KR800001068B1 - A method of preparing acyolic alicyclic & aromatic n-substituted halo-2-pyrrolidinones herbicides - Google Patents

Abstract

Title compds. (II; R = lower alkyl, haloalkyl, alkenyl, cycloalkyl, benzyl or chlorobenzyl; X = H, Cl; Y = Cl, Br; Z = Cl, Br), useful as herbicides, were prepd. by substitution reaction of N-alkenylhaloamide(I) at 50-190≰C in the presence of Fe++ catalyst. Thus, 20.8g N,N-diallyldichloroacetamide and 25g diethyeneglycol dimethylester were refluxed for 30 min in the presence of FeCl24H2O, and heated for 30 min adding 1 g FeCl24H2O to give 8.4 g N-allyl-3-chloro-4-chloro-methyl-2-pyrrolidinone.

Description

[Name of invention]

Preparation of Acyclic, Alicyclic and Aromatic N-Substituted Halo-2-pyrrolidinone Herbicides

Detailed description of the invention

The present invention relates to a process for the preparation of novel N-substituted halo-2-pyrrolidi (also known as azacyclopentane-3-oz) useful as herbicides, more particularly acyclic, alicyclic and monocyclic. A method for producing an aromatic or phenyl2- or N-substituted halo-2-pyrrolidinone and a method for use as a herbicide of two.

Acyclic and alicyclic herbicidal compounds according to the production method of the present invention have the following general formula.

Wherein R is lower alkyl, alkenyl, haloalkyl, cycloalkyl, cycloalkylalkyl, benzyl and chlorobenzyl, X is hydrogen or chlorine, Y is chlorine or cancellation, Z is chlorine or cancellation, with R Y and Z are chlorine or cancellation when it is this allyl, and X is other than chlorine when R is cyclohexyl.

The monocyclic, aromatic or phenyl herbicidal compounds according to the preparation method of the present invention have the following general formula.

Wherein X is hydrogen, chlorine or methyl, Y is hydrogen, chlorine or cancelled, Z is chlorine or cancelled, R ₂ is alkyl or hydrogen, R is hydrogen, alkyl, acetyl, chlorine, cancelled, fluorine, Oxo, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropion Amido or 3-methylureido and R ₁ is hydrogen, alkyl, chlorine or trifluoro methyl.

Examples of the various substituted groupings which are preferable in relation to the above are, for example, members having 1 to 6 carbon atoms in a linear or sustained chain arrangement, unless otherwise specified, such as lower alkyl. Methyl, ethyl, n-furophyl, isofurophyl, n-butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like collectively, " haloalkyl " means from 1 to 6 carbon atoms With one or more hydrogens, substitutions mono, di, tree. It means an alkyl member as described above having additional tetra and perfluoro, chloro, bromo or iodine and the like, and as alkenyl, unless otherwise defined, at least one olefin double bond and a carbon atom Allyl, metaallyl, etalyl, 1-butenyl, 3-butenyl, 2-methyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, having 3 to 6, Collectively including 2-methyl-1-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl and the like; Cycloalkyl includes collectively those having 3 to 7 carbon atoms such as cyclofurophyll, cyclobutyl, cyclopentyl, cyclohexyl and the like; As cycloalkyl yl, all carbon atom containing numbers of 4-8 are included, for example, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, etc. collectively. And various substituted groupings having alkyl or alkyl members in alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, unless otherwise defined, for example, methyl, ethyl having 1 to 4 carbon atoms in a straight or sustained chain configuration. , n-propyl, isopropyl, n-butyl, isotil and the like are included collectively.

Among the compounds falling within the scope of the present invention, by having an asymmetric substituted carbon center, there is a possibility of the presence of cistrans isomers or geometric isomers. Such a cis-trans isomer is a stereoisomer having a structure in which only the arrangement of the atoms or groupings of the stationary positions with respect to a specific correlation plane is slightly different. It means a phylloridinone ring. In specifying the cis-trans configuration in a monocyclic compound, all substitutions having non-identical groupings are considered to take a correlation configuration. According to the general structure of such correlation, the pyrrolidinone ring system is considered to be a flat surface, and when the atom or grouping of the cross object is located on the same side of the plane. When it is located on the opposite side of the plane as cis, it is called trans. (See Gilman, Organic Chemistry Organic Chemistry Vol. 1, p. 477)

The compounds according to the invention have been found to exhibit overall herbicidal activity. That is, the compounds according to the present invention are herbicidal to a wide range of plants, and exhibit an inhibitory effect of unwanted plants by applying an effective herbicidal amount to the plant or the area to be protected.

