycloalken-1-yl)-chloroacetamides which are used according to the present invention. These compounds are effective as general phytotoxic agents including post-emergence and pre-emergence phytotoxic agents, but their most prominent utility is as pre-emergence phytotoxic agents. Moreover, these compounds are characterized by a spectrum of herbicidal or phytotoxic activity, i.e. they modify the growth of a number of different plant systems including broad-leaved plants and grass plants..

For the sake of brevity and simplicity, the term "active component" will be used in the following to describe the N-(1-cycloalken-1-yl) tt-chloroacetamides used in the preparations according to the invention.

The phytotoxic preparations according to the present invention contain at least one active component and a material which is referred to in the field as a phytotoxic aid in liquid or solid form. The preparations are made by mixing the active component with an aid including diluents, emollients, carriers and conditioners to produce the preparation in the form of finely divided, particulate solids, granules, pellets, solvents and aqueous dispersions or emulsions. Thus, the active component can be used with an aid such as a finely divided solid, a solvent of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.

Typical finely divided carriers and retarding agents for phytotoxic preparations according to the present invention include e.g. talc, clay, pumice, silicon oxide, diatomaceous earth, walnut flour, chalk, quartz, fuller's earth, sulphur, powdered cork, powdered wood, tobacco dust, volcanic ash etc. 1. Typical liquid diluents are kerosene, petroleum naphtha, hexane, toluene, benzene, acetone, ethylene dichloride, xylene, alcohols, diesel oils, glycols

beer.

The phytotoxic preparations according to the invention, especially liquids and wettable articles, usually contain as a conditioning agent one or more surfactants in quantities sufficient to make a given preparation easily dispersible in water or oil. The term "surfactant" is understood to include wetting agents, dispersing agents, suspending agents and emulsifying agents. The term "phytotoxic preparation" is used here and in the following claims in the sense of not only including preparations in a suitable form for use, but also concentrated preparations that require dilution etc. with a suitable amount of liquid or solid aid before use.

The following examples will illustrate the preparation of the active compounds and their phytotoxic action. In the following examples as well as in the description, parts and percentages are given by weight, unless otherwise stated.

Example 1

This example describes the production of

N-(1-cyclohexan-1-yl) N-(isobutyl) -chloroacetamide.

To a solution of 33.9 parts of chloroacetyl chloride in ZOO parts of benzene held at a temperature of approx. 5°C, 45.9 parts of N-cyclohexylidene N-isobutylamine are added slowly while stirring. After stirring for a further 30 minutes at approx. 5°C, 30.3 parts of triethylamine are added. The reaction mixture is allowed to warm up to approx. 25°C and 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 give a product fraction which boils within the range 130 - 134°C at a pressure of 3 mm Hg. The product comprises 36.1 parts of an oil-active liquid and the structure is confirmed by nuclear magnetic resonance (NMR) spectral analysis.

Calculated for C12H2QNOCl: C. 63.0; H. 8.74; CI. 15.50 Found: C. 63.63; H. 8.85; Cl. 15.39

Example 2

This example describes the production of

N-(1-cyclohexan-1-yl) N-(n-propyl) A-chloroacetamide.

To a solution of 33.9 parts of chloroacetyl chloride in 250 parts of benzene, kept at a temperature of about At 5°C, 41.7 parts of N-cyclohexylidene N-(n-propyl)amine are added slowly while stirring. After stirring for a further 30 minutes at approx. 5°C, 30.3 parts of triethylamine are added and the reaction mixture is allowed to warm up to approx. 25°C. The reaction mixture is stirred for 1 hour at 25°C, filtered, washed twice with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives a product fraction which boils at 125°C - 126°C at a pressure of 3 mm Hg. This fraction is dissolved in hexane and recrystallized to give 37.8 parts of a solid product with a melting point of 45 - 47°C. The structure is confirmed by NMR spectral analysis.

Calculated for CjjHjgNOCl: C, 61.40; H, 8.37; Cl, 4.50 p.m

Found: C, 61.54; H, 8.50; Cl, 16.08

Example 3

This example describes the production of

N-(1-cyclohexen-1-yl) N-(ethyl) d -chloroacetamide.

