KR810000377B1 - Preparation of ester of thiocarbamic - Google Patents

Abstract

Title compds., useful as herbicide, bacteriostatic agent and insecticide, are prepd. from the reaction of mercaptan (RSH; R = C1-12 alkyl, haloalkyl, C2-10 alkylthioalkylene, alkoxyalkylene, C3-7 cycloalkyl, etc.) with carbamyl chloride CR1R2NCOCl; R1,R2 = C1-12 alkyl, C2-8 alkenyl, haloalkyl, C2-6 substd. cyanoalkyl, etc.) in the presence of an inorganic base e.g. mixt. of NaOH, KOH, VOH and phase-transfer catalyst [(R3R4R5R6M)+X- ; R3,R4,R5,R6 = alkyl, alkenyl, aryl, aralkyl, cycloalkyl ; M = N, P, As Sb, Bi ; X = anion . By this method final compds. are obtained from low conc. of inorganic acid and reaction time is shortened.

Description

[Name of invention]

Method for preparing thiocarbamic acid ester using a phase transfer catalyst

Detailed description of the invention

Thiocarbamic acid esters are used in many ways, some as active herbicides and some as bacterial growth inhibitors or as insecticides.

The present invention relates to a novel process for preparing various compounds known as thiocarbamaart. More specifically, the present invention relates to a process in which thiocarbamaart is reacted with an appropriate mercaptan and an appropriate mercaptan in the presence of a suitable caustic solution and a phase transfer catalyst. It relates to a process for preparing carbamic acid esters.

Generally, any mercaptan or carbamyl chloride can be used in this process, and the general reaction is as follows.

Examples of mercaptans and carbamyl chloride groups which can be used here include the following. That is, R is alkyl having 1-12 carbon atoms; Haloalkyl having 1-12 carbon atoms, preferably chloro or bromo substituted alkyl; Alkylthio alkylenes all having 2 to 10 carbon atoms; Alkoxy alkylene having carbon atoms ranging from mode 2 to 10; Cycloalkyl having 3 to 7 carbon atoms; Alkenyl having at least one double bond and 2-8 carbon atoms; Alkynyl having at least one triple bond and 3-6 carbon atoms such as isobutynyl, 3-methyl-butyne (1) Yl (3); Phenyl; Naphthyl; benzyl;

α-alkylbenzyl, wherein alkyl has 1-4 carbon atoms;

Substituted phenyl wherein the substituents are alkoxy and nitro, having 1 to 4 carbon atoms, chloro, trifluoro, methyl, for example 0-methoxy, m-butoxy, P-nitro, 3,4-dinitro, 2,4-dinitro);

Substituted naphthyl, wherein the substituents include alkoxy, nitro, chloro, bromo, trifluoromethyl;

Haloalkenyl (where alkenyl has 2-6 carbon atoms, halo is chloro, bromo, iodine or fluoro, for example 2,3-dichloroallyl, 3,4,4-crifluoro-3) Butenyl-2-brooallyl and the like); Cyclohexenyl;

Substituted benzyl (where the substituents are, for example, cloyl, bromine, fluorine, methyl-P-methyl, 0-methyl, 2,4-dimethyl, 2,6-dimethyl, 2,4-dichloro, 3 , 4-dichloro ar, ar, ar-trichloro, 5-chloro-2-methoxy, nitro); Carboalkoxyalkyl having 2 to 8 carbon atoms; Phenylthioethyl; Phenyloxyethyl; Pyrimidyl; Pyridyl; Indazolyl; Quinolyl; Isoquinolyl; Furyl; Dibenzofuryl;

R ₁ and R ₂ are each; Alkyl having 1 to 12 carbon atoms; Alkenyl having at least one double bond and 2-8 carbon atoms; Haloalkyl having 1-12 carbon atoms and halo being chloro, fluoro or bromo; Cyano substituted alkyl having 2-6 carbon atoms; Alkynyl having at least one triple bond and 3-6 carbon atoms such as propazyl, isobutynyl and the like; Cyclohexenyl; Haloalkenyl having 2-8 carbon atoms and halo being chloro, fluoro or bromo; benzyl; Substituted benzyl, wherein the substituents are, for example, chloro, lower alkoxy and cyano with 1-4 carbon atoms, nitro and trifluoromethyl; Haloalkoxy having 1-8 carbon atoms and halochloro, fluoro or bromo; Alkoxy having 1-8 carbon atoms; Alkoxy having at least one double bond and 2-8 carbon atoms; Alkenyloxy having at least one double bond and 2-8 carbon atoms; Nitroalkoxy having 1-6 carbon atoms; Phenyl; Substituted phenyl, wherein the substituents are, for example, chloro, bromo, nitro, cyano, alkoxy having 1-4 carbon atoms, phenyl and the like; Phenoxy substituted alkyl, wherein alkyl has 1-4 carbon atoms; Naphthal; Furfuryl, tetrahydro furfuryl; Cycloalkyl having 3 to 7 carbon atoms; Heterocyclic oxygen, nitrogen or sulfur-containing cyclic groups (e.g. pyridyl, teranyl, furyl, pyranyl, pyrimidinyl, indolyl, quinolyl, isothioazolyl, piperidine, piperazinyl, morpholinyl Etc.): Alkyl-substituted pyridyl, wherein alkyl has 1-4 carbon atoms:

Belonging to R ₁ and R ₂ , which are bound together by nitrogen, are heterocyclic groupings, for example pyryl, phytolidine, pyrazolyl, pyrazolinyl, piperidinyl, imidazolyl, indolyl, having 3-6 carbon atoms; β-methylindolyl, aziridinyl, carbazolyl, morpholinyl, 3-azabicyclo- [3,2,2] nonanyl-3, polyalkyleneimines and 5-ethyl-2-methyl piperidine It is the same alkyl substituted piperidine.

Compared to the recent US Patent No. 3,836,524 of the present invention has the following advantages.

1) The same conversion and purity can be obtained with very low corrosion concentrations, 2) the low excess of mercaptan to carbamyl chloride yields the same conversion, and 3) less agitation, and 4) reaction time. This is markedly shortened.

As described above, the carbamyl chloride is reacted with metcaptan in the presence of a caustic aqueous solution and a phase transfer catalyst, but the components of the reaction mixture may be added in any order. For example, (a) A mixture of mercaptan and phase transfer catalyst can be added to the corrosion solution, and after that, the resulting mixture is added to carbamyl chloride. (B) A phase transfer catalyst and a mixture of mercaptan and carbamyl can be added to the corrosion solution, and (c) A phase transfer catalyst can be added to carbamyl chloride, which is then added to the mixture of mercaptan and planting solution. do.

The latter method is generally the preferred method for the addition of carbamyl chloride and mercaptan. The method of (b) is preferable when the mercaptite salt is not dissolved in the corrosion solution. In either method, the resulting reaction mixture consists of two liquid phases, the organic phase containing crabmill chloride and the aqueous phase containing caustic and mercaptan.

The term "phase transfer catalyst" as used herein refers to a catalyst that facilitates the transfer of a chemical from one liquid phase to another. Examples of such catalysts include (R ₃ R ₄ R ₅ R ₆ M ) + X ^- may be sacrificed salts having the formula: Wherein R ₃ , R ₄ , R ₅ and R ₆ are hydrocarbon groups freely selected from the groupings consisting of alkyl, alkenyl, aryl, alkaryl aralkyl and cycloalkyl groups. M is a member selected from the group consisting of nitrogen, phosphorus, arsenic, antimony and bismuth, with nitrogen or phosphorus being preferred. X is an anion to be separated from the cation in the liquid state, preferably halogenated ions or hydroxyl ions, most preferably chloride or solubles.

In the terminology used in the above description of R ₃ , R ₄ , R ₅ and R ₆ , alkyl refers to a saturated aliphatic hydrocarbon grouping having 1 to 25 carbon atoms of a monovalent linear or sustained chain. For example, ethyl, propyl, I-propyl, n-butyl, s-butyl, t-butyl, n-octyl, 2-methyloctyl, decyl, 6-methyl undecyl, dodecyl and the like.

Alkenyl refers to a monovalent straight-chain or maintenance chain aliphatic hydrocarbon having 2-25 carbon atoms and contains at least one double bond, for example, allyl, butenyl, buradienyl and the like.

Aryl refers to monovalent monocyclic or cyclic aromatic hydrocarbon groupings, ie phenyl and naphthal.

Alkaryl refers to an aryl group, as identified above, wherein at least one hydrogen atom is substituted with an alkyl group as described above, for example tolyl, xyline, mesityl, ethylphenyl, and the like.

Aralkyl refers to alkyl groupings as identified above, where one hydrogen atom is substituted with the above-mentioned aryl or alkaryl groupings, such as benzyl, phenethyl, methylbenzyl, naphthalmethyl, etc. to be.

