JP5918678B2 - Method for producing dibenzyltrithiocarbonate derivative - Google Patents

Description

    The present invention relates to a method for producing a dibenzyltrithiocarbonate derivative.

  Conventionally, a polymer having a hydroxy group at a terminal is used as a crosslinking agent by using a compound having a functional group capable of reacting with the hydroxy group, for example, a functional group such as isocyanate, carboxyl and ester, as a crosslinking agent. It is known that cross-linking can be formed and a functional material having excellent heat resistance, water resistance, weather resistance, durability, compatibility and the like can be obtained.

  In particular, when functional groups are introduced at both ends of the polymer, chain extension occurs efficiently by crosslinking between the ends, and a linear or network high molecular weight polymer can be formed depending on the crosslinking agent used. A resin that exhibits excellent tensile strength and elongation can be obtained.

In JP 2007-23094 7 is described for the synthesis of dibenzyl trithiocarbonate derivatives (Patent Document 1). For example, bis [4- [N-ethyl-2- (hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate of the following formula (1) is composed of N-ethyl-ethanolamine of the following formula (3) and the following general formula: The amide derivative hydroxide represented by the following general formula (4) is condensed with 4-chloromethylbenzoyl chloride (2). Next, after protecting the hydroxyl group of the general formula (4) with an acetyl group, it is condensed with carbon disulfide / potassium carbonate, and then deacetylated with potassium hydroxide to give a general formula (1). In an overall yield of 72%.

JP 2007-230947 A

  However, in the above method, since the acetylate which is not necessary for the final target product is passed, the reaction process is long, and further, purification by column chromatography is required in 3 steps out of all 4 steps. There was a problem in terms of manufacturing cost.

  In view of the above problems, an object of the present invention is to provide a method for efficiently producing a high-purity dibenzyltrithiocarbonate derivative in a short process.

As a result of intensive studies to solve the above problems, the present inventors have found a method for producing a dibenzyltrithiocarbonate derivative in a high yield by all two steps that do not require purification by column chromatography.
That is, the present invention provides a dibenzyltrithiocarbonate characterized by reacting a compound represented by the general formula (4) with a trithiocarbonate prepared at the time of use to obtain a dibenzyltrithiocarbonate of the general formula (1). The manufacturing method of the thiocarbonate derivative was discovered.

Thus, according to the present invention, the general formula (4):
[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]
The amide compound represented by general formula (1) is characterized by reacting with a trithiocarbonate in an amide solvent to form a trithiocarbonate.

[Wherein Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, and R ₂ represents a (C ₂ -C ₄ ) alkylene group]
A method for producing a dibenzyltrithiocarbonate derivative represented by the formula:

According to the present invention, the general formula (4):
[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]
An amide compound represented by the following general formula (2):

[Wherein Ar represents a phenylene or naphthylene group, and X represents a halogen atom]
A compound represented by formula (3):

[Wherein R ₁ represents a (C ₁ -C ₄ ) alkyl group, and R ₂ represents a (C ₂ -C ₄ ) alkylene group]
The above-mentioned production method is provided, which is obtained by reacting a compound represented by formula (I) in the presence of a base.

Further, according to the present invention, the trithiocarbonate conversion is carried out by converting the trithiocarbonate in the amide solvent to the general formula (4):
[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]
The said manufacturing method performed by dripping at the compound represented by is provided.

Also according to the present invention, the trithiocarbonate is represented by the following formula:
[Wherein M represents an alkali metal such as lithium, sodium, potassium, rubidium or cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium or barium]
Selected from the group consisting of lithium trithiocarbonate, sodium trithiocarbonate, potassium trithiocarbonate, rubidium trithiocarbonate, cesium trithiocarbonate, beryllium trithiocarbonate, magnesium trithiocarbonate, calcium trithiocarbonate, strontium trithiocarbonate and barium trithiocarbonate. The above manufacturing method is provided.

  According to the invention, the amide compound is obtained in the presence of triethylamine, tributylamine, pyridine, dimethylaminopyridine, and the trithiocarbonate is used as a mixed solution of water and N, N-dimethylacetamide. The above manufacturing method is provided.

  Therefore, according to the present invention, a method for efficiently producing a high-purity dibenzyltrithiocarbonate derivative in a short process is provided.