To a solution of 33.9 parts of chloroacetyl chloride in 250 parts of benzene, kept at a temperature of about At 5°C, 37.5 parts of N-cyclohexylidene-ethylamine are added slowly while stirring. After stirring for a further 30 minutes at approx. 5°C, 30.3 parts of triethylamine are added, and the reaction mixture is allowed to warm up to approx. 25°C. The reaction mixture is stirred for 1 hour at 25°C, filtered, washed twice with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction which boils within the range 115 - 120°C at a pressure of 2 mm Hg. This fraction is dissolved in hexane and recrystallized to give 37.4 parts of a solid with a melting point of 27 - 28°C. The structure is confirmed by NMR spectral analysis.

Calculated for C1()H16NOCl: N, 6.98; Cl, 17.65; mole. 201

Found: N, 7.30; Cl, 18.20; mole. 200

Example 4

This example describes the production of

N-(1-cyclohexen-1-yl)N-(2-methoxyisopropyl)α-chloroacetamide.

To a solution of 22.4 parts of chloroacetyl chloride in 150 parts of benzene, kept at a temperature of approx. 5°C, add 34 parts while stirring

N-cyclohexylidene N-(2-methoxyisopropyl)amine. After stirring for a further 30 minutes, 20.2 parts of triethylamine are added, and the reaction mixture is allowed to warm up to approx. 25°C. The reaction mixture is stirred for one hour at 25°C, filtered, washed twice with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction which boils within the range 146 - 150 C at a pressure of 2 mm Hg. The product fraction comprises 24.1 parts of an oily liquid and has the attributed structure.

Calculated for C12H19OzNCl: CI, 14.4; N, 5.7

Found: Cl , 14, 19; N, 5.94

Example 5

This example describes the production of

N-(1-cyclopenten-1-yl)N-(isopropyl)<t-chloroacetamide.

To a solution of 22.6 parts chloroacetyl chloride in benzene noldt

at a temperature of approx. 5°C, 25 parts of N-cyclopentylidene N-isopropylamine are added while stirring. After stirring for a further 30 minutes, 20 parts of triethylamine are added.' The reaction mixture is filtered, washed with water and the filtrate is dried over MgSO 4 . The residue is fractionally distilled and gives the product fraction which boils within the range 120 - 122°C at a pressure of 2 mm Hg. The product comprises 12.5 parts and the attributed structure is confirmed by NMR spectral analysis.

Calculated for C1QHl6<N>OCl: Cl, 17.7; N, 6.95

Found: Cl, 19.20; N, 7.05

Example 6

This example describes the production of

N-(1-cyclohexen-1-yl)N-(2-propen-1-yl) d-chloroacetamide.

To a solution of 33.9 parts of chloroacetyl chloride in 250 parts of benzene, kept at a temperature of approx. 5°C, 41 parts of N-(cyclohexylidene)N-(2-propen.-1-yl)amine are added while stirring. After stirring for a further 30 minutes, 30.3 parts of triethylamine are added and the reaction mixture is allowed to warm up to approx. 25°C.

The reaction mixture is stirred for one hour at 25°C, filtered, washed twice with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction which boils at 136°C at a pressure of 2 mm Hg. The product comprises 37.7 parts and the attributed structure is confirmed by NMR spectral analysis.

Calculated for CnHl6NOCl: C, 62.0; H, 7.52; Cl, 16.65 Found C, 61.4; H. 7.29; Cl, 16.73

Example 7

This example describes the production of

N-(2-methyl-6-cyclohexen-1-yl) N-methyl <1-chloroacetamide.

To a solution of 5.6 parts of chloroacetyl chloride in 250 parts of benzene, kept at a temperature of approx. 5°C, add slowly while stirring 7.2 parts of N-(2-methylcyclohexylidene)N-methylamine. After stirring for a further 30 minutes at approx. 5°C, 6.9 parts of triethylamine are added and the reaction mixture is heated under reflux for approx. 1 hour. The reaction mixture is cooled, filtered, washed with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction which boils within the range 125°C - 130°C at a pressure of 1 mm Hg. This fraction is dissolved in hexane and recrystallized to give a solid product which has a melting point of 36 - 38°C. The attributed structure is confirmed by NMR spectral analysis.

Calculated for Cl0H16NOCl: C, 59.50; H, 7.95; Cl, 17.70; N, 6.95 Found: C, 59.50; H, 7.89; CI, 17.84; N, 7.06

Example 8

This example describes the production of

N-(4-methylcyclohexen-1-yl)N-isopropyl Ct-chloroacetamide.

