KR810001693B1 - Process for the preparation of dibromo substituted propionamides antidote for thiocarbamate herbicidal antidote - Google Patents

Abstract

The 2,3-dibromopropionamides(I; R1 = H, alkyl or alkenyl; R2 = alkyl, alkenyl, alkynyl, etc.) ! decrease the toxicity of thiocarbamate herbicides. I as prepd. by reacting 2,3-dibromopropionyl chloride with amine(II) in solvent. Thus, 3.0 g diallylamine was mixed with 3.5 g triethylene and 25ml methylene chloride and stirred with 7.5 g 2,3-dibromopropionyl chloride, washed with water, dried and isolated as crude oiltype material. Vernam, applied in-furrow for the control of Echinochloa crus-galli and Setaria virida, was phytotoxic to barley(Hordeum vulgare).

Description

Preparation of dibromo-substituted propionamide antidote for thiocarbamate herbicide detoxification

The present invention relates to the preparation of a dibromo substituted propionamide detoxifying agent for thiocarbamate herbicide detoxification having the structural formula [I].

Wherein R ₁ is alkenyl or lower alkyl and R ₂ is alkyl, alkenyl, alkynyl, dimethoxyethyl or 1-ethynylcyclohexyl.

As described above, examples of the various substituted groupings are as follows. That is, for R ₁ and R ₂ , alkenyl includes members having a straight chain and a sustained chain configuration, preferably having three or four carbon atoms and at least one to four carbon atoms, and alkyl is one to six And a member having a straight chain and a maintenance chain configuration having 4 carbon atoms, and alkynyl preferably includes a member having at least one triple bond or acetylene bond and all 3 to 8 carbon atoms.

As one of the forms of action that such an antidote according to the present invention may have, the action of the thiocarbamate-based herbicides or other herbicides is interfered with the conventional herbicidal action to make them selective. In other words, whatever form of action is present, it reduces the herbicidal toxicity of thiocarbite to crops, while bringing the beneficial and desirable effect of the desired herbicidal effect on desired preparations. And novel effects will become more apparent from the following detailed description of the invention.

The antidote according to the present invention is particularly effective and useful against small grain crops. Here, the grain crops refer to various grain vinegars, and representative examples thereof include wheat, barley, rice, oats, and rye.

The antidote compound or detoxification amount for the herbicide is used to exert an effect against the normal harmful re-harvesting that can occur between the herbicides. Therefore, depending on the specific type of effect it exhibits, it is called a masking agent, an interfering agent, or a protective agent. The antidote should be dry, and the effect of treating the soil where the crop is sown should always be desirable. There have been ways to meet these conditions.

The dibromosubstituted propionol amide detoxifier compound for detoxification of a thiocarbamate herbicide having the above structural formula [I] according to the present invention is prepared by using 2,3-dibromopropionyl chloride in the presence of a suitable solvent. By reacting with an amine having

Wherein R ₁ and R ₂ are as defined in Structural Formula [I].

Suitable solvents include toluene methylene chloride, Freon-113, methylene chloride and the like. The use of such a solvent facilitates the progress of the reaction, and by adding an appropriate amount, not only helps to stir the reaction mixture, but also helps to ensure the safety of the reagent, it is beneficial.

In the addition of acid chloride and amine the solution is kept cooled in the range of about -20 ° C to 0 ° C and the reaction is completed by heating from room temperature to a temperature in the range of about 50-60 ° C after the addition of the reagents is complete. The use of an excess of amine allows the excess to act as an acid acceptor, or catalyst, in the reaction. Other amines such as tertiary amines can be used as acid acceptors when the reactant ratio is other than 1: 1. In each case the product after the reaction is completed is recovered by conventional finishing procedures, i.e. by crystallization, sublimation or distillation.

An antidote according to the present invention and a method for producing the same will be illustrated in more detail in the following Examples. And the compound prepared by the Example is shown by table. Compound numbers in the table are used as the same identification throughout the specification.

Example 1

Preparation of N, N-diallyl-2,3-dibromopropionamide

Diarylamine (3.0) was mixed with 3.5 g of triethylene contained in 25 ml of methylene chloride, and 7.5 g of 2,3-dibromopropionyl chloride contained in a mixture of Freon-113 and methylene was water bathed. It was added dropwise with stirring. The mixture was washed with water, dried and desorbed in vacuo. The title compound was obtained as an oil, yielding 6.6, yielding 1.5308.

