JP2019143018A - Production method of polycarbonate polyol - Google Patents

Abstract

To provide a production method of a polyfunctional polycarbonate polyol with a controlled structure, which is useful as an ingredient of a high-performance urethane resin excellent in durability such as heat resistance, weather resistance, hydrolysis resistance and chemical resistance.SOLUTION: The invention provides a compound of the general formula (7). In the formula, Xis a hydrogen atom, a methyl group, an ethyl group, or a carbonate-substituted methyl group; and 3 or 4 occurrences of m are identical or different and each represent an integer from 0 to 9 inclusive, and n represents an integer from 1 to 10 inclusive, provided that m+n should be an integer from 1 to 10 inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polycarbonate polyol for producing a polyurethane resin.

  The polycarbonate polyol is useful as a raw material for producing a polyurethane resin by reacting with a polyisocyanate compound, as well as a polyester polyol and a polyether polyol, and as a raw material for an adhesive, a paint, and the like. Since the polyester polyol has an ester bond, the polyurethane resin obtained therefrom has a disadvantage that it is inferior in hydrolysis resistance, and the polyether polyol has an ether bond, so that it has a disadvantage in that it is inferior in weather resistance and heat resistance. On the other hand, a polyurethane resin having excellent durability such as heat resistance, weather resistance, hydrolysis resistance and chemical resistance can be obtained from polycarbonate polyol.

  Such a polycarbonate polyol is usually produced by a transesterification reaction between a carbonate ester and a diol in the presence of a catalyst.

  Furthermore, in order to improve the mechanical strength and durability of the polyurethane resin, a polycarbonate polyol obtained by transesterifying an aryl carbonate and a first aliphatic triol such as trimethylolpropane and an aliphatic or alicyclic diol is provided. It has been proposed (Patent Document 1). In addition, a polycarbonate polyol obtained by transesterification of a polycarbonate diol with a triol compound and / or a tetraol compound has also been proposed (Patent Documents 2 and 3).

  However, the transesterification reaction with triol or tetraol is difficult to proceed, and as a by-product, monool, diol and cyclic compound are produced as an insoluble mixture, there is a possibility that satisfactory physical properties may not be obtained. is there.

Japanese Patent Publication No.57-39650 JP-A-3-220233 JP 2012-184380 A

  This invention is made | formed in view of the above background arts, and makes it a subject to provide the method of manufacturing the polyfunctional polycarbonate polyol by which the structure was controlled.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyfunctional polycarbonate polyol (7) can be produced from poly (p-nitrophenyl) carbonate represented by the following general formula (4). The invention has been completed.

  That is, the present invention relates to the general formula (4)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ⁴ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (4a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁴ represents a hydrogen atom, a methyl group or an ethyl group. The poly (p-nitrophenyl) carbonate represented by the general formula (9)

(Wherein R represents the same meaning as described above, n represents an integer of 1 to 10; m + n satisfies an integer of 1 to 10). The general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a).

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. It is related with the manufacturing method of the polycarbonate polyol represented by this.

  Further, the present invention provides a general formula (4)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ⁴ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (4a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁴ represents a hydrogen atom, a methyl group or an ethyl group. The poly (p-nitrophenyl) carbonate represented by the general formula (5)

(In the formula, R represents the same meaning as described above. Y ¹ represents a methoxymethyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms; or a benzyl group optionally substituted with a methoxy group. n represents an integer of 1 or more and 10 or less, provided that m + n satisfies an integer of 1 or more and 10 or less.

(In the formula, R, Y ¹ , m, n and q represent the same meaning as described above. X ⁶ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (6a).

(Wherein R, Y ¹ , m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁶ represents a hydrogen atom, a methyl group or an ethyl group. ), Followed by a deprotection reaction, wherein the general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a).

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. It is related with the manufacturing method of the polycarbonate polyol represented by this.

  Further, the present invention provides a compound represented by the general formula (10)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ¹⁰ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (10a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group. The polyol represented by the general formula (8)

(In the formula, R represents the same meaning as described above. Y ¹ represents a methoxymethyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms; or a benzyl group optionally substituted with a methoxy group. A represents a chlorine atom or a (p-nitrophenyl) oxy group, n represents an integer of 1 or more and 10 or less, provided that m + n satisfies an integer of 1 or more and 10 or less. And general formula (6)

(In the formula, R, Y ¹ , m, n and q represent the same meaning as described above. X ⁶ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (6a).

(Wherein R, Y ¹ , m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁶ represents a hydrogen atom, a methyl group or an ethyl group. ), Followed by a deprotection reaction, wherein the general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a).

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. It is related with the manufacturing method of the polycarbonate polyol represented by this.

  By the production method of the present invention, a polyfunctional polycarbonate polyol (7) having a controlled structure can be obtained, and when the obtained polycarbonate polyol and a polyisocyanate compound are reacted, heat resistance, weather resistance, A polyurethane resin having excellent durability such as hydrolysis resistance and chemical resistance can be obtained.

6 is a GPC chart of glyceryl = tris [(6-hydroxyhexyl) carbonate] obtained in Example 5. FIG. 3 is a GPC chart of the product obtained in Comparative Example 1.

Hereinafter, the present invention will be described in detail. The definitions of R and Y ¹ in the present invention will be described.

  The divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms represented by R may be any of a linear, branched or cyclic aliphatic hydrocarbon group, such as a tetramethylene group or a pentamethylene group. Examples thereof include a group, a hexamethylene group, a heptamethylene group, an octamethylene group, a 2,2-dimethyltrimethylene group, and a 1,4-cyclohexylene group.

Examples of the methoxymethyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms represented by Y ¹ include a methoxymethyl (MOM) group, a 1-ethoxyethyl (EE) group, and 1-methyl-1- A methoxyethyl group, a tetrahydropyran-2-yl (THP) group, a tetrahydrofuran-2-yl group, etc. can be illustrated. From the viewpoint of good yield, a methoxymethyl group is preferable.

