KR840000859B1 - Method of preparing oxazolidine herbicide antidotes - Google Patents

Abstract

Oxazolidines II [R=C1-C5 haloalkyl (halo=Cl, Br), pmethylphenyl sulfonylamide; R1=Ph, alkyl, alkenyl; R2, R3 independently=C1-C3 lower alkyl; X=O, S; XR1=phenoxy were prepd. by acylation of 5-substituted oxazolidines (I) with an acid chloride. Thus, 419g p-toluene sulfonyl isocyanate was treated with 20.7mL (25% w/v) 2, 2-dimethyl-5-phenoxymethyl oxazolidine in 50mL benzene to give 12.8g 2, 2-dimethyl-3-(p-toluene-sulfonyl carbamyl)-5-phenoxymethyl oxazolidine.

Description

[Name of invention]

Method for preparing 5-substituted oxazolidine herbicide detoxifier

Detailed description of the invention

The present invention relates to a method for preparing a 5-substituted oxazolidine herbicide detoxifying agent, and the present invention also relates to a 5-substituted oxazolidine detoxifying agent consisting of a thiol carbamemate herbicide and a non-phytotoxic effective amount of the detoxifying agent and a herbicide herbicide. will be.

In many ways, it has been found that when applied in combination with thiolcarbamate type herbicides and other compounds, it is possible to reduce the injuries caused by thiolcarbamate type herbicides and to protect the crops.

In addition, as another effect, the resistance of the crop to the herbicide by adding a 5-position substituted N-haloacyl oxazolidine type antidote compound to the soil according to the following method Can be increased significantly.

In the present invention, a two-component herbicide system comprising a phenoxymethyl grouping comprising a first component of one or more thiolcarbamate herbicides and a second component of an effective amount of an antidote compound of the formula .

Wherein XR ₁ is phenoxy and R is selected from the groupings consisting of haloalkyl containing 1-5 carbon atoms, where ＂halo＂ is chloro or bromo and P-methylphenylsulfonylamide, and R ₂ and R ₃ are selected exclusively from low alkyl containing 1 to 3 carbon atoms.

The compounds according to the invention represented by the structural formulas as described above may be prepared by various other procedures depending on the starting materials.

When X is oxygen and R is phenyl, the starting materials for the compounds according to the invention are 1-amino-3- by amination of 1,2-epoxy-3-phenoxy propane ammonium aqueous solution or ammonium hydroxide. Phenoxy-2-propanol can be prepared. Reaction and cyclization with acetone or other ketones then yield the N-substituted 2,2-dialkyl 5-phenoxymethyloxazolidine product. The reaction sequence is as shown in the following equation.

Wherein R ₁ , R ₂ , and R ₃ are the same as defined above.

In the above procedure:

a) N-acyl-substituted compounds (wherein R is haloalkyl) according to the present invention are directly substituted with 5-substituted oxazolidine compounds and acid chlorides in the presence of a hydrogen chloride solution such as triethylamine or an inorganic salt such as sodium hydroxide. It can be produced by misfire.

(b) The thiocarbamyl 3-substituted compound (R is alkylthioin) according to the present invention is prepared by direct alkylthio formylation of a 5-substituted oxazolidine compound with an alkylchlorothioformate in the presence of an acid chloride acceptor. Can be prepared.

(c) P-toluenesulfonyl carbamyl 3-substituted compound (R is P-toluenesulfonyl) according to the present invention is prepared by direct carbamylation of P-toluenesulfonyl isocyanate with 5-substituted oxazolidine. Can be.

In the above reaction, the reaction is carried out in the presence of an organic solvent such as benzene. Solvents are generally used to accelerate the reaction and aid in the formation of the product. Catalysts are generally known to be used, but in some cases no catalyst is required. The reaction temperature is in the range of −10 ° C. to 90 ° C., and the reaction pressure may be atmospheric pressure, atmospheric pressure or lower, or atmospheric pressure or higher. However, the pressure to make the reaction convenient is generally atmospheric pressure. Of course, the reaction time varies depending on the reactants and the reaction temperature. After completion of the reaction, the product is recovered by filtration, extraction and drying. The product can be further purified by grinding with hexane or recrystallization from a suitable solvent. In most cases, the structure has been confirmed by infrared spectroscopic nuclear magnetic resonance or mass spectrometry.

