JP2013067598A - Process for production of 1,3-diol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct (one step), high-reaction-rate, high yield and highly selective process for production of a 1,3-diol compound from a dioxolane compound having a hydroxymethyl group.SOLUTION: The process for production of the 1,3-diol compound includes contacting the dioxolane compound having the hydroxymethyl group with a catalyst for hydrogenolysis in the presence of a hydrogen source.

Description

  The present invention relates to a process for producing a corresponding 1,3-diol compound by hydrocracking a dioxolane compound having a hydroxymethyl group.

  The 1,3-diol compound produced by the hydrocracking catalyst of the present invention is a useful compound, for example, as a raw material for polyesters, a solvent, an antifreeze solution, an additive for an adhesive agent, and the like.

Conventionally, there is no known method for producing a corresponding 1,3-diol compound by hydrogenolysis of a dioxolane compound having a hydroxymethyl group. Examples of a method for producing a 1,3-diol compound include: The following method is disclosed.
(1) A method of obtaining 1,3-propanediol by reducing glycerin in the presence of a catalyst in which iridium is supported on silica (see, for example, Patent Document 1 and Non-Patent Document 1).
(2) A method for obtaining 1,3-propanediol by hydrogenolysis of glycerin in the presence of a catalyst containing platinum, palladium, ruthenium or the like (see, for example, Patent Document 2).

JP 2009-275029 A JP 2008-163000 A Applied. Cat. B. , 105 (2011) 117

In the method (1), not only the selectivity of 1,3-propanediol at the maximum yield is very low, 39.2%, but also the reaction rate is very slow. To make it 30% or more, a reaction time of 12 hours or more was required. Further, there is a problem that a large amount of 1,2-propanediol, which is difficult to separate, is produced as a by-product.
In the method (2), not only the conversion rate of glycerin is low, but also 1,3-propanediol, which is a by-product and is difficult to separate, is produced in preference to the required 1,3-propanediol. There was a problem to do.

  On the other hand, a glycerol compound can be obtained, for example, by reacting a dioxolane compound having a hydroxymethyl group with water. Therefore, it is considered that the 1,3-diol compound can be produced by the above method (1) or (2) by reacting the dioxolane compound with water to obtain a glycerin compound.

  However, since this method is a two-step reaction, the operation becomes extremely complicated, and there is a possibility that the yield decreases as the number of steps increases. Moreover, it was necessary to control and manage each by-product generated by the two processes. Accordingly, there has been a demand for a method for directly producing a corresponding 1,3-diol compound by hydrogenolysis of a dioxolane compound having a hydroxymethyl group.

  The object of the present invention is to solve the above-mentioned problems, and from a dioxolane compound having a hydroxymethyl group directly (in one step), with a high reaction rate, high yield and high selectivity, 1,3-diol. An object of the present invention is to provide a method for producing a 1,3-diol compound that gives a compound. In particular, it is to selectively produce a 1,3-diol compound without by-producing a 1,2-diol compound as a by-product.

  The subject of this invention is general formula (1) in presence of a hydrogen source.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z represents a keto group, a thioketo group, a methylene group or a dimethylmethylene group.

Represents a single bond or a double bond. )
A dioxolane compound having a hydroxymethyl group represented by general formula (2), and a hydrocracking catalyst are brought into contact with each other.

(In the formula, R ¹ has the same meaning as described above.)
It solves by the manufacturing method of the 1, 3-diol compound shown by these.

  According to the present invention, a 1,3-diol compound corresponding to a high yield and high selectivity can be produced at a high reaction rate by hydrogenolysis of a dioxolane compound having a hydroxymethyl group.

(Catalyst for hydrocracking)
The hydrocracking catalyst of the present invention is any of the following catalysts (hereinafter, the catalysts 1 to 3 may be collectively referred to as a hydrocracking catalyst).

(A) a metal compound containing Group 8 or Group 9 of the periodic table,
And (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
Then, a catalyst obtained by reducing the resulting mixture (hereinafter sometimes referred to as catalyst 1).

(A) a metal compound containing Group 8 or Group 9 of the periodic table,
(B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
And (C) a ruthenium oxide compound,
Then, a catalyst obtained by reducing the resulting mixture (hereinafter also referred to as catalyst 2).

(A) a metal compound containing a metal of Group 8 or 9 of the periodic table,
(B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
And (D) a polyvalent acid salt,
Then, a catalyst obtained by reducing the resulting mixture (hereinafter sometimes referred to as catalyst 3).

  Hereinafter, each component of the hydrocracking catalyst will be sequentially described.

(A) Metal compound containing Group 8 or Group 9 of the periodic table (hereinafter sometimes simply referred to as metal compound)
Examples of the metal of the metal compound containing any of Group 8 or Group 9 metals used in the present invention include iron, ruthenium, osmium, cobalt, rhodium, iridium, etc., preferably ruthenium, Cobalt, rhodium and iridium are more preferable, and ruthenium, rhodium and iridium are more preferable.

  The form of the metal compound is not particularly limited, and may be any form such as a simple metal, a metal alloy, a metal salt, a metal complex, or a metal oxide, and is an adduct of a hydrate or an organic compound. May be. Further, it may be supported on a carrier. In addition, you may use these metal compounds individually or in mixture of 2 or more types.

