JP2014210738A - Dibenzyl trithiocarbonate derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dibenzyl trithiocarbonate derivative having various functional groups at both terminals of the molecule and to provide a method for producing the same.SOLUTION: There is provided a dibenzyl trithiocarbonate derivative represented by the following general formula (1): wherein, Ar is a phenylene group or a naphthylene group; R is an acetoxy group, a hydroxy group, a hydroxymethyl group, or a methoxycarbonyl group having a substituent represented by the formula, -C(O)-O-CH-R(wherein, Ris a Cto Calkyl or a Cto Calkenyl group having a substituent). There is provided a method for producing a dibenzyl trithiocarbonate derivative represented by the general formula (1) in which a compound represented by the formula (3) (wherein X is a halogen atom) is reacted with a trithiocarbonate in an amide-based solvent to trithiocarbonate.

Description

  The present invention relates to a dibenzyltrithiocarbonate derivative and a method for producing the same. More specifically, the present invention relates to a dibenzyltrithiocarbonate derivative useful as a RAFT polymerization reagent having a reactive functional group at both ends of a molecule and a method for producing the same.

  A polymer having a hydroxy group at the terminal is crosslinked with a hydroxy moiety of the polymer by using a functional group capable of reacting with the hydroxy group, for example, a compound having a functional group such as an isocyanate or a carboxyl group and an ester as a cross-linking agent. Can be formed.

Similarly, a polymer having an epoxy group at the terminal can be crosslinked by using a compound having a functional group capable of reacting with the epoxy group, for example, a functional group such as an amine, an alcohol, or a carboxyl group, as a crosslinking agent. Can be formed.
And it is conventionally known that the obtained crosslinked polymer can be a functional material having excellent heat resistance, water resistance, weather resistance, durability, compatibility and the like.

  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.

  Patent Document 1 describes a dibenzyltrithiocarbonate derivative and a synthesis method thereof, but the above method is limited to a compound having an amide skeleton.

JP 2007-230947 A

  An object of the present invention is to provide a dibenzyltrithiocarbonate derivative useful as a RAFT polymerization reagent having various functional groups at both ends of a molecule and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found a dibenzyltrithiocarbonate derivative useful as a RAFT polymerization reagent having various functional groups at both ends of the molecule and a simple production method thereof. Completed the invention.

Thus, according to the present invention, the following general formula (1):
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is a substituted represented by C ₁ -C a ₅ alkyl or C ₂ -C ₅ alkenyl group) having a group, a methoxy carbonyl group having a substituent]
The dibenzyltrithiocarbonate derivative represented by these is provided.

According to the invention, R in the general formula (1) is a methoxycarbonyl group having a substituent, and the following general formula (2):
[In the formula, Ar represents a phenylene or naphthylene group, R ₁ represents a C ₁ -C ₅ alkyl group having a hydroxy group at the terminal, a C ₂ -C ₅ alkyl group having a hydroxy group at the terminal and its adjacent position, between terminal and their adjacent position represent a C ₂ -C ₅ alkyl group having epoxy C ₂ -C ₅ alkenyl group or terminal and its adjacent position having a double bond]
The said dibenzyl trithiocarbonate derivative represented by these is provided.

According to the invention, R in the general formula (1) is a methoxycarbonyl group having a substituent, Ar represents a phenylene group, and R ₁ is a C ₁ -C having a hydroxy group at the terminal. ₃ alkyl group, C ₂ -C ₃ alkyl group having a hydroxy group at the terminal and its adjacent position, C ₂ -C ₃ alkenyl group having a double bond between the terminal and its adjacent position, or epoxy at the terminal and its adjacent position a C ₂ -C ₃ alkyl radical having the dibenzyl trithiocarbonate derivative.

According to the invention, R in the general formula (1) is a methoxycarbonyl group having a substituent, Ar is a phenylene group, R ₁ is hydroxymethyl, 2-hydroxyethyl, 1,2 -The dibenzyltrithiocarbonate derivative is provided which is a dihydroxyethyl, vinyl or epoxy group.

Furthermore, according to the present invention, the following general formula (3):
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is A methoxycarbonyl group having a substituent represented by C ₁ -C ₅ alkyl or a C ₂ -C ₅ alkylene group having a substituent, and X is a halogen atom]
The compound represented by general formula (1) is characterized by reacting with a trithiocarbonate in an amide solvent to form a trithiocarbonate.

[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is represented by a is) C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a substituent group, a methoxy group having a substituent]
The manufacturing method of the dibenzyltrithiocarbonate derivative represented by these is provided.

Moreover, according to the present invention, R in the general formula (1) is a methoxycarbonyl group having a substituent, and the following general formula (4):
[Wherein Ar is a phenylene or naphthylene group, and X is a halongen atom]
A compound represented by formula (5):

[Wherein R ₁ is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a substituent]
A general formula (6) obtained by reacting an alcohol compound represented by general formula (6):
[Wherein Ar is a phenylene or naphthylene group, R ₁ is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a substituent, and X is a halogen atom]
The ester compound represented by the formula (2) is characterized by reacting with a trithiocarbonate in an amide solvent to form a trithiocarbonate.

[In the formula, Ar represents a phenylene or naphthylene group, R ₁ represents a C ₁ -C ₅ alkyl group having a hydroxy group at the terminal, a C ₂ -C ₅ alkyl group having a hydroxy group at the terminal and its adjacent position, between terminal and their adjacent position represent a C ₂ -C ₅ alkyl group having epoxy C ₂ -C ₅ alkenyl group or terminal and its adjacent position having a double bond]
The manufacturing method of the dibenzyltrithiocarbonate derivative represented by these is provided.

  According to the invention, the ester 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.