Example 2

Preparation of N-methyl-N-3-butynyl-2,3-dibromopropionamide

5.1 g of 3-methylamino-1-butyne is dissolved in 25 ml of methylene chloride, and 7.5 g of 2,3-dibromopropionyl chloride dissolved in a mixture of Freon-113 and methylene chloride is dissolved in this solution. It was dissolved and added dropwise with stirring in the water bath. The mixture was washed with water and dried to detach under vacuum, i.e. as an oil for the title compound, yielding 7.5 g and N _D ³⁰ of 1.5548.

Example 3

Preparation of N-t-amyl-2,3-dibromopropionamide

A solution containing 30 g (0.12 mole) of 2,3-dibromopropionylchloride in 160 ml of toluene and a solution containing t-amyl-amine (21.6 g, 0.248 mole) in 80 ml of toluene Add at a temperature of 15 ° C. The mixture was stirred at room temperature for 1 hour and then at 40-45 [deg.] C. for 1 hour and then filtered to wash the precipitate thoroughly with water and the insoluble portion was dried to give 11.6 g (32% yield) of product. The structure of the product was confirmed by the title compound by IR, NMR and mass spectrometry.

Example 4

Preparation of N- (1-ethylcyclohexyl) -2,3-dibromopropionamide

To a solution containing 1-ethynylcyclohexylamine (6.49 g, 0.052 mol) in 60 ml of toluene, a solution containing 20 ml of toluene acid chloride (6.3 g, 0.025 mol) was added at -5 to 0 ° C. The mixture was stirred at rt for 3 h and then filtered. The filtrate was washed with water and the insoluble portion was dried, yielding 3.3 g (39% yield) of product having a melting point of 135-137 DEG C. The structure was identified by IR as the title compound.

The novel detoxification compounds according to the present invention made by the above-described procedures and examples are shown in the following table. Compound numbers used in this table are used as is throughout this specification with the same confirmation.

TABLE 1

The herbicides described and exemplified in the present invention exhibit a predetermined herbicidal effect, and the degree of herbicidal action depends on the combination of a compound of each characteristic or a specific compound among homologues, and a specific herbicide compound Their combination depends on the type of plant used. Therefore, specific herbicidal compounds or combinations thereof can be easily selected for suppressing unwanted plant species. In addition, according to the present invention, it is possible to prevent damage to wheat, barley, and the like, in particular, during the crop cultivation, particularly grain cultivation, in the presence of a specific compound or a combination thereof.

Examples of the herbicide compounds to be applied to the present invention are all active thiocarbamate herbicides of the general type. In other words, this class has the same herbicidal effect on a wide range of plant species without the distinction of unnecessary plants. Thus, the method of suppressing omnivorous plants uses an effective amount of the herbicidal compounds described herein in any desired region or plant cultivation.

In the present specification, the herbicidal refers to a compound whose action is to inhibit or alter the growth of a plant. The inhibitory or altering action referred to here includes all deviations from the natural growth of the plant, namely, live, arrest, defoliation, dehydration, atrophy of regulation, callout, stimulation and dwarfism. And here, the term "plant" means a settled plant including germinating shoots, seedlings and roots and the ground.

[Evaluation Procedures and Methods]

Fill the loam soil with the growing plants and weeds to grow and grow herbicides and detoxifiers.

It can be applied in several ways: 1) herbicide and antidote are applied separately before sowing and 2) herbicide and antidote are mixed together in a tank. An effective amount of herbicide and antidote, sowing the seed prior to sowing into the soil treated beforehand and seeding the bones of the herbicide treated soil before sowing into the bone treated herbicide treated soil There is a way to handle it.

Stock solutions of representative thiocarbamatege herbicides and antidote to be tested were prepared as follows.

[Herbicide]

6E 130mg을 증류수 125ml에 용해함으로써, 재배함의 토양에 적용한 5ml에이커당 물 80gal에 적용한 1Ib/A와 동등하겠끔 하였다.A) S-Proofil Di-n-Profite Thiocarbamate-VERNAM

By dissolving 130 mg of 6E in 125 ml of distilled water, it was equivalent to 1 Ib / A applied to 80 gallons of water per 5 ml acre applied to the growing soil.