</> To a solution of 36.8 parts of chloroacetyl chloride in 250 parts of benzene, 100 parts of N-(4-methylcyclohexylidene)-isopropylamine are added while stirring. The reaction mixture is allowed to warm up to approx. 50°C and stirred for 3 hours. The reaction mixture is filtered, washed with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction, 36.6 parts, which has a boiling point of 150°C at a pressure of 1.5 mm Hg. The attributed structure of the product oil has been confirmed by NMR spectral analysis.

Calculated for C12H21<N>OCl: N, 6.09; Cl, 15.4

Found: N, 6.07; Cl, 15.35

Example 9

This example describes the production of

N-(1,3-cyclohexadien-1-yl)N-isopropyl O-chloroacetamide.

To a solution of 22.4 parts of chloroacetyl chloride in 250 parts of benzene, kept at a temperature of approx. 5°C slowly add 27.6 parts of N-(3-cyclohexen-1-ylidene)N-isopropylamine with stirring. After stirring for a further 30 minutes at approx. 5°C, 8.6 parts of triethylamine are added and the reaction mixture is allowed to warm up to approx. 25°C. The reaction mixture is filtered, washed twice with water and the benzene is removed by evaporation. The residue is fractionally distilled and gives the product fraction which boils within the range of 125 - 129°C at a pressure of 1 mm Hg. This fraction is dissolved in hexane and recrystallized to give the white solid which has a melting point of 34-36°C. The attributed structure is confirmed by NMR spectral analysis.

Calculated for CnH17NOCl: N, 6.56; Cl, 16.7

Found: N , 6. 63; C 1, 16. 52

This example describes the production of

N-(3,5,5-trimethyl-1,3-cyclohexadien-1-yl)N-(ethoxyethyl)O-chloroacetamide. N-(3,5,5-trimethyl-2,6-cyclohexadien-1-yl)N-ethoxyethyl «-chloroacetamide, and

N-(3,5,5-trimethyl-3,6-cyclohexadien-1-yl)N-ethoxyethyl Ot-chloroacetamide.

To a solution of 11.3 parts of chloroacetyl chloride in 150 parts of benzene, kept at a temperature of approx. 5°C, 20.9 parts of N-(3,5,5-trimethyl-2-cyclohexen-1-ylidene)N-ethoxyethylamine are added slowly while stirring. After stirring for a further 30 minutes at 5°C, 4.3 parts of triethylamine are added and the reaction mixture is allowed to warm up to approx. 25°C. The reaction mixture is filtered, washed twice with water and the benzene is removed by evaporation. NMR spectral analysis shows that the residue contains the compounds produced in the formulas a), b) and c) above. The residue is fractionally distilled and gives the fraction product, 12.7 parts, which has a boiling point of 135°C at a pressure of 6 mm Hg. NMR spectral analysis shows that the product together

is set mainly by the compound according to formula a) above.

Calculated for C15HNOCl: C, 63.20; H, 8.42; N, 4.90; Cl, 12.45 Found: C, 63.33', H, 8.35; N, 4.90; Cl, 12.42

By following the procedure of the preceding examples and by using chloroacetyl chloride and the prepared imine compound, the following N-(1-cycloalken-1-yl)-chloroacetamides are prepared.

Example

11. N-(1-cyclohexen-1-yl) N-(isopropyl) O -chloroacetamide

12. N-(1-cyclohexen-1-yl) N-(ethoxyethyl) cc -chloroacetamide

13. N-(1-cyclohexen-1-yl)N-(methoxyethyl)&. -chloroacetamide

14. N-(1-cyclopenten-1-yl)N-(ethoxyethyl)O-chloroacetamide

15. N-(3-methyl-1-cyclohexen-1-yl) N-(isopropyl) OC-chloroacetamide

16. N-(1-cyclohexen-1-yl) N-(methyl) R -chloroacetamide

17. N -(1-cyclohexen-1-yl) N -(heptyl) α-chloro racetamide

18. N-(1-cyclohexen-1-yl) N-(methoxybutyl) α-chloroacetamide

19. N-(1-cyclohexen-1-yl) N-(2-buten-1-yl) CC -chloroacetamide

20. N-(1-cyclopenten-1-yl) N-(n-butyl) CC -chloroacetamide

21. N-(1-cyclopenten-1-yl)N-(2-propen-1-yl)OC-chloroacetamide

22. N-(1-cyclohepten-1-yl)N-(isopropyl)α-chloroacetamide

23. N-(1,3-cyclohexadien-1-yl)N-(methyl) (x-chloroacetamide

24. N-(3-methyl-1-cyclopenten-1-yl) N-(methyl) α-chloroacetamide

25. N-(3,4-dimethyl-1-cyclopenten-1-yl)N-(methyl)CK-chloroacetamide

26. N-(3,4-dimethyl-5-cyclopenten-1-yl)N-(isopropyl)ct-chloroacetamide 27. N-(5-(tert-butyl)-! -cyclopenten-1-yl/N-(isopropyl)O-chloroacetamide