  Specific examples of metal compounds include, for example, ruthenium trichloride, ruthenium tribromide, ruthenium diammonium pentachloride, ruthenium triammonium chloride, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, ruthenium hexabromide 3 Ruthenium compounds such as potassium and ruthenium hexabromide; cobalt compounds such as cobalt dichloride, cobalt dibromide, cobalt diiodide, cobalt difluoride, cobalt dinitrate, cobalt oxide, cobalt phosphate and cobalt diacetate Rhodium compounds such as rhodium trichloride, rhodium trichloride, tripotassium hexachloride, trisodium hexachloride, trisodium hexachloride, rhodium trinitrate; iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, iridium Acid ammonium salt, hexaan Iridium trichloride, pentaamminechloroiridium dichloride, iridium hexachloride triammonium hexachloride, iridium trichloride potassium, iridium hexachloride trisodium, iridium tetrachloride diammonium, iridium hexachloride diammonium, iridium hexachloride dipotassium, Examples thereof include iridium compounds such as hexachloroiridium acid and iridium hexachloride disodium, and preferably ruthenium trichloride, cobalt dichloride, rhodium trichloride, iridium trichloride, iridium tetrachloride, and iridium hexachloride.

  In addition to the metal compound containing Group 8 or Group 9 of the periodic table, a metal compound containing any of metals of Groups 3 to 7 or Groups 10 to 11 of the periodic table can be used as appropriate.

(B) A metal oxide containing a metal of Group 5, 6 or 7 of the periodic table (hereinafter sometimes simply referred to as a metal oxide)
Examples of the metal oxide metal containing a metal of Group 5, 6 or 7 of the periodic table used in the present invention include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium and the like. Of these, vanadium, molybdenum, tungsten, and rhenium are preferable.

  The form of the metal oxide is not particularly limited as long as it is a compound having one metal-oxygen bond, and may be, for example, a hydrate or an adduct of an organic compound. Further, it may be supported on a carrier. In addition, you may use these metal oxides individually or in mixture of 2 or more types.

  As the metal oxide, at least one compound selected from the group consisting of metal oxides and metal peroxide salts is preferably used. Specific examples thereof include, for example, vanadium trichloride, oxidation Vanadium, divanadium trioxide, vanadium dioxide, divanadium pentoxide, vanadium tribromide, potassium pyrovanadate, potassium tetraoxovanadate (V), potassium trioxovanadate (V), sodium trioxovanadate (V) , Vanadium oxides such as sodium pyrovanadate and lithium trioxovanadate (V); silicomolybdic acid, molybdenum pentachloride, ammonium tetracosaoxoheptamolybdate (VI), potassium tetraoxomolybdate (VI), tetraoxomolybdenum Calcium acid, tetraoxomolyb (VI) sodium, tetraoxomolybdenum (VI) magnesium, tetraoxomolybdenum (VI) lithium, molybdenum dioxide, molybdenum trioxide and other molybdenum oxides; tetraoxotungsten (VI) sodium, tetraoxotungsten ( VI) Cadmium (II) acid, potassium tetraoxotungsten (VI), calcium tetraoxotungsten (VI), etc .; rhenium trichloride, rhenium pentachloride, ammonium tetraoxorhenium (VII), tetraoxorhenium (VII) Preferred are rhenium oxides such as potassium acid, sodium tetraoxorhenium (VII), tripotassium hexachloride, dipotassium hexachloride, rhenium dioxide, rhenium trioxide, and dirhenium heptoxide. Is divanadium pentoxide, potassium trioxovanadate (V), sodium trioxovanadate (V), sodium pyrovanadate, sodium tetraoxotungsten (VI), silicomolybdic acid, tetracosaoxoheptamolybdenum (VI) acid Ammonium, sodium tetraoxomolybdate (VI) ammonium tetraoxorhenium (VII), potassium tetraoxorhenium (VII), dirhenium heptoxide are used.

(C) Ruthenium oxide compound As the ruthenium oxide compound used in the present invention, at least one compound selected from the group consisting of ruthenium oxide and ruthenium peroxide is preferably used. Examples of ruthenium oxide include ruthenium dioxide, ruthenium trioxide, and ruthenium tetroxide, but ruthenium tetroxide is preferably used. Examples of the ruthenate peroxide include potassium perruthenate, perruthenate (tetrapropylammonium), perruthenate (tetrabutylammonium), and dipotassium tetraoxoruthenium (VI). Potassium perruthenate and perruthenic acid (tetrapropylammonium) are used. These ruthenium oxide compounds may be hydrates or adducts of organic compounds, or may be supported on a carrier.