According to the present invention, there are provided dibenzyltrithiocarbonate derivatives useful as RAFT polymerization reagents having various functional groups at both ends of the molecule, and production thereof.
That is, the dibenzyltrithiocarbonate derivative according to the present invention can be used for RAFT polymerization as a reagent for RAFT polymerization.
Moreover, since the obtained RAFT polymer has functional groups at both ends of the molecule, it can be used significantly as a cross-linked material of the RAFT polymer by using a suitable cross-linking agent.

1 is a ¹ H-NMR spectrum of the compound obtained in Example 1. 2 is a ¹ H-NMR spectrum of the compound obtained in Example 2. 2 is a ¹ H-NMR spectrum of the compound obtained in Example 10. ¹ is a ¹ H-NMR spectrum of the compound obtained in Example 11. 2 is a ¹ H-NMR spectrum of the compound obtained in Example 12. ¹ is a ¹ H-NMR spectrum of the compound obtained in Example 13. ¹ is a ¹ H-NMR spectrum of the compound obtained in Example 14. 2 is a ¹ H-NMR spectrum of the compound obtained in Example 16.

The dibenzyltrithiocarbonate derivative of general formula (1) according to the present invention has the following reaction scheme:
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is a substituted represented by C ₁ -C a ₅ alkyl or C ₂ -C ₅ alkenyl group) having a group, a methoxycarbonyl group having a substituent, X is halogen atom]
Can be manufactured according to

  The above reaction scheme shows a reaction for obtaining a dibenzyltrithiocarbonate represented by the general formula (1) from the compound represented by the general formula (3) using a trithiocarbonate.

Further, the dibenzyltrithiocarbonate derivative of the general formula (2) in which R in the general formula (1) is a methoxycarbonyl group having a substituent has the following reaction scheme:
[In the formula, Ar represents a phenylene or naphthylene group, R ₁ represents a C ₁ -C ₅ alkyl group having a hydroxy group at the terminal, a C ₂ -C ₅ alkyl group having a hydroxy group at the terminal and its adjacent position, represents a terminal and C ₂ -C ₅ alkenyl group or terminal and C ₂ -C ₅ alkyl group having an epoxy to the adjacent position having a double bond between the adjacent position, X represents a halogen atom]
Can be manufactured according to.

  In the above reaction scheme, the compound represented by the general formula (4) and the compound represented by the general formula (5) are reacted to obtain a compound represented by the general formula (6) (Step 1), The reaction (step 2) which obtains the dibenzyl trithiocarbonate represented by General formula (2) using a trithio carbonate is shown for a compound.

X in the above general formulas (3), (4) and (6) is a halogen atom, and specifically includes fluorine, chlorine, bromine and iodine atoms. From the viewpoint of reactivity and ease of handling, a chlorine atom Is preferred.
Examples of Ar in the general formulas (1) to (4) and (6) include a phenylene group and a naphthylene group, and a phenylene group is preferable from the viewpoint of reactivity and availability.

Further, R in the general formulas (1) and (3) is an acetoxy, hydroxy or hydroxymethyl group, or a group of formula —C (O) —O—CH ₂ —R ₁ (wherein R ₁ is a substituted group) A methoxycarbonyl group having a substituent represented by a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a group. Incidentally, the R _1, the above general formula (2) is identical to R ₁ in (5) and (6).

The R ₁ above, C ₁ -C ₅ alkyl groups, terminal and C ₁ -C ₅ alkyl group having dihydroxy or dimethyl methylenedioxy group on the adjacent position having a hydroxy group at the terminal, terminal and between the adjacent position And a C ₂ -C ₅ alkenyl group having a double bond, or a C ₂ -C ₅ alkyl group having an epoxy at the terminal and its adjacent position.

The C ₁ -C ₅ alkyl group containing a hydroxyl group to the terminal, 5-hydroxypentyl, 4-hydroxybutyl, 3-hydroxy propyl, 2-hydroxyethyl and hydroxymethyl groups.
Further, as the C ₁ -C ₅ alkyl group having a dihydroxy or dimethylmethylenedioxy group at the terminal and its adjacent position, 4,5-dihydroxypentyl, 3,4-dihydroxybutyl, 2,3-dihydroxypropyl, and 1, A 2-dihydroxyethyl group is mentioned.

Examples of the C ₂ -C ₅ alkenyl group having a double bond between the terminal and its adjacent position include 4-pentenyl, 3-butenyl, allyl and vinyl groups.
Examples of the C ₂ -C ₅ alkyl group having an epoxy at the terminal and its adjacent position include 4,5-epoxypentyl, 3,4-epoxybutyl, 2,3-epoxypropyl, and an epoxy group.

Preferably, R ₁ is a C ₁ -C ₃ alkyl group having a hydroxy group at the terminal, a C ₂ -C ₃ alkyl group having a hydroxy or dimethylmethylenedioxy group at the terminal and its adjacent position, a terminal and its adjacent position C ₂ -C ₃ alkenyl group having a double bond between or terminal and C ₂ -C ₃ alkyl group having an epoxy to the adjacent position, like.

More specifically, examples of the C ₁ -C ₃ alkyl group having a hydroxy group at the terminal include hydroxymethyl, 2-hydroxyethyl, and 3-hydroxypropyl.
In addition, as the C ₂ -C ₃ alkyl group having a hydroxy or dimethylmethylenedioxy group at the terminal and the adjacent position, 1,2-dihydroxyethyl, 2,3-dihydroxypropyl, 1,2-dimethylmethylene Examples include dioxyethyl and 2,3-dimethylmethylenedioxypropyl groups.

As the C ₂ -C ₃ alkenyl group having a double bond between said terminal and its adjacent position, vinyl and allyl groups.
Moreover, as a C2-C3 alkyl group which has an epoxy in the terminal and its adjacent position, an epoxy ethyl group and a _{2, 3-} epoxy propyl group are mentioned.