Examples of the benzyl group optionally substituted with the methoxy group represented by Y ¹ include a benzyl (Bn) group, a 2-methoxybenzyl group, a 4-methoxybenzyl (PMB) group, a 3,4-dimethoxybenzyl group, and the like. Can be illustrated. A benzyl group is preferable in terms of good yield.

  Next, the manufacturing method of this invention is demonstrated.

(Wherein R, X ² , X ³ , l and q have the same meaning as described above).

  Step-1 is a step of reacting the polyol (2) with p-nitrophenyl chloroformate to produce poly (p-nitrophenyl) carbonate (3). The poly (p-nitrophenyl) carbonate (3) obtained in step 1 is used in the production method (step-6) of the polycarbonate polyol (7) of the present invention in place of poly (p-nitrophenyl) carbonate (4). be able to.

  Examples of the polyol (2) that can be used as the raw material of step-1 include all glycerol, methyl glycerol, ethyl glycerol, trimethylol methane, trimethylol ethane, and trimethylol propane. And pentaerythritol, which are commercially available. Further, as the polyol (2) in which 3 or 4 l is 1 or more and 9 or less, the above polyol (2) is used as a raw material, and the polycarbonate polyol (7) that can be produced through Steps 1 to 6 is used as the polyol (2). Can be used.

  Step-1 is preferably performed in the presence of a base. Examples of the base include tertiary aliphatic amines such as triethylamine, diisopropylethylamine and N-methylmorpholine, aromatic amines such as pyridine, picoline and 4- (dimethylamino) pyridine, sodium carbonate, potassium carbonate and cesium carbonate. And alkali metal carbonates such as sodium hydrogencarbonate. Of these, aromatic amines are preferably used, and pyridine is more preferably used from the viewpoint of good yield.

  Step 1 is preferably performed in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, toluene, Examples include aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Two or more of these solvents may be mixed and used. Of these, dichloromethane and tetrahydrofuran are preferably used from the viewpoint of good yield.

  There is no particular limitation on the molar ratio of the polyol (2) and p-nitrophenyl chloroformate, but it is preferably in the range of 1: 1 to 1:10, among which 1: 3 to 1: More preferably, it is in the range of 5. The molar ratio of p-nitrophenyl chloroformate to base is not particularly limited, but is preferably in the range of 1: 1 to 1:10, and in particular, the range of 1: 1 to 1: 3 in terms of good yield. More preferably.

  The reaction temperature in Step-1 can be carried out at a temperature appropriately selected from the range of -78 ° C to 150 ° C. Among them, the range of 20 ° C. to 120 ° C. is preferable in terms of a good yield.

  The poly (p-nitrophenyl) carbonate (3) obtained in Step-1 is preferably purified from the reaction solution after completion of the reaction as necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

  The method shown in the following reaction formula (steps 2 to 4) is a method for producing the polycarbonate polyol (7) of the present invention.

(In the formula, R, X ⁴ , X ⁶ , X ⁷ , Y ¹ , m, n, and q represent the same meaning as described above).

  Step-2 is a step of producing polycarbonate (6) by reacting poly (p-nitrophenyl) carbonate (4) with alcohol (5).

  The poly (p-nitrophenyl) carbonate (4) that is the raw material of Step-2 is obtained by changing the poly (p-nitrophenyl) carbonate (3) obtained in Step-1 to poly (p-nitrophenyl) carbonate (4). You may replace and use.

  The alcohol (5) which is the raw material of Step-2 is obtained from the corresponding commercially available polycarbonate diol by the method described in the literature (Tetrahedron, 56, 9281-9288, 2000; Tetrahedron Letters, 48, 6105-6108, 2007). Year).

  Step-2 is preferably performed in the presence of a base. Examples of the base include tertiary aliphatic amines such as triethylamine, diisopropylethylamine and N-methylmorpholine, aromatic amines such as pyridine, picoline and 4-dimethylaminopyridine, sodium carbonate, potassium carbonate, cesium carbonate and carbonic acid. Examples thereof include alkali metal carbonates such as sodium hydrogen. Of these, pyridine, 4-dimethylaminopyridine, and potassium carbonate are preferably used from the viewpoint of good yield.

  Step-2 is preferably performed in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, toluene, Examples include aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Two or more of these solvents may be mixed and used. Of these, dichloromethane and tetrahydrofuran are preferably used from the viewpoint of good yield.

  The molar ratio of poly (p-nitrophenyl) carbonate (4) to alcohol (5) is not particularly limited, but is preferably in the range of 1: 1 to 1: 100, and in particular, the yield is good from 1: 3. 1: 5 is more preferable. The molar ratio of alcohol (5) to base is not particularly limited, but is preferably in the range of 1: 1 to 1:10, and more preferably 1: 1 to 1: 3 in terms of good yield.

  The reaction temperature in step-2 is preferably carried out at a temperature appropriately selected from the range of -78 ° C to 150 ° C. Among these, a range of 20 ° C. to 120 ° C. is preferable in terms of a good yield.

  The polycarbonate (6) obtained in step-2 is preferably purified from the reaction solution after completion of the reaction, if necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

Step-3 is a step of producing a polycarbonate polyol (7) by a deprotection reaction for deprotecting the benzyl group of the polycarbonate (6: Y ¹ = benzyl group optionally substituted with a methoxy group).

  Step-3 is preferably performed in the presence of a metal catalyst, in a hydrogen gas atmosphere, or in the presence of a hydrogen equivalent. Examples of hydrogen equivalents include cyclohexene, 1,4-cyclohexadiene, formic acid, decalin, ammonium formate, and the like. It is preferable to carry out in a hydrogen gas atmosphere in terms of good yield. The pressure of the hydrogen gas is not particularly limited, but it is preferable to carry out the reaction at a low pressure from normal pressure to about 10 atm. When the hydrogen equivalent is used in an equivalent amount or more with respect to the polycarbonate (6), the polycarbonate polyol (7) can be obtained with good yield.

  Examples of the metal catalyst used in Step-3 include palladium carbon, palladium black, palladium alumina, palladium chloride, palladium hydroxide, Raney nickel, rhodium alumina, and the like. Palladium carbon is preferably used from the viewpoint of good yield.