(D) Polyvalent acid salt The polyvalent acid salt used in the present invention refers to a salt derived from a divalent or higher acid such as carbonic acid, sulfuric acid, phosphoric acid and oxalic acid. As such polyvalent acid salt, if it is a polyvalent inorganic acid salt, for example, tripotassium phosphate, dipotassium monohydrogen phosphate, trisodium phosphate, disodium monohydrogen phosphate, triammonium phosphate, Phosphate such as diammonium phosphate (as a broad meaning including hydrogen phosphate); carbonates such as ammonium carbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate (hydrogen carbonate) A broad meaning including a salt); sulfates such as potassium sulfate, sodium sulfate, ammonium sulfate and the like. Examples of polyvalent organic acid salts include polyvalent organic acid salts such as dipotassium oxalate and disodium oxalate. These polyvalent acid salts may be hydrates or adducts of organic compounds, or may be supported on a carrier.

  The polyvalent inorganic acid salt is preferably tripotassium phosphate, trisodium phosphate, triammonium phosphate, diammonium monohydrogen phosphate, ammonium carbonate, potassium carbonate, sodium carbonate, potassium sulfate, sodium sulfate, Ammonium sulfate, more preferably tripotassium phosphate, triammonium phosphate, ammonium carbonate, diammonium monohydrogen phosphate, potassium carbonate, potassium sulfate is used.

(Manufacture of catalyst 1)

  The catalyst 1 of the present invention is produced by physically mixing a metal compound and a metal oxide.

  More specifically, after adding a metal compound and a metal oxide to a solvent (for example, water) to form a solvent solution (for example, an aqueous solution), the obtained aqueous solution is preferably 60 to 200 ° C. Preferably, the mixture is obtained by heating and stirring at 100 to 150 ° C.

  The amount of the metal oxide used in the mixing is preferably 1 to 30 mol, more preferably 0.5 to 20 mol, per 1 mol of the metal compound. These values are in terms of metal atoms.

  The obtained mixture can be used as catalyst 1 by subsequent reduction treatment. The reduction treatment can be performed using a normal reducing agent capable of generating hydrogen, but a method of contacting with hydrogen gas is preferably employed. The contact temperature when contacting the mixture with hydrogen gas is preferably 40 to 300 ° C., more preferably 50 to 200 ° C., and the contact pressure is preferably 1 to 12 MPa, more preferably 4 to 8 MPa. .

  The catalyst 1 obtained by the above reduction treatment can be used as it is for the production of 1,3-diol compound even if it is used after being isolated by filtration, washing or the like. In addition, the ruthenium oxide compound (C) and / or the polyvalent acid salt (D) can be mixed and subjected to a reduction treatment under the above-mentioned conditions to be used as a hydrocracking catalyst. That is, a catalyst obtained by physically mixing the catalyst 1 in a reduced state with the ruthenium oxide compound and / or the polyvalent acid salt can be used as the hydrocracking catalyst of the present invention.

  The amount of ruthenium oxide compound or polyvalent acid salt used at that time is preferably 0.1 to 30 mol, more preferably 0.2 to 20 mol, per 1 mol of the metal compound.

(Manufacture of catalyst 2)
In the production of the catalyst 2 of the present invention, first, a metal compound, a ruthenium oxide compound and a metal oxide are mixed. Although the mixing order is not particularly limited, a method of adding a metal oxide after mixing a metal compound and a ruthenium oxide compound is preferably employed.

  More specifically, after adding a metal compound and a ruthenium oxide compound to a solvent (for example, water) to form a solution (for example, an aqueous solution), the obtained aqueous solution is preferably 60 to 200 ° C., more preferably Is heated and stirred at 100 to 150 ° C., then a metal oxide is added, and the mixture is preferably heated and stirred at 60 to 200 ° C., more preferably 100 to 150 ° C.

  The amount of the ruthenium oxide compound used in the mixing is preferably 0.1 to 30 mol, more preferably 0.2 to 20 mol, relative to 1 mol of the metal compound. The amount of metal oxide used is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, per 1 mol of the metal compound. These values are in terms of metal atoms.

  The obtained mixture can then be used as the catalyst 2 by reducing it as it is. The reduction treatment can be performed using a normal reducing agent capable of generating hydrogen, but a method of contacting with hydrogen gas is preferably employed. The contact temperature when contacting the mixture with hydrogen gas is preferably 40 to 300 ° C., more preferably 50 to 200 ° C., and the contact pressure is preferably 1 to 12 MPa, more preferably 4 to 8 MPa. .

  Even if the catalyst 2 obtained by the reduction treatment is isolated by, for example, filtration and washing, and then used for the production of the 1,3-diol compound, it can be used as it is for the production of the 1,3-diol compound. May be used.

(Manufacture of catalyst 3)
In the production of the catalyst 3 of the present invention, first, a metal compound, a polyvalent acid salt and a metal oxide are mixed. Although the mixing order is not particularly limited, a method of adding a metal oxide after mixing a metal compound and a polyvalent acid salt is suitably employed.

  More specifically, after adding a metal compound and a polyvalent acid salt to a solvent (for example, water) to form a solution (for example, an aqueous solution), the obtained aqueous solution is preferably 60 to 200 ° C. Preferably, the mixture is heated and stirred at 100 to 150 ° C., then the metal oxide is added, and the mixture is preferably heated and stirred at 60 to 200 ° C., more preferably 100 to 150 ° C.

  The amount of polyvalent acid salt used in the mixing is preferably 0.1 to 30 mol, more preferably 0.2 to 20 mol, per 1 mol of the metal compound. The amount of metal oxide used is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, per 1 mol of the metal compound. These values are in terms of metal atoms.