More specifically, the above R ₁ includes hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, vinyl, epoxyethyl, and 2,2-dimethyl-1.3-dioxolan-4-yl group. Can be mentioned.

  The above step 1 can be produced by reacting the compound represented by the general formula (4) and the compound represented by the general formula (5) in the presence of an organic or inorganic base. By using this solvent, it is possible to suppress impurities and reduce production costs by using inexpensive chemicals.

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

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

  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. .

  The post-treatment of the above step 1 is performed by adding a saline solution after the completion of the reaction for liquid separation, and concentrating the organic layer. Although the density | concentration of the salt solution to be used is not specifically limited, Since a yield falls with the fall of salt solution concentration, as salt solution concentration, 10-20% is preferable, and also 15-20% is more preferable. The number of washings is not particularly limited, but is preferably 1 to 2 times from the viewpoint of work efficiency.

  The reaction in the above step 1 can proceed to the next step without post-treatment, but it is post-treated from the viewpoint of reduction in the reaction rate in the above step 2 and yield of the target product due to generation of impurities. It is preferable.

  The compound obtained in the above step 1 can be used without purification or after purification by a conventional method such as distillation, recrystallization or column chromatography.

  Solvents used for the recrystallization in Step 1 above include diethyl ether, dioxane, tetrahydrofuran, dimethoxyethane, methyl ethyl ketone, acetonitrile, propionitrile, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethyl. Inactive solvents such as aprotic polar solvents such as acetamide, N-methylpyrrolidinone and dimethyl sulfoxide or protic polar solvents such as methanol, ethanol and isopropyl alcohol, and aprotic nonpolar solvents such as benzene and toluene However, toluene and ethyl acetate are preferable from the viewpoint of the yield of the target product.

  The trithiocarbonate formation is carried out by reacting the compound represented by the above general formula (3) or (6) with a trithiocarbonate to obtain a dibenzyltrimethyl group represented by the general formula (1) or (2). This is a reaction to obtain a thiocarbonate derivative.

For the above trithiocarbonate formation, there is no problem even if a commercially available trithiocarbonate is used.
However, as the above-mentioned trithiocarbonate, those prepared at the time of use can be used. In that case, the trithiocarbonate is prepared under stirring of a solvent, water, an inorganic base and carbon disulfide.

  Solvents that can be used for the preparation of the above trithiocarbonates include aprotic polar solvents such as tetrahydrofuran, N, N-dimethylacetamide, N-methylpyrrolidine and dimethylsulfoxide, or protic polarities such as methanol, ethanol, isopropyl alcohol, etc. Examples of the solvent include inert solvents such as aprotic nonpolar solvents such as benzene and toluene, and N, N-dimethylacetamide is preferred from the viewpoint of the yield of the target product.

  Examples of the inorganic base that can be used for the preparation of the above trithiocarbonate include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, magnesium hydroxide, barium hydroxide, etc. In view of the above, potassium hydroxide is preferable.

  The amount of N, N-dimethylacetamide and water used for the preparation of the trithiocarbonate is not particularly limited, but from the viewpoint of the yield of the target product in the trithiocarbonate reaction, the general formula (3) or ( 6 to 5 times the weight of the compound represented by 6), preferably 1.0 to 3.0 times the weight, and more preferably 1.0 to 1.5 times the weight.

  The molar ratio of potassium hydroxide used for the preparation of the above-mentioned trithiocarbonate is 1.0 to 3.0 times moles relative to the compounds represented by the general formulas (3) and (6), and further 1. 5-2.0 times mole is more preferable.

  The molar ratio of carbon disulfide used for the preparation of the above trithiocarbonate is 1.0 to 3.0 times the mole of the compound represented by the general formula (3) or (6), and further 1. 5-2.0 times mole is more preferable. Further, the molar ratio with potassium hydroxide is more preferably 1.0 to 2.0 times mole, more preferably 1.0 to 1.5 times mole with respect to potassium hydroxide, from the viewpoint of the yield of the target product.

  As preparation temperature of said trithiocarbonate, it can carry out at the temperature of the range of 0 to 40 degreeC, However, Preferably it can carry out at the temperature of the range of 30 to 40 degreeC.

  Solvents that can be used for the above trithiocarbonates include aprotic polar solvents such as tetrahydrofuran, ethyl acetate, butyl acetate, dimethoxyethane, N, N-dimethylacetamide, N-methylpyrrolidine and dimethylsulfoxide, or methanol, ethanol Inert solvents such as protic polar solvents such as isopropyl alcohol and aprotic nonpolar solvents such as benzene and toluene are preferred, and tetrahydrofuran is preferred from the viewpoint of yield of the target product and ease of operation.

The water used in the above-mentioned trithiocarbonate conversion is preferably added later, since the formation of impurities can be promoted and lead to a decrease in the yield of the target product if it has been added beforehand.
The amount of water to be added later 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 general formula (3) or (6). preferable.

As a reaction method for the above-mentioned trithiocarbonate formation, a method of dropping a trithiocarbonate solution from the viewpoint of yield of the target product and ease of operation is preferable.
The dropping temperature of the above trithiocarbonate 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.
The reaction temperature for the above trithiocarbonate formation 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.

  As a post-treatment method for the above-mentioned trithiocarbonate conversion, the reaction solution is separated, washed with an aqueous ammonium chloride solution and brine, the organic layer is dried, and the solvent is distilled off to obtain a crude target product. .