28. N-(3-methyl-5-cyclopenten-1-yl) N-methyl «--chloroacetamide

29. N-(3,4-dimethyl-1-cyclohexen-1-yl)N-(isopropyl)α-chloroacetamide

30. N-(5-methyl-1-cyclohexen-1-yl) N-(isopropyl) o -chloroacetamide

31. N-(3,4-dimethyl-6-cyclohexen-1-yl)N-(isopropyl)eth-chloroacetamide 32.N-(2,4-dimethyl-1-cyclohexen-1-yl)N-(isopropyl )ot-chloroacetamide 33. N-(2, 4, 6-trimethyl -1 - cyclohexen-1 -yl) N-(isopropyl) «-chloroacetamide 34. N-(2, 6-dimethyl-6-cyclohexen-1- yl) N-(isopropyl) o -chloroacetamide 35. N-(2,6-di (tert-butyl)-1 -cyclohexen-1 -yl) N -(isopropyl) a -chloroacetamide

36. N-(3-methyl-6-cyclohexen-1-yl) N-methyl OC-chloroacetamide

37. N-(6-methyl-1,3-cyclohexadien-1-yl)N-(isopropyl)-chloroacetamide. '38. N-(5-methyl-4, 6-cyclohexadien-1-yl) N-(isopropyl)oC-chloroacetamide 39. N-(3-methyl-4, 6-cyclohexadien-1-yl) N-(isopropyl) a -chloroacetamide 40. N-(3,5-dimethyl-1,3-cyclohexadien-1-yl)N-(isopropyl)«-chloroacetamide 41.N-/2,6-di(tert-butyl)-1,3 -cyclohexadien-1 -yl/-N-methylOt-chloroacetamide 42. N - (2-methyl -1, 3 - cyclohexadien -1 -yl) -N-methyl « -chloroacetamide 43. N -(4-methyl - 1, 3 - cyclohexadien-1 -yl) -N-methyl O -chloroacetamide 44. N-(3 , 5 - dimethyl - 1, 4-cyclohexadien - 1 -yl) -N-methyl O( -chloroacetamide 45. N - (2 , 6-dimethyl-1, 4-cyclohexadien-1-yl)-N-methyl«-chloroacetamide 46. N-(3, 3-dimethyl-1, 4-cyclohexadien-1-yl)-N-methyl O -chloroacetamide 47. N-(6-tert-butyl-1,4-cyclohexadien-1-yl)-N-methyl O -chloroacetamide 48. N -(4-isopropyl-1,4-cyclohexadien-1-yl)-N- methyl ot -chloroacetamide 49. N-(4-methyl-1,4-cyclohexadien-1 -yl)-N-isopropyl ot -chloroacetamide

50. N -(3-methyl-2,6-cyclohexadien-1-yl)-N-methyl O*-chloroacetamide

51. N-(3,4-dimethyl-2,6-cyclohexadien-1-yl)-N-methyl CS-chloroacetamide 52.N-(4,4-dimethyl-2,6-cyclohexadien-1-yl)- N-methylO -chloroacetamide 53 . N-(6-tert-butyl-2,6-cyclohexadien-1-yl)-N-methyl Ot-chloroacetamide 54. N-(2,6-dimethyl-2,6-cyclohexadien-1-yl)-N- isopropyl O-chloroacetamide 55. :'' N - (2, 4-dimethyl -2, 6-cyclohexadien-1 -yl)-N-isopropyl o -chloroacetamide 56. N-(3-methyl-1 , 5-cyclohexadien-1- yl)-N-methyl OC -chloroacetamide 57. N -(3,4-dimethyl-1,4-cyclohexadien-1-yl)-N-methyl<X-chloroacetamide