  Step 3 is preferably performed in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, toluene, Aromatic hydrocarbons such as xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, methanol, ethanol Water and the like can be exemplified, and two or more of these solvents may be mixed and used. Of these, tetrahydrofuran and ethanol are preferably used from the viewpoint of good yield.

  The addition amount of the metal catalyst may be a so-called catalyst amount, and it is preferable to use about 0.1 to 20 mol% with respect to the polycarbonate (6).

  There is no restriction | limiting in particular in the reaction temperature of process-3, It is preferable to implement at the temperature chosen suitably from 20 to 100 degreeC.

  The polycarbonate polyol (7) obtained in step-3 is preferably purified from the reaction solution after completion of the reaction, if necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

Step 4 is a deprotection reaction in which the methoxymethyl group of the polycarbonate (6: Y ¹ = methoxymethyl group optionally substituted with an alkyl group having 1 to 8 carbon atoms) is deprotected by acid treatment. It is a process for producing a polyol (7).

  Examples of the acid that can be used in Step-4 include Bronsted acids such as hydrochloric acid, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. Of these, hydrochloric acid is preferably used because of its good yield.

  Step-4 is preferably performed in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, 1,2-dimethoxyethane, aliphatic hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, Aromatic hydrocarbon solvents such as toluene, xylene, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, methanol, ethanol , Isopropyl alcohol, water, and the like, and two or more of these solvents may be mixed and used. Of these, tetrahydrofuran and isopropyl alcohol are preferably used from the viewpoint of good yield.

  There is no restriction | limiting in particular in the molar ratio of the polycarbonate (6) used for process-4, and an acid.

  The reaction temperature in step-4 is preferably carried out at a temperature appropriately selected from the range of 0 ° C to 100 ° C. Among these, the range of 0 ° C. to 50 ° C. is preferable in terms of good yield.

  The polycarbonate polyol (7) obtained in step-4 is preferably purified from the reaction solution after completion of the reaction, if necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

  Moreover, the method (Process-5) shown by the following Reaction Formula is a manufacturing method of the polycarbonate polyol (7) of this invention by combining with the process 3 or 4.

(In the formula, R, X ⁶ , X ¹⁰ , Y ¹ , A, m, n and q have the same meaning as described above).

  Step-5 is a step of producing a polycarbonate (6) by reacting the polyol (10) with the protective alcohol (8).

  In the polyol (10) that can be used as the raw material of Step-5, as the polyol in which 3 or 4 m are all 0, for example, glycerol, methylglycerol, ethylglycerol, trimethylolmethane, trimethylolethane, trimethylolpropane And pentaerythritol, which are commercially available. Further, as the polyol (10) in which 3 or 4 m is 1 or more and 9 or less, the polyol (2) is used as a raw material, and the polycarbonate polyol (7) that can be produced through steps 1 to 6 is used as the polyol (10). You may replace and use.

  The protected alcohol (8) which is the raw material of Step-5 is obtained from alcohol (5) according to a method described in the literature (US Pat. No. 4,654,366, Journal of the American Chemical Society, 138, 16380-16387, 2016). Can be prepared.

  Step-5 is preferably performed in the presence of a base. Examples of the base include tertiary aliphatic amines such as triethylamine, diisopropylethylamine and N-methylmorpholine, aromatic amines such as pyridine, picoline and 4-dimethylaminopyridine, sodium carbonate, potassium carbonate, cesium carbonate and carbonic acid. Examples thereof include alkali metal carbonates such as sodium hydrogen. Of these, pyridine is preferably used because of its good yield.

  Step-5 is preferably performed in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, toluene, Examples include aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Two or more of these solvents may be mixed and used. Of these, dichloromethane and tetrahydrofuran are preferably used from the viewpoint of good yield.

  The molar ratio of the polyol (10) and the protected alcohol (8) is not particularly limited, but is preferably in the range of 1: 1 to 1:10, and more preferably 1: 3 to 1: 5 in terms of good yield. . The molar ratio of the protected alcohol (8) and the base is not particularly limited, but is preferably in the range of 1: 1 to 1:10, and more preferably 1: 1 to 1: 3 in terms of good yield.

  The reaction temperature in Step-5 can be carried out at a temperature appropriately selected from the range of -78 ° C to 150 ° C. Among these, a range of 20 ° C. to 120 ° C. is preferable in terms of a good yield.

  The polycarbonate (6) obtained in Step-5 is preferably purified from the reaction solution after completion of the reaction, if necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

  The method shown in the following reaction formula (step-6) is a method for producing the polycarbonate polyol (7) of the present invention.

(In the formula, R, X ⁴ , X ⁷ , m, n and q have the same meaning as described above).

  Step-6 is a step of producing polycarbonate polyol (7) by reacting poly (p-nitrophenyl) carbonate (4) with alcohol (9).

  The poly (p-nitrophenyl) carbonate (4), which is the raw material of Step-6, turns the poly (p-nitrophenyl) carbonate (3) obtained in Step-1 into poly (p-nitrophenyl) carbonate (4). It can be used as a replacement.

  Commercially available polycarbonate diol can be used for alcohol (9) which is a raw material of process-6.

  Step-6 is preferably performed in the presence of a base. Examples of the base include tertiary aliphatic amines such as triethylamine, diisopropylethylamine and N-methylmorpholine, aromatic amines such as pyridine, picoline and 4-dimethylaminopyridine, sodium carbonate, potassium carbonate, cesium carbonate and carbonic acid. Examples thereof include alkali metal carbonates such as sodium hydrogen. Of these, pyridine is preferably used because of its good yield.

  Step-6 is preferably carried out in a solvent as long as it does not inhibit the reaction. Examples of the solvent that can be used in this step include ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,2-dimethoxyethane, hydrocarbon solvents such as hexane, pentane, and cyclohexane, benzene, toluene, Examples include aromatic hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Two or more of these solvents may be mixed and used. Of these, dichloromethane and tetrahydrofuran are preferably used from the viewpoint of good yield.