Cycloalkyl refers to monovalent cyclic saturated hydrocarbon groupings having 4 to 8 carbon atoms, ie cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Mixtures of these fourth salts can all be used in the examples of the present invention. Double or multifunctional quaternary salts in which the general formula (R ₃ R ₄ R ₅ R ₆ M) + X ⁻ is repeated several times as the same or different substituent combinations can also be used effectively.

Most preferred phase transfer catalysts are tetra-n-butylphosphonium chlora, hexadecyltributyl phosphonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, tricaprylylmethylammonium chloride and dimethyldicoco Ammonium chloride. The two catalysts at the end are manufactured by General Mills, Department of Chemistry, Kankaki, Illinois, and are designated as “Alicat 336” or “Alicat 221”.

The catalytic amount refers to any amount of phase transfer catalyst that promotes the progress of the reaction. The amount of catalyst is usually in the range of 0.2-5.0% of the weight of the reaction mixture, preferably about 0.5-1.0% by weight.

The proportion of reactants used in the manufacturing process can be varied over a wide range. Usually the molar ratio of mercaptan (RSH) to crombaryl chloride (R ₁ R ₂ NCOCL) is at least about 1.0, but the preferred ratio is 1.1.

에 따라 메르캅티드 RS^-이온의 메르캅탄으로 가수분해를 방지 또는 억제하여야 한다.The molar ratio of caustic to vercaptan is at least about 0.5, but the preferred ratio is at least 1.0. Thus, in the most preferred state, the process is carried out with excess corrosion. As used herein, the term caustic means any inorganic substance that sufficiently produces hydroxyl ions in aqueous solution to operate the method. The nature of the caustic makes enough alkalinity in aqueous solution,

The mercaptide of mercaptide RS ^- ions should be prevented or inhibited by hydrolysis.

The caustic agent to be used in this method is, among other things, sodium hydroxide, potassium hydroxide, barium hydroxide and the like and mixtures thereof. The caustic is supplied to the reactants as an aqueous solution in the range of approximately 5% to 50%, so the solution is liquid. For example, when using sodium hydroxide, the preferred range of corrosion solution is about 10% -30% by weight.

The state of the reaction can be varied in a wide range without a visible influence on the yield and quality of the product. The reaction temperature is about 10 ° C. to 100 ° C., preferably 20 ° C.-80 ° C. Within the temperature ranges pointed out here, it has been found that thiocarbamic acid esters can be made and that the unwanted byproduct acids of the corresponding urea can be reduced. The temperature chosen also determines the reaction rate. In other words, the amount of carbamyl chloride remaining in economically viable time is negligible. The reaction time therefore depends on several interaction factors such as temperature and agitation.

Stirring is not necessary for effective reaction progression, but can increase the interfacial area between the two liquid phases and benefit from reaction time. For the stirrer, a stirrer is used or a baffle plate or a turbulence colam in the reactor is used.

The practice of the invention may be in the form of a bacterium, pollen, or as a continuous or similar continuous form. When carrying out in the same way as the batch operation, all kinds are mixed in one liquid in order according to the order determined at the appropriate time. In the case of adopting a continuous or pseudocontinuous form, the desired reaction rate is achieved by selecting appropriate stirring means and appropriate reaction conditions. The choice of various types of operating methods to be adopted will depend on the desired manufacturing conditions. The reactor is preferably made of non-corrosive, such as mild steel, that does not interfere with the main reaction.

Upon completion of the reaction, the thiocarbamate ester product remains in the organic phase. Salts precipitated during the reaction can be readily dissolved by the addition of water. Then separate the two liquid phases. Drying the wet phase gives thiocarbamite esters. The product is purged with argon or nitrogen while heating to remove residual water and volatiles. In order to purify further can be accomplished by the usual method.

Characteristic examples describing the preparation of thiocarbamic acid esters by the process of the invention are described below. This embodiment is for illustrative purposes only and is not intended to add any limitation to the scope of the invention described herein. Such limitations are set out in the claims.

EXAMPLE

(General method)

The general method used in the following experiment is as follows. An aqueous solution of sodium hydroxide is placed in a stirring flask with a stirrer and the appropriate mercaptan is added to this aqueous solution. The flask and its contents are kept at the indicated temperature while the essential carbamyl in which the phase transfer catalyst is dissolved is added to the mixture.

At the end of the experiment, water is added if necessary to dissolve any precipitated salts. The organic layer containing thiocarbamic acid ester is then separated. The organic layer is heated in vacuo or purified by heating layer nitrogen to remove residual water and mercaptan. Reactants, products, catalyst preparations and results are summarized in the following Tables I, II and III. The result is the area percentage by gas chromatography analysis of the material. In some instances, weight percent purity was also determined and found to be within experimental error in light of gas chromatography analysis.