It is IR spectrum of N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide. It is an IR spectrum of bis [4- [N-ethyl-2- (hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate. ^{1 is} a ¹ H-NMR spectrum of N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide. ¹ H-NMR spectrum of bis [4- [N-ethyl-2- (hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate

The dibenzyltrityl carbonate derivative of the general formula (1) according to the present invention can be produced according to the following reaction scheme.
[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]

  Ar in the general formula (2) includes a phenylene group and a naphthylene group, and X includes a halogen atom, that is, a fluorine, chlorine, bromine, and iodine atom. From this point of view, Ar is preferably a phenylene group, and X is preferably a chlorine atom.

Ar and X in the above general formula (3) and / or (4) are as defined in the above general formula (2), and R ₁ is ethyl, n-propyl, isopropyl, n-butyl and t. -Butyl group is mentioned, As R < ₂ >, ethylene, propylene, and a butylene group are mentioned.

  Step 1 described above is a reaction in which the compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted to obtain the compound represented by the general formula (4).

  The above step 1 can be performed by using only the compound represented by the general formula (2) and 2 equivalents or more of the compound represented by the general formula (3). By using an organic or inorganic base, the amount of the compound represented by the general formula (3) is almost the theoretical amount, and reaction by-products can be suppressed, and the production cost can be reduced.

Examples of the organic base that can be used in Step 1 above include tertiary amines such as triethylamine, tributylamine, pyridine, and dimethylaminopyridine.
Examples of the inorganic base include sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.

  Solvents that can be used in Step 1 above are water, diethyl ether, dioxane, tetrahydrofuran, dimethoxyethane, methyl ethyl ketone, acetonitrile, propionitrile, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide. , Inert solvents such as N-methylpyrrolidinone and aprotic polar solvents such as dimethyl sulfoxide or aprotic nonpolar solvents such as benzene and toluene or the resulting mixed solvents.

  The reaction in the above step 1 is preferably, for example, anhydrous tetrahydrofuran or toluene among the above solvents, and the reaction temperature can be carried out with stirring at a temperature in the range of -20 to 50 ° C, preferably 0 to 30 ° C. .

After the completion of the reaction, the post-treatment of the above step 1 is performed by adding a saline solution to the reaction mixture for liquid separation, drying the organic layer by a conventional method, and concentrating under reduced pressure. In addition, when the liquid separation by addition of the saline solution to the reaction product is not easy, a saturated saline solution can be used.
The concentration of the saline solution to be used is not particularly limited. However, since the yield decreases as the concentration of the saline solution decreases, the saline concentration is preferably 10 to 20%, more preferably 15 to 20%, but saturation. Saline may be used. The amount of saline used is 0.5 to 5 times the amount of the reaction product to be added, preferably 0.8 to 2 times, and the organic layer is preferably washed once or twice. It is preferable that the desired product can be obtained almost quantitatively by extracting with an organic solvent again.
By repeating the extraction after completion of the above reaction 2-3 times, the target compound represented by the general formula (4) can be obtained almost quantitatively in a yield of 98% to 99%. This is one of the features of the present invention.

  Although the reaction of the above step 1 can proceed to the next step without post-treatment, it is possible to reduce the reaction rate in the above step 2 or decrease the yield of the target product due to the formation of reaction by-products. Therefore, it is preferable to perform post-processing.

  The compound represented by the general formula (4) obtained in the above step 1 can be purified by a conventional method such as distillation, recrystallization or column chromatography, but this compound is crystallized after concentration of the reaction under reduced pressure. Purification by recrystallization is simple and preferable.

  Examples of the recrystallization solvent for the compound represented by the general formula (4) obtained in Step 1 above include diethyl ether, dioxane, tetrahydrofuran, dimethoxyethane, methyl ethyl ketone, acetonitrile, propionitrile, ethyl acetate, butyl acetate, N, Aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethyl sulfoxide or aprotic polar solvents such as methanol, ethanol and isopropyl alcohol, aprotic and nonpolar such as benzene and toluene An inert solvent such as a solvent can be mentioned, and toluene and ethyl acetate are preferable from the viewpoint of the yield of the target product.

  Step 2 is a reaction for obtaining a compound represented by the general formula (1) by reacting the compound represented by the general formula (4) with a trithiocarbonate.