  The molar ratio of the poly (p-nitrophenyl) carbonate (4) and the alcohol (9) is not particularly limited, but is preferably in the range of 1: 1 to 1:10, particularly from 1: 3 in terms of good yield. 1: 5 is more preferable. The molar ratio of alcohol (9) to base is not particularly limited, but is preferably in the range of 1: 1 to 1:10, and more preferably 1: 1 to 1: 3 in terms of good yield.

  The reaction temperature in Step-6 is preferably carried out at a temperature appropriately selected from the range of -78 ° C to 150 ° C. Among these, a range of 20 ° C. to 120 ° C. is preferable in terms of a good yield.

  The polycarbonate polyol (7) obtained in Step-6 is preferably purified from the reaction solution after completion of the reaction, if necessary. The purification method is not particularly limited, but the target product may be purified by a general method such as solvent extraction, silica gel column chromatography, thin layer preparative chromatography, preparative liquid chromatography, recrystallization or sublimation. preferable.

  EXAMPLES Next, although an Example and a reference example demonstrate this invention further in detail, this invention is not limited to these.

  <Reference Example 1>

N, N-diisopropylethylamine (1.1 mL, 6.2 mmol) was added dropwise at 0 ° C. to a mixture of triphosgene (915 mg, 3.1 mmol) and hexane (12 mL). Subsequently, a solution of 6- (methoxymethoxy) hexanol (1.0 g, 6.2 mmol) in hexane (6 mL) was added dropwise, and the mixture was heated to 20 ° C. and stirred for 30 minutes. Water (10 mL) was added to the reaction mixture to stop the reaction. The obtained mixture was extracted with ethyl acetate (20 mL × 3), and the organic layer was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (20% ethyl acetate / hexane) to give 6- (methoxymethoxy) hexyl chloroformate (1.25 g, yield 90%). ) Was obtained as a colorless transparent oil. ¹ H NMR (400 MHz, CDCl ₃ ): δ 4.62 (s, 2H), 4.32 (t, J = 6.6 Hz, 2H), 3.53 (t, J = 6.6 Hz, 2H), 3 .36 (s, 3H), 1.75 (tt, J = 7.3, 14.0 Hz, 2H), 1.61 (tt, J = 6.7, 13.5 Hz, 2H), 1.44 1.40 (m, 4H).

  <Reference Example 2>

6- (Benzyloxy) hexanol (31.6 g, 152 mmol) and 4-nitrophenyl chloroformate (33.6 g, 167 mmol) were dissolved in tetrahydrofuran (150 mL), and pyridine (13.4 mL, 167 mmol) was added at 0 ° C. It was dripped. After completion of the dropwise addition, the temperature was raised to 20 ° C. and reacted for 1 hour, and water (50 mL) was added to stop the reaction. The reaction mixture was extracted with ethyl acetate (50 mL × 3), and the organic layer was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was recrystallized from ethyl acetate, whereby 6- (benzyloxy) hexyl = 4-nitrophenyl carbonate (45.3 g, yield 80%) was white. Obtained as a solid.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.29 (d, J = 9.2 Hz, 2H), 7.39 (d, J = 9.2 Hz, 2H), 7.35-7. 26 (m, 5H), 4.51 (s, 2H), 4.29 (t, J = 6.7 Hz, 2H), 3.49 (t, J = 6.5 Hz, 2H), 1.81- 1.74 (m, 2H), 1.69-1.62 (m, 2H), 1.49-1.42 (m, 4H).

  <Reference Example 3>

  To triphosgene (750 mg, 2.5 mmol) was added tetrahydrofuran (5 mL), and N, N-diisopropylethylamine (1.3 mL, 7.5 mmol) was added dropwise at 0 ° C. Subsequently, 6- (benzyloxy) hexanol (1.04 g, 5 mmol) was added dropwise, then the mixture was heated to 20 ° C. and reacted for 1 hour, and water (10 mL) was added to stop the reaction. The reaction mixture was extracted with hexane (10 mL × 3), and the organic layer was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product of 6- (benzyloxy) hexyl chloroformate (1.42 g) as a pale yellow transparent oil.

  <Example 1>

To a solution of glycerol (2.77 g, 30 mmol) and 4-nitrophenyl chloroformate (18.9 g, 93 mmol) in tetrahydrofuran (100 mL) was added dropwise pyridine (9.7 mL, 120 mmol) at 0 ° C., and the mixture was then raised to 20 ° C. Warmed and allowed to react for 2 hours. Water (100 mL) was added to the reaction mixture to precipitate a solid. The precipitated solid was collected by filtration, washed with water and ethanol, and the resulting crude product was recrystallized from toluene to give glyceryl = tris [(4-nitrophenyl) carbonate] (14.8 g, yield 84%). Was obtained as a white solid. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.31 (d, J = 9.2 Hz, 6H), 7.41 (d, J = 9.2 Hz, 6H), 5.42 (tt, J = 3.8, 5.9 Hz, 1H), 4.78 (dd, J = 3.8, 12.2 Hz, 2H), 4.59 (dd, J = 5.9, 12.2 Hz, 2H) .

  <Example 2>

To a solution of pentaerythritol (136 mg, 1 mmol) and 4-nitrophenyl chloroformate (806 mg, 4 mmol) in tetrahydrofuran (4 mL) was added dropwise pyridine (0.32 mL, 4 mmol) at 0 ° C., then the temperature was raised to 20 ° C. and 7 Reacted for hours. Water (50 mL) was added to the reaction mixture to precipitate a solid. The precipitated solid was collected by filtration and washed with water and ethanol. The obtained crude product was purified by flash silica gel column chromatography (40% ethyl acetate / hexane), and pentaerythrityl tetrakis [(4-nitrophenyl) carbonate] (0.683 g, yield 86%) was obtained. Obtained as a white solid. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.29 (d, J = 9.1 Hz, 8H), 7.39 (d, J = 9.1 Hz, 8H), 4.57 (s, 8H).
<Example 3>