  The obtained mixture can be used as a hydrocracking catalyst by subsequent reduction treatment. The reduction treatment can be performed using a normal reducing agent capable of generating hydrogen, but a method of contacting with hydrogen gas is preferably employed. The contact temperature when contacting the mixture with hydrogen gas is preferably 40 to 300 ° C., more preferably 50 to 200 ° C., and the contact pressure is preferably 1 to 12 MPa, more preferably 4 to 8 MPa. .

  Even if the catalyst 3 obtained by the reduction treatment is isolated by, for example, filtration and washing, and then used for the production of the 1,3-diol compound, it can be used as it is for the production of the 1,3-diol compound. May be used.

  The catalyst for hydrocracking may be a catalyst supported on a carrier, and such a supported catalyst can be produced by the presence of a carrier when obtaining the mixture. As the carrier to be used, a porous carrier is preferably used. Specifically, for example, silica, alumina, silica lumina (aluminosilicate), ceria, magnesia, calcia, titania, silica titania (titanosilicate), Zirconia, activated carbon, zeolite, mesoporous material (mesoporous-alumina, mesoporous-silica, mesoporous-carbon) and the like are used. In addition, you may use these support | carriers individually or in mixture of 2 or more types.

  When the hydrocracking catalyst is a supported catalyst, it may be used after calcination. The temperature for firing is preferably 50 to 800 ° C., more preferably 100 to 600 ° C., and the firing time is appropriately adjusted, preferably 0.1 to 20 hours, more preferably 0.25 to 15 It's time.

  The hydrocracking catalyst obtained by the above method can be a catalyst for producing a 1,3-diol compound from a dioxolane compound having a hydroxymethyl group.

(Production of 1,3-diol compound)
In the present invention, in the presence of a hydrogen source, the general formula (1)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z represents a keto group, a thioketo group, a methylene group or a dimethylmethylene group.

Represents a single bond or a double bond. )
A dioxolane compound having a hydroxymethyl group represented by formula (1) and a hydrocracking catalyst (catalysts 1 to 3) are brought into contact with each other.

(Wherein R ¹ and

Is as defined above. )
A 1,3-diol compound represented by the formula:

In the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, specifically, for example, a hydrogen atom; methyl group, ethyl group, propyl group, butyl group, pentyl It is a group. These groups include various isomers.

  or,

Represents a single bond or a double bond.

  Specific examples of the dioxolane compound having a hydroxymethyl group represented by the general formula (1) include general formulas (1a) to (1h).

(Wherein R ¹ has the same meaning as described above.)
The compound shown by these is mentioned.

  Specific examples of the dioxolane compound having a hydroxymethyl group represented by the general formula (1) include, for example, 4- (hydroxymethyl) -1,3-dioxolan-2-one (denoted as glycerin carbonate in the examples), 4- (hydroxymethyl) -5-methyl-1,3-dioxolan-2-one, 5-ethyl-4- (hydroxymethyl) -1,3-dioxolan-2-one, 4- (hydroxymethyl) -5 -Propyl-1,3-dioxolan-2-one, 5-butyl-4- (hydroxymethyl) -1,3-dioxolan-2-one, 4- (hydroxymethyl) -5-pentyl-1,3-dioxolane 2-one, 4- (hydroxymethyl) -1,3-dioxol-2-one, 4- (hydroxymethyl) -5-methyl-1,3-dioxol-2- 5-ethyl-4- (hydroxymethyl) -1,3-dioxol-2-one, 4- (hydroxymethyl) -5-propyl-1,3-dioxol-2-one, 5-butyl-4- (Hydroxymethyl) -1,3-dioxol-2-one, 4- (hydroxymethyl) -5-pentyl-1,3-dioxol-2-one, (1,3-dioxolan-4-yl) methanol, (5 -Methyl-1,3-dioxolan-4-yl) methanol, (5-ethyl-1,3-dioxolan-4-yl) methanol, (5-propyl-1,3-dioxolan-4-yl) methanol, (5 -Butyl-1,3-dioxolan-4-yl) methanol, (5-pentyl-1,3-dioxolan-4-yl) methanol, (1,3-dioxol-4-yl) methanol, (5 Methyl-1,3-dioxol-4-yl) methanol, (5-ethyl-1,3-dioxol-4-yl) methanol, (5-propyl-1,3-dioxol-4-yl) methanol, (5 -Butyl-1,3-dioxol-4-yl) methanol, (5-pentyl-1,3-dioxol-4-yl) methanol, 4- (hydroxymethyl) -1,3-dioxolan-2-thione, 4 -(Hydroxymethyl) -5-methyl-1,3-dioxolane-2-thione, 5-ethyl-4- (hydroxymethyl) -1,3-dioxolane-2-thione, 4- (hydroxymethyl) -5 Propyl-1,3-dioxolane-2-thione, 5-butyl-4- (hydroxymethyl) -1,3-dioxolane-2-thione, 4- (hydroxymethyl) -5-pentyl -1,3-dioxolane-2-thione, 4- (hydroxymethyl) -1,3-dioxol-2-thione, 4- (hydroxymethyl) -5-methyl-1,3-dioxol-2-thione, 5 -Ethyl-4- (hydroxymethyl) -1,3-dioxol-2-thione, 4- (hydroxymethyl) -5-propyl-1,3-dioxol-2-thione, 5-butyl-4- (hydroxymethyl) ) -1,3-dioxol-2-thione, 4- (hydroxymethyl) -5-pentyl-1,3-dioxol-2-thione, (2,2-dimethyl-1,3-dioxolan-4-yl) Methanol, (2,2,5-trimethyl-1,3-dioxolan-4-yl) methanol, (5-ethyl-2,2-dimethyl-1,3-dioxolan-4-yl) methanol, (2,2 Dimethyl-5-propyl-1,3-dioxolan-4-yl) methanol, (5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl) methanol, (2,2-dimethyl-5- Pentyl-1,3-dioxolan-4-yl) methanol, (2,2-dimethyl-1,3-dioxol-4-yl) methanol, (2,2,5-trimethyl-1,3-dioxol-4-yl) Yl) methanol, (5-ethyl-2,2-dimethyl-1,3-dioxol-4-yl) methanol, (2,2-dimethyl-5-propyl-1,3-dioxol-4-yl) methanol, (5-butyl-2,2-dimethyl-1,3-dioxol-4-yl) methanol, (2,2-dimethyl-5-pentyl-1,3-dioxol-4-yl) methanol and the like. Preferably 4- (hydroxymethyl) -1,3-dioxolan-2-one, 4- (hydroxymethyl) -5-methyl-1,3-dioxolan-2-one, 5-ethyl-4- (hydroxymethyl) ) -1,3-dioxolan-2-one, 4- (hydroxymethyl) -5-propyl-1,3-dioxolan-2-one, 5-butyl-4- (hydroxymethyl) -1,3-dioxolane-2 -One, 4- (hydroxymethyl) -5-pentyl-1,3-dioxolan-2-one, (2,2-dimethyl-1,3-dioxol-4-yl) methanol, more preferably 4- (hydroxy Methyl) -1,3-dioxolan-2-one is used.