The amount of the ammonium chloride aqueous solution used for the above-mentioned trithiocarbonate post-treatment is not particularly limited, but it is preferably 1 to 10 times, more preferably 1 to 5 times.
The concentration of the aqueous ammonium chloride solution is not particularly limited, but the amount of ammonium chloride used is 1.0 to 2.0 times moles of the metal hydroxide used in the trithiocarbonate formation, Is preferably used in an amount of 1.0 to 1.2 moles, and the concentration of the aqueous ammonium chloride solution is preferably 5 to 29%, more preferably 15 to 25%.

Although the density | concentration of the salt solution used for said post-treatment of trithiocarbonate is not specifically limited, The density | concentration of 10-25%, Furthermore, 15-20% is preferable.
Moreover, although the quantity of said salt solution is not specifically limited, It is preferable to use 1-10 times amount, Furthermore, 1-5 times amount is more preferable. The number of times of washing is not particularly limited, but one time is sufficient in terms of work efficiency.

  The crude product obtained by the above trithiocarbonate conversion can be used after being purified by a conventional method such as distillation, recrystallization or column chromatography.

  Solvents used for recrystallization of the crude product obtained by the above trithiocarbonate conversion include diethyl ether, dioxane, tetrahydrofuran, dimethoxyethane, methyl ethyl ketone, acetonitrile, propionitrile, ethyl acetate, butyl acetate, N, N- Of aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone and dimethyl sulfoxide or aprotic polar solvents such as methanol, ethanol and isopropyl alcohol, and aprotic apolar solvents such as benzene and toluene Such an inert solvent is mentioned.

  Therefore, according to the present invention, in the method for producing a compound represented by the general formula (1) or (2), the compound represented by the general formula (3) or (6) is reacted with carbon disulfide. A method for producing a dibenzyltrithiocarbonate derivative, wherein the reaction for obtaining the compound represented by (1) or (2) is carried out in an aprotic polar solvent in the presence of a metal hydroxide at 0 ° C. to heating. Is provided.

The dibenzyltrithiocarbonate derivative having a reactive functional group at both ends of the molecule according to the present invention is characterized in that it can be used for RAFT polymerization as a reagent for RAFT polymerization.
Further, since the obtained RAFT polymer has functional groups at both ends of the molecule, it has a feature that it can be significantly used as a cross-linked material constituting the RAFT polymer by using a suitable cross-linking agent.

  Hereinafter, the present invention will be described in detail with reference to specific examples. The following examples are shown as representative examples of compounds that can be easily conceived based on these examples, and the present invention is described in the following examples. It is not limited.

Production Example 1
Production of 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane (11)
4-Hydroxymethyl-2,2-dimethyl-1,3-dioxolane (2,2-dimethyl-1,3-dioxolane-4-methanol) can be purchased and used commercially, but Organic Synthesis, Vol. 28, p.73 (1948); Coll. Vol. 3, p.502 (1955).

  That is, 25.3 g (275.1 mmol) of glycerin, 63.8 g (1.1 mol) of acetone, 760 mg of paratoluenesulfonic acid monohydrate, and 64 g of n-hexane were added to a 200 mL three-necked flask equipped with a stirrer and a Dean-Stark apparatus. The solution was heated and stirred for 24 hours while maintaining the temperature at 65 to 70 ° C. After completion of the reaction, the reaction mixture was cooled, 1 g of sodium acetate was added thereto, and the mixture was stirred at room temperature for 1 hour. After removing inorganic substances, the solvent was distilled off. The resulting crude product was distilled under reduced pressure to obtain 31.3 g (yield 85.3%) of the title compound. The resulting compound was confirmed by comparison with the standard NMR and IR data.

Example 1
Production of 2-hydroxyethyl 4-chloromethylbenzoate (7)
Ethylene glycol 82.07 g (1.32 mol) and triethylamine 14.72 g (146 mmol) were added to a 500 mL three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel, and 4-chloromethylbenzoyl was maintained while maintaining the reaction solution at 0 to 20 ° C. A solution of 25 g (132 mmol) of chloride in 25 g of tetrahydrofuran was added dropwise with stirring, and the mixture was further stirred for 1 hour. To this, 75 g of toluene and 50 g of city water were added for liquid separation, washed twice with 50 g of city water, and the organic layer was dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure, 50 g of methanol was added thereto, and the crystals precipitated after stirring for 1 hour at room temperature and 2 hours under ice-cooling were filtered off. The filtrate was concentrated under reduced pressure to obtain 20.6 g (yield 72.5%) of the title compound as white crystals.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.17 (1H, s, OH), 3.95-3.97 (2H, s, CH ₂ OH), 4.46-4.48 (2H, m, COOCH ₂ ), 4.61 _{(2H, S, CH 2 Cl} ), 7.45-7.47 (2H, m, ArH), ( a NMR spectrum in Figure 1) 8.04-8.06 (2H, m, ArH).
IR (KBr) (cm ^-1 ): 3442, 1718, 1415, 1278, 1179, 1124, 712.
Melting point: 38.6 ° C