58. N-(5-methyl-1,5-cyclohexadien-1-yl)-N-methylOt-chloroacetamide

59. N-(4-methyl-1,5-cyclohexadien-1-yl)-N-methyl O -chloroacetamide

60. N - (2, 6-dimethyl -1, 5 - cyclohexadien -1 -yl) -N-methyl O -chloroacetamide 61. N -(2, 4, 4-trimethyl - 1, 5-cyclohexadien -1 -yl ) -N-methylOf-chloroacetamide 62. N-(6-tert-butyl-1,5-cyclohexadien-1-yl)-N-methyl α-chloroacetamide

63. N-(3-methyl-3,6-cyclohexadien-1-yl)-N-methyl O-chloroacetamide

64. N-(2-methyl-3,6-cyclohexadien-1-yl)-N-methylOL-chloroacetamide

65 . N - (2 , 5 - dimethyl-3 , 6-cyclohexadien-1 -yl)-N-methyl 01 -chloroacetamide 66. N-(6 -tert-butyl-3 , 6 -cyclohexadien-1 -yl) -N- isopropylOt-chloroacetamide 67 . N-(3,6-dimethyl-3,6-cyclohexadien-1-yl)-N-isopropylO-chloroacetamide

68. N-(3-methyl-1-cyclohepten-1-yl) N-(isopropyl)or -chloroacetamide

69 . N-(3,4-dimethyl-1-cyclohepten-1-yl)N-(isopropyl)OL-chloroacetamide 70. N-(7-tert-butyl-1-cyclohepten-1-yl)N-(isopropyl)Ot -chloroacetamide 71. N-(3,4-diisopropyl-1-cyclohepten-1-yl)N-(isopropyl)ot-chloroacetamide

72. N-(6-methyl-7-cyclohepten-1-yl) N-(isopropyl) o -chloroacetamide

73. N-(3,5-dimethyl-1-cyclohepten-1-yl)N-(isopropyl)o-chloroacetamide.

The pre-emergence phytotoxicity for N-(1-cycloalken-1-yl) O - chloroacetamide, which is illustrative of the invention, is shown by the following:

Good quality soil is placed in aluminum pans 25 x 14.5 x 7

cm and packed together to a depth of approx. 1 - 1.25 cm from the top of the pan. A certain number of seeds from 19 different plant species are placed on top of the soil in different pans. The phytotoxic preparations are added to the soil

two methods:

1) supply to the surface of the top soil layer, and

2) mixing with or incorporation into the top soil layer.

With the surface application method, the seeds are covered with an approx. 1 cm layer of soil and leveled. The phytotoxic preparation is applied by spraying the surface of the top layer of the soil before the seeds are watered with a solution containing a sufficient amount of active components to achieve the desired amount per unit area on the soil surface.

Where incorporation into the soil takes place, the required amount of soil to fill the pans is weighed and mixed with a phytotoxic preparation containing a known quantity of active component. The pan is then filled with the mixture and levelled. Watering is carried out by allowing the soil in the pan to absorb moisture through the perforated bottom of the pan.

The pans containing seeds are placed in a moist sand bench and kept for 14 days under normal conditions of sunlight and watering. The plants are removed after 14 days and the results are recorded. The phytotoxic pre-emergent activity index is based on the average germination percentage for each seed proportion. The activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the examples. The pre-emergence phytotoxic activity index used in the following examples is defined as follows:

Pre-emergence phytotoxic activity for some of the N-(1-cycloalken-1-yl)-oc-chloroacetamides used in the preparations according to the present invention are recorded in Table I for different addition amounts of the active components both to the surface and for incorporation in the earth. The terms "SA" and "SI" in the column for the application method mean surface application or incorporation into the soil. In Table I, the different plant seeds are designated by letters as follows:

A - ordinary grass

B - broad-leaved plants

C - Iponioea

D - spelled oats

E - Bromine

F - rye grass (Lolium perenne)

G - radish

H - sugar beet

I - cotton J - wheat

K - fox tail

Li - chicken millet (Echinochloa crus-galli)

M - millet (Digitaria

N - Chenopodium quinoa (Chenopodium quinoa)

O - soybean

P - wild buckwheat

Q - tomato

R - Sorghum S - rice

T - Chenopodium album

U - Sebania exaltata

The figures in Table I show the general phytotoxic activity as well as the selective phytotoxic activity for representative preparations according to the invention. It will be noted that exceptional specificity towards grass is achieved at extremely low application amounts, such as e.g. at 1125 g/da with N-(1-cyclohexen-1-yl)-N-isopropyl-et-chloroacetamide and N-(1-cyclohexen-1-yl)-N-(n-propyl)oc-chloroacetamide.

