DK145891B - N-SUBSTITUTED HALOGEN-2-PYRROLIDINONES FOR USE IN HERBICIDES AND PROCEDURES FOR PREPARING THEREOF - Google Patents

Description

(19) DENMARK (w) \ rr /

© (12) PUBLICATION <n> 145891 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 1557/76 (51) lnt.CI.3 G 07 D 207/24 (22) Filing date 26 Mar. 1976 A 01 N 43/36 (24) Race day 26 Mar 1976 (41) Aim. available 29 · S ep. 1976 (44) Submitted 5 · Apr · 1 9 ^ 5 (86) International Application No. - (86) International Filing Day (85) Continuation Day - (62) Stock Application No. -

(30) Priority Mar 28 1975, 565279, US Mar 28 1975, 565280, US

Jan 9 1976, 6 ^ 7962, US 9 · Jan. 1976, 647965, US

(71) Applicant STAUFFER CHEMICAL COMPANY, Westport, US.

(72) Inventor Eugene Gordon Teach, US.

(74) Associate Company Chas. Hude.

(54) N-substituted halogen-2-pyrrolidinones for use in herbicides and their method of preparation.

The present invention relates to some novel N-substituted halogen-2-pyrrolidinones (also called azacyclopentan-3-ones) for use in herbicides as well as a novel process for their preparation.

The compounds are peculiar in that they have the general formula m -

CD

ISLAND ISLAND

LO X Q

d- * 11; l i-— c — i— c-v g z - CH 2 - C - CH /

H

Wherein Q is oxygen or sulfur, R is alkyl of 1-6 carbon atoms, alkenyl of 3-6 carbon atoms, haloalkyl of 1-6 carbon atoms, cycloalkyl of 3-7 carbon atoms, cycloalkylalkyl of 4-8 carbon atoms, benzyl and chlorobenzyl, X is hydrogen or chlorine, Y is chlorine or bromine, and Z is chlorine or bromine, provided that when R is alkyl, Y and Z are both chlorine or bromine and provided that when R is cyclohexyl, X not chlorine.

R in the sense alkyl can e.g. be methyl, ethyl, n-propyl, iso = propyl, n-butyl, isobutyl, amyl, isoamyl, hexyl and isohexyl. R in the meaning of haloalkyl may be the alkyl substituents described which further have one or more halogen substituents such as mono-, di-, tri-, tetra- and perfluoro, chloro, bromo or iodo. Alkenyl preferably, unless otherwise stated, includes those representatives which contain at least one olefinic double bond, e.g. allyl, methallyl, etallyl, 1-butenyl, 3-butenyl, 2-methyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 2-methyl-1-pentenyl, 1-hexenyl, 2- hexenyl and 3-hexenyl. Cycloalkyl may be e.g. cyclopropyl, cyclobutyl, cyclo = pentyl and cyclohexyl. Cycloalkylalkyl may be e.g. cyclopropyl = methyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl and cyclo = hexylmethyl.

Due to the presence of asymmetrically substituted carbon = centers in some of the compounds of the invention, there is the possibility of the existence of cis, trans or geometric isomerism. These cis, trans isomers are stereoisomers whose structures differ only in the arrangement of certain "rigid" atoms or groups relative to a given reference plane. The reference planet here is the pyrrolidinone ring. When specifying cis, trans configurations in a monocyclic compound, any of the ring positions having non-identical groups are considered to determine relative configurations. By using the pictorial hint to produce these relative positions in structural formulas, the pyrrolidinone ring system is considered flat. The atoms or groups considered are described as cis when on the same side of the planet and trans when on opposite sides of the planet (see Gilman's Organic Chemistry, Vol. I, page 477).

The compounds of the invention have been found to be active herbicides of a general type. That is, representatives of this class have been found to be herbicidally effective against a wide range of plant species.

The invention further relates to a process for the preparation of said N-substituted halogen-2-pyrrolidinones, which is characterized by rearranging an N-alkenyl haloacylamide of the formula CXY - οχ

Z N-R

Wherein R, X, Y and Z are as defined in claim 1, in the presence of a catalytic amount of ferro ion at a temperature between ca. 50 ° C and approx. 190 ° C and recovery of the resulting product.