A typical example of the above general scheme can be found in the preparation method using the following specific starting materials and intermediates.

100 g of 3-phenoxy-1,2-epoxypropane was added dropwise with stirring to 1 L of an aqueous 28% ammonium solution cooled to about 0 ° C. overnight in a refrigerator. A fine precipitate formed during the addition for about 2 hours or more, and when left overnight, a layer formed on the surface of the mixture. This precipitate was dissolved in methylene chloride, dried over magnesium sulfate and scooped to yield 58 g of the title compound (mp 69-75 ° C.) with a small amount determined from methylene chloride being mp 79 ° -82 ° C. The structure was confirmed by infrared and nuclear magnetic resonance analysis.

30 g of 1-amino-3-phenoxyisopropanol and 15 g of acetone were combined in 150 ml of benzene and refluxed in an Dean-Stark apparatus. The mixture was cooled when about 4 milliliters of water was removed undesirably and the volume was adjusted to 165.2 ml to make a 25% W / V solution (4 ml = 1 g). Stripping a small amount of sample yielded the title compound n ³⁰ _p 1.5150, the structure of which was confirmed by infrared and nuclear magnetic resonance. In the subsequent reaction, the integer of the mixture was used.

Compounds according to the invention and methods for their preparation are described in further detail by the following examples.

In the table following the Examples, the compounds prepared according to the procedures described herein are indicated, and the compound numbers given for each of these compounds are used for identification throughout this specification.

Example I

5.5 g of trichloroacetyl chloride was added to 24.8 ml (25% W / V) of dimethyl-5-phenoxymethyl oxyzolidine contained in 50 ml of benzene. After washing with water and drying and removing benzene in vacuo, 8.1 g of n ³⁰ _p title compound n ³⁰ _p 1.5272 was obtained. The structure of this compound was confirmed by the analysis results.

Example II

In a similar manner to Example 1, 2.6 g of 2,3-dibromopropionyl chloride was added to 20.7 ml (25% W / V) of 2,2-dimethyl-5-phenoxymethyl oxa contained in 50 ml of benzene. Zolidine and 6.6 g of 2.3-dibromopropionylchloride were added. After appropriate reaction procedures, the title compound was obtained as 4.3g, n ³⁰ _p 1.5423. The structure of this compound was confirmed by the analytical data.

Example III

419 g of P-toluenesulfonyl isocyanate was added to 20.7 ml (25% W / V) of 2,2-dimethyl-5-phenoxymethyl oxazolidine contained in 50 ml of benzene. Removal of benzene in vacuo yielded 12.8 g of the title compound, whose structure was confirmed by analytical data.

TABLE 1

The herbicidal compounds usefully used in combination with the compounds according to the present invention are general active thiolcarbamate herbicides. That is, they belong to the herbicidal active compounds which are effective against a wide range of plant types, without distinguishing between plant types which are either desirable or undesirable. The method of suppressing the plant is achieved by applying the effective herbicidal amount described herein to the region or plant in need of inhibition.

As described herein, the herbicide composition comprises an active compound selected from the above antidotes and the following thiolcarbamate herbicides. Representative thiolcarbamate herbicides are, for example, S-propyl di-n-propyl thiolcarbamate, S-ethyl cyclohexylethin thiolcarbamate, S-ethyl hexahydro-1H-azepine-1-carbothioate , 2,3,3-trichloroallyl, N, N-diisopropyl thiolcarbamate, S-isopropyl-1- (5-ethyl-3-methyl-piperidine) carbothioate and S- 4-chlorobenzyl diethyl thiolcarbamate and the like.

As in embodiments of the present invention, the present invention is a two-part, ie combined herbicide system consisting of a first constituent of one or more thiolcarbamates and a second constituent of an antidote. It should be understood that the antidote used in an effective amount may give rise to a selective action for a two-part herbicide system that maintains phytotoxicity to the desired, ie less desired, ie less toxic, unwanted plant life. . Thus, the soil treated by the garten system is very useful and desirable, and can cause crops that are injured by the herbicide when only herbicide is used to be sown in the soil treated with the Part 2 herbicide system. Therefore, soils treated with herbicides and antidotes as described herein are desirable and useful. Similarly, seeds treated with antidote compounds are also useful and preferred.