6E-VE NAM

6E 550mg을 증류수 400ml에 용해함으로써 재배함의 토양에 적용한 4ml가 활성성분 1 Ib/A 또는 5ml가 1.25 Ib/A와 동등하겠끔 하였다.B) S-Proofil Di-n-propyl Thiocarbamate-VERNAM

6E-VE NAM

By dissolving 550 mg of 6E in 400 ml of distilled water, 4 ml applied to the cultivated soil would be equal to 1 Ib / A of active ingredient or 5 ml equal to 1.25 Ib / A.

6E 130mg을 증류수 125mg에 용해함으로써, 재배함의 토양에 적용한 5ml가 에이커당 물 80gal에 적용한 1 Ib/A와 동등케 하였다.C) S-ethyl di-n-furophyl thiocarbamate-EPTC-EPTAM

By dissolving 130 mg of 6E in 125 mg of distilled water, 5 ml applied to the cultivated soil was equivalent to 1 Ib / A applied to 80 gal of water per acre.

함유의 아세톤 50ml에 용해함으로써 재바함에 적용한 용액 5ml가 파종전 처리 2 Ib/A와 동등케 하였다.D) 78 ml of S-isopurophyl 1- (5-ethyl-2-methyl-piperidine) carbothioate (R-12001) 1% Tween 20

By dissolving in 50 ml of acetone contained, 5 ml of the solution applied to the resurfacing was made equivalent to 2 Ib / A of pre-sowing treatment.

6E 54mg 또는 S-에틸 시클로헥실 에틸 티오카르바메이트-RONEET

6E 108mg을 증류수 50ml에 용해함으로써, 재배함의 토양에 적용한 5ml가 에이커당 물 80gal에 적용한 1 Ib/A 또는 2 Ib/A와 각각 동등케하였다.E) S-ethyl di-isobutyl thiocarbamate-SUTAN

6E 54 mg or S-ethyl cyclohexyl ethyl thiocarbamate-RONEET

By dissolving 108 mg of 6E in 50 ml of distilled water, 5 ml applied to the cultivated soil were equivalent to 1 Ib / A or 2 Ib / A, respectively, applied to 80 gal of water per acre.

4E 509mg을 증류수 100ml에 용해함으로써, 재배함의 토양에 파종전 처리로 적용되는 5ml가 3 Ib/A와 동등케 하였다.F) 2,3,3-trichloro allyl N, N-diasoprophyl thiocarbamate-AVADEXBW

By dissolving 509 mg of 4E in 100 ml of distilled water, 5 ml applied by the pre-sowing treatment to the soil of the grower was equivalent to 3 Ib / A.

6E 303mg을 증류수 50ml에 용해함으로서 재배함의 토양의 파종전처리로 적용한 5ml가 8 Ib/A와, 그리고 3.75ml가 6 Ib/A와 각각 동등케하였다.G) S-ethyl hexahydro-1H-azepine-1-carbothioate-ORDRAM

By dissolving 303 mg of 6E in 50 ml of distilled water, 5 ml applied to the sowing pretreatment of the cultivated soil were equivalent to 8 Ib / A, and 3.75 ml to 6 Ib / A, respectively.

[antidote]

(플리옥시-에틸렌 소트비난 모노리우레이트)함유의 아세톤 2.5ml에 용해함으로서 종자 10gm 당의 용액 0.5ml가 1/2% W/W와 등케에 하였다. 1/4% 처리의 종자에 대해서는 0.25ml을 아세톤 0.25ml로 희석함으로써 종자 10gm에 대한 용액 0.5ml가 1,/4%W/W와 동등케 하였는데 이 용액은 종자처리 절차에 사용하였다.H) 250 mg of each active ingredient of the detoxification compound to be tested

By dissolving in 2.5 ml of acetone containing (polyoxy-ethylene sorbinan monourirate), 0.5 ml of a solution per 10 gm of seeds was subjected to 1/2% W / W and backing. For seeds of 1/4% treatment, 0.5 ml of the solution for 10 gm of seeds was equivalent to 1, / 4% W / W by diluting 0.25 ml with 0.25 ml of acetone, which was used in the seed treatment procedure.

함유의 아세톤 15ml에 용해함으로써 재배함의 절반에 걸쳐 종자와 토양에 적용되는 1.5ml가 5 Ib/A와 동등케 하였다.I) 95% of each active ingredient of the detoxification compound to be applied to the bone treatment method 1% Tween20

By dissolving in 15 ml of acetone contained, 1.5 ml applied to seeds and soil over half of the cultivation was equivalent to 5 Ib / A.