It will also be noted that N-(1-cycloalken-1-yl) O -chloroacetamide phytotoxic agents according to the present invention do not. are limited to removing grasses from broadleaf plants as their selective weeding is such that certain species of grasses are removed from maize which is also a grass species. The tables also show that N-(1-cyclohexen-1-yl)-N-allyl-o-chloroacetamide has a particularly strong effect. Preparations containing this compound are therefore preferred.

The lack of phytotoxic activity for ot-chloroacetamide is similar to the N-(l-cycloalken-1-yl) ot-chloroacetamides used in the preparations according to the present invention are shown as follows: Pre-emergence greenhouse samples are used and the seeding method and application of Ot -chloroacetamide is carried out in the same way as in the aforementioned pre-emergence examples. Results and further details are shown in Table II. The identification of the seeds, the phytotoxic activity index and the symbols for the application are the same as those used above.

It is known from British patent 781, 702 that the compound N-cyclohexyl-N-allyl-*-chloroacetamide has a herbicidal effect.

Reference is also made to German publication 1,108,978, which relates to N-substituted Ot-haloacetamides with the formula:

where R denotes hydrogen or a hydrocarbon radical with 1-4 carbon atoms, R' denotes an aliphatic hydrocarbon radical, hydrogen, alkoxyalkyl, benzyl, phenyl, furfuryl or cyclohexyl radical, and X denotes chlorine, bromine or iodine. However, the radical Y, which distinguishes the present invention, is different from the corresponding substituents for the nitrogen in the German patent. Y denotes, as defined above, a cycloalkenyl radical with 5-7 carbon atoms. That the compounds used according to the invention are advantageous compared to the previously known compounds (2), (4) and (6) appears from the following table Hb. Norwegian patent application no. 166,647

Compound 90: N-(1-cyclohexen-1-yl)-N-phenyl-"--chloroacetamide (N-(1-cyclohexen-1-yl)-<%-chloroacetanilide),

Post-emergent phytotoxic activity for various N-(1-cycloalken-1-yl)O-chloroacetamides used in the preparations according to the present invention is shown as follows. The active components are applied in atomized form

to 21-day-old specimens of the same plants used in the aforementioned pre-emergence tests. The phytotoxic spray liquid is an acetone-water solution containing 0.5% active components. The solution is applied to the plants in different sets of pans with an amount that is approximately 1125 g of active components per then. The treated plants are placed in a greenhouse and the effect is observed and recorded after 14 days.

The post-emergence phytotoxic activity index used in the following examples is based on the average percentage damage to each plant species and is defined as follows:

The identification of the plants used is the same as in the aforementioned pre-emergence samples. The results and further details are reproduced in Table III.

As indicated above, the phytotoxic preparations according to the invention consist of an active component and one or more phytotoxic aids which can be

solid or liquid propellants, carriers, conditioning agents, etc. Preferred phytotoxic preparations containing the active components according to the present invention have been developed so that the active components can be used with the greatest advantage to modify the growth of plant systems in the soil. The preferred preparations consist of wettable powders, aqueous suspensions, dusting powders, granules, emulsifiable oils and solutions in solvents. Usual-

however, these preferred preparations may all contain one or more surfactants.

Surface-active agents that can be used in the phytotoxic preparations according to the invention are indicated, e.g. in the U.S. patent 2 426 417, 2 655 447, 2 412 510

and 2,139,276. An exhaustive list of such agents is also provided by J. W. McCutcheon in "Soap and Chemical Specialties", November 1947, pages 8011 et seq. , designated "Synthetic Detergents"; "Detergents and Emulsifiers - Up to Date" (1960) by J.W. McCutcheon, Inc., and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the U.S.D.A. Usually less than 10 parts by weight of several active agents are present per 100 parts by weight of phytotoxic preparations.

Wettable powders are water-dispersible preparations that contain one or more active components, an inert solid suspending agent and one or more wetting and dispersing agents. The inert solid suspending agents are usually of mineral origin, such as the natural clays, diatomaceous earth and synthetic minerals derived from silicon oxide and the like. Examples of such retarding agents include kaolinites, attapulgites and synthetic magnesium silicate.