Herbicides as used herein refer to compounds that inhibit or modify the growth of plants. Such inhibitory or fertilizing effects include all deviations from the natural growth of plants, such as killing, delaying, deciduous, dry, regulated, atrophy, sprouting from the stump, stimulating and dwarfing. "Plant" means a settled plant including germinating seeds, sprouting seedlings, roots and ground parts.

Crops and weed varieties were used as a loam soil, and the same application methods were used, such as mixing the herbicide and the antidote separately (PPI of 1) and tank mixing the herbicide and the antidote together (PPI-TM). Application was by mixing, after which crops and weed seeds were sown in the soil. A method of treating seed and adjacent soil pretreated with seeds and herbicides in the bone. Treatment of crop seeds (ST) with detoxification agents before they are sown in treated soil, and treatment of soil prior to plant germination with individual application of herbicide detoxification (PEC) and tank mix (PEC-TM) have.

Stock solutions of typical thiolcarbamate herbicides and antidotes were prepared as follows.

6E 413mg를 800ml의 물에 용해하여 재배함의 토양에 적용된 5ml가 5Lb/A PPI와 동등하도록 하든지 또는 3844mg를 600ml의 물에 용해하여, 그 5ml가 6Lb/A PPI과 동등하도록 하였다.A. S-ethyl di-n-propyl thiolcarbamate-EPCT-EPTAM

413 mg of 6E were dissolved in 800 ml of water so that 5 ml applied to the cultivated soil was equivalent to 5 Lb / A PPI or 3844 mg was dissolved in 600 ml of water so that 5 ml was equivalent to 6 Lb / A PPI.

B. S-isopropyl 1- (5-ethyl-2-methyl-piperidine) carbothioate (R-12001) for industrial use.

The list of various prepared stock solutions is as follows, and Lb / A equivalent per 5ml PPI is as follows.

120 mg / 150 ml acetone; 5ml = 1Lb / A PPI

176 mg / 150 ml acetone; 5ml = 1.5Lb / A PPI

117 mg / 150 ml acetone; 5ml = 2Lb / A PPI

975 mg / 250 ml acetone; 5ml = 5Lb / A PPI

585 mg / 125 ml acetone; 5ml = 6Lb / A PPI

6E 또는 S-에틸 시클로헥실 에틸 티올카르바메이트- RONEET

6E-390mg을 125ml의 물에 용해하여 재배함 토양에 적용되는 5ml가 3Lb/A와 동등하게 하였다. 4Lb/A에 동등하게 하기 위하여는 1456mg을 350ml에 용해하였다.C. S-Ethyl Di-isobutyl Thiolcarbamate-SUTAN

6E or S-ethyl cyclohexyl ethyl thiolcarbamate-RONEET

6E-390 mg dissolved in 125 ml of water. 5 ml applied to the soil was equal to 3 Lb / A. To equalize to 4 Lb / A, 1456 mg was dissolved in 350 ml.

8E-164mg을 75ml의 물에 용해하여 5ml가 PPI 재배함 토양에 적용된 2Lb/A와 동등하게 하였다.D. S-ethyl hexahydro-1H-azepine-1-carbothioate ORDRAM

8E-164 mg was dissolved in 75 ml of water, 5 ml equalized to 2 Lb / A applied to PPI grown soils.

E. Various stock solutions made with S-propyl di-n-propyl thiolcarbamate-VERNAM-6E (80%) are as follows. Also included is the Lb / A equivalent for 5m PPI.

122 mg / 125 ml H ₂ O; 5ml = 1Lb / A PPI

182 mg / 150 ml H ₂ O; 5ml = 1.25Lb / A PPI

975 mg / 250 ml H ₂ O; 5ml = 4Lb / A PPI

2632 mg / 450 ml H ₂ O; 5ml = 6Lb / A PPI

3412 mg / 500 ml H ₂ O; 5ml = 7Lb / A PPI

(폴리옥시에틸렌 소르비탄 모노로오테이트)을 함유하는 2.5ml의 아세톤에 용해하여 10g의 종자당 0.5ml의 용액이 ½% W/W에 동등하게 하였다.F. For each candidate compound to be used in the application by soil treatment, 250% of the active ingredient in 1% TWEEN20

It was dissolved in 2.5 ml of acetone containing (polyoxyethylene sorbitan monolotate) to make 0.5 ml of solution per 10 g of seeds equal to ½% W / W.