함유의 아세톤 15ml에 용해함으로써 재배함에 적용되는 5ml가 5 Ib/A와 동등케 하였다.J) 1% Tween 20 of 58mg of each active ingredient of the detoxification compound to be applied to the tank mix before sowing.

By dissolving in 15 ml of acetone contained, 5 ml applied to growing was equal to 5 Ib / A.

함유아세톤으로서 그 5ml가 1.0 Ib/A와 그리고 2.5ml가 0.5 Ib/A와 동등케하였다.In addition to the stock solution, 11mg / 20ml 1% Tween 20

As the containing acetone, 5 ml were equalized with 1.0 Ib / A and 2.5 ml with 0.5 Ib / A.

The undiluted solution was used for seeding bone treatment of the detoxification composition. In preparation, one pint of soil samples in each cultivation box were set aside so as to cover the seed seed treated with the undiluted solution, and the soil was evenly distributed before sowing. . The herbicide solution was applied to the soil at the ratio of the active ingredient corresponding to 1 Ib / A or the above-mentioned ratio as the pre-sowing treatment.

The seeding bone is then beat to the depth of 1/4 inch in the length of the growing box.

After sowing, cultivation into wood block is divided into two parts, and 1-1 / 2 ml of the additive stock (Ⅰ) is sprayed directly on the exposed seeds and bones. The untreated section of the grower is used to examine the herbicide impact and to determine whether the antidote is active or not, and the seeds are covered with a single pint soil sample.

The following stock solutions are used for the tank mixing procedure applied by surface treatment before germination or impregnation before implantation. That is, 5 ml of the herbicide stock (A) or (C) was mixed with 5 ml of the antidote stock (J), respectively, so that the herbicide and the antidote were applied to the soil of each grower at a ratio of 1 Ib / A and 5 Ib / A. In application before dispatch, the mixed stock solution was injected during mixing by a 5 gallon rotary mixer. Other undiluted solutions shall be applied at the rates specified in the tank mixing procedure.

As for the pineal treatment, 10 gm of pine nuts were placed in a suitable container and shaken with 0.5 ml of the antidote stock solution (H) or the specified amount of the stock solution, and the pines were treated at 0.5% W / W, 0.25% W / W, or 0.125% W / W. Shake the container well until the treatment solution is evenly coated on the sender.

The detoxification compound may be applied as liquid slurry, powder or fine treatment, as the case may be. The treated sender was sent to the treated soil prior to sending the herbicide stock (B) at an active ingredient ratio corresponding to 1 Ib / A.

Now, the cultivation was placed on the nursery plate to maintain the room temperature at 70-90 ° C., and watered as much as needed for the growth of plants. Two weeks after the intestinal tract treatment, four weeks after the treatment, it was used as a standard for comparing the injuries given by the herbicide detoxifier by placing the separate cultivation boxes treated only with the preparation. The test results are presented in Table 2.

TABLE 2

Herbicide detoxification

The antidote according to the present invention can be used in a form convenient for use.

That is, the herbicidal detoxifying agent can be prepared in emulsion form, emulsion concentrate, liquid substance, wet ingredient powder, powder, granule or other convenient form. An amount of herbicide detoxification compounds that is not toxic to the plant can be added to the selected herbicides in a convenient form and mixed in the soil before or after sowing. However, it should be pointed out that herbicides can first be mixed into the soil and then the antidote can be mixed into the soil. Furthermore, the seed of the cultivated plant may be seeded in the herbicide-treated soil after being positively-treated to the extent that it does not poison the plant of the antidote compound according to the present invention. You may do it. It should be noted here that the addition of the antidote compound according to the present invention does not affect the herbicidal action of the herbicide at all.

Claims (1)

Preparation of a dibromosubstituted propionamide detoxifier for detoxification of a thiocarbamate herbicide having a structural formula [I] formed by reacting 2,3-dibromopropionyl chloride in the presence of a solvent with an amine having the structural formula [II] .

Wherein R ₁ is hydrogen, alkenyl or lower alkyl and R ₂ is alkyl, alkenyl, alkynyl, dimethoxy ethyl or 1-ethynyl cyclohexyl.