Preferred wetting agents are alkylbenzene and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils and ditertiary acetyl glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid) taurates.

The wettable powder preparations according to the invention usually contain 25 - 90 parts by weight of active components, 0.25 - 3.0 parts by weight of wetting agents, 0*25 - 7 parts by weight of dispersing agent and 9.5 - 74.5 parts by weight of inert solid suspending agents, and all parts are parts by weight of the total preparation. Where necessary, 0.1 - 2.0 parts by weight of the solid inert suspending agent can be replaced by a corrosion-inhibiting or anti-foaming agent or both.

Aqueous suspensions are prepared by mixing and grinding a

Aqueous slurry of the water-insoluble active component in the presence of dispersants to obtain a concentrated slurry of very finely divided particles. The resulting concentrated aqueous suspension is characterized by extremely small particle size so that when diluted and sprayed, the coverage is very uniform.

Dusting powders are dense, finely divided particulate preparations intended for introduction into the soil in dry form. Dusting powders are characterized by their free-flowing and rapid deposition properties so that they are not easily wind-borne in areas where they have no value. Dusting powders primarily contain an active component and a dense, free-flowing, finely divided, particulate suspending agent. However, their action is sometimes aided by the incorporation of a wetting agent such as those listed above under wetting powder preparations, and ease of manufacture often requires the incorporation of an inert absorbent grinding aid. Suitable classes of malhing aids are the natural clays, diatomaceous earth and synthetic minerals derived from silicon oxide and silicate. Preferred grinding aids include attapulgites, diatomaceous earth silica, synthetic fine silica, and synthetic calcium and magnesium silicates.

The inert finely divided solid emulsifiers for the dusting powders can be of either vegetable or mineral origin. The solid suspending agents are characterized by having a relatively small surface area and low liquid absorption. Suitable inert solid propellants for phytotoxic dusting powders include mica-like talc, pyrophyllite, dense kaolin clays, ground calcium phosphate and tobacco dust. The powders usually contain from 0.5 - 95 parts active components, 0-50 parts grinding aids, 0 - 3 parts wetting agent and 5 - 99, 5 parts dense solid thickening agents, and all parts are parts by weight and based on the total weight of the powders.

The wettable powders as described above can also be used in the production of dusting powders. While such wettable powders can be used directly in dust form, it is very advantageous to dilute them by mixing with a dense dusting diluent. In this way, dispersing agents, corrosion inhibitors and anti-foam agents can also be found as components of a dusting powder.

Emulsifying oils are usually solutions of the active component in water-immiscible solvents together with a surface-active agent. Suitable solvents for the active component according to the present invention include hydrocarbons and water-immiscible ethers, esters or ketones. Suitable surfactants are anionic, cationic and non-ionic such as alkyl-aryl-polyethoxy alcohols, alkyl and alkyl-aryl polyether alcohols, polyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty acid esters, fatty alcohol amide condensates, amine salts from fatty alcohol sulphates together with long-chain alcohols and oil-soluble petroleum sulphonates or mixtures thereof. The emulsifiable oil preparations usually contain from 5-95 parts of active components, approx. 1 - 10 parts surfactant and approx. 4-94 parts solvent and all parts are by weight and based on the total weight of emulsifying oil.

Granules are physically stable particulate preparations that contain the active component attached to or distributed over a basic carrier of an inert, finely divided particulate emollient. To aid leaching of the active component from the particulate agent, a surface-active agent such as that indicated above under wetting powders may be present in the preparation. Natural clays, pyrophyllites and vermiculite are examples of usable species of particulate mine alders. The preferred suspending agents are porous, absorbent, 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 bentonite clays. These wetting agents are sprayed on or mixed with the active component to form the phytotoxic granules.

The mineral particles used in the granulated phytotoxic preparations according to the present invention usually have a size of 10 - 100 mesh, but preferably such that the larger part of the particles is from 14 to 60 mesh with the optimal size from 20 to 40 mesh. Clay that has essentially all particles between 14 and 80 mesh and at least approx. 80 percent between 20 and 40 mesh is particularly preferred for use in the granular preparations. The term "mesh" as used herein means US sieve series.

The granular phytotoxic preparations according to the invention usually contain 5-30 parts by weight of N-(1-cycloalken-1-yl)o:-chloroacetamide per 100 parts by weight of clay and 0-5 parts by weight of particulate clay. The preferred phytotoxic granulate preparations contain 10-25 parts by weight of active components per 100 parts by weight of clay.