을 함유하는 15ml의 아세톤에 용해하여 재배함 ½면적의 골에서 종자 및 토양에 적용된 1.5ml가 5Lb/A에 동등하게 하였다. 1.0Lb/A가 바람직할 경우에는 0.3ml가 사용되었다.G. 95% active ingredient (1% TWEEN) is added for each candidate compound to be used in the method of applying bone bone.

It was cultivated by dissolving in 15 ml of acetone containing 1.5 ml of 1.5 ml applied to seeds and soil in the ½ area of bone equal to 5 Lb / A. 0.3 ml was used where 1.0 Lb / A was preferred.

을 함유하는 100ml의 아세톤에 용해하여, 10ml의 원액이 90ml의 아세톤에 추가로 용해되었을때에 4ml가

Lb/A PPI에 동등하게 하였다. 39mg의 상기화합물을 10ml의 아세톤에 용해하였을 때에 5ml는 5Lb/A PPI에 동등하며, 1ml는 1Lb/A PPI에 대하여 동등하였다. 16mg을 20ml로 용해하였을 때에는 10ml는 2Lb/A PPI에 대하여 동등하고, 16mg을 40ml에 용해하였을 때에는 5ml는 0.5Lb/A PPI에 동등하였다.Tank mix For each candidate compound to be used in the PPI test or the individual application PPI test, 50% of the active ingredient (1% TWEEN)

Is dissolved in 100 ml of acetone containing 4 ml of the solution when 10 ml of the stock solution is further dissolved in 90 ml of acetone.

Equivalent to Lb / A PPI. When 39 mg of the compound was dissolved in 10 ml of acetone, 5 ml was equivalent to 5 Lb / A PPI and 1 ml was equivalent to 1 Lb / A PPI. When 16 mg was dissolved in 20 ml, 10 ml was equivalent to 2 Lb / A PPI, and when 16 mg was dissolved in 40 ml, 5 ml was equivalent to 0.5 Lb / A PPI.

In-furrow of the antidote using the stock solution is as follows. As a preparatory step, one pint of specimen was removed from each grower and used to cover the seed after treatment with the stock solution.

After sowing the soil of the cultivator before sowing, the herbicide stock solution was applied to the individual cultivator and mixed before sowing at the same ratio as the 1 Lb / A active ingredient or at the rate indicated above.

Before sowing, each treated grower was scored ¼ inch deep. After sowing, the growers were partitioned into two equal parts using a wooden barrier and 1½ ml of additional stock was sprayed directly onto the exposed seeds and the seeds in the uncovered bone of the ½ grower. The untreated portion of the grower aided herbicide testing and allowed the lateral movement of the antidote through the soil. Seeds were covered with one pint of untreated soil (sample soil), which had been transferred separately.

The following solutions and procedures were used for the tank mix to be applied as a PPI application method.

5 ml of the preparation stock solution was mixed with 5 ml of the target detoxifier stock solution, and the same amount of 1 Lb / A and 5 Lb / A herbicide and antidote were applied to the soil of each grower and mixed. For application, the mixed stock solution was injected into the soil during mixing in a 5 gallon rotary mixer. Other stocks were used in the proportions indicated in the tank mixing procedure.

In parallel testing of various weed varieties and crops, it was found that they could reduce the injuries of crops compared with the control while maintaining the weed suppression effect. The control did not contain the antidote compound.

The parallel test results are as described in the following table.

For seed treatment methods, 10 g of seeds in a suitable container are vibrated with 0.5 ml of antidote H or other indicated and other solutions, so that the seed treatment is 0.5% W / W, 0.25% W / W, 0.125% W / W. Or equal to 0.1% W / W.