In the present specification, the herbicide refers to a compound having a function of inhibiting or altering the growth of a plant, and the amount of growth inhibition refers to an amount of inducing a alteration effect on growth in a plant, wherein the alteration effect Includes all deviations from the natural development of the plant, namely killing, stopping, defoliation, dehydration, gastric, malformation, irritation, and dwarf. In this context, the term "plant" refers to a plant body in which germinated shoots, seedlings, roots and ground parts are collectively collected.

Intermediates for the preparation of N-monocyclic aromatic halo-2-pyrrolidinone according to the present invention are unsubstituted N-alkenyl haloacyl anilide by acyl substitution of a suitable unsubstituted N-alkenyl anilide. If no suitable anilide is available, it can be prepared in a number of ways as described, for example, in Chapter 24 of Wagner and Zuck, "Synthetic organic chemistry" (John Werey & Sons, New York, 1961). In the following examples, specific examples of preparation of unsubstituted N-alkenyl haloacylanilide intermediates will be given.

Mono-cyclic aromatic N-substituted halo-2-pyrrolidinone can be prepared in various ways depending on the nature of the starting material and the desired product. One of the preferred methods, known or unknown to date, is halo. N-alkenyl containing acylamide is a method of rearrangement in the presence of a catalytic amount of iron divalent ions.

It is preferable to use a solvent in order to promote the progress of the reaction, to aid in stirring in an appropriate amount, and at the same time to stabilize the reagent. Suitable solvents for this purpose are high boiling points and do not interfere with the reaction, for example, diethylene glycol dimethyl. Ethers, dimethylformamide, dimatylacetamide, dimethylsulfoxide, mesitylene and the like. The iron divalent ion catalyst source can be obtained, for example, from a copper reagent such as ferrous chloride, ferrous iron, iron petal, ferrocene, acetonyl acetonate ferrous and the like.

Intermediates for the preparation of N-substituted halo-2-pyrrolidinones are unsubstituted haloacylimides obtained by acyl substitution of suitable unsubstituted amines. Unsubstituted commercially available unsubstituted amines refer to the "synthetic organic chemistry It can be prepared by the method described in Chapter 24 and other known methods, specific examples for the preparation of unsubstituted acylamide intermediate in the following examples.

Acyclic and alicyclic N-substituted halo-2-pyrrolidinone can be prepared in various ways depending on the nature of the starting material and the desired product. One of the preferred methods, known or unknown to date, is halo. N-alkenyl containing acetamide is subjected to a potential reaction in the presence of a catalytic amount of iron divalent ions. Here too, it is preferable to use a solvent in order to promote the progress of the reaction, to aid the stirring in an appropriate amount, and at the same time to stabilize the reagent. Suitable solvents for this purpose include, for example, diethylene glycol, dimethyl ether, dimethylformamide, dimenylacetamide, dimethyl sulfoxide, mesitylene, etc., which have a high boiling point and do not interfere with the reaction. The iron divalent ionic catalyst source can be obtained from various reagents such as ferrous chloride, ferrous iron, iron methyl, ferrocene, and acetonyl acetonate ferrous.

As described above, the proton of the reagent is not a big problem because the reaction is a potential reaction of unsubstituted haloacylamide which is carried out in the presence of a catalytic amount of iron divalent ion. However, the reaction is preferably carried out at reflux temperature. The temperature for the reaction is best determined in the temperature range between the temperature near room temperature and the reflux temperature for that solvent, preferably from 50 ° C. to 190 ° C., and the best reaction temperature is about 125 ° C. At a temperature in the range of about 170 ° C. In general, however, under elevated temperatures, the reaction proceeds faster to give the desired product. In each case, the recovery after completion of the reaction is carried out by normal finishing procedures such as crystals and sublimation.