A 1,3-diol compound obtained by contacting a dioxolane compound having a hydroxymethyl group represented by the general formula (1) with a hydrocracking catalyst is represented by the general formula (2). In the general formula (2), R ¹ and

Is as defined above.

  Specific examples of the 1,3-diol compound represented by the general formula (2) include, for example, 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol, 1,3-hexanediol, 1,3-heptanediol, 1,3-oaktandiol and the like are mentioned, but 1,3-propanediol, 1,3-butanediol and 1,3-pentanediol are preferable, and 1,3-pentanediol is more preferable. 3-propanediol.

  Hereinafter, a reaction in which a 1,3-diol compound is produced by bringing a dioxolane compound having a hydroxymethyl group into contact with a hydrogenolysis catalyst in the presence of a hydrogen source may be referred to as a reaction of the present invention.

  The reaction of the present invention will be described in more detail. In the dioxolane compound having a hydroxymethyl group, the bond between the carbon to which the hydroxymethyl group is bonded and the oxygen forming the ether group is cut to correspond. This is a reaction for obtaining a 1,3-propanediol compound.

(Wherein R ¹ , Z and

Is as defined above. )

  The amount of the hydrocracking catalyst used in the reaction of the present invention is preferably from 0.0005 to 0.1 mol, more preferably from 1 mol of the dioxolane compound having a hydroxymethyl group, in terms of atoms of the metal compound. 0.001 to 0.075 mol. By using this amount, the hydroxy compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. As the hydrocracking catalyst, a plurality of types of catalysts may be separately prepared and used.

  The hydrogen source used in the reaction of the present invention is not particularly limited as long as it is a compound that provides hydrogen. For example, it is diluted with a reducing gas such as hydrogen gas or ammonia gas (diluted with an inert gas such as nitrogen, helium, or argon). Water; alcohols such as methanol, ethanol, and isopropyl alcohol; organic acids such as formic acid, acetic acid, and chloroformic acid; and inorganic acids such as hydrochloric acid and sulfuric acid, preferably reducing gases, and more preferably Hydrogen gas is used.

  The amount of the hydrogen source is preferably 5 to 200 mol, more preferably 10 to 160 mol, per 1 mol of the dioxolane compound having a hydroxymethyl group. By using this amount, the 1,3-diol compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. As the hydrocracking catalyst, a plurality of types of catalysts may be separately prepared and used.

  The reaction of the present invention is preferably carried out in a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t Alcohols such as butyl alcohol and ethylene glycol; hydrocarbons such as heptane, hexane, cyclohexane and toluene; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, dioxane; methylene chloride, dichloroethane And halogenated hydrocarbons such as chloro cyclohexane, preferably hydrocarbons, ethers, more preferably cyclohexane, 1,2-diethoxyethane. In addition, you may use these solvents individually or in mixture of 2 or more types.

  The amount of the solvent used is preferably 0.05 to 100 g, more preferably 0.1 to 20 g, with respect to 1 g of the dioxolane compound having a hydroxymethyl group. By setting it as this usage-amount, stirring can be performed rapidly and reaction can be advanced smoothly.