Example 2
Production of bis (4- (2-hydroxyethoxycarbonyl) benzyl) trithiocarbonate (RAFT reagent (8))
To a 100 mL three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel was added 6.2 g (110.9 mmol) of potassium hydroxide and 14 g of city water, and 8.9 g of carbon disulfide (117.4) while maintaining the reaction solution at 0 to 5 ° C. mmol) in N, N-dimethylacetamide (14 g) was added, and the mixture was stirred 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, add 14.0 g (65.2 mmol) of 2-hydroxyethyl 4-chloromethylbenzoate, 70 g of tetrahydrofuran, and 21 g of toluene to a 300 mL three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel. While maintaining, the above-mentioned trithiocarbonate solution was added dropwise. After the dropwise addition, the mixture was stirred at the same temperature. After 0.5 hours, 42 g of water was added, and the mixture was further stirred for 19 hours. After separation of the reaction solution, the organic layer was washed successively with 21% aqueous ammonium chloride solution (28 g) and 10% brine solution (28 g) and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was recrystallized from 45 g of ethyl acetate to obtain 17.3 g (yield: 83.5%) of the title compound (RAFT reagent (8)) as pale yellow crystals.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.03 (2H, s, OH), 3.94-3.98 (4H, m, CH ₂ S), 4.45-4.47 (4H, m, OCH ₂ ), 4.65 (4H, s, ArCH ₂ S) 7.40-7.42 (4 H, m, ArH) 7.99-8.01 (4H, m, ArH) (NMR spectrum is shown in FIG. 2).
IR (KBr) (cm ^-1 ): 3422, 1716, 1279, 1066, 869, 792, 709.
Melting point: 121.2 ° C

Example 3
Production of 3-hydroxypropyl 4-chloromethylbenzoate (9)
Using 100.6 g of propanediol instead of ethylene glycol in Example 1, 26.3 g (yield 86.9%) of the title compound was obtained in exactly the same manner as in Example 1.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.77-2.08 (2H, m, CCH ₂ C), 2.53 (1H, s, OH), 3.75-3.85 (2H, m, C CH ₂ OH) , 4.46-4.59 (2H, m, COOCH ₂ ), 4.60 (2H, s, CH ₂ Cl), 7.42-7.46 (2H, m, ArH), 7.99-8.02 (2H, m, ArH).
IR (KBr) (cm ^-1 ): 3413, 1717, 1415, 1275, 1178, 1104, 712.
Melting point: 68.0 ° C

Example 4
Production of allyl 4-chloromethylbenzoate (10)
Instead of ethylene glycol in Example 1, 31.9 g of allyl alcohol, 80 g (420 mmol) of 4-chloromethylbenzoyl chloride, 300 g of toluene as a solvent, and 90.9 g of the title compound (yield 93.2 g) were carried out in the same manner as in Example 1. %).
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.62 (2H, s, CH ₂ Cl), 4.82-4.84 (2H, m, COOCH ₂ ), 5.28-5.99 (2H, m, CH ₂ = C ), 6.00-6.09 (1H, m, C = CH ), 7.46-7.48 (2H, m, ArH), 8.04-8.07 (2H, m, ArH).
IR (NaCl) (cm ⁻¹ ): 1715, 1414, 1361, 1270, 1178, 1104, 713.

Example 5
Preparation of 2,2-dimethyl-1,3-dioxolan-4-ylmethyl 4-chloromethylbenzoate (12)
Instead of ethylene glycol in Example 1, 25.2 g of 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane obtained in Production Example 1 and 30 g of 4-chloromethylbenzoyl chloride were used, and 120 g of toluene was used as a solvent. In the same manner as in Example 1, 37.3 g (yield 99.0%) of the title compound was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.40 (3H, s, CH ₃ ), 1.46 (3H, s, CH ₃ ), 3.87-3.89 (1H, m, CH CH ₂ O), 4.13 -4.17 (1H, m, CH CH ₂ O), 4.34-4.49 (3H, m, COO CH ₂ CH ), 4.62-4.84 (2H, s, CH ₂ Cl), 7.46-7.48 (2H, m, ArH) , 8.03-8.06 (2H, m, ArH).
IR (NaCl) (cm ⁻¹ ): 1721, 1372, 1275, 1179, 1104, 847, 713.

Example 6
Production of 2,3-dihydroxypropyl 4-chloromethylbenzoate (13)
To a 500 mL three-necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel were added 28 g of 2,2-dimethyl-1,3-dioxolan-4-ylmethyl 4-chloromethylbenzoate obtained in Example 6 and 140 g of tetrahydrofuran. . While stirring at room temperature, 140 g of a 1 mol / L hydrochloric acid aqueous solution was added dropwise, and the mixture was stirred at the same temperature for 17 hours. A solution obtained by dissolving 5.6 g of sodium hydroxide in 30 g of water was added dropwise thereto, and 140 g of ethyl acetate was further added. The reaction solution was separated, and the organic layer was washed twice with 56 g of 5% aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified with 90 g of toluene to obtain 21.2 g (yield 88.1%) of the title compound as white crystals.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.21 (1H, s, OH), 2.68 (1H, s, OH), 3.67-3.71 (1H, m, CH CH ₂ O), 3.77-3.80 (1H, m, CH CH ₂ O), 4.06-4.11 (1H, m, COOCH ₂ CH ), 4.39-4.48 (2H, m, COOCH ₂ ), 4.62 (2H, s, CH2Cl), 7.47-7.49 (2H , m, ArH), 8.03-8.05 (2H, m, ArH).
IR (KBr) (cm ⁻¹ ): 3390, 1715, 1416, 1285, 1129, 1052, 709.
Melting point: 85.5 ° C

Example 7
Production of 4-chloromethylbenzyl alcohol (14)
To a three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel was added 53.2 g of sodium borohydride, 530 g of tetrahydrofuran, 266 g of N, N-dimethylformamide, and a solution of 266 g of chloromethylbenzoyl chloride in 130 g of tetrahydrofuran. Was added dropwise and stirred at room temperature for 1 hour. To the reaction solution, 530 g of production water, 293 g of 10% hydrochloric acid aqueous solution and 1060 g of ethyl acetate were added for liquid separation, then washed with 665 g of sodium carbonate aqueous solution and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified with 100 g of toluene to obtain 147.7 g (yield 66.9%) of the title compound as white crystals.
¹ H NMR (400 MHz, DMSO) δ (ppm): 1.79 (1H, s, OH), 4.59 (2H, s, ArCH ₂ S), 4.70 (2H, s, COOCH ₂ ), 7.35-7.41 (4 H , m, ArH).
IR (KBr) (cm ⁻¹ ): 3342, 1420, 1263, 1011, 731.
Melting point: 52.6 ° C