The reaction equations for preparing the acyclic and alicyclic N-substituted compounds according to the present invention are as follows.

Wherein X, Y, Z and R are as defined above.

In addition, the reaction equation of the mono-cyclic or phenyl N-substituted compound according to the present invention is generally as follows.

Wherein X, Y, Z, R, R ₁ and R ₂ are as defined above.

In order to further elucidate the preparation of the herbicidal compounds and their intermediates produced by the method of the present invention, specific examples are given below, followed by the herbicidal compounds prepared by the above-described procedure.

Example A

[Preparation of N-allyl-N-butyl dichloroacetamide intermediate from allyl-n-butyl amine]

[Allyl-n-butyl amine adjuvant]

가 300ml의 벤젠에 함유된 용액을 질소외기(窒素外氣)하에 환류 교반하면서 적하상(滴下狀)으로 첨가하였다. 이러한 첨가완료 후 1시간 동안 환류를 계속하고 나서 혼합물을 냉각하였다가 200ml의 50%소듐하이드록사이드와 300g의 쇄빙으로 마련한 용액에 적하상으로 첨가하였다. 이제 수성층(水成層)을 100ml의 벤젠 세몫으로 추출하고, 벤젠추출물을 모아서 황산마그네슘상에서 건조시킨즉 생성물은 염산염으로 변환되고, 20% 에에테르성의 염상의 여분이 남었다. 상기 염산염을 여취(濾取)하여 건조하여 생성물 35.4g를 얻었는데 이 염은 더 이상 정제하지 않고 사용되었다.50 g of N-alkyl butylamide obtained by reacting allylamine with butyryl chloride was dissolved in 100 ml of benzene, and 168 g of sodium bis (2-methoxy ethoxy) aluminum hydride (Red Al)

The solution contained in 300 ml of benzene was added to the dropwise phase with stirring under reflux under nitrogen atmosphere. After completion of this addition, reflux was continued for 1 hour, and then the mixture was cooled and added dropwise to a solution prepared with 200 ml of 50% sodium hydroxide and 300 g of crushed ice. The aqueous layer was now extracted with three parts of 100 ml of benzene, and the benzene extracts were collected and dried over magnesium sulfate. The product was converted to hydrochloride, leaving a 20% ether of salt. The hydrochloride was filtered off and dried to give 35.4 g of product, which was used without further purification.

[Preparation of N-allyl-N-butyl dichloro acetamide]

) 13g이 얻어졌다. 중간체는 더 이상 정체하지 않고 화합물 번호 12번(실시예 7)의 조제에 사용하였다.10.5 g of allyl-n-butylamine hydrochloride was added to 100 ml of methylene chloride followed by 14.5 g of triethylamine. 10.4 g of dichloroacetyl chloride was added dropwise while stirring the mixture at room temperature in a water bath (water bath), and stirring was continued for 30 minutes after the addition was completed. The mixture was washed and the solvent was removed in vacuo, ie 13 g of product (

13 g was obtained. The intermediate was no longer stagnant and was used in the preparation of compound No. 12 (Example 7).

Example 1

[Preparation of N-allyl-3-chloro-4-chloromethyl-2-phyllolidinone]

20.8 g of N, N-diallyldichloroacetamide was mixed with 25 g of diethylene glycol dimethyl ether (diglyme) and 1 g of ferrous chloride (FeCl ₂ .4H ₂ O) was added thereto. Heated to reflux for 30 minutes.

The transformation checks in infrared to see the new carbonyl peak value appear as 5.8 microns.

=1.4850)이 얻어졌다.1 g of the ferrous chloride was added and further heated for 30 minutes. The reaction mixture was diluted with methylene chloride, washed with water, dried and desorbed to give a dark liquid product, which was distilled under vacuum to give 8.4 g of pale yellow oil (淡黄色 油 狀物); Boiling point 124-127 ° C. at 0.25 mm;

= 1.4850).

Quantum and carbon-13 NMR spectra revealed that the product was a mixture of cis and trans isomers with a cis to trans ratio of 2: 1.