  Examples of the trithiocarbonate used in Step 2 above include lithium trithiocarbonate, sodium trithiocarbonate, potassium trithiocarbonate, rubidium trithiocarbonate, cesium trithiocarbonate, beryllium trithiocarbonate, magnesium trithiocarbonate, calcium trithiocarbonate, strontium trithiocarbonate and Examples include barium trithiocarbonate.

From the viewpoint of reactivity, potassium trithiocarbonate, sodium trithiocarbonate and lithium trithiocarbonate are preferred. Of these, potassium trithiocarbonate is preferable from the viewpoint of reactivity and availability.
A commercial item can be used for said trithiocarbonate.

  Trithiocarbonate can also be prepared and used. In that case, an alkali metal sulfide such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide or cesium sulfide, or an alkaline earth metal sulfide alkali metal sulfide such as beryllium sulfide, magnesium sulfide, calcium sulfide, strontium sulfide or barium sulfide. It may be prepared by adding carbon disulfide to an ethanol solution or an aqueous solution.

Further, instead of using the alkali metal sulfide or alkaline earth metal sulfide, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide, or beryllium hydroxide, water An alkaline earth metal hydroxide such as magnesium oxide, calcium hydroxide, strontium hydroxide or barium hydroxide can also be used, but potassium hydroxide is preferred from the viewpoint of the yield of the target product and production cost.
In this case, trithiocarbonate can be prepared by reacting the above alkali metal hydroxide or alkaline earth metal hydroxide with carbon disulfide in a solvent.

  Solvents that can be used for the preparation of the trithiocarbonate in Step 2 above include aprotic polar solvents such as water, tetrahydrofuran, N, N-dimethylacetamide, N-methylpyrrolidine and dimethylsulfoxide, or methanol, ethanol, isopropyl alcohol and the like. Examples thereof include an inert solvent such as a protic polar solvent, an aprotic nonpolar solvent such as benzene and toluene, or a mixed solvent thereof. N, N-dimethylacetamide is preferred from the viewpoint of the yield of the target product.

  The amount of N, N-dimethylacetamide and water used for the preparation of the trithiocarbonate in Step 2 above is not particularly limited, but from the viewpoint of the yield of the desired product in the trithiocarbonylation reaction, the general formula (4 ) To 0.5 to 4 times the weight, preferably 1.0 to 3.0 times the weight, and more preferably 1.0 to 1.5 times the weight of the compound represented by).

  The molar ratio of potassium hydroxide used for the preparation of the trithiocarbonate in the above step 2 is 1.0 to 3.0 times mol, more preferably 1.5 to the compound represented by the general formula (4). -2.0 times mol is more preferable.

  The molar ratio of carbon disulfide used for the preparation of the trithiocarbonate in the above step 2 is 1.0 to 3.0 times the mole, and further 1. for the compound represented by the general formula (4). 5 to 2.25 moles are more preferable, and 1.0 to 2.0 moles, and even more preferably 1.0 to 1.5 moles with respect to potassium hydroxide.

The preparation temperature of the trithiocarbonate in the above step 2 can be carried out at a temperature in the range of 0 ° C. to 40 ° C., and more preferably at a temperature in the range of 30 to 40 ° C.
The produced trithiocarbonate can be used for trithiocarbonylation by concentrating the reaction solution under reduced pressure by concentrating the reaction solution, but preferably it is used as it is without producing the trithiocarbonate reaction solution prepared at the time of use. One feature of the present invention is that it can be used for trithiocarbonylation.

  Solvents that can be used for the trithiocarbonylation in Step 2 above include aprotic polar solvents such as tetrahydrofuran, ethyl acetate, butyl acetate, dimethoxyethane, N, N-dimethylacetamide, N-methylpyrrolidine and dimethylsulfoxide, or Examples include inert solvents such as protic polar solvents such as methanol, ethanol and isopropyl alcohol, and aprotic nonpolar solvents such as benzene and toluene. Tetrahydrofuran is preferred because of the yield of the target product and ease of operation. .

  As the reaction method of the trithiocarbonylation in the above step 2, a method in which a trithiocarbonate solution is dropped from the viewpoint of yield of the target product and ease of operation is preferable.