The use of a solvent is desirable to facilitate the course of the reaction and to facilitate stirring by providing sufficient volume and by solubilizing the reaction participants. The preferred solvents include those which are high boiling and which do not generate the reaction, e.g. diethylene glycol dimethyl ether, dimethylformamide, dimethylacetamide, dimethylsulfoxide, mesitylene and the like. Preferred sources of ferrous ion catalyst are ferrochloride, ferrobromide, metallic iron, ferrocene and ferroacetonylacetonate.

The intermediates for the preparation of the N-substituted halo-2-pyrrolidinones are the unsaturated haloacylamides obtained by acylation of the unsaturated amines. Saturated amines that are not industrially available can be prepared by methods described in various sources in the chemical literature and various inventories of the subject, such as "Synthetic Organic Chemistry" by Wagner and Zook, Chapter 24, John Wiley and Sons, New York, 1961. The following examples describe a concrete example of the preparation of an unsaturated haloacylamide as an intermediate.

In general, the reaction to prepare the compounds of the invention may be represented by the following equation: X

I II

> CXY - C. ++ Y - C - cx

Z ---— p-I ^ N-R

__ / High Boiling I / CH CHg Solution CHpZ - CH- CHp Agent 4 145891 wherein X, Y, Z and R have the above meaning.

The compounds of the invention and their intermediates are further illustrated in the following examples which describe their preparation. Following the examples is a table of compounds prepared by the methods described.

Preparation of the intermediate U-allyl-U-butyldichloroacetamide from allyl-n-butylamine.

Preparation of allyl-n-butylamine, 50 g of IT-allyl butyramide prepared by reaction of allylamine with butyryl chloride was dissolved in 100 ml of benzole and added dropwise to a stirred solution of 168 g of sodium bis (2-methoxyethoxy) aluminum hydride (Red Al ) In 300 ml of benzene under reflux under a nitrogen atmosphere. The refluxing was maintained for 1 hour after the addition, after which the mixture was cooled and added dropwise to a solution made from 200 ml of 50 $ sodium hydroxide and 300 g of crushed ice. Bold aqueous layers were extracted with 3 portions of 100 mL of benzene, and the combined benzene extracts were dried over magnesium sulfate and the product converted to the hydrochloride with excess 20 $ ethereal hydrochloric acid. The hydrochloride was filtered off and dried. The yield was 35.4 g and the salt was used without further purification.

Preparation of U-allyl-N-butyldichloroacetamide. 10.5 g of allyl-n-butyl = amine hydrochloride was added to 100 ml of methylene chloride followed by 14.5 g of triethylamine. The mixture was stirred in a water bath at room temperature while 10.4 g of dichloroacetyl chloride was added dropwise and stirring was continued for 30 minutes after addition was complete. The mixture was washed and the solvent distilled off in vacuo. The yield was 13 g, n = 1.4603 * The intermediate was used without further purification to prepare Compound No. 12 (Example 7).

Example 1

Preparation of U-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone.

20.8 g of υ, ίΓ-diallyldichloroacetamide were mixed with 25 g of diethylene gly = carbon dimethyl ether (diglyme), and 1 g of ferrochloride (FeClg 2 O) was added and the mixture was heated under reflux for 30 minutes. The conversion was controlled by the emergence of a new carbonyl peak at ca.

5.8 microns in the infrared. An additional gram of ferrochloride (FeCl 2, 4H 2 O) was added and heating was continued for another 50 minutes. The reaction mixture was diluted with methylene chloride, washed with water, dried and distilled. The dark liquid product was distilled in vacuo to give 8.4 g of a pale yellow oil, bp 124-127 ° C at 0.25 mm. n | ° 1.4850.

The proton and carbon-13 MR spectra show that the product is a mixture of cis and trans isomers with a ratio of 2: 1 between cis and trans.

Example 2 Preparation of 1-allyl-5-bromo-4-bromomethyl-2-pyrrolidinone.

10.9 g of F, F-diallyldibromoacetamide was added to 15 ml of diglyme followed by 1 g of anhydrous ferrobromide. The mixture was heated to reflux and the conversion to pyrrolidinone controlled by GEPC. Once the conversion was complete, the product was diluted with methylene chloride, washed with water, dried over anhydrous magnesium sulfate and treated with silica gel to remove tar-like material. The solvent was distilled off under vacuum to give 8.1 g of product, n = 1.5350.