Example 8
Production of 3-chloro-2-hydroxypropyl 4-chloromethylbenzoate (15)
In the same manner as in Example 1, 250 g of 3-chloro-1,2-propanediol was used instead of ethylene glycol in Example 1, 85.5 g of 4-chloromethylbenzoyl chloride and 256 g of tetrahydrofuran were used as the solvent. This gave 112.3 g (yield 94.1%) of the title compound.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.74 (1H, s, OH), 3.66-3.76 (2H, m, CH CH ₂ Cl), 4.21-4.24 (1H, m, CH ₂ CH OH ), 4.46-4.48 (2H, m, COOCH ₂ ), 4.62 (2H, s, CH ₂ Cl), 7.46-7.48 (2H, m, ArH), 8.02-8.06 (2H, m, ArH).
IR (NaCl) (cm ⁻¹ ): 3459, 1719, 1415, 1277, 1179, 1105, 712.

Example 9
Production of 2,3-epoxypropane 4-chloromethylbenzoate (16)
To a 300 mL three-necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 100 g of 3-chloro-2-hydroxypropyl 4-chloromethylbenzoate obtained in Example 9, 57.6 g of potassium carbonate, N, N-dimethyl 500 g of formamide was added and stirred at room temperature for 40 hours. The reaction solution was cooled and the precipitated inorganic substance was removed, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel chromatography (silica gel: Merk7734, mobile phase: toluene) to obtain 52.5 g (yield 61.1%) of the title compound.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.70-2.72 (2H, m, CCH ₂ O), 2.87-2.89 (2H, m, CCH ₂ O), 3.32-3.34 (2 H, m, CCHO), 4.12-4.17 (2H, m, COOCH ₂ ), 4.60 (2H, s, ArCH ₂ S), 4.63-4.66 (2H, m, ArCH ₂ S, COOCH ₂ ), 7.44-7.47 (2H, m, ArH), 8.03-8.05 (2H, m, ArH).
IR (NaCl) (cm ⁻¹ ): 1720, 1275, 1179, 1104, 1020, 712.

Example 10
Production of bis (4- (3-hydroxypropoxycarbonylbenzyl) trithiocarbonate (RAFT reagent (17))
Instead of 2-hydroxyethyl 4-chloromethylbenzoate in Example 2, 15 g of 3-hydroxypropyl 4-chloromethylbenzoate obtained in Example 3 was used, and the title compound (RAFT reagent ( 17)) 13.2 g (yield 81.4%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.97-2.03 (6H, m, OH, CCH ₂ C), 3.74-3.78 (4H, m, CH ₂ OH), 4.46-4.49 (4H, m , COOCH ₂ ), 4.64 (4H, s, ArCH ₂ S), 7.39-7.41 (4 H, m, ArH), 7.96-7.99 (4H, m, ArH) (NMR spectrum is shown in FIG. 3).
IR (KBr) (cm ^-1 ): 3284, 1714, 1413, 1282, 1124, 1059, 866, 797, 709.
Melting point: 107.1 ℃

Example 11
Production of bis (4-allyloxycarbonylbenzyl) trithiocarbonate (RAFT reagent (18))
Instead of 2-hydroxyethyl 4-chloromethylbenzoate in Example 2, 15 g of allyl 4-chloromethylbenzoate obtained in Example 4 was used, and the title compound (RAFT reagent (18)) was obtained in exactly the same manner as in Example 2. 14.8 g (yield 89.7%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.65 (4H, s, ArCH ₂ S), 4.80-4.82 (4H, m, COOCH ₂ ), 5.27-5.31 (4H, m, CH ₂ = C ), 5.98-6.08 (2H, m, C = CH), 7.39-7.42 (4 H, m, ArH), 8.00-8.02 (4H, m, ArH) (NMR spectrum is shown in FIG. 4).
IR (KBr) (cm ⁻¹ ): 1714, 1608, 1273, 1118, 1063, 867, 796, 706.
Melting point: 89.4 ° C

Example 12
Production of bis (4- (2,3-dihydroxypropoxycarbonylbenzyl) trithiocarbonate (RAFT reagent (19))
Instead of 2-hydroxyethyl 4-chloromethylbenzoate in Example 2, 10 g of 2,3-dihydroxypropyl 4-chloromethylbenzoate obtained in Example 7 was used, and the title compound (RAFT) was treated in the same manner as in Example 2. Reagent (19)) (9.3 g, yield 86.4%) was obtained.
¹ H NMR (400MHz, DMSOd6) δ (ppm): 3.77-3.79 (2H, m, COOCH ₂ CH ), 4.13-4.18 (2H, m, CH CH ₂ OH), 4.28-4.30 (2H, m, CH CH ₂ OH), 4.69-4.72 (4H, t, COOCH ₂ ), 4.76 (4H, s, CH2Cl), 5.01 (2H, s, OH), 5.03 (2H, s, OH), 7.52-7.54 (4H, m , ArH), 7.94-7.96 (4H, m, ArH) (NMR spectrum is shown in FIG. 5).
IR (KBr) (cm ^-1 ): 3334, 1715, 1279, 1061, 867, 797, 709.
Melting point: 143.0 ° C