  In the trithiocarbonylation in the above step 2, it is preferable to add the water used after the addition of the trithiocarbonate solution after the addition of the trithiocarbonate solution. When water is added first, the production of the side reaction product is promoted, leading to a decrease in the yield of the target product. By adding water after the end of the addition of the trithiocarbonic acid solution, generation of side reaction products can be suppressed. The amount of water added after the above is not particularly limited, but from the viewpoint of operability and efficiency, it is used in an amount of 1 to 10 times, more preferably 2 to 5 times the weight of the compound represented by the general formula (2). It is preferred that

  The dropping temperature of trithiocarbonate and the reaction temperature of trithiocarbonylation in the above step 2 can be carried out at a temperature in the range of 0 to 40 ° C, preferably 0 to 20 ° C, more preferably 0 to 10 ° C. Is more preferable.

As a post-treatment method for the trithiocarbonylation in the above step 2, the reaction solution separated into two layers is separated, the organic layer is washed with an aqueous ammonium chloride solution and a saline solution, dried, and the solvent is distilled off. Thus, a crude product of the target product is obtained.

  The concentration of the aqueous ammonium chloride solution used for the post-treatment in Step 2 above is not particularly limited, but the amount of ammonium chloride used is 1.0 to 2.0 with respect to the metal hydroxide used in Step 2 above. It is preferably used in an amount of 1.0 to 1.2 mol, and the concentration of the aqueous ammonium chloride solution is 5 to 29%, more preferably 15 to 25%, and 1 to 5 times the amount of the organic layer to be washed. It is preferably used, and more preferably 1 to 2 times the amount.

  The amount and concentration of the saline used for the post-treatment in Step 2 above can be the same as that used in Step 1 above.

The crude product obtained in the above step 2 can be purified and used by a conventional method such as distillation, recrystallization or column chromatography, but this compound is crystallized after concentration of the reaction under reduced pressure. Purification is convenient and preferred.
As the solvent used for purification by recrystallization in the above step 2, the solvent used for recrystallization of the compound represented by the general formula (4) obtained in the above step 1 can be similarly used.

  Therefore, the present invention reacts as it is with the trithiocarbonate prepared by reacting the compound represented by the general formula (4) with carbon disulfide and a metal hydroxide in the production method of the general formula (1). It is also a feature of the present invention that the compound represented by the general formula (1) can be obtained.

  The dibenzyltrithiocarbonate derivative according to the present invention can be used for RAFT polymerization.

Example 1
Production of N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide 14.8 g (166 mmol) of N-ethylaminoethanol in a 500 mL three-necked flask equipped with a stirrer, reflux condenser and dropping funnel Then, 17.7 g (175 mmol) of triethylamine and 210 g of toluene were added, and a solution of 30 g (159 mmol) of 4-chloromethylbenzoyl chloride in 30 g of toluene was added dropwise with stirring while keeping the reaction solution at 0 to 20 ° C. Stir for 1 hour. The operation of adding 120 g of 10% saline and separating the solution after warming was repeated twice. The separated saline was extracted with toluene, the combined toluene solution was dried by a conventional method, and the solvent was distilled off. Thus, 37.9 g (yield 99%) of the title compound was obtained as white crystals.

¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.15 (3 H, m, CH ₃ ), 3.33 (2 H, m, CH ₂ CH ₃ ), 3.59 (1 H, s, OH), 3.70 (2 H, m, CH ₂ CH ₂ O), 3.89 (2 H, m, CH ₂ CH ₂ O), 4.60 (2 H, s, CH ₂ Cl), 7.40-7.43 (4 H, ArH).
IR (KBr) (cm ^-1 ): 3386, 1601, 1464, 1272, 1156, 1064, 1021.

Example 2
Production of N-methyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide Using 12.5 g of N-methylaminoethanol in place of N-ethylaminoethanol in Example 1, completely the same as in Example 1 Similarly, 35.15 g (93% yield) of the title compound was obtained.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 1.

Example 3
Production of N-propyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide Using 17.1 g of N-propylaminoethanol in place of N-ethylaminoethanol in Example 1, completely the same as in Example 1 Similarly, 39.9 g (yield 94%) of the title compound was obtained.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 1.

Example 4
Production of N-methyl-N- (3-hydroxypropyl) -4- (chloromethyl) benzamide Exactly the same as in Example 1 except that 14.8 g of N-methylaminopropanol was used instead of N-ethylaminoethanol in Example 1. Thus, 38.1 g (yield 95%) of the title compound was obtained.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 1.