Example 5 Preparation of F-allyl-5-chloro-4-chloromethyl-2-pyrrolidinethone 6.2 g of F-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone was dissolved in 100 ml of methylene chloride and 10 g of phosphorus pentasulfide in 2 portions of 5 g were added with approx. 1 hour apart while the mixture was allowed to stir at room temperature overnight. The mixture was filtered to remove solids and distilled to form 5 g of liquid containing some precipitated solid. This was taken up in pentane, filtered to remove solid and distilled. 3 g of the product was obtained as an oil, n ^ 1.5487. Investigation of the infrared spectrum showed almost no carbonyl absorption at ca. 5.8 microns.

Example 4 Preparation of F-propyl-5-chloro-4-chloromethyl-2-pyrrolidinone.

This compound can be prepared by rearranging F-allyl-F-propyl = dichloroacetamide or by reducing F-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone, as shown below.

6,889 g of U-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone was dissolved in 150 ml. ethanol and 150 mg of platinum oxide were added. The mixture became. shaken under hydrogen at 3.25 atm until hydrogen uptake was complete (22 minutes). The mixture was treated with a few grams of di-calcite and filtered to remove the catalyst and the solvent was distilled off under vacuum. The yield was 21 g of product, n £. 1.4748.

Example 5

Preparation of U-benzyl-5-chloro-4-chloromethyl-2-pyrrolidinone.

11.1 g of U-allyl-U-benzyl dichloroacetamide was dissolved in 12 ml of diglyme and 1 g of anhydrous ferrochloride was added. The mixture was heated to reflux under nitrogen until the conversion to the pyrrolidine was complete, as indicated by G-IPO. The mixture was diluted with methylene chloride, washed with 5 $ hydrochloric acid, separated, dried over anhydrous magnesium sulfate, treated with activated charcoal and Florisil and distilled in vacuo. The yield was 6 g of the title compound, n ^ 1.5387. Example '6

Preparation of U-cyclopropylmethyl-5-chloro-4-chloromethyl-2-pyrrolidinone.

12.1 g of U-allyl-H-cyclopropylmethyl dichloroacetamide was dissolved in 15 ml of diglyme and 1 g of anhydrous ferrochloride was added. The mixture was heated under reflux under a nitrogen atmosphere for 25 minutes and the conversion checked by (rBPC) When the conversion was complete, the diglym was distilled off in vacuo and the mixture was dissolved in benzene, washed with 5 $ hydrochloric acid, separated, dried over anhydrous magnesium sulfate. , treated with activated charcoal, filtered through Florisil and the solvent removed in vacuo The yield was 8.8 g of product, n = 1.4922.

Example 7

Preparation of U-butyl-5-chloro-4-chloromethyl-2-pyrrolidinone.

11 g of U-allyl-U-butyl dichloroacetamide was dissolved in 15 ml of diglyme and 1 g of anhydrous ferrochloride was added. The mixture was heated under reflux in a nitrogen atmosphere for 25 minutes and the conversion controlled by gas-liquid distribution chromatography (GEFG). The diglyme was distilled off in vacuo and the mixture diluted with benzene, washed with 5% hydrochloric acid, dried over anhydrous magnesium sulfate and treated with activated charcoal to remove tar-like by-products and filtered through Florisil. The solvent was distilled off in vacuo to give 8.1 g of product, nD 1.4731.

The following is a table of compounds prepared by the above process. The numbers given to the compounds are used for identification throughout the remainder of the present description.

8 145891

Table I

X Q

I !! Y-C - C.

I Ίϊ-Ε Z - CH2 -— C - CH ^

H

n ^ 0 or

part JJ

No. _R_ X Y Z O boiling point ° C

1 CH2CH = CH2 H GI Cl O 125 / 0.25 mm 2 CH2CH = CH2 Cl Cl Cl 0 1.4938 5 C2H5 Ξ Cl Cl 0 1.4720 4 C2H5 Cl Cl Cl 0 1.4735 5 c- ° 6H11 H 01 01 0 1> 4788 6 CH2CH = CH2 H Cl Cl S 1.5487 7 CH3 H Cl Cl 0 1.4860 8 n-C3H7 H Cl Cl 0 1.4748 9 CH2 = CHCH2 H Br Br 0 1.5350 10 CH2BrCHBrCH2 H Cl Cl O 1.5653 11 n-C5Hll H Cl Cl O 1.4700 12 n-C4H9 H Cl Cl O 1.4731 13 i-C4.H9 H Cl Cl O 1.4720 14 D> CH2 H Cl Cl O 1 , 4922 15 c6H5GH2 ξ Cl Cl O 1.5387 16 p-Cl-C6H5CH2 H Cl Cl O 1.5502 9 145891