A solution of pentaerythrityl = tetrakis [(4-nitrophenyl) carbonate] (20.8 g, 26 mmol), 1,6-hexanediol (62 g, 522 mmol) and potassium carbonate (22 g, 157 mmol) in tetrahydrofuran (260 mL) at 40 ° C. For 12 hours. Water (10 mL) was added to the reaction mixture, the resulting mixture was extracted with ethyl acetate (30 mL × 3), and washed with 1N aqueous sodium hydroxide solution until the resulting organic layer became colorless and transparent. After confirming the removal of hexanediol by TLC, it was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (20% methanol / chloroform) to obtain pentaerythrityl tetrakis [(6-hydroxyhexyl) carbonate] (14 g, yield). 75%) was obtained as a colorless transparent oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.23 (s, 8H), 4.14 (t, J = 6.9 Hz, 8H), 3.65 (dd, J = 6.2) 11.6 Hz, 8H), 1.70-1.63 (m, 8H), 1.62-1.54 (m, 8H), 1.47-1.36 (m, 20H).

  <Example 4>

Glyceryl = tris [(4-nitrophenyl) carbonate] (1.17 g, 2 mmol), 6- (benzyloxy) hexanol (1.38 g, 6.6 mmol), pyridine (0.64 mL, 8 mmol) and N, N- A solution of dimethylaminopyridine (28 mg, 0.2 mmol) in tetrahydrofuran (8 mL) was heated at 70 ° C. for 19 hours. Water (10 mL) was added to the reaction mixture, extracted with toluene (20 mL × 3), and washed with 1N aqueous sodium hydroxide solution until the organic layer became colorless and transparent. The obtained organic layer was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene) to obtain glyceryl tris [[6- (benzyloxy) hexyl) carbonate] ( 1.02 g, yield 64%) was obtained. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.36-7.31 (m, 12H), 7.29-7.27 (m, 3H), 5.10 (tt, J = 3. 9, 5.9 Hz, 1 H), 4.49 (s, 6 H), 4.42 (dd, J = 4.3, 12.0 Hz, 2 H), 4.29 (dd, J = 5.6, 12 .0 Hz, 2H), 4.14 (t, J = 6.7 Hz, 2H) 4.13 (t, J = 6.7 Hz, 4H), 3.46 (t, J = 6.5 Hz, 6H), 1.70-1.59 (m, 12H), 1.44-1.34 (m, 12H).

  <Example 5>

After adding 10% palladium / carbon powder (26 mg) to a solution of glyceryl tris [(6- (benzyloxy) hexyl) carbonate] (1.02 g, 1.28 mmol) (645 mg) in tetrahydrofuran (4 mL), The inside of the reaction vessel was replaced with hydrogen gas and reacted at 20 ° C. for 12 hours. The reaction mixture was filtered through celite, and the filtrate was concentrated to obtain a crude product. The crude product was purified by flash silica gel column chromatography (20% methanol / chloroform), and glyceryl tris [(6-hydroxyhexyl) carbonate] (369 mg, 0.70 mmol, yield 55%, GPC purity 94%, FIG. 1 (GPC))) was obtained as a colorless transparent oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 5.11 (tt, J = 4.2, 5.8 Hz, 1H), 4.44 (dd, J = 4.2, 12.0 Hz, 2H ), 4.30 (dd, J = 5.8, 12.0 Hz, 2H), 4.17 (t, J = 6.5 Hz, 2H) 4.15 (t, J = 6.5 Hz, 4H), 3.65 (t, J = 6.4 Hz, 6H), 1.72-1.66 (m, 6H), 1.60-1.56 (m, 6H), 1.42-1.38 (m , 15H).

  <Example 6>

Glyceryl = tris [(4-nitrophenyl) carbonate] (17.9 g, 30.5 mmol) and 4- (benzyloxy) butanol (18.2 g, 101 mmol) were dissolved in tetrahydrofuran (100 mL). N, N-dimethylaminopyridine (401 mg, 3.2 mmol) and pyridine (10 mL, 122 mmol) were added to the mixture, and the mixture was heated to reflux for 12 hours. After completion of the reaction, water (100 mL) was added to the reaction solution, and extraction was performed with toluene (100 mL × 2). The organic layer was washed with a 1N aqueous sodium hydroxide solution until the yellow color of the aqueous layer disappeared, then washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene) to give glyceryl tris [[4- (benzyloxy) butyl] carbonate] (17 0.5 g, 81% yield) was obtained as a colorless oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.36-7.27 (m, 15H), 5.09 (tt, J = 4.2, 5.7 Hz, 1H), 4.50 ( s, 6H), 4.40 (dd, J = 4.2, 11.9 Hz, 2H), 4.26 (dd, J = 5.7, 11.9 Hz, 2H), 4.17 (t, J = 6.4 Hz, 2H), 4.16 (t, J = 6.4 Hz, 4H), 3.49 (t, J = 6.1 Hz, 6H), 1.81-1.75 (m, 6H) , 1.72-1.65 (m, 6H).

  <Example 7>

Glyceryl = tris [(4- (benzyloxy) butyl) carbonate] (17.5 g, 24.6 mmol) was dissolved in tetrahydrofuran (15 mL) and replaced with argon gas. After adding 10% palladium / carbon powder (368 mg, 2 wt%) to the mixed solution, the mixture was replaced with hydrogen gas and stirred at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified by flash silica gel column chromatography (10% methanol / chloroform), and glyceryl = tris [(4-hydroxybutyl) carbonate] (8.56 g, yield 79%, GPC purity 96%). Was obtained as a pale yellow oil. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 5.07 (tt, J = 3.4, 6.5 Hz, 1H), 4.43 (t, J = 5.1 Hz) 4.34 (Dd, J = 3.4, 12.0 Hz, 2H), 4.22 (dd, J = 6.5, 12.0 Hz, 2H), 4.12-4.08 (m, 6H), 3. 40 (t, J = 6.2 Hz, 6H), 1.66-1.59 (m, 6H), 1.48-1.41 (m, 6H).