Example 5
Production of N-ethyl-N- (4-hydroxybutyl) -4- (chloromethyl) benzamide Using 19.5 g of N-ethylaminobutanol in place of N-ethylaminoethanol in Example 1, exactly the same as Example 1 Thus, 40.8 g (yield 91%) of the title compound was obtained.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 1.

Example 6
Preparation of bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate 14.2 g of potassium hydroxide in a 200 mL three-necked flask equipped with a stirrer, reflux condenser and dropping funnel (254 mmol) and 30 g of water were added, and 20.6 g (270 mmol) of N, N-dimethylacetamide in 20.6 g (270 mmol) of carbon disulfide was added while stirring the reaction solution at 0 to 5 ° C., followed by stirring at the same temperature for 0.5 hour. . The mixture was further stirred at 25 ° C. for 1 hour and at 40 ° C. for 2 hours to obtain a potassium trithiocarbonate solution.

  Separately, in a 500 mL three-necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 36.4 g (150.6 mmol) of N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide, 180 g of tetrahydrofuran and toluene 45 g was added, and the above trithiocarbonate solution was added dropwise while maintaining the reaction solution at 0 to 5 ° C. After the dropwise addition, the mixture was stirred at the same temperature. After 0.5 hour, 90 g of water was added, and the mixture was further stirred for 19 hours. The reaction solution was separated and further washed successively with 23% aqueous ammonium chloride solution 60 g and 10% brine 60 g. Dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified with 60 g of ethyl acetate to obtain 34.5 g of the title compound (yield: 87.8%, total yield of all 2 steps: 87.0%) as pale yellow crystals.

¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.15-1.25 (6 H, m, CH ₃ ), 3.33 (4 H, m, CH ₂ CH ₃ ), 3.65 (2 H, s, OH) , 3.70 (4 H, m, CH ₂ CH ₂ O), 3.89 (4 H, m, CH ₂ CH ₂ O), 4.64 (4 H, s, CH ₂ S), 7.37 (8 H, m, ArH) .
IR (KBr) (cm ⁻¹ ): 3389, 1602, 1460, 1302, 1241, 1071, 1018.

Example 7
Preparation of bis [4- [N-methyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl in Example 6 ) Using 35.2 g of N-methyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide instead of benzamide, the same procedure as in Example 6 was carried out, and 33.1 g of the title compound (2 step yield: 81%) Got.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 6.

Example 8
RAFT polymerization of butyl acrylate using bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate 100 mL 3 equipped with stirrer, reflux condenser and nitrogen inlet In a neck flask, 2.0 g (3.90 mmol) of bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate obtained in Example 2 and 20.0 g of butyl acrylate (156.0 mmol) and 56.0 mg (0.19 mmol) of VA-086 were added, and after degassing under reduced pressure, the gas was replaced with nitrogen gas, followed by stirring at 110 ° C. for 24 hours under a nitrogen stream. After completion of the reaction, the reaction was stopped by cooling to room temperature.

The molecular weight (M _n ) and molecular weight distribution (M _w / M _n ) of the obtained polymer were analyzed by gel permeation chromatography (GPC). As a result of analysis in terms of polystyrene, the polymer obtained had a molecular weight (M _n ) of 4,949 and a molecular weight distribution (M _w / M _n ) of 1.19.

Example 9
RAFT polymerization of styrene using bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate 100 mL three-necked flask equipped with stirrer, reflux condenser and nitrogen inlet Bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate obtained in Example 2 2.0 g (3.84 mmol), styrene 20.0 g (192.0 mmol) and VA −086 55.4 mg (0.19 mmol) was added, degassed under reduced pressure, and then purged with nitrogen gas, followed by stirring at 110 ° C. for 24 hours under a nitrogen stream. After completion of the reaction, the reaction was stopped by cooling to room temperature.

The molecular weight (M _n ) and molecular weight distribution (M _w / M _n ) of the obtained polymer were analyzed by gel permeation chromatography (GPC). As a result of analysis in terms of polystyrene, the polymer obtained had a molecular weight (M _n ) of 4,989 and a molecular weight distribution (M _w / M _n ) of 1.17.

