KR830000467B1 - Method for preparing thiocarbamate using quaternary ammonium salt catalyst - Google Patents

Abstract

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Description

Method for preparing thiocarbamate using quaternary ammonium salt catalyst

Thio carbamate has the following structural ^{formula, (R 4 R 5 R 6} R 7 N) + Y - ( wherein, R ⁴ and R ⁵ is a group (基consisting of C ₁ -C ₂₅ alkyl and C ₂ -C ₂₅ alkenyl) Independently selected from R ⁶ and R ⁷ are independently selected from the group consisting of C ₆ -C ₂₅ alkyl and C ₆ -C ₂₅ alkenyl, and Y ⁻ is selected from the group consisting of chloride and An aqueous solution of a thiocarbamate salt is reacted with an organohalogen compound in the presence of a catalytic amount of a quaternary ammonium salt with an anion) to prepare a thiocarbamate from the aqueous solution.

Esters of thiocarbamic acid, referred to herein as thiocarbamates, are well known in the art of agrochemicals because of their usefulness and commercial value. Some thiocarbamates are active agents, other thiocarbamates are effective in inhibiting the growth of bacteria, such as bacteria, and others are active pesticides. In addition, thiocarbamate is widely used in combination with other active compounds for a synergistic effect (上昇 作用), and can be applied to various kinds of uses with numerous formations.

Thiocarbamates have the general structure

In this structure, the R- group can be represented by a wide variety of organic radicals. The compound of bimolecular arrangement is called "thiol carbamate" which is a term used interchangeably in chemical literature to call a compound of the same type.

It is an object of the present invention to provide a novel method for the preparation of thiocarbamate, which can achieve improvements in overall yield and process savings. Other objects and benefits of the present invention will become apparent from the following detailed description.

The present invention provides a novel process for preparing compounds known as thiocarbamates. More specifically, the fact that other quaternary ammonium salts do not result in any improvement by the present invention, whereas the use of any kind of quaternary ammonium salts as phase transfer catalysts can greatly improve thiocarbamate production. This was found.

That is, the present invention (a) an aqueous solution of a thiocarbamate salt having the following structural formula [II] in the presence of an organic halide having the following structural formula [III] and a fourth ammonium salt having the catalytic amount of the following structural formula [IV], After reacting, (b) it is related with the manufacturing method of thiocarbamate using the 4th ammonium salt catalyst which has the following structural formula [I] which isolate | separates thiocarbamate from the said aqueous solution.

Wherein R ¹ and R ² are substituted or unsubstituted groups such as C ₁ -C ₁₂ alkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₆ alkynyl, phenyl, C ₇ -C ₁₀ Phenylalkyl, C ₃ -C ₇ cycloalkyl, C ₅ -C ₇ cycloalkenyl, C ₂ -C ₈ alkoxy alkyl, C ₂ -C ₈ alkylthioalkyl, C ₃ -C ₈ alkoxy alkenyl and C ₃ -C ₈ independently selected from groupings consisting of groups such as alkylthioalkenyl, where the substitution consists of halo, cyano, nitro, trifluoromethyl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy Independently selected from the groupings, or R ¹ and R ² together with the nitrogen atom to which they are attached form a member selected from groupings consisting of pyryl, pyridyl and C ₂ -C ₆ polyalkyleneimines And R ³ is a substituted or unsubstituted group such as C ₁ -C ₁₂ alkyl, C ₂ -C ₈ alkenyl, C ₃ -C ₆ alkynyl, phenyl, C ₇ -C ₁₀ phenylalkyl , C ₃ -C ₇ cycloalkyl, C ₅ -C ₇ cycloalkenyl, C ₂ -C ₈ alkylthio-alkyl, C ₃ independently selected from the loop consisting of -C ₈ alkoxy alkenyl and C ₃ -C ₈ alkylthio alkenyl Substituents are independently selected from the group consisting of halo, cyano, nitro, trifluoromethyl, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy.

Wherein R ¹ and R ² are as defined above and M ⁺ consists of alkali or alkaline earth metal ions, R ¹ R ² NH ⁺ ₂ ions and trialkylammonium ions each of which contains 1 to 4 carbon atoms Is a cation selected from the groupings.

R ³ X [III]

Wherein R ³ is as defined above and X is chlorine or nitrogen.