  <Example 8>

To a mixture of glycerin (21 mg, 0.23 mmol) and dichloromethane (2 mL) and pyridine (0.06 mL, 0.70 mmol) was added 6- (methoxymethoxy) hexyl chloroformate (314 mg, 1.40 mmol) in dichloromethane (2 mL). ) The solution was added dropwise at 0 ° C., the temperature was raised to 20 ° C., and the mixture was reacted for 1 hour. Water (10 mL) was added to the reaction mixture to stop the reaction. The resulting mixture was extracted with dichloromethane (10 mL × 3), and the organic layer was washed with saturated brine (30 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (20% ethyl acetate / hexane, then 30% ethyl acetate / hexane), and glyceryl tris [(6- (Methoxymethoxy) hexyl) carbonate] (145 mg, 97% yield) was obtained as a colorless transparent oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ: 5.10 (tt, J = 4.2, 5.7 Hz, 1H), 4.61 (s, 6H), 4.43 (dd, J = 4.2) , 11.9 Hz, 2H), 4.30 (dd, J = 5.7, 11.9 Hz, 2H), 4.16 (t, J = 6.7 Hz, 2H) 4.14 (t, J = 6 .7 Hz, 4H), 3.52 (t, J = 6.5 Hz, 6H), 3.36 (s, 9H) 1.72-1.65 (m, 6H), 1.64-1.57 ( m, 6H), 1.42-1.38 (m, 12H).

  <Example 9>

To a solution of glyceryl tris [(6- (methoxymethoxy) hexyl) carbonate] (174 mg, 0.27 mmol) in tetrahydrofuran (1 mL) was added a mixture of 2-propanol and concentrated hydrochloric acid (2: 1 v / v, 3 mL). And reacted at 20 ° C. for 9 hours. After adding water (5 mL) to the reaction mixture, saturated aqueous sodium bicarbonate was added until bubbling ceased. The obtained mixture was extracted with ethyl acetate (20 mL × 3), washed with saturated brine (25 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain glyceryl = tris [(6-hydroxyhexyl) carbonate] (136 mg, yield 98%) as a colorless transparent oil (sample-1). ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 5.11 (tt, J = 3.9, 5.9 Hz, 1H), 4.44 (dd, J = 3.9, 12.0 Hz, 2H ), 4.30 (dd, J = 5.9, 12.0 Hz, 2H), 4.17 (t, J = 6.6 Hz, 2H) 4.16 (t, J = 6.5 Hz, 4H), 3.65 (t, J = 6.5 Hz, 6H), 1.72-1.66 (m, 6H), 1.60-1.56 (m, 6H), 1.42-1.38 (m , 12H).

  <Example 10>

Glycerol (2.77 g, 30 mmol) was dissolved in tetrahydrofuran (100 mL), and pyridine (9.7 mL, 120 mmol) was further added dropwise, followed by cooling to 0 ° C. 6- (Methoxymethoxy) hexyl chloroformate (27.6 g, 100 mmol) was added dropwise, and the mixture was heated to 20 ° C. and reacted for 2 hours. After completion of the reaction, water (100 mL) was added to the reaction solution, the reaction mixture was extracted with diethyl ether (100 mL × 3), and the organic layer was washed with saturated brine (100 mL) and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene) to obtain glyceryl tris [(6- (benzyloxy) hexyl) carbonate] (20.5 g, yield 86%). Obtained as a colorless transparent oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.36-7.31 (m, 12H), 7.29-7.27 (m, 3H), 5.10 (tt, J = 3. 9, 5.9 Hz, 1 H), 4.49 (s, 6 H), 4.42 (dd, J = 4.3, 12.0 Hz, 2 H), 4.29 (dd, J = 5.6, 12 .0 Hz, 2H), 4.14 (t, J = 6.7 Hz, 2H) 4.13 (t, J = 6.7 Hz, 4H), 3.46 (t, J = 6.5 Hz, 6H), 1.70-1.59 (m, 12H), 1.44-1.34 (m, 12H).

  <Example 11>

Glyceryl tris (6-hydroxyhexyl) carbonate (6.53 g, 12.5 mmol) and 6- (benzyloxy) hexyl 4-nitrophenyl carbonate (15.4 g, 41.1 mmol) were dissolved in tetrahydrofuran (50 mL). . N, N-dimethylaminopyridine (165 mg, 1.35 mmol) and pyridine (4.0 mL, 49.8 mmol) were added to the mixture, and the mixture was heated to reflux for 36 hours. After completion of the reaction, water (50 mL) was added to the reaction solution, and extraction was performed with toluene (50 mL × 3). The organic layer was washed with a 1N aqueous sodium hydroxide solution until the yellow color of the aqueous layer disappeared, then washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene), and glyceryl tris [6- (6- (benzyloxy) hexyloxycarbonyloxy). ) Hexyl) carbonate] (10.7 g, 70% yield) was obtained as a colorless oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.36-7.27 (m, 15H), 5.10 (tt, J = 4.2, 5.7 Hz, 1H), 4.50 ( s, 6H), 4.40 (dd, J = 4.2, 11.9 Hz, 2H), 4.26 (dd, J = 5.7, 11.9 Hz, 2H), 4.16-4.10. (M, 18H), 3.46 (t, J = 6.5 Hz, 6H), 1.70-1.59 (m, 24H), 1.44-1.35 (m, 24H).

  <Example 12>

Glyceryl = tris [6- (6- (benzyloxy) hexyloxycarbonyloxy) hexyl) carbonate] (10.7 g, 8.73 mmol) was dissolved in tetrahydrofuran (20 mL) and replaced with argon gas. After adding 10% palladium / carbon powder (229 mg, 2 wt%) to the mixed solution, the mixture was replaced with hydrogen gas and stirred at 20 ° C. for 13 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified by flash silica gel column chromatography (10% methanol / chloroform), and glyceryl = tris [6- (6-hydroxyhexyl) oxycarbonyloxy) hexyl) carbonate] (6.52 g, yield). Yield 78%, GPC purity 95%) as a pale yellow oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 5.11 (tt, J = 4.2, 5.7 Hz, 1H), 4.41 (dd, J = 4.2, 11.9 Hz, 2H ), 4.28 (dd, J = 5.7, 11.9 Hz, 2H), 4.17-4.11 (m, 18H), 3.64 (q, J = 6.3 Hz, 6H), 1 .72-1.65 (m, 18H), 1.62-1.55 (m, 6H), 1.49-1.37 (m, 24H), 1.35 (t, J = 5.3 Hz, 3H).