Example 2

[Preparation of 1-allyl-3-bromo-4-bromomethyl-2-pyrrolidinone]

=1.5350)을 얻었다.10.9 g of N, N-diallyl-dibromo-acetamide is added to 15 ml of diglyme, and the mixture to which 1 g of anhydrous fertilizer is added is heated to reflux to pyrrolidinone. After the conversion was completed, the product was diluted with methylene chloride, washed with water, dried over anhydrous magnesium sulfate, treated with silica gel to remove tar material, and the solvent was removed in vacuo to give 8.1 g of product (

= 1.5350).

Example 3

[Preparation of N-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone-thione]

=1.5487)을 얻었는데, 이것을 적외선 스펙트럼으로 조사(照射)한즉 5.8미크론에 있어 카아보닐 흡수는 볼 수 없었다.6.2 g of N-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone was dissolved in 100 ml of methylene chloride, and 10 g of phosphorous petasulfide was added in two portions of 5 g at about 1 hour intervals followed by the mixture. It is left to stir overnight at room temperature. The mixture was filtered to remove the solids and the solids were separated. That is, 5 g of a liquid in which some solids were precipitated was obtained. The mixture was placed in pentane and filtered to remove the solids.

= 1.5487), which was irradiated in the infrared spectrum, so that at 5.8 microns, no carbonyl absorption was seen.

Example 4

[Preparation of N-furophyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

The compound is prepared by the translocation of N-allyl-N-furofildichloroacetamide or reduction of N-allyl-3-chloro-4-chloromethyl-2-ferolidinone as follows.

)하여 수소가스를 모두 빼내었다(소요시간 22분). 이 혼합물을 수(數)그램의 디칼라이트(Decalite)로 처리하고 여과하여 촉매를 제거하고, 용매는 진공하에 탈리한즉 21g의 생성물(

=1.4748)를 얻었다.That is, 20.8 g of N-allyl-3-chloro-4-chloromethyl-2-pyrrolidinone is dissolved in 150 ml of ethanol, and 150 mg of platinum oxide is added thereto, and the mixture is shaken under a pressure of 48 psi under hydrogen gas.振

), All the hydrogen gas was removed (required 22 minutes). The mixture was treated with a few grams of decalite and filtered to remove the catalyst, and the solvent was released in vacuo to give 21 g of product (

= 1.4748).

Example 5

[Preparation of N-benzyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

=1.5387)을 얻었다.11.1 g of N-allyl-N-benzyl dichloroacetamide was dissolved in 12 ml of diglyme and 1 g of ferrous anhydrous chloride was added thereto. The whole mixture is heated to reflux under nitrogen and converted to pyrrolidinone, which can be seen by GLPC. The mixture was then diluted with methylene chloride, washed with 5% hydrochloric acid, separated, dried over anhydrous magnesium sulfate, treated with activated charcoal and Florisil and then removed in vacuo to give 6 g of title ( Iii) a compound (

= 1.5387).

Example 6

[Production of N-cyclopropylmethyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

=1.4922) 8.8g을 얻었다.12.1 g of N-allyl-N-cyclopropyl-methyl dichloroacetamide was dissolved in 15 ml of diglyme, to which anhydrous ferrous chloride was added. The mixture was heated to reflux for 25 minutes under the geometry of nitrogen to check the conversion into GLPC. After completion of the conversion, diethylene glycol dimethyl ether was removed in vacuo, 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 solvent Under vacuum to remove the product (

= 1.4922) to yield 8.8 g.

Example 7

[Preparation of N-butyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

=1.4731)을 얻었다.11 g of N-allyl-N-butyl dichloro acetamide was dissolved in 15 ml of diglyme and 1 g of anhydrous ferrous chloride was added thereto. The mixture was heated to reflux for 25 minutes under the addition of nitrogen, and the conversion was checked by GLPC. After completion of conversion, the diglyme is desorbed in vacuo, the mixture is diluted with benzene, washed with 5% hydrochloric acid, dried over anhydrous magnesium sulfate, treated with activated charcoal to remove tarry by-products, and then through florisil. Filtered. The solvent was then stripped off under vacuum, i.e. 8.1 g of product (

= 1.4731).