^{(R 4 R 5 R 6 R} 7 N) + Y - [Ⅳ]

Wherein R ⁴ and R ⁵ are independently selected from the groupings consisting of C ₁ -C ₂₅ alkyl and C ₂ -C ₂₅ alkenyl, R ⁶ and R ⁷ are C ₆ -C ₂₅ alkyl and C ₆ -C Independently selected from the grouping consisting of ₂₅ alkenyl, Y ⁻ is an anion selected from grouping consisting of chlorine and thixotropy. Within the scope of the present invention, several embodiments are preferred.

In one of these embodiments, R ¹ , R ² and R ³ are independently selected from the groupings consisting of C ₁ -C ₁₂ alkyl and C ₂ -C ₈ alkenyl, each having one, two or three Optionally substituted with halogen atoms and M ⁺ is an alkali or alkaline earth metal cation.

In another embodiment, R ¹ and R ² are independently C ₁ -C ₁₂ alkyl, R ³ is C ₂ -C ₈ alkenyl and is optionally substituted with one, two or three halogen compound atoms, respectively And M ⁺ is sodium or potassium ions.

In a more preferred embodiment, R ⁴ methyl, R ⁵ is selected from the group consisting of methyl, C ₆ -C ₂₀ alkyl and C ₆ -C ₂₀ alkenyl, and R ⁶ and R ⁷ are C _6- Independently selected from groupings consisting of C ₂₀ alkyl and C ₆ -C ₂₀ alkenyl.

Furthermore, in a more preferred embodiment R ⁴ is methyl, R ⁵ , R ⁶ and R ⁷ are independently C ₆ -C ₁₂ alkyl and Y ⁻ is chloride.

More preferred embodiments will be apparent from the description which follows.

The process for producing thiocarbamate according to the present invention is most conveniently carried out by adding an organic halogen compound to an aqueous solution of thiocarbamate salt. The catalyst may already be present in the reaction mixture, or may be added simultaneously with or immediately after the addition of the organohalogen compound. Since this reaction is exothermic, it is necessary to avoid the sensitive temperature rise by slowly adding a halogen compound according to the amount of each reactant used, its concentration in the reaction mixture and the individual Enthalpy.

There is no critical temperature for this reaction, but temperature control is often desirable. This is because thiocarbamate salts tend to decompose in proportion to rising temperatures. Thus, the operating temperature fluctuation range is determined in consideration of the economics of the process: desired purity, allowable reaction time, and cost for external cooling and product recovery. From the economics of the process it is most convenient to continue the reaction at temperatures between about 0 ° C and 30 ° C. Temperature control can be achieved by external cooling, including coils, jackets and the like.

The stability of the thiocarbamate salt becomes higher when the latter is in an aqueous solution. Use of an aqueous solution is convenient in this step. As explained more fully below, the thiocarbamate salt itself is particularly convenient when produced in such a solution by reaction between amines, carbonylsulfides and bases.

The reaction can proceed with undissolved salts, but it is generally desirable to allow the salts to dissolve sufficiently in the aqueous phase in order to be easier to handle and to enhance the contact of the reactants. The organohalogen compounds are generally insoluble in the aqueous phase or can only be partially dissolved, so the reaction mixture constitutes two liquid phases with a single reactant in each phase. For this reason, the rate of progress of the reaction is very high due to external agitation. The reaction will proceed without such agitation but it is desirable to use some kind of agitation to increase the reaction rate and provide a more uniform temperature to prevent the formation of hot spots in the reaction mixture. Stirring can be supplied by commonly used means, including stirrers, baffle plates in the reaction vessel, stirring towers, and the like.

The organic phase may consist of the organic halogen compound itself or the latter dissolved in an unreactive solvent. Common aliphatic, aromatic or chlorine substituted derivatives thereof are suitable for this purpose. Solvents unsuitable for use for this purpose because of their reactivity with carbonylsulfide include alcohols, amines and mercaptans.

The thiocarbamate salt used in this reaction can be made by any technique well known in the thiocarbamate art. As mentioned above, in the conventional production process, a suitable second amine (R ¹ R ² NH) is reacted with carbonylsulfide and a suitable base. The base used is determined by the thiocarbamate salt required for the final reaction. Thus, the base may be an alkali group, each containing 1 to 4 carbon atoms, or an alkaline earth metal hydroxide and trialkylamine, or the same amine used to form a salt anion, R ¹ R ² NH. Thus, an aqueous solution of amine and base is prepared and gaseous carbonyl sulfide is added thereto.