  As the reaction form of the present invention, either a batch type (batch type) or a continuous type can be selected depending on the form of the catalyst. Further, depending on the nature of the catalyst, the reaction can be carried out in either a homogeneous system or a heterogeneous system (suspension reaction), and the reaction can be carried out continuously in a fixed bed as long as the catalyst is supported on a carrier.

  In the reaction of the present invention, for example, a dioxolane compound having a hydroxymethyl group, a hydrocracking catalyst (may be prepared in the system) and a solvent are mixed and reacted in the presence of a hydrogen source with stirring. Etc. are performed. The reaction temperature at that time is preferably 25 to 200 ° C., more preferably 50 to 150 ° C., and the reaction pressure is preferably a normal pressure to 20 MPa, and more preferably 0.2 to 15 MPa as a hydrogen partial pressure. By setting the reaction temperature and the reaction pressure, the 1,3-diol compound, which is the target product, can be obtained with high yield and high selectivity at a high reaction rate without generating by-products.

  The target 1,3-diol compound is obtained by the reaction of the present invention. This 1,3-diol compound is obtained by, for example, filtering, concentrating, extracting, distilling, It can be isolated and purified by general operations such as sublimation, recrystallization and column chromatography.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

Example 1 (Synthesis of 1,3-propanediol)

In an autoclave with an inner volume of 50 ml equipped with a glass inner tube, iridium tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) 51.9 mg (0.11 mmol), sodium tetraoxomolybdate (VI) dihydrate (Wako Pure) 42.3 mg (0.17 mmol) manufactured by Yakuhin Co., Ltd.) and 5.00 g of a 5 mass% glycerin carbonate / 1,2-diethoxyethane solution (containing 0.250 g (2.12 mol) of glycerin carbonate) are added to the nitrogen atmosphere. And stirred at 120 ° C. for 1 hour. Next, after pressurizing to 8 MPa with hydrogen gas, the reaction was performed at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 98.3% and the selectivity for 1,3-pentanediol was 25.5%. Incidentally, 1,2-propanediol and glycerin, which are by-products, were produced at 0.3% and 1.3%, respectively.

Example 2 (Synthesis of 1,3-propanediol)
In an autoclave with an inner volume of 50 ml equipped with a glass inner tube, 39.9 mg (0.11 mmol) of iridium trichloride n hydrate (Ishizu Co., 53% iridium content), sodium tetraoxomolybdate (VI)・ Add 42.3 mg (0.17 mmol) of dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.00 g of 1,2-diethoxyethane solution (containing 0.250 g (2.12 mol) of glycerin carbonate) After nitrogen substitution, the mixture was stirred with heating at 120 ° C. for 1 hour. Subsequently, after pressurizing with hydrogen gas to 8 MPa, it was made to react at 160 degreeC for 2 hours, stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 56.5% and the selectivity for 1,3-propanediol was 57.9%. In addition, 0.3% of 1,2-propanediol as a by-product was generated, and glycerin was not generated at all.

Example 3 (Synthesis of 1,3-propanediol)
In an autoclave with an internal volume of 50 ml equipped with a glass inner tube, 29.0 mg (0.11 mmol) of rhodium trichloride trihydrate (manufactured by Wako Reagent), potassium tetraoxorhenium (VII) (manufactured by Aldrich) ) 92.0 mg (0.32 mmol) and 1,2-diethoxyethane solution 5.00 g (containing glycerol carbonate 0.250 g (2.12 mol)) were added, and the inside of the tube was purged with nitrogen, followed by heating and stirring at 120 ° C. for 1 hour. did. Next, after pressurizing to 8 MPa with hydrogen gas, the reaction was performed at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 100%, and the selectivity for 1,3-propanediol was 75.7%. In addition, 1,2-propanediol which is a by-product was not generated, and 22.7% of glycerin was generated.

Example 4 (Synthesis of 1,3-propanediol)
In Example 3, the reaction was performed in the same manner as in Example 3 except that the reaction time was changed from 2 hours to 1 hour. As a result, the conversion of glycerin carbonate was 49.1%, and the selectivity for 1,3-propanediol was 87.5%. By-products 1,2-propanediol and glycerin were not produced at all.

Comparative Example 1 (Synthesis of 1,3-propanediol)
In Example 3, the reaction was carried out in the same manner as in Example 3 except that 1,2-diethoxyethane was replaced with water and the reaction temperature was changed from 180 ° C to 120 ° C. As a result, the conversion of glycerin carbonate was 47.6%, and 1,3-propanediol was not produced at all. In addition, glycerin as a by-product was produced at 95.4%.