The phytotoxic preparations according to the present invention may also contain other additives, e.g. fertilizers, other phytotoxic agents, etc. as an aid or in combination with any of the above aids. Phytotoxic agents which can be used in combination with the compounds described above include, e.g. 2, 4-dichlorophenoxy-acetic acid, 2, 4, 5-trichlorophenoxy-acetic acid, 2-methyl-4-chlorophenoxy-acetic acid and their salts, esters and amides, triazine derivatives, such as 2, 4-bis(3-methoxypropylamino)- 6-methyl-thio-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethyl-amino-4-isopropylamino-6-methylmercapto-S-triazine, urea derivatives such as 3 r (3,4-dichlorophenyl)-1,1-dimethyl-urea and 3-(p-chlorophenyl)-1,1-dimethyl-urea, acetanilides such as N-isopropyl-O-chloroacetanilide and N-ethyl-O-chloro -2-methylacetanilide and 2-tert-butyl-2'-chloro-6-methylacetanilide, and acetamides such as N,N-diallyl-tt -chloroacetamide, N-( <* -chloroacetyl)hexamethyleneimine,

and N,N-diethyl-<*-bromoacetamide, etc. Fertilizers that can be used in combination with the active components include e.g. ammonium nitrate, urea and superphosphate. Other usable additives include materials in which plant organisms take root and grow, such as compost, fertiliser, humus, sand and the like.

When working in accordance with the present invention, effective amounts of N-(1-cycloalken-1-yl)-chloroacetamides are distributed in the soil or plant growth agents and applied to the parts of the plant that are above ground in a suitable manner. Application to the soil or growing medium can be accomplished by simple mixing with the medium by applying to the surface of the soil and then working into the soil to the desired depth, or by using a liquid carrier to effect penetration and impregnation. The application of liquid and particulate solid phytotoxic preparations to the surface of the soil or to the plants above the soil can be carried out in a suitable manner, e.g. by shower, tea powders and hand spreaders and atomizing devices. The preparations can be applied from aircraft as a powder or dust due to their effectiveness at low dosages. In a further method, the distribution of an active component in the soil can be carried out by mixing with the water used to irrigate the soil. With such means, the amount of water can be varied with the porosity and water-holding capacity of the soil to achieve the desired depth of distribution of the phytotoxic agents.

The supply of an effective or phytotoxic amount of the N-(1-cyclo-alken-1-yl)-,-chloroacetamides used in the preparations according to the invention to the soil or the growth medium or the plant system is essential and critical. The exact amount of active component to be used depends on

the desired response in the plant as well as other factors such as the plant species and their development, the particular soil and the depth to which the active components are distributed in the soil, and the amount of rain as well as the specific N-(l-cycloalkene-1-yl) OC-chloroacetamide used. When treating leaves for control or modification of plant growth, the active components are applied in quantities of 100 - 6000 or more g per then. When used in soil to control or modify the growth of germinating seeds, sprouting cuttings and established vegetation, the active components are added in quantities of 1 - 3000 or more g per day. For such application in soil, it is desirable that the active components are distributed to a depth of at least 5 mm. In case of selective pre-emergence application, the active components are usually added in amounts of 1 - 600 g per then. It is assumed that a

a person skilled in the field can easily determine from this description including the examples the amount of application for each particular situation.

The terms "soil" and "growth media" are used in the present description in the broadest sense and include all conventional "soil" as defined in Webster's New International Dictionary, Second Edition, Unabridged (l96l). Thus, the expressions refer to each substance or media in which vegetation takes root and grows, and thus includes not only soil, but also compost, fertiliser, bog soil, humus, sand etc. with the ability to support plant growth.

Claims (2)

1. Phytotoxic preparation consisting of or containing «. -chloroacetamides, characterized in that it consists of or contains as an active ingredient an N-(1-cycloalken-1-yl)-α-chloroacetamide with the formula where R denotes alkyl of 1-8 carbon atoms, alkoxyalkyl of 2-8 carbon atoms, alkenyl of 2-8 carbon atoms or phenyl, and Y is selected from the group consisting of where R' is alkyl of 1-4 carbon atoms, and n is an index from 0 to 3. 2. Phytotoxic preparation according to claim 1, characterized in that the O-chloroacetamide is N-(1-cyclohexen-1-yl)-N-allyl-"-chloroacetamide.