Carbonyl sulfide is added below the liquid surface to bubbling in solution. The reaction rate for this reaction is very fast and causes an immediate conversion of the reactant which is essentially equivalent to a thiocarbamate salt. Like the salt / halogenated reactions, the amine / COS / base reactions are also exothermic and the decomposition of salts is again a problem. In fact, this problem is of great importance in this reaction. This is because a high concentration of thiocarbamate salt is present for a long time. Therefore, it is desirable to keep the temperature low by external cooling to prevent decomposition as much as possible. In addition to the cooling method described above, the reaction temperature is also controlled by the rate of addition of carbonyl sulfide. There is no critical operating range, but it is most convenient to continue the reaction at a temperature of about 0 ° C. to about 30 ° C., preferably at about 0 ° C. to about 15 ° C.

For maximum amine efficiency it is preferred to conduct the reaction with an excess of carbonyl sulfide and base. The excess is purely a process saving problem such as raw material costs and referral costs, but the reaction is most conveniently done with an excess of up to 100% carbonyl sulfide and an excess of about 20% base.

The present invention can be carried out in a batch operation or continuous operation, or in an operation form combining these two operations. When the present invention is carried out in a batch operation, chemical species will bind to a series of predetermined staircase rows into a single liquid. When a continuous mode of operation is used, the desired reaction rate can be achieved by selecting the appropriate type of agitation, addition rate, feed point and suitable reaction conditions. Which type of process to choose from among the different types of processes to be used depends on the manufacturing conditions required. The reaction vessel is preferably made of a material that does not interfere with the main reaction, that is, a corrosion resistant material such as mild steel.

When the process is complete the thiocarbamate product will remain in the organic phase. Salts precipitated during the reaction can be readily dissolved by the addition of water. The two liquid phases then separate. An organic phase consisting predominantly of thiocarbamate can be made to be used without further purification.

As used herein, "alkyl" refers to a monovalent straight or branched saturated aliphatic hydrocarbon grouping such as methyl, ethyl, propyl, i-propyl "alkenyl" refers to a monovalent straight or branched chain containing at least one double bond, for example allyl, butenyl or butadienyl; Phosphorus aliphatic hydrocarbon groupings;

"Alkynyl" refers to an aliphatic hydrocarbon grouping which is a monovalent straight or branched chain containing at least one triple bond, ie, propargyl or isobutynyl, etc .;

"Phenylalkyl" refers to an alkylgroup as defined above wherein the hydrogen atom is replaced by a phenylgroup such as, for example, benzyl or phenylethyl;

"Cycloalkyl" refers to a monovalent cyclic saturated hydrocarbon such as cyclobutyl or cyclohexyl;

"Cycloalkenyl" refers to a monovalent cyclic hydrocarbon group containing at least one double bond, ie, sclohexenyl;

"Alkoxyalkyl" refers to an alkyl group as defined above wherein the hydrogen atom is substituted by a monovalent straight or branched chain saturated aliphatic hydrocarbooxy group group such as, for example, methoxyethyl or ethoxyethyl;

"Alkylthioalkyl" refers to an alkylgroup as defined above wherein the hydrogen atom is replaced by, for example, a monovalent straight or branched chain saturated aliphatic hydrocarbonbonthio such as methylthioethyl or ethylthioethyl;

"Alkoxyalkenyl" refers to an alkenyl grouping as defined above wherein the hydrogen atom is replaced by a monovalent straight or branched chain saturated aliphatic hydrocarbooxy, for example ethoxy;

"Alkylthioaltenyl" refers to an alkenyl grouping as defined above wherein the hydrogen atom is substituted by a monovalent straight or branched chain saturated aliphatic hydrocarbonthiothio group such as, for example, ethylthiobutenyl. ;

"Halo" refers to chloro, fluoro or bromo; And

"Polyalkyleneimine" refers to a ring of a monovalent saturated heterocyclic, a configuration minutes the ring there is a nitrogen atom and the other constituents are the ring general formula, (CH _{2) n N} are carbon atoms, and ^- a Where n stands for the term such as, for example, aziridinyl (n = 2), pyrrolydyl (n = 4), or piperidyl (n = 5). Indicates the number of carbon atoms indicated here.

All carbon atom limits mentioned herein are intended to include the upper and lower limits thereof.

The terms " alkyllimetal " and " alkylolitometal " respectively refer to elements belonging to the IA and IIA groupings of the Periodic Table of Elements, respectively (chemical chemistry of "Range", McGraw-Hill's tenth edition of 1967). Alkali metals are more preferred than alkaline earth metals and sodium and potassium, particularly sodium, are most preferred among alkali metals.