Example B

[Preparation of N-allyl-m-trifluoromethyl aniline intermediate from m-trifluoromethyl acetanilide]

[Preparation of N-allyl-m-trifluoromethyl aniline]

=1.4532)가 얻어졌는데, 이 생성물은 더 이상의 정제할 필요없이 다음 단계에 사용할 수 있을 충분한 순도를 가지고 있었다.M-trifluoromethyl acetanilide was prepared from aniline by reaction with acetic anhydride. 192 g of this acetanilide was dissolved in 300 ml of tetrahydrofuran (THF), and stirred and participated in 24 g of nitric sodium hydride contained in 200 ml of THF under nitrogen atmosphere and ambient temperature. After the evaporation of hydrogen had stopped, 121 g of allylbromide was added and the mixture was refluxed for 1 hour and stirred overnight. The mixture was then filtered off and removed in vacuo, the residue diluted with methylene chloride and washed with water, dried and released in vacuo, i.e. 205 g of product, N-allyl-m-trifluoromethyl acetanilide (

= 1.4532) was obtained, and the product had sufficient purity for the next step without further purification.

This product was added to 200 ml of concentrated hydrochloric acid and 250 ml of water, and the biphasic system was heated to reflux with stirring to obtain a clarification solution in about 2 hours. The mixture is cooled to give the product a crystal which is treated with 50% sodium hydroxide with cooling to liberate N-allyl anilide, which is extracted with methylene chloride and dried over magnesium sulfate to give 170 g of product. Got it. However, the product was only 85% pure by GLPC, so it was dissolved in ether and reprecipitated with 20% ether hydrochloric acid and hydrochloric acid. The yield was 173g. 106%.

[Preparation of N-allyl-m-trifluoromethyl-dichloroacetanilide]

=1.4740)을 얻었다.23.8 g of N-allyl-m-trifluoromethylaniline hydrochloride was suspended in 200 ml of methylene chloride and a mixture of 21 g of triethylamine was added thereto while 15 g of dichloroacetyl chloride was added thereto while stirring in a water bath at room temperature. It was added to the bed. After about 30 minutes of stirring and addition, the mixture was washed in order of sodium hydroxide diluted to 1%, hydrochloric acid and water diluted to 1%, separated, dried over magnesium sulfate and the solvent was removed in vacuo. The product was dissolved in ethyr and treated with 10 g of 20% ether nitrate and then the precipitate was filtered off and the ether was removed in vacuo to give 25 g of product (

= 1.4740).

Example 8

[Preparation of N-m-trifluoromethylphenyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

=1.5032)을 얻었다.30 ml of ethylene glycol dimethyl ether (diglyme) was added to ₂ g of ferrous chloride (FeCl ₂ 4H ₂ O) and heated to boiling point under a nitrogen blanket to remove 10 g of water-diglyme mixture. It became. To this was added 12.5 g of N-allyl-m-trifluoromethyl dichloroaceto anilide and heated at reflux for 15 minutes to confirm the conversion product by GLPC. When the conversion is complete (at the end of reflux for about 30 minutes), the mixture is cooled, diluted with methylene chloride, washed with 5% hydrochloric acid, separated, dried over magnesium sulfate, dried over magnesium sulfate, filtered and filtered to remove the solvent under vacuum. 10 g of oily product (

= 1.5032).

As described above, stereoisomers are possible for compounds having a carbon atom in the pyrrolidinone ring and having a grouping which is not the same. The compound of the present example is also one of such compounds, and is used as an example of separation and identification of subsequent production processes of cis and trans arrangements.

=1.5032)은 하루밤 방치하여 그 일부가 결정되었다.The oily compound obtained in the above-mentioned procedure (

= 1.5032) was left overnight and part of it was determined.

This was triturated with carbon disulfide to give a crystalline slurry. Crystals were taken by filtration of this slurry, which was found to have a trans batch as shown below (1) (melting point; 54-55 ° C.) by NMR.