TABLE I Reactants and Products

TABLE II Catalysts

Table III Reaction Conditions and Results

※ 130ml water is added to caustic / C ₂ H ₅ SH solution

Of particular interest in the data in Table III is the comparison between Experiments 8 and 8a, 9 and 9a, and 10 and 10a. Each pair represents the progress of the unused reaction, such as with a phase transfer catalyst. In this data, the use of a catalyst shows remarkable advantages in reaction time and product purity in each case. In the comparison between Experiments 16 and 9a, the data do not show the gains shown to be obtained with the use of benzyltriethylammonium chloride, but not in the table, but an increase in ratio occurred. The reaction did not proceed until completion because the catalyst did not dissolve in carbamyl chloride. The complete reaction will occur when the same catalyst is used with carbamyl chloride in which it can be dissolved or with another catalyst that is soluble in carbamyl chloride used in Experiment 16. The advantage of the system is that all components are dissolved. The phase transfer catalyst used also acts as an emulsifier to promote mixing.

[Compound Action Data]

Thiocarbamic acid esters produced by the method of the present invention can be used as herbicides, growth inhibitors, and insecticides.

The action of the compound prepared by the above examples by the method of the present invention as a herbicide is measured by the following test.

[Herbicide test before germination]

Using the analytical balance, 20 mg of the test compound was placed in glassine, which was placed in a 30 ml wide bottle and 3 ml of acetone containing 1% twenty ⓚ (polyoxyethylene sorbitan monolaurate). Add. If the substance is insoluble in acetone, use something like water, alcohol or dimethylformamide (DMF) instead.

When using DMF, only 0.5 ml or less is used to dissolve the compound, and another solvent is used to increase the amount to 3 ml.

The 3 ml solution is evenly sprayed on the soil after a day of sowing the grass seeds in the fiber box. When spraying, a 152 Debyvis sprayer was used, which used an air pressure of 5 pounds per square inch. The utilization rate is 8 pounds per acre and the spread is 143 gallons per acre.

Prior to processing, a 7 inch long, 5 inch deep 2.75 inch fiber box was laid with a 2-inch thick sandy loam soil, spreading seven varieties of grass seed in each row across the box to a depth of 0.5 inches. To cover. Seeds used are hairy kingfisher, yellow beetle, red root tusks, Indian mustard, dried swimming watergrass and red oats. Sprinkle enough seeds according to the size of the plant, so that after germination, 20-50 seedlings can be obtained in each row.

After treatment, the box is placed in a greenhouse at 70-85 ° C. and watered. Two weeks after treatment, injury or inhibition is measured by comparison with untreated control plants of the same age. The degree of injury in the ratio of 0-100% is recorded for each type, with 0% for no injury and 100% for complete death.

[Herbicide test after germination]

Seeds of six species of hairy king courgette, watergrass, red oats, mustard, dried leaves and stained squirt cones are sprayed into the same styrofoam box used in the pre-germination test and placed in a greenhouse at 70-85 ° C, daily spring Water with a cooler. After about 10 to 14 days, when the legumes were almost fully extended to reach the first trifolium, 20 mg of the test compound was dissolved in 5 ml of acetone containing 1% 20 won, and 5 ml of water was added to the plant leaves. Sprinkle. The spraying solution uses a No. 152 Devivis atomizer to utilize 5 pounds of air pressure per square inch. The spray concentration is 0.2 and the rate is 8 pounds per acre. The spray volume is 476 gallons per acre. Record the injury level after 14 days of treatment. The rate indication is as described in the pre-germination test.

The test results are shown in Table IV.

Table IV Herbicide Action

Average of 7 plants in pre-germination test and 6 plants in post-germination test

Claims (1)

As described above in the text, carbamyl chloride is reacted in the presence of an effective amount of a mercaptan, an aqueous solution of a caustic agent, and a fourth salt of the fourth salt of the following structural formula to separate an organic phase and an aqueous phase, and the thiocar from the organic phase. A method for producing a thiocarbamic acid ester obtained by recovering a baric acid ester. _{(R 3 R 4 R 5 R} 6 M) + X - [Wherein R ₃ , R ₄ , R ₅ and R ₆ are hydrocarbon groups independently selected from groupings consisting of alkyl, alkenyl, aryl, aralkyl and cycloalkyl groups, and M is nitrogen, phosphorus, arsenic, antimony Is a member selected from the loop consisting of and bismuth, and X is an anion separated from the cation in the liquid state]