Examples of thiocarbamate acid esters that may be prepared by the process of the present invention are as follows.

S-ethyl d _i -n-propylthiocarbamate

S-ethyl hexahydro1-H-azepine-1-carbothioate

S-ethyl diisobutylthiocarbamate

S-propyl d _i -n-propylthiocarbamate

S-ethylcyclohexylethylthiocarbamate

S-n-propyl n-butyl ethylthiocarbamate

S-P-chlorobenzyl diethylthiocarbamate

S-2,3,3-trichloroallyl diisopropyl thiocarbamate

336) 및 디메틸디코코암모늄 클로라이드(ALIQUAT

221)가 있다. 이들 두 종류의 촉매는 상업적으로 입수될 수 있는 제품이며 미국 일리노이즈주 캄카키소재 제너럴밀회사 화학부에서 제조되고 있다.Examples of quaternary salts that may be used in the process of the present invention are for example tricapryl methylammonium chloride (ALIQUAT

336) and dimethyldicoammonium chloride (ALIQUAT

221). Both catalysts are commercially available products and are manufactured by the Department of Chemistry, General Mills, Kamkaki, Ill., USA.

The term "captyl" refers to a mixture of straight-chain saturated alkyl groupings having 8 to 10 carbon atoms with significantly higher 8 carbon chains, while "coco" refers to straight chain alkyl groupings having 8 to 18 carbon atoms. Points to mixtures, with 12 to 14 carbon chains, both saturated and unsaturated.

The fourth salt mixture can also be used in the practice of the present invention. In general, (R ⁴ R ⁵ R ⁶ R ⁷ N) ⁺ X ^-a di- or polyfunctional fourth salt in which the same or different substitutional bonds are repeated many times can also be effectively used. have.

The term "catalyst amount" as used herein refers to the amount of the fourth salt that enhances and enhances the progress of the reaction. The amount of the fourth salt usually ranges from about 0.2 to 5.0% of the weight of the reaction mixture, with about 0.2 to 5.0% by weight being preferred.

The following specific examples describe the preparation of thiocarbamates by the method of the present invention. These examples are included for illustrative purposes only, and should not be construed to exceed any limitation on the scope of the invention described herein. Such limitations are set forth in the appended claims.

Example 1

, 제너럴 및 회사)를 사용했으며, 그리고 세번째 방법에서는 촉매로서 벤질트리에틸암모늄 클로라이드를 사용하였다. 이 촉매들은 제각기 제 4 암모늄 염이지만서도 다만 트리카프릴메틸 암모늄 클로라이드만이 본원 발명의 특허청구의 범위 안에 든다. 본원 발명으로부터 벤질트리에틸 암모늄 클로라이드가 제외된 것은 위에서 설명된 R⁴,R⁵,R⁶및 R⁷그루우프의 정의를 검토하면 쉽게 이해될 수 있다.This example describes three methods for the preparation of S-2,3,3-trichloroallyl diisopropylthiocarbamate: ie, no catalyst was used in the first method and tri-catalyst in the second method. Captylmethylammonium chloride (ALIQTAT 336

, General and Company), and benzyltriethylammonium chloride as catalyst in the third method. These catalysts are each quaternary ammonium salts, but only tricaprylmethyl ammonium chloride falls within the scope of the claims of the present invention. The exclusion of benzyltriethyl ammonium chloride from the present invention can be readily understood by reviewing the definitions of R ⁴ , R ⁵ , R ⁶ and R ⁷ groupings described above.

)는 미국 일리노이즈주 칸카키 소재 제너럴 및 회사화학부의 제품이다. "카프릴"이란 용어는 8개의 탄소쇄가 월등히 많은 8~10 탄소원자를 지닌 직쇄포화알킬그루우프의 혼합물을 가르킨다.Tricaprylmethylammonium chloride (ALIQUAT 336

) Is a product of the General and Corporate Chemistry of Kankaki, Illinois, USA. The term " capryl " refers to a mixture of straight-chain saturated alkyl groupings having 8 to 10 carbon atoms with a lot of 8 carbon chains.