After cooling the carbon disulfide filtrate, crystals were newly obtained. The crystals were separated and dried and found to have a sheath configuration as shown below (II) (melting point; 79-80 ° C) by NMR.

Example 9

[Preparation of N-m-chlorophenyl-3-chloro-4-chloromethyl-2-pyrrolidinone]

2 g of FeCl ₂ . 4H ₂ O was suspended in 30 ml of diethylene glycol dimethyl ether (diglyme), and heated to reflux under a nitrogen atmosphere to discharge 10 g of water-diglyme mixture.

11.1 g of N-allyl-m-chloro-dichloroacet anilide was added to continue heating for 20 minutes, and the reaction was terminated by GLPC. Thus, after the conversion was completed (in 20 minutes), the mixture was cooled, diluted with methylene chloride, washed with 5% hydrochloric acid, separated, dried over magnesium sulfate, treated with polisilyl and activated charcoal, and the solvent was vacuumed. Detachment yielded a dark-colored oily product. This was left to look at the crystals and then purified by recrystallization with carbon tetrachloride, ie, 2.9 g of a product (melting point, 93-94 ° C.) was obtained.

Example 10

[Preparation of N-phenyl-3,3-dichloro-4-chloromethyl-2-pyrrolidinone]

1 g FeCl ₂ . 4H ₂ O was suspended in 25 ml of diglyme and the mixture to which 20 g of N-allyl-trichloroacetanilide was added was heated under nitrogen atmosphere. After 15 minutes the conversion to the product is complete, the mixture is diluted with benzene and washed with water. The product was subjected to crystallization in benzene solution and taken, and the sample was recrystallized in ethanol to give a product having a melting point of 133-134 ° C.

Example 11

[Preparation of N-m-prefluoromethylphenyl-3-bromo-4-bromomethyl-2-pyrrolidinone]

1 g of anhydrous fertilizer (FeBr ₂ ) was suspended in 15 ml of diglyme and 9.6 g of N-allyl-m-trifluoromethyl dibromo acetanilide was added to heat the nitrogen mixture. It was refluxed for 15 minutes under outside air. The mixture was cooled, diluted with methylene chloride, extracted with 5% hydrochloric acid, dried, treated with florisil, filtered, and the solvent was removed in vacuo to yield 7.6 g of a dark liquid product.

Example 12

[Preparation of N-m-nitrophenyl-3-chloro-4-chloro methyl-2-pyrrolidinone]

A mixture of 10.2 g of N-allyl-m-nitro-dichloroacet anilide, 15 ml of (diglyme) and 1 g of anhydrous ferrous chloride (FeCl ₂ ) was heated to reflux under nitrogen atmosphere for 1 hour and then cooled. . The mixture was then diluted with benzene, washed with 5% hydrochloric acid, the solution was then treated with magnesium sulfate and activated charcoal, filtered through Florisil filter media, and the solvent was removed in vacuo to give 6 g of product. It was a dark oil, but solidified upon standing, which was triturated with ether to give 3 g of crystalline solid product (melting point: 102-104 ° C.).

The herbicidally active compounds made according to the procedure described above by the process of the invention are shown in Table 1. The compound numbers in this table are later used throughout the specification for identification.

[Table 1]

[Table 2]

＊ = Structure confirmed by infrared fraction

The herbicides according to the method of the present invention listed in Table 1 are named as follows.

Herbicide Screening Test

Compounds made according to the above-described procedure by the method of the present invention has a herbicidal action as described above and plays a valuable and useful role in the inhibition of various weed plants, such herbicidal properties are carried out in the following manner It was.

[G germicide screening test]

(플리옥시에틸렌솔비탄모노라우레이트)를 함유하는 3ml의 아세톤을 첨가하여 화합물을 용해한다. 만약 아세톤으로 용해되지 않을 경우에는, 물, 알코올 또는 디메틸포름아미드(DMF) 등의 용매를 대신 사용하되, DMF를 사용할 경우는 화합물을 용해하는데 0.5ml나 또는 그 이하양으로 사용하고 기타 용매를 사용하여 용량을 3ml로 채워준다. 이리하여 3ml의 용액을 소규모재배함에 채운 토양에 잡초종자를 파종한 하루 후에 골고루 뿌려준다. 이 분무는 압력 51b/psi의 압축 공기가동의 분무기로 시행하고, 적용비율은 81b/에어커에 분무용량을 에이커당 143갈론으로 한다.Using chemical balance, 20 mg of the compound under test was placed on glassine, and the paper and the compound were transferred to a 30 ml bottle of photosphere.