Example 5 (Synthesis of 1,3-propanediol)
0.104 g (0.31 mmol) of iridium tetrachloride (99.5% made by Wako Pure Chemical Industries) was dissolved in 1.13 g of water in 1.5 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6). Impregnated with an aqueous solution and dried at 110 ° C. for 12 hours. This powder was impregnated with an aqueous solution in which 0.055 g (0.044 mmol) of tetracosaoxoheptamolybdate (VI) acid tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1.13 g of water, and 110 after drying for 12 hours at ° C., and calcined 3.5 hours at 500 ° C., to obtain an iridium 4% molybdenum 2% on solids (hereinafter also referred to as "Ir-Mo / SiO _2") It was.
To an autoclave equipped with a 50 ml glass inner tube, 25 mg of the previously obtained “Ir—Mo / SiO ₂ ” and 2.50 g of 1,2-diethoxyethane were added and pressurized to 8 MPa with hydrogen. Then, the mixture was heated and stirred at 200 ° C. for 1 hour. After cooling this to room temperature and releasing the hydrogen pressure, 2.50 g of a 1,2-diethoxyethane solution (containing 0.250 g (2.12 mol) of glycerin carbonate) was added and then heated to 8 MPa with hydrogen gas. The mixture was reacted at 200 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerol carbonate was 5.4%, and the selectivity for 1,3-propanediol was 42.1%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 6 (Synthesis of 1,3-propanediol)
1.51 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) and 0.61 g of hexachloroiridate / hexahydrate (H ₂ IrCl ₄ .6H ₂ O; manufactured by Wako Pure Chemical Industries, Ltd.) .31 mmol) was impregnated with an aqueous solution dissolved in 1.13 g of water and dried at 110 ° C. for 12 hours. The obtained powder was impregnated with an aqueous solution obtained by dissolving 0.086 g (0.32 mmol) of ammonium tetraoxorhenate (VII) in 1.13 g of water, dried at 110 ° C. for 12 hours, and then further heated to 500 ° C. For 3.5 hours to obtain a solid carrying 4% iridium and 4% rhenium (hereinafter sometimes referred to as “Ir—Re / SiO ₂ ”).
To an autoclave equipped with a 50 ml glass inner tube, 25 mg of the previously obtained “Ir-Re / SiO ₂ ” and 2.50 g of 1,2-diethoxyethane were added and pressurized to 8 MPa with hydrogen. Then, it was heated and stirred at 200 ° C. for 1 hour. After cooling this to room temperature and releasing the hydrogen pressure, 2.50 g of a 1,2-diethoxyethane solution (containing 0.250 g (2.12 mol) of glycerin carbonate) was added and then heated to 8 MPa with hydrogen gas. The mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerol carbonate was 7.7%, and the selectivity for 1,3-propanediol was 65.5%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 7 (Synthesis of 1,3-propanediol)
1.54 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) and 0.154 g (0.58 mmol) of rhodium trichloride trihydrate (manufactured by Soekawa Riken) in 1.13 g of water The dissolved aqueous solution was impregnated and dried at 110 ° C. for 12 hours. The obtained powder was impregnated with an aqueous solution prepared by dissolving 0.078 g (0.29 mmol) of ammonium tetraoxorhenate (VII) in 1.13 g of water and dried at 110 ° C. for 12 hours. Thereafter, it was further calcined at 500 ° C. for 3.5 hours to obtain a solid carrying rhodium 4% and rhenium 3.6% (hereinafter sometimes referred to as “Rh—Re / SiO ₂ ”).
In an autoclave equipped with a 50 ml glass inner tube, 25 mg of “Rh-Re / SiO ₂ ” obtained previously and 5.00 g of 1,2-diethoxyethane solution (0.250 g of glycerol carbonate (2.12 mol) ))), And then pressurized to 8 MPa with hydrogen gas, followed by reaction at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 19.6% and the selectivity for 1,3-propanediol was 97.5%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 8 (Synthesis of 1,3-propanediol)
Silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) and ruthenium trichloride nhydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.123 g (0.59 mmol) in water 1.13 g The dissolved aqueous solution was impregnated and dried at 110 ° C. for 12 hours. The obtained powder was impregnated with an aqueous solution prepared by dissolving 0.0259 g (0.1 mmol) of ammonium tetraoxorhenate (VII) in 1.13 g of water and dried at 110 ° C. for 12 hours. Thereafter, it was further calcined at 500 ° C. for 3.5 hours to obtain a solid carrying 4% ruthenium and 1.2% rhenium (hereinafter sometimes referred to as “Ru—Re / SiO ₂ ”).
In an autoclave equipped with a 50-ml glass inner tube, 25 mg of “Ru—Re / SiO ₂ ” obtained previously and 5.00 g of 1,2-diethoxyethane solution (0.250 g of glycerol carbonate (2.12 mol) ))), And then pressurized to 8 MPa with hydrogen gas, followed by reaction at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 41.0% and the selectivity for 1,3-propanediol was 50.2%. By-products 1,2-propanediol and glycerin were not produced at all.

Comparative Example 2 (Synthesis of 1,3-propanediol)
A catalyst was prepared in the same manner as in Example 7 except that the ammonium tetraoxorhenate (VII) used in Example 7 was not used, and a solid loaded with 4% rhodium (hereinafter referred to as “Rh / SiO ₂ ”). Sometimes).
When the reaction was carried out in the same manner as in Example 7 except that 25 mg of the previously obtained “Rh / SiO ₂ ” was used in an autoclave equipped with a 50 ml glass inner tube, the conversion rate of glycerin carbonate was 7.7%, 1,3-propanediol and by-products 1,2-propanediol and glycerin were not produced at all.