The processes in all three manufacturing methods were the same. A mixture of 31.9 g (0.315 mole) diisopropylamine, 12 g (0.300 mole) sodium hydroxide and 100 cubic cm (Cc) water was prepared. The mixture was placed in an ice fath with constant stirring, where the thermometer was held at 2 ° C.-6 ° C. while 20 g (0.330 mole) of carbonyl sulfide bubbling below the liquid surface. By adding carbonyl sulfide to the mixture, the thiocarbamate salt formed in situ was allowed to react with 54.0 g (0.300 mole) of 1,1,2,3-tetrachloro-1-propene. When a catalyst was used it was added immediately following the addition of tetraclopropene. When a tricaprylmethammonium chloride catalyst was used, tetrachloropropene was added as a solution in 20CC methylene chloride. When benzyltriethylammonium chloride was used, tetrachloropropene was added as a solution in benzene at 100 CC. In the above cases, 0.50 g of catalyst were used, respectively.

The mixture was kept in the ice bath for a few more hours following the addition of tetrachloropropene and catalyst. Samples of the mixture were analyzed by gas chromatography at various time intervals, and the analysis results are shown in Table 1. Examining these results shows that tricaprylmethylammonium chloride (catalyst A) is much faster in reaction rate than was achieved without the use of a catalyst. Benzyltriethylammonium chloride (catalyst B) showed a slight improvement in the beginning, but after 90 minutes of reaction time, the improvement of the reaction rate could not be maintained. The conversion was actually behind what was achieved without the use of a catalyst. These analytical results clearly show an unexpected improvement in the reaction rate achieved using the method of the present invention.

After sifting the final sample, the mixture was transferred from the ice bath and stirred overnight to room temperature. The biphasic mixture was then diluted with an organic solvent to separate the phases. The organic phase was then washed with diluted aqueous hydrochloric acid, dried over magnesium sulfate and concentrated by rotary evaporator to yield the title compound. The molecular structure of this product was confirmed by nuclear magnetic resonance (NMR) and mass spectrometry.

TABLE 1

Preparation of S-2,3,3-trichloroallyl diisopropyl thiocarbamate

(a) The reaction time was measured from the time when the halogen compound (1,1,2,3-tetrachloro-1-propene) was added.

(b) The results presented were normalized to show only thiocarbamate products and unreacted halogen compounds.

)이다.(c) Catalyst A is tricaprylmethylammonium chloride (ALIQUAT 336

)to be.

(d) Catalyst B is benzyltriethylammonium chloride (purity 97%).

Example 2

, 제너럴 및 회사)를 사용하였다.This example describes two preparations of S-2,3-dichloroaltyldiisopropylthiocarbamate: ie, no catalyst was used at the first and tricaprylmethylammonium chloride (ALIQUAT) as the catalyst at the second. 336

, General and Company).

The procedure carried out in these two preparation methods was carried out in 1 above, except that 1,2,3-trichloropropene was used instead of 1,1,2,3-tetrachloro-1-propene. Same as described. The results obtained by gas chromatography are shown in Table 2. Examining the numbers shown in Table 2 as in Table 1 it can be clearly seen that a large improvement in the reaction rate is achieved by using a catalyst within the scope of the present invention.

TABLE 2

Preparation of S-2,3-Dichloroaltyl Diisopropyl Thiocarbamate

(a) The reaction time was measured from the time when the halogen compound (1,1,2,3-tetrachloro-1-propene) was added.

(b) The results presented were normalized to show only thiocarbamate products and unreacted halogen compounds.

)이다.(c) Catalyst A is tricaprylmethylammonium chloride (ALIQUAT 335

)to be.

Claims (1)

After an aqueous solution of a thiocarbamate salt having the following structural formula [II] was reacted in the presence of an organic halide having the following structural formula [III] and a quaternary ammonium salt having the catalytic amount of the following structural formula [IV], The manufacturing method of thiocarbamate using the quaternary ammonium salt catalyst which has the following structural formula [I] formed by isolate | separating carbamate.

Wherein R ¹ , R ² and R ³ are independently selected from the grouping consisting of C ₁ -C ₁₂ alkyl and C ₂ -C ₈ alkenyl optionally substituted with 1, 2 or 3 atoms.

Wherein R ¹ and R ² are as defined above and M ⁺ is sodium or potassium ion. R ³ X [III] Wherein X is chlorine or cancelled. ^{(R 4 R 5 R 6 R} 7 N) + Y - [Ⅳ] Wherein R ⁴ and R ⁵ are independently selected from the groupings consisting of C ₁ -C ₂₅ alkyl and C ₂ -C ₂₅ alkenyl, R ⁶ and R ⁷ are C ₆ -C ₂₅ alkyl and C ₆ -C Independently selected from the grouping consisting of ₂₅ alkenyl, Y ⁻ is an anion selected from grouping consisting of chlorine and cancellation.