  <Example 13>

Glyceryl tris [(4-nitrophenyl) carbonate] (8.81 g, 15 mmol), 6- [6- [6- (benzyloxy) hexyloxycarbonyloxy] hexyloxycarbonyloxy] hexanol (24.6 g, 49 0.5 mmol), pyridine (4.8 mL, 60 mmol) and N, N-dimethylaminopyridine (183 mg, 1.5 mmol) in tetrahydrofuran (50 mL) were heated to reflux at 70 ° C. for 19 hours. After completion of the reaction, water (100 mL) was added to the reaction solution, and extraction was performed with toluene (100 mL × 3). The organic layer was washed with a 1N aqueous sodium hydroxide solution until the yellow color of the aqueous layer disappeared, then washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene) to obtain glyceryl tris [[6- (6- [6- (benzyloxy)). Hexyloxycarbonyloxy] hexyloxycarbonyloxy)] hexyl carbonate] (22.1 g, 85% yield) was obtained as a pale yellow oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.36-7.31 (m, 12H), 7.29-7.27 (m, 3H), 5.10 (tt, J = 4. 2, 5.7 Hz, 1H), 4.50 (s, 6H), 4.40 (dd, J = 4.2, 11.2 Hz, 2H), 4.26 (dd, J = 5.7, 11 .9 Hz, 2H), 4.16-4.10 (m, 30H), 3.46 (t, J = 6.5 Hz, 6H), 1.72-1.59 (m, 36H), 1.44 -1.36 (m, 36H).

  <Example 14>

Glyceryl = Tris [[6- (6- [6- (benzyloxy) hexyloxycarbonyloxy] hexyloxycarbonyloxy)] hexyl carbonate] (22.1 g, 13.3 mmol) was dissolved in tetrahydrofuran (20 mL). Replaced with argon gas. After adding 10% palladium / carbon powder (440 mg, 2 wt%) to the mixed solution, the mixture was replaced with hydrogen gas and stirred at 20 ° C. for 2 days. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified by flash silica gel column chromatography (10% methanol / chloroform), and glyceryl = tris [[6- [6- (6-hydroxyhexyl) oxycarbonyloxy] hexyloxycarbonyloxy] hexyl. Carbonate] (14.6 g, yield 79%, GPC purity 95%) was obtained as a pale yellow oil. ¹ H NMR (400 MHz, CDCl ₃ ) NMR (400 MH0 (tt, J = 4.2, 5.7 Hz, 1H), 4.50 (s, 6H), 4.40 (dd, J = 4.2, 11 .9 Hz, 2H), 4.28 (dd, J = 5.6, 11.9 Hz, 2H), 4.17-4.10 (m, 30H), 3.46 (dt, J = 5.2). 6.5 Hz, 6H), 1.72-1.63 (m, 30H), 1.61-1.56 (m, 6H), 1.45-1.36 (m, 36H), 1.32 ( br, 3H).

  <Example 15>

Trimethylolpropane (67 mg, 0.5 mmol) and 6- (benzyloxy) hexyl 4-nitrophenyl carbonate (579 mg, 1.55 mmol) were dissolved in tetrahydrofuran (2 mL). N, N-dimethylaminopyridine (6 mg, 0.05 mmol) and pyridine (0.16 mL, 2 mmol) were added to the reaction solution, and the mixture was heated to reflux for 10 hours. After completion of the reaction, water (10 mL) was added to the reaction solution, and extraction was performed with toluene (10 mL × 2). The organic layer was washed with a 1N aqueous sodium hydroxide solution until the yellow color of the aqueous layer disappeared, then washed with saturated brine (20 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene), and trimethylolpropane = tris [(6- (benzyloxy) hexyl) carbonate]. (282 mg, 67% yield) was obtained as a colorless oil. ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.36-7.31 (m, 12H), 7.29-7.27 (m, 3H), 4.50 (s, 6H), 4 .11 (s, 6H), 4.11 (t, J = 6.6 Hz, 6H), 3.46 (t, J = 6.6 Hz, 6H), 1.70-1.59 (m, 12H) 1.52 (q, J = 7.6 Hz, 2H), 1.43-1.35 (m, 12H), 0.90 (t, J = 7.6 Hz, 3H).

  <Example 16>

Trimethylolpropane = tris [(6- (benzyloxy) hexyl) carbonate] (282 mg, 0.34 mmol) was dissolved in tetrahydrofuran (2 mL) and replaced with argon gas. After adding 10% palladium / carbon powder (11 mg, 4 wt%) to the mixed solution, the mixture was replaced with hydrogen gas and stirred at 20 ° C. for 5 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified by flash silica gel column chromatography (10% methanol / chloroform), and trimethylolpropane = tris [(6-hydroxyhexyl) carbonate] (171 mg, yield 89%) was obtained as a colorless oil. Obtained. ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 4.13 (t, J = 6.6 Hz, 6H), 4.12 (s, 6H), 3.65 (dd, J = 6.4) 4.0 Hz, 6H), 1.72-1.65 (m, 6H), 1.62-1.58 (m, 6H), 1.53 (q, J = 7.6 Hz, 2H), 1. 44-1.37 (m, 15H), 0.91 (t, J = 7.6 Hz, 3H).