Example 13
Production of bis (4-hydroxymethylbenzyl) trithiocarbonate (RAFT reagent (20))
Instead of 2-hydroxyethyl 4-chloromethylbenzoate in Example 2, 145 g of (4- (chloromethyl) phenyl) methanol obtained in Example 8 was used and the title compound ( 105.2 g (yield 64.8%) of RAFT reagent (20) was obtained.
¹ H NMR (400 MHz, DMSO) δ (ppm): 1.67 (2H, m, OH), 4.61 (4H, s, ArCH ₂ S), 4.68 (4H, s, COOCH ₂ ), 7.30-7.36 (8 H , m, ArH) (NMR spectrum is shown in FIG. 6).
IR (KBr) (cm ^-1 ): 3313, 1072, 1013, 867, 798, 723.
Melting point: 136.7 ° C

Example 14
Production of bis (4- (2,3-epoxypropoxycarbonyl) benzyl) trithiocarbonate (RAFT reagent (21))
Instead of 2-hydroxyethyl 4-chloromethylbenzoate in Example 2, 20 g of 2,3-epoxypropane 4-chloromethylbenzoate obtained in Example 10 was used, and the title compound (RAFT) was treated in the same manner as in Example 2. Reagent (21)) 8.0 g (yield 36.8%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 2.72-2.74 (2H, m, CCH ₂ O), 2.89-2.91 (2H, m, CCH ₂ O), 3.32-3.36 (2 H, m, CCHO), 4.13-4.17 (2H, m, COOCH ₂ ), 4.64-4.68 (6H, m, ArCH ₂ S, COOCH ₂ ), 7.41-7.43 (4H, m, ArH), 8.00-8.03 (4H, m, ArH) (NMR spectrum is shown in FIG. 7).
IR (KBr) (cm ^-1 ): 1724, 1607, 1276, 1102, 903, 866, 800, 708.
Melting point: 108.9 ° C

Example 15
Production of bis (4-acetoxybenzyl) trithiocarbonate (22)
Carbon disulfide (3.64 g, 47.8 mmol), potassium carbonate (7.55 g, 54.6 mmol) and 21 mL of DMF were added to a 100 mL flask, and the mixture was stirred at room temperature for 30 minutes. 4-Chloromethylphenyl acetate (8.4 g, 45.5 mmol) was added thereto, and then the mixture was heated and stirred at an external temperature setting of 45 ° C. for 46 hours. After confirming the end point of the reaction by TLC (AcOEt / n-hexane = 1/3), 85 mL of city water was added thereto, and extracted with 3 × 85 mL of ethyl acetate. The organic layers were combined and washed twice with 85 mL of 15% aqueous sodium chloride solution. The organic layer was dehydrated with sodium sulfate, the inorganic matter was removed, and the solvent was concentrated under reduced pressure. To 9.98 g of the obtained residue, 20 mL of toluene and 40 mL of n-hexane were added and stirred at room temperature for 0.5 hour, and the precipitated crystals were collected by filtration (washed with 10 mL of n-hexane). The obtained crystals were dried under reduced pressure (room temperature for 3 hours) to obtain 6.48 g of primary crystals in a yield of 70.1%. In addition, 2.2 g of the mother liquor was roughly purified on silica gel (SiO2: 13.2 g, mobile phase: AcOEt / n-hexane = 1/5 to 1/3) to obtain 1.00 g of secondary crystals with a yield of 10.8% (total 7.48 g , Yield 80.9%) and used as such in the next Example 16.

Example 16
Production of bis (4-hydroxybenzyl) trithiocarbonate (RAFT reagent (23))
Acetyl (7.2 g, 17.7 mmol), THF 108 mL and MeOH 7 mL were added to a 100 mL flask, and KOH (2.1 g, 53.1 mmol) and city water 36 mL were added to this under cooling (setting 0 ° C.) (internal temperature 1.0 to 5.2 ° C., dropwise) It was stirred for 24 hours at the same temperature for 20 minutes). After confirming the end point of the reaction by TLC (AcOEt / n-hexane = 1/3), the pH was adjusted to 7 with 2.5 mL of concentrated hydrochloric acid. The organic layer was separated, and the aqueous layer was secondarily extracted with 70 mL of ethyl acetate. The organic layers were combined and washed with a 15% sodium chloride aqueous solution 36 mL × 3 times, and then the organic layer was dehydrated with sodium sulfate to remove inorganic substances, and then the solvent was concentrated under reduced pressure. The obtained residue 6.56 g was subjected to column crude purification (SiO2: 33 g, mobile phase: AcOEt / n-hexane = 1/3), and then 4.12 g of the obtained crude crystals were washed with 12 g of toluene and then 20 g. . 2.46 g of the obtained crystals were purified again by column purification (SiO 2: 50 g, mobile phase: CH ₂ Cl ₂ ), and then the crystals were washed with 20 g of toluene. The obtained crystals were dried under reduced pressure at 50 ° C. for 16 hours to obtain 0.82 g of the title compound (RAFT reagent (23)) in a yield of 14.4% (mother liquor + recovered product from the column: about 1.3 g in total).
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.60 (2 H, s, CH ₂ ), 6.70 (2 H, m, ArH), 7.20 (2 H, m, ArH), 9.50 (1 H , s, OH) (NMR spectrum shown in FIG. 8).
IR (KBr) (cm ⁻¹ ): 3389, 1602, 1460, 1302, 1241, 1071, 1018.

Example 17
RAFT polymerization with ethyl acrylate using bis (4- (2-hydroxyethoxycarbonyl) benzyl) trithiocarbonate (RAFT reagent (8)) 200 mL three-necked flask equipped with stirrer, reflux condenser, and nitrogen inlet Bis (4- (2-hydroxyethoxycarbonyl) benzyl) trithiocarbonate (RAFT reagent (8)) 7.0 g (15.0 mmol), ethyl acrylate 75.1 g (750.0 mmol) and VA- [086] 216 mg (0.75 mmol) was added, degassed under reduced pressure, purged with nitrogen gas, and stirred at 90 ° 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 2,890 and a molecular weight distribution (M _w / M _n ) of 1.20.