The vibration continued until the seeds were evenly coated. The antidote compound may be applied as liquid slurry, powder or fine powder treatment. Treated seeds were sown in soil mixed with herbicide solution before sowing in soil at an equal ratio to 1 Lb / A active ingredient.

All growers were placed on greenhouse growers and the temperature in the greenhouse was maintained at 70-90 ° F. In order for the seeded bodies to grow well, the sprinkler was used to irrigate the soil. Injuries were measured at 2 and 4 weeks after application. Individual multiculture plants treated with only herbicides were included to provide a basis for determining the amount of injury reduction achieved by the antidote.

The test results are as described in Table II.

TABLE II

The compounds and compositions according to the present invention have been used in effective herbicide compositions consisting of antidote and thiolcarbamate herbicides as described above, which herbicide compositions have been tested in this manner.

Preferred herbicide compositions consist essentially of a thiolcarbamate herbicide and an antidote compound having an effective amount of a structural formula (known as 5-oxy or 5-thiomethyl substituted haloacyloxazolidine).

The composition according to the present invention, which is used for the protection of cultivated crop plants, comprises an activator herb compound and an antidote selected from the above compounds. It can be manufactured by the conventional method of mixing and grinding uniformly with a solvent.

Antidote compounds and compositions according to the invention can be used in any convenient form. No solvents or antifreezes are necessary in light of the low volume spraying technology which allows the use of sprays as pure industrial grade materials. Therefore, the antidote compounds and compositions may be formed in thiolcarbamate herbicides and emulsion emulsion concentrates, liquids, wet powders, granules or any other convenient form. It is preferable that the non-phytotoxic amount of herbicide antidote compound is mixed with the selected herbicide and mixed in the soil before or after sowing. However, it should be understood that herbicides may be mixed in the soil. In addition, the crop seed itself may be treated with a non-phytotoxic amount of the compound, the herbicide may be sown in the already treated soil, and also the herbicide may be treated with the herbicide after sowing in untreated soil. The addition of the antidote does not affect the herbicidal action of the herbicide. In the above embodiment, an alternative method of application is illustrated.

The amount of the antidote compound used ranges from 0.001 to 30 parts by weight of the antidote per herbicide by weight. The exact amount of antidote compound is determined by the economic ratio amount for the maximum effective amount that can be used. It will be appreciated that nonphytotoxic but effective amounts of antidote compounds are used in the herbicide compositions and methods of application.

After treatment with the antidote and herbicide, as a result, new soil in composition is obtained. The soil is improved crop growth and weed control capacity of the soil by the treatment of the antidote and herbicide. In addition, soils treated with herbicides and detoxifiers have the unique utility of allowing plant seeds that are injured by herbicides to be sown and grown. Herbicides have utility in inhibiting unwanted plants, antidotes reduce the rate of injury from herbicides in crops, and soils treated with herbicides and antidote compounds provide an improved medium that is otherwise harmful. Allow crops to grow in the presence of herbicides.

In using the antidote compound and the improved herbicide system according to the invention, thiolcarbamate can be applied to the soil. The application of herbicides to soil is carried out by pre-sowing mixing (PPI).

Crop seeds were sown in combination with the herbicidal action using the antidote according to the invention.

As a surface application before germination after sowing, application of the antidote was followed.

As mentioned above, the procedure for herbicide sowing and application of antidote is unique and sufficiently effective in reducing injuries to crops that are injured by thiolcarbamate herbicides.

Claims (1)

Under atmospheric pressure, 5-substituted oxazolidine represented by the following structural formula [I] chlorides in the presence of a hydrogen chloride acceptor such as triethylamine or an inorganic base such as sodium hydroxide at a temperature of −10 ° C. to 90 ° C. for 0.25 to 24 hours. A method for producing a 5-substituted oxazolidine herbicide detoxifier represented by the following structural formula [II] formed by acylation and acylation.

Wherein X is oxygen or sulfur and R ₁ is phenyl, alkyl or alkenyl.

Wherein XR ₁ is phenoxy and R consists of haloalkyl containing 1 to 5 carbon atoms And halo is chloro or bromo and P-methyl phenyl sulfonylamide, and R ₂ and R ₃ are selected independently containing 1 to 3 carbon atoms.