  <Example 17>

Pentaerythritol (68 mg, 0.5 mmol) and 6- (benzyloxy) hexyl = 4-nitrophenyl carbonate (823 mg, 2.2 mmol) were dissolved in tetrahydrofuran (5 mL). N, N-dimethylaminopyridine (6 mg, 0.05 mmol) and pyridine (0.20 mL, 2.5 mmol) were added to the reaction solution, and the mixture was heated to reflux for 23 hours. After completion of the reaction, water (10 mL) was added to the reaction solution, and extraction was performed with toluene (10 mL × 2). The organic layer was washed with a 1N aqueous sodium hydroxide solution until the yellow color of the aqueous layer disappeared, then washed with saturated brine (20 mL), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by flash silica gel column chromatography (10% ethyl acetate / toluene), and pentaerythrityl tetrakis [6- (benzyloxy) hexyl carbonate] (358 mg). Yield 67%) as a colorless oil. ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.36-7.31 (m, 16H), 7.29-7.27 (m, 4H), 4.50 (s, 8H), 4 .11 (s, 6H), 4.22 (s, 8H), 4.11 (t, J = 6.7 Hz, 8H), 3.46 (t, J = 6.6 Hz, 8H), 1.70 -1.59 (m, 16H), 1.4-1.34 (m, 16H).

  <Example 18>

  Pentaerythrityl tetrakis [6- (benzyloxy) hexyl] carbonate (18.5 g, 17.2 mmol) was dissolved in tetrahydrofuran (20 mL) and replaced with argon gas. After adding 10% palladium / carbon powder (370 mg, 2 wt%) to the mixed solution, the mixture was replaced with hydrogen gas and stirred at 20 ° C. for 24 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain a crude product. The obtained crude product was purified by flash silica gel column chromatography (10% methanol / chloroform), and pentaerythrityl tetrakis [(6-hydroxyhexyl) carbonate] (9.77 g, yield 80%) was colorless oily. Obtained as a thing.

<Comparative Example 1>
Dimethyl carbonate (9.02 g, 100 mmol), glycerol (1.18 g, 12.8 mmol), 1,6-hexanediol (8.87 g, 75.0 mmol), lithium hydroxide (1.0 mg, 0.042 mmol). The mixture was gradually heated from 80 ° C. to 190 ° C. under normal pressure and stirring, and the ester exchange reaction was carried out for 6 hours while distilling off the mixture of methanol and dimethyl carbonate. Thereafter, the pressure was reduced, and the ester exchange reaction was further carried out at 190 ° C. for 30 minutes while distilling off the mixture of methanol and dimethyl carbonate. When the distillation of methanol and dimethyl carbonate was completed, the reaction solution was cooled to 20 ° C. As a crude product, a mixture of various polycarbonate polyols (yield 12.3 g, number average molecular weight 543, FIG. 2) was obtained. From the fact that a peak at 1800 cm ⁻¹ was observed by IR, it was confirmed that a cyclic 5-membered carbonate was formed.

  The polycarbonate polyol obtained by the production method of the present invention described above can be suitably used as a raw material for urethane resin.

Claims (11)

General formula (4)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ⁴ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (4a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁴ represents a hydrogen atom, a methyl group or an ethyl group. The poly (p-nitrophenyl) carbonate represented by the general formula (9)

(Wherein R represents the same meaning as described above, n represents an integer of 1 to 10; m + n satisfies an integer of 1 to 10). The general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a).

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. The manufacturing method of the polycarbonate polyol represented by this.   The method for producing a polycarbonate polyol according to claim 1, wherein 3 or 4 m are all the same integer.   The method for producing a polycarbonate polyol according to claim 1 or 2, wherein n = 1. General formula (4)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ⁴ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (4a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁴ represents a hydrogen atom, a methyl group or an ethyl group. The poly (p-nitrophenyl) carbonate represented by the general formula (5)

(In the formula, R represents the same meaning as described above. Y ¹ represents a methoxymethyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms; or a benzyl group optionally substituted with a methoxy group. n represents an integer of 1 or more and 10 or less, provided that m + n satisfies an integer of 1 or more and 10 or less.

(In the formula, R, Y ¹ , m, n and q represent the same meaning as described above. X ⁶ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (6a).

(Wherein R, Y ¹ , m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁶ represents a hydrogen atom, a methyl group or an ethyl group. ), Followed by a deprotection reaction, wherein the general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a)

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. The manufacturing method of the polycarbonate polyol represented by this. The method for producing a polycarbonate polyol according to claim 4, wherein Y ¹ is a methoxymethyl group or a benzyl group.   The method for producing a polycarbonate polyol according to claim 4 or 5, wherein 3 or 4 m are all the same integer.   The method for producing a polycarbonate polyol according to claim 4, wherein n = 1. General formula (10)

(In the formula, R represents a divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms. 3 or 4 m's are the same or different and represent an integer of 0 or more and 9 or less. Q represents 0 or 1. X ¹⁰ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (10a)

(Wherein R and m represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group. The polyol represented by the general formula (8)

(In the formula, R represents the same meaning as described above. Y ¹ represents a methoxymethyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms; or a benzyl group optionally substituted with a methoxy group. A represents a chlorine atom or a (p-nitrophenyl) oxy group, n represents an integer of 1 or more and 10 or less, provided that m + n satisfies an integer of 1 or more and 10 or less. And general formula (6)

(In the formula, R, Y ¹ , m, n and q represent the same meaning as described above. X ⁶ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (6a).

(Wherein R, Y ¹ , m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁶ represents a hydrogen atom, a methyl group or an ethyl group. ), Followed by a deprotection reaction, wherein the general formula (7)

(In the formula, R, m, n and q represent the same meaning as described above. X ⁷ represents a hydrogen atom, a methyl group, an ethyl group or a general formula (7a).

(Wherein R, m and n represent the same meaning as described above), and represents a carbonate-substituted methyl group. However, when q is 0, X ⁷ represents a hydrogen atom, a methyl group or an ethyl group. The manufacturing method of the polycarbonate polyol represented by this. The method for producing a polycarbonate polyol according to claim 8, wherein Y ¹ is a methoxymethyl group or a benzyl group.   The method for producing a polycarbonate polyol according to claim 8 or 9, wherein 3 or 4 m are all the same integer.   The method for producing a polycarbonate polyol according to claim 8, wherein n = 1.

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