The compounds of the foregoing may be designated: 1. 1-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone 2. 1-allyl-3,3-dichloro-4-chloromethyl-2-pyrrolidinone 3. 1-ethyl-3 -chloro-4-chloromethyl-2-pyrrolidinone 4. 1-ethyl-3β-dichloro-4-chloromethyl-2-pyrrolidinone 5. 1-cyclohexyl-3-chloro-4-chloromethyl-2-pyrrolidinone 6. 1-allyl -3-chloro-4-chloromethyl-2-pyrrolidinone ethion 7. 1-methyl-3-chloro-4-chloromethyl-2-pyrrolidinone 8. 1-propyl-3-chloro-4-chloromethyl-2-pyrrolidinone 9. 1- allyl-3-bromo-4-bromomethyl-2-pyrrolidinone 10. N-2,3-dibromopropyl-3-chloro-4-chloromethyl-2-pyrrolidinone 11. N-amyl-3-chloro-4-chloromethyl-2- pyrrolidinone 12. N-butyl-3-chloro-4-chloromethyl-2-pyrrolidinone 13. N-isobutyl-3-chloro-4-chloromethyl-2-pyrrolidinone 14. N-cyclopropylmethyl-3-chloro-4-chloromethyl-2 -pyrrolidinone 15. N-benzyl-3-chloro-4-chloromethyl-2-pyrrolidinone 16. Np-chlorobenzyl-3-chloro-4-chloromethyl-2-pyrrolidinone

Herbicide assessment tests.

As mentioned above, the compounds described are prepared in the manner described above, phytotoxic compounds which are useful and valuable in controlling various plant species. The compounds of the invention are tested as herbicides in the following manner.

Herbicide test before the plants emerge from the north.

Using an analytical weight, weigh 20 mg of the compound to be tested on a piece of parchment paper weighing paper. The paper and the compound are placed in a 30 ml wide mouthed bottle and 3 ml of acetone containing Ifo Tween 20® (polyoxyethylene sorbitan = monolaurate) is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml or less is used to dissolve the compound, and then another solvent is used to bring the volume up to 3 ml. The 3 ml solution is uniformly sprayed onto the soil contained in a small flat tray 1 day after sowing weed seeds in the soil in the tray. An atomizer is used to apply the spray liquid during use

ISLAND

of compressed air at a pressure of 0.35 kg / cm. The amount applied is 9 kg / ha and the spray volume is 1359 l / ha.

The day before the treatment, the flat tray, which is 17 »5 x 12.5 cm and has a depth of 6.9 cm, is filled to a height of 5 cm with sandy clay soil. Seeds of 7 different weed species are sown in individual rows, using one species per year. row across the width of the hill. The islands are covered with soil so that they are sown to a depth of 1.2 cm. Ample seeds are sown to yield approx. 20-50 seedlings per row after the emergence of the soil, depending on the size of the plants.

The seeds used are fox tail (Setaria spp.) - El; water grass (Echino = chloa crusgalli) - WG; red oats (Avena sativa) - RO; red-red amaranth (Amaranthus retroflexus) - PW; mustard (Brassiea juncea) - MD; rumped debris (Rumex crispus) - CD; and hairy finger axis (Digitaria sanguinalis) - CG.

After treatment, the trays were placed in greenhouses at a temperature of 21-29 ° C and watered by sprinkling. Two weeks after treatment, the degree of injury or control was determined by comparison with untreated control plants of the same age. The damage rated on a scale of 0 to 100 $ for each species is recorded as percent combat, with 0 $ representing no damage and 100 $ representing complete killing.

Herbicide assessment test after the emergence of plants from the soil.

Seeds of 6 plant species, including hairy finger ax (CG), watergrass (WG), red oats (RO), mustard (MD), rippled debris (CD) and pinto bean (Phaseolus vulgaris) (BH) are sown in the trays, as described above for the test of the effect before the emergence of the plants by the soil. The bales are placed in greenhouses at 21-29 ° C and watered daily with a sprinkler. Ca. 10-14 days after sowing, when the primary leaves of the bean plants are almost fully unfolded and the first three-leafed leaves are just beginning to form, the plants are sprayed. The spray liquid is prepared by weighing 20 mg of the test compound, dissolving it in 5 ml of acetone containing 1 $ Tween 20® (polyoxyethylene sorbitan monolaurate) and then adding 5 ml of water. The solution is sprayed onto the foliage using an atomizer with an air pressure of 0.35 kg / cm. The spray concentration is $ 0.2 and the amount is 9 kg / ha. The spray volume is 4523 l / ha.