3 ml of acetone containing (polyoxyethylene sorbitan monolaurate) is added to dissolve the compound. If it is not dissolved in acetone, use solvent such as water, alcohol or dimethylformamide (DMF) instead. If DMF is used, use 0.5ml or less to dissolve the compound and use other solvent. Fill the volume with 3 ml. Thus, 3 ml of solution is evenly sprayed after a day of sowing the weed seeds in the soil filled with small-scale cultivation. The spraying was carried out with a pressurized air operated nebulizer at a pressure of 51b / psi, with an application rate of 81b / air with a spray volume of 143 gallons per acre.

One day prior to the treatment, 7 cm long, 5 inches wide, and 2.75 inches deep are filled with 2 inches deep loam soil. Seven weed seeds are sown individually, one bone each in the width (horizontal) direction of the box, covered with sandy loam and buried 0.5 inch deep. After seeding, the seedlings of one bone sugar are sown about 80 to 50 depending on the size of the plants after germination.

Seeds used here were setaria SPP-FT, myelin sheath (Echinochloa crusgalli) -WG, avenue, sativa-RO, Amaranthus retroflexus-PW, mustard (Brissica juncea) -MD, curly Rumex crispus-CD and Digitaria Sanguinalis-CG.

After treatment, the growers are placed in a greenhouse to bring the room temperature to 70-85 ° F. and the water is sprayed by the furnace. After 2 weeks of treatment, injury or control is determined by comparison of untreated plants with the same number of days after germination. The degree of injury of various plants is recorded as a control percentage of 0% to 100% with 0% as no injury and 100% as complete annihilation.

[After-germination Herbicide Screening Test]

(폭리옥시에틸렌 솔비탄 모노라우레이트)를 함유하는 아세톤 5ml에 넣어 녹인 다음 물 5ml를 첨가하여 형성한 용액을 압력 5파운드/평방인치인 압축공기가동의 분무기로 잎위에 뿌려주되, 그 분무농도를 0.2%로 비율을 8파운드/에이커로 하고, 분무량을 에이커당 476갈론으로 한다.Germination pre-screening as described above for 6 types of plant seeds: hairy squirrel (CG), aquatic plant (WG), red lotus (RO), mustard (MD), curly rhinoceros (CD) and Phaseolus Vulgaris (BN) As in the case of the test, the seedlings are sown, placed in a greenhouse and kept at 70-85 ° F., and watered using a mail bath. About 10 to 14 days after sowing, the seedling leaves of the soybean seed are fully expanded and the plant is sprayed when the first three leaves are about to form. This spray treatment tested 20 mg of non-compound 1% Tween 20

Dissolve in 5 ml of acetone containing (phosphoxyoxyethylene sorbitan monolaurate), add 5 ml of water, and spray the solution on a leaf with a compressed air sprayer of 5 pounds per square inch. The ratio is 8 pounds / acre at 0.2% and the spray volume is 476 gallons per acre.

The test results are presented in Table 2.

[Table 2]

* Screening Results-Per germination and post-germination control percentages at -20 pounds / acre

* Pre-germination screening results in 20 pounds / acre

＊＊＊ After germination treatment screening in 20 pounds / acre

For the herbicidal compounds Nos. 53 (cis) and 59 (trans), the results of bioassay were performed at 0.25 lb / A, 0.5 lb / A and 1.0 lb / A for the surface treatment herbicidal screen before germination. It is presented in Table 3 below. The assay included a mixture of 40% cis and 60% trans to demonstrate the superiority of the cis seed.