Comparative Example 1
Production of bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate In conformity with Example 3 of JP-A-2007-230947.
To a 200 mL three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel was added 6.29 g (45.5 mmol) of potassium carbonate and 28 mL of N, N-dimethylformamide, and 3.46 g (45.5 mmol) of carbon disulfide was added thereto. In addition, the mixture was stirred at 50 ° C. in an oil bath. After 15 minutes, a solution of N-ethyl-N- (2-acetoxyethyl) -4- (chloromethyl) benzamide 10 g (41.4 mmol) in N, N-dimethylacetamide 35 mL was added, and the mixture was further stirred at 50 ° C. for 24 hours. .

The reaction solution was added to 200 mL of cold water to stop the reaction, and extracted twice with 200 mL of ethyl acetate. The combined organic layers were washed sequentially with 200 mL of water and 100 mL of saturated brine, and then dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent according to a conventional method was purified by silica gel column chromatography (filler: Merck 7734 100 g, eluent: ethyl acetate) to give 5.75 g (yield 53.4%) of the title compound. ) Was obtained as pale yellow crystals.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 6.

Comparative Example 2
Preparation of bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate The solvent used in preparing the trithiocarbonate solution was changed from N, N-dimethylacetamide to tetrahydrofuran. Except for the changes, the reaction and post-treatment methods were exactly the same as in Example 1 and Example 6, and 10 g of N-ethyl-N- (2-hydroxyethyl) -4- (chloromethyl) benzamide was used as a crude product. Got. Since the obtained crude product was difficult to purify by recrystallization, it was purified by column chromatography (filler: Merck 7734 100 g, eluent: ethyl acetate) to give the title compound (3. 73 g) was obtained with a yield of 34.6%.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 6.

Comparative Example 3
Production of bis [4- [N-ethyl-N- (2-hydroxyethyl) aminocarbonyl] -benzyl] trithiocarbonate In the reaction method, from the method of adding a trithiocarbonate solution dropwise to the trithiocarbonate solution, N-ethyl Except for changing to the method of adding -N- (2-hydroxyethyl) -4- (chloromethyl) benzamide, the reaction and post-treatment methods were exactly the same as in Example 6, and N-ethyl-N- (2- A crude product was obtained using 10 g of hydroxyethyl) -4- (chloromethyl) benzamide. Since the obtained crude product was difficult to purify by recrystallization, it was purified by column chromatography (filler: Merck 7734 100 g, eluent: ethyl acetate) to give the title compound (6. 52 g) was obtained with a yield of 60.5%.
The structure of the obtained compound was confirmed by IR spectrum and ¹ H-NMR spectrum in the same manner as in Example 6.

  According to the present invention, an efficient and high-yield production method of a dibenzyltrithiocarbonate derivative is provided.

Claims (5)

Trithiocarbonate in an amide solvent is represented by the general formula (4):

[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]
In dropwise to represented by the amide compound, characterized by trithiocarbonate of the formula (1):

[Wherein Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, and R ₂ represents a (C ₂ -C ₄ ) alkylene group]
A process for producing a dibenzyltrithiocarbonate derivative represented by the formula: General formula (4):

[Wherein, Ar represents a phenylene or naphthylene group, R ₁ represents a (C ₁ -C ₄ ) alkyl group, R ₂ represents a (C ₂ -C ₄ ) alkylene group, and X represents a halogen atom]
An amide compound represented by the following general formula (2):

[Wherein Ar represents a phenylene or naphthylene group, and X represents a halogen atom]
A compound represented by formula (3):

[Wherein R ₁ represents a (C ₁ -C ₄ ) alkyl group and R ₂ represents a (C ₂ -C ₄ ) alkylene group], and is obtained by reacting in the presence of a base. The manufacturing method according to claim 1. The trithiocarbonate has the following formula:

[Wherein M represents an alkali metal such as lithium, sodium, potassium, rubidium or cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium or barium]
Selected from the group consisting of lithium trithiocarbonate, sodium trithiocarbonate, potassium trithiocarbonate, rubidium trithiocarbonate, cesium trithiocarbonate, beryllium trithiocarbonate, magnesium trithiocarbonate, calcium trithiocarbonate, strontium trithiocarbonate and barium trithiocarbonate. The manufacturing method according to claim 1 or 2 . The production method according to any one of claims 1 to 3 , wherein the amide compound is obtained in the presence of triethylamine, tributylamine, pyridine, or dimethylaminopyridine. The production method according to any one of claims 1 to 4 , wherein the trithiocarbonate is used as a mixed solution of water and N, N-dimethylacetamide.