The results of these experiments are shown in Table II.

12 145891

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Fri 13 145391

The compounds of the invention are used as herbicides before and after the emergence of the soil and are applied in various ways at different concentrations. In practice, the compounds are formulated with an inert carrier using well known methods so as to make them suitable for application as dust preparations, sprays or soil soaking agents and the like in the manner and form necessary. The mixtures can be dispersed in water by a wetting agent or they can be used in organic liquid preparations, oil and water, water-in-oil emulsions, with or without the addition of wetting agents, dispersing agents or emulsifying needles. A herbicidal effective amount depends on the nature of the seeds or plants to be controlled, and the amount applied ranges from 0.11 to approx. 55 kg / ha. The concentration of a compound of the invention which constitutes an effective amount in the best mode of administration is readily determined by one skilled in the art.

The phytotoxic agents using a herbicidally effective amount of the compound described above are applied to the plants in the usual manner. Methods of selective killing or control of undesirable plants consist of applying to at least one of (a) these weed plants and (b) their growing site, i.e. the area to be protected, a herbicidal effective or toxic amount of the active compound concerned alone or together with a carrier or additive. Thus, the dust preparations and the liquid preparations can be applied to the plant using powder sprays, mechanical and hand operated sprayers and dusting devices. The agents can also be applied from airplanes such as a powder or spray liquid because they are effective in very low doses. As a typical example, to modify or control the growth of germinating or germinating seedlings, dust or liquid preparations are applied to the soil in conventional ways and distributed in the soil to a depth of at least 1.2 cm below the soil surface. It is not necessary for the phytotoxic agents to be mixed with the soil particles and these agents can only be applied by spraying or sprinkling on the soil surface. The phytotoxic agents may also be applied by addition to irrigation water which is fed to the field being treated. This mode of application allows the agents to penetrate the soil as the water is absorbed therein. Dust preparations, granular preparations or liquid preparations applied to the surface of the soil can be distributed below the surface of the soil in conventional ways, such as with a plate.

Claims (2)

14 145891 harrow, tiller or in mixing operations. The phytotoxic agents may also contain other additives, e.g. fertilizers, pesticides and the like, used as additives or in combination with any of the additives described above. Other phytotoxic compounds useful in combination with the above-described compounds include, e.g. 2,4-dichlorophen = oxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxy = acetic acid and their salts, esters and amides, triazine derivatives such as 2,4-bis- (3-methoxypropylamino) -6 -methylthio-5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine and 2-ethylamino-4-isopropyl = amino-6-methylmercapto-s-triazine, urea derivatives such as 3- (3.4 -dichlorophenyl) -1,1-dimethylurea and acetamides such as N, N-diallyl-α-chloroacetamide, N- (α-chloroacetyl) hexamethylenimine and N, N-diethyl-α-bromoacetamide and the like, amino-2,5-dichlorobenzoic acid and thiocarbamates such as S-propyldipropylthiocarbamate, S-ethyl di-propylthiocarbamate, S-ethylhexahydro-1H-azepine-1-thiocarboxylate and the like. Fertilizers useful in combination with the active ingredients are e.g. ammonium nitrate, urea and superphosphate. Other useful additives include materials in which plant organisms form and grow, such as compost, manure, humus, sand and the like. Claims. N-substituted halogen-2-pyrrolidinones for use in herbicides, characterized in that they have the general formula XQII »Y - c - C \ NR Z - CH 2 - C - CH 2 H where Q is oxygen or sulfur, R is alkyl of 1-6 carbon atoms, alkenyl of 3-6 carbon atoms, haloalkyl of 1-6 carbon atoms, cycloalkyl of 3-7 carbon atoms, cycloalkylalkyl of 4-8 carbon atoms, benzyl and chlorobenzyl, X is hydrogen or chlorine , Y is chlorine or bromine and Z is chlorine or bromine, provided that when R is alkyl, Y and Z are both