[Table 3]

CG, FT, WG and WO

PB, AMG and COT = Snow beans, Ipomoea purpurea and cotton (Ipomoea trichocarpa)

The compound prepared by the method of the present invention has a herbicidal effect before germination or after germination and is used in various concentrations. In practical application, these compounds, together with inert carriers, are formulated in the form of fine powders, sprays, wetting agents and the like in a manner known to those skilled in the art and applied in a manner suitable for the application. Such a mixture may be dispersed in water with the aid of a wetting agent, or may be used by adding a wetting agent, a dispersing agent, or an emulsifier to an organic liquid composition, oil, water, or an oil emulsion. The herbicidal effective amount depends on the nature of the plant to be controlled or the seed, but the application rate varies within the range of 0.10 to 50 pounds per acre. The concentration and method of application best suited for the application are readily available to those in the field. Will be decided.

A herbicidal composition containing an effective amount of the herbicidal compound produced by the method of the present invention is applied to plants in a conventionally known manner. That is, by applying the herbicidally effective amount alone or in combination with an enemy carrier or suppository to a) controlled weeds, or b) their origin, ie protected areas, killing, constructing or controlling unwanted plants is achieved. Thus, in the form of powder or liquid composition, it is applied directly to the plant using a power sprayer or a manual sprayer or a powder sprayer. In addition, since the herbicidal composition according to the method of the present invention is effective in a very small amount, it is also possible to spray by airplane in the form of fine powder or spray. Herbicide compositions according to the method of the present invention, for the purpose of suppressing or controlling the germination or growth of weeds or unwanted plants, are treated as a fine powder or liquid composition and spread to a depth of at least 0.5 inches. Therefore, it is not necessary to mix the manufacturing active composition with the soil particles, and only the surface of the soil may be treated by a simple spraying or spraying method. In addition, the herbicidal composition according to the present invention can be applied to irrigation water to treat arable land, this application method is effective because the composition penetrates into the soil as the water is absorbed into the soil. And the soil surface treatment by the fine powder composition, granule composition or liquid phase formation of the herbicidal composition according to the present invention can be dispersed under the ground by conventional mixing methods such as plowing or sledding.

The herbicidal composition according to the present invention may also be applied containing other adducts, that is, fertilizers, insecticides, etc. may be applied in the form of suppositories or in a combination of enemy combinations. Examples of other herbicidal compounds usable in combination with the herbicidal compounds according to the present invention include 2,4-dichlorophenoxycetic acid, 2,4,5-trichlorophenoxycetic acid, 2-methyl-4- Chlorophenoxyacetic acid and salts, esters, amides thereof, and 2,4-bis (3-methoxyfurophylamino) -6-methyl-thio-S-driazine, 2-chloro- Triazine derivatives such as 4-ethyl-amino-6-isopurophylamino-S-triazine and 2-ethylamino-4-isopurophyl-amino-6-methylmelcapto-S-triazine, 3- Urea derivatives such as (3,4-dichlorophenyl) -1,1-dimethyl urea, N, N-diallyl-α-chloroacetamide, N- (α-chloroacetyl) hexamethyleneimine and N Acetamides such as N-diethyl-α-bromoacetamide, benzoic acids such as 3-amino-2 and 5-dichloro benzoic, and S-furofil difurophyl thiocarba Mate, S-ethyldifurofilthiocarbamay , And the like thio carbamates, such as S- ethyl hexahydro -1H- azepin-1-thio-at-carbonyloxy. Fertilizers usable in combination with the active ingredient of the present invention include, for example, ammonium acetate, urea and superphosphate lime. Other useful adjuncts include composting, growing, humus sand, etc., which are rooting and growing plants.

It is to be understood that the present invention is not limited to the above, and that various modifications can be easily made by those skilled in the art without departing from the spirit and scope of the present invention according to the case and use. Of course.

Claims (1)

As described above in the text, the N-alkenyl haloamide of the following general formula [1] is reacted by incubation at a temperature in the range of 50 to 190 ° C. in the presence of a catalytic amount of iron divalent ions. Method for preparing haliccyclic N-substituted halo-2-pyrrolidinone

In the formulas [I] and [II], R is a benzyl group substituted with lower alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkylalkyl, or chlorine, bromine or trifluoromethyl.