Examples 18-20
Instead of the RAFT reagent (8) in Example 17 above, the RAFT reagent (17) obtained in Example 10, the RAFT reagent (18) obtained in Example 11, and the RAFT reagent obtained in Example 12 RAFT polymerization was carried out as Examples 18 to 20 in exactly the same manner as in Example 17 except that (19) was used.
The molecular weight and molecular weight distribution of the obtained polymer are shown in the following table together with the data of the polymer obtained in Example 17.

Example 21
RAFT polymerization with styrene using bis (4- (2-hydroxyethoxycarbonyl) benzyl) trithiocarbonate (RAFT reagent (8)) Implemented in a 100 mL three-necked flask equipped with a stirrer, reflux condenser, and nitrogen inlet 1.8 g (3.84 mmol) of bis (4- (2-hydroxyethoxycarbonyl) benzyl) trithiocarbonate obtained in Example 2 (RAFT reagent (8)), 20.0 g (192.0 mmol) of styrene and 55.4 mg of VA-086 ( 0.19 mmol) was added, degassed under reduced pressure, purged with nitrogen gas, and stirred 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 4,690 and a molecular weight distribution (M _w / M _n ) of 1.22.

Examples 22-25
Instead of the RAFT reagent (8) in Example 21 above, the RAFT reagent (17) obtained in Example 10, the RAFT reagent (18) obtained in Example 11, and the RAFT reagent obtained in Example 12 RAFT polymerization was carried out as Examples 22 to 25 in exactly the same manner as in Example 21 except that (19) and the RAFT reagent (20) obtained in Example 13 were used.
The molecular weight and molecular weight distribution of the obtained polymer are shown in the following table together with the data of the polymer obtained in Example 21.

According to the present invention, there are provided dibenzyltrithiocarbonate derivatives useful as RAFT polymerization reagents having various functional groups at both ends of the molecule, and production thereof.
That is, the dibenzyltrithiocarbonate derivative according to the present invention can be used for RAFT polymerization as a reagent for RAFT polymerization.
Moreover, since the obtained RAFT polymer has functional groups at both ends of the molecule, it can be used significantly as a cross-linked material of the RAFT polymer by using a suitable cross-linking agent.

Claims (8)

The following general formula (1):
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is a substituted represented by C ₁ -C a ₅ alkyl or C ₂ -C ₅ alkenyl group) having a group, a methoxy carbonyl group having a substituent]
A dibenzyltrithiocarbonate derivative represented by: R in the general formula (1) is a methoxycarbonyl group having a substituent, and the following general formula (2):
[In the formula, Ar represents a phenylene or naphthylene group, R ₁ represents a C ₁ -C ₅ alkyl group having a hydroxy group at the terminal, a C ₂ -C ₅ alkyl group having a hydroxy group at the terminal and its adjacent position, between terminal and their adjacent position represent a C ₂ -C ₅ alkyl group having epoxy C ₂ -C ₅ alkenyl group or terminal and its adjacent position having a double bond]
The dibenzyltrithiocarbonate derivative of Claim 1 represented by these. R in the general formula (1) is a methoxycarbonyl group having a substituent, Ar represents a phenylene group, R ₁ is a C ₁ -C ₃ alkyl group having a hydroxy group at the terminal, the terminal and its adjacent position each C ₂ -C ₃ alkyl group having hydroxy groups, terminal and C ₂ -C ₃ alkyl with epoxy to C ₂ -C ₃ alkenyl or terminal and its adjacent position having a double bond between the adjacent position The dibenzyltrithiocarbonate derivative according to claim 1 or 2, which is a group. In the general formula (1), R is a methoxycarbonyl group having a substituent, Ar is a phenylene group, and R ₁ is a hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, vinyl or epoxy group. The dibenzyltrithiocarbonate derivative according to any one of claims 1 to 3, wherein The following general formula (3):
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is A methoxycarbonyl group having a substituent represented by C ₁ -C ₅ alkyl or a C ₂ -C ₅ alkylene group having a substituent, and X is a halogen atom]
The compound represented by general formula (1) is characterized by reacting with a trithiocarbonate in an amide solvent to form a trithiocarbonate.
[Wherein Ar is a phenylene or naphthylene group, R is an acetoxy, hydroxy or hydroxymethyl group, or the formula —C (O) —O—CH ₂ —R _1, where R ₁ is It is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkylene group having a substituent, and a methoxycarbonyl group having a substituent]
The manufacturing method of the dibenzyltrithiocarbonate derivative represented by these. R in the general formula (1) according to claim 5 is a methoxycarbonyl group having a substituent, and the following general formula (4):
[Wherein Ar is a phenylene or naphthylene group, and X is a halongen atom]
A compound represented by formula (5):
[Wherein R ₁ is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkylene group having a substituent]
A general formula (6) obtained by reacting an alcohol compound represented by general formula (6):
[Wherein Ar is a phenylene or naphthylene group, R ₁ is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a substituent, and X is a halogen atom]
The ester compound represented by the formula (2) is characterized by reacting with a trithiocarbonate in an amide solvent to form a trithiocarbonate.
[Wherein Ar is a phenylene or naphthylene group, and R ₁ is a C ₁ -C ₅ alkyl or C ₂ -C ₅ alkenyl group having a substituent]
The manufacturing method of the dibenzyltrithiocarbonate derivative represented by these.   The production method according to claim 6, wherein the ester compound is obtained in the presence of triethylamine, tributylamine, pyridine, or dimethylaminopyridine.   The production method according to claim 5 or 6, wherein the trithiocarbonate is used as a mixed solution of water and N, N-dimethylacetamide.