Example 9 (Synthesis of 1,3-propanediol)
Dissolve 0.0093 g (0.035 mmol) of ammonium tetraoxorhenium (VII) in 0.25 g of water in 0.30 g of 5% Rh / C (manufactured by NE Chemcat, 51.7% water-containing product) The impregnated aqueous solution was impregnated and dried at 110 ° C. for 12 hours to obtain a solid carrying 5% rhodium and 4.5% rhenium (hereinafter also referred to as “Rh-Re / C”).
In an autoclave equipped with a 50 ml glass inner tube, 25 mg of the previously obtained “Rh-Re / C” and 5.00 g of 1,2-diethoxyethane solution (containing 0.250 g (2.12 mol) of glycerol carbonate) Then, after pressurizing with hydrogen gas to 8 MPa, the mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerol carbonate was 97.8%, and the selectivity for 1,3-propanediol was 80.7%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 10 (Synthesis of 1,3-propanediol)
In Example 9, the reaction was performed in the same manner as in Example 9 except that the reaction temperature was lowered from 180 ° C to 160 ° C. As a result, the conversion of glycerol carbonate was 44.0%, and the 1,3-propanediol selectivity was 89.7%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 11 (Synthesis of 1,3-propanediol)
In Example 7, the reaction was conducted in the same manner as in Example 7 except that the reaction temperature was raised from 180 ° C to 200 ° C and the solvent was changed from 1,2-diethoxyethane to 1,2-dichloroethane. As a result, the conversion rate of glycerol carbonate was 5.2%, and the selectivity of 1,3-propanediol was 63.2%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 12 (Synthesis of 1,3-propanediol)
In Example 9, the reaction was performed in the same manner as in Example 9 except that the reaction temperature was lowered from 180 ° C to 160 ° C and the solvent was changed from 1,2-diethoxyethane to tetrahydrofuran. As a result, the conversion of glycerin carbonate was 35.1%, and the selectivity for 1,3-propanediol was 75.3%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 13 (Synthesis of 1,3-propanediol)
In Example 12, the reaction was performed in the same manner as in Example 12 except that the reaction temperature was increased from 160 ° C to 200 ° C. As a result, the conversion of glycerol carbonate was 43.7%, and the selectivity for 1,3-propanediol was 63.4%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 14 (Synthesis of 1,3-propanediol)
In Example 7, the reaction was performed in the same manner as in Example 7 except that the solvent was changed from 1,2-diethoxyethane to 1,2-dimethoxyethane. As a result, the conversion rate of glycerol carbonate was 10.4%, and the 1,3-propanediol selectivity was 95.2%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 15 (Synthesis of 1,3-propanediol)
In an autoclave equipped with a 50 ml glass inner tube, 0.10 g of “Rh-Re / SiO ₂ ” prepared in the same manner as in Example 7 and 1.00 g (8.47 mol) of glycerin carbonate were added. After pressurizing with hydrogen gas to 8 MPa, the reaction was carried out at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerol carbonate was 48.7% and the selectivity for 1,3-propanediol was 67.9%. By-products 1,2-propanediol and glycerin were not produced at all.

Comparative Example 3 (Synthesis of 1,3-propanediol)
In Example 7, the reaction was carried out in the same manner as in Example 7 except that the reaction temperature was lowered from 180 ° C to 120 ° C and the solvent was changed from 1,2-diethoxyethane to water. As a result, the conversion of glycerol carbonate was 22.7%, and 1,3-propanediol was not produced at all. In addition, 23.6% of glycerin as a by-product was produced.

Example 16 (Synthesis of 1,3-propanediol)
1.54 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) and 0.154 g (0.58 mmol) of rhodium trichloride trihydrate (manufactured by Soekawa Riken) in 1.13 g of water The dissolved aqueous solution was impregnated and dried at 110 ° C. for 12 hours. The obtained powder was fired at 500 ° C. for 3.5 hours to obtain a solid (hereinafter sometimes referred to as “Rh / SiO ₂ ”) in which 4% rhodium was supported.
In an autoclave equipped with a 50 ml glass inner tube, 0.10 g of “Rh / SiO ₂ ” obtained earlier, 1.9 mg (0.004 mmol) of dirhenium heptoxide and 1.00 g of glycerol carbonate (8.47 mol) Then, after pressurizing to 8 MPa with hydrogen gas, the mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 46.7% and the selectivity of 1,3-propanediol was 69.1%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 17 (Synthesis of 1,3-propanediol)
In Example 16, the reaction was performed in the same manner as in Example 16 except that 1.9 mg (0.007 mmol) of ammonium tetraoxorhenate was used instead of dirhenium heptoxide. As a result, the conversion of glycerin carbonate was 43.5%, and the selectivity for 1,3-propanediol was 70.3%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 18 (Synthesis of 1,3-propanediol)
In an autoclave equipped with a 50 ml glass inner tube, iridium tetrachloride 13.9 mg (0.04 mmol), ammonium carbonate 4.0 mg (0.04 mmol), dirhenium heptoxide 10.1 mg (0.02 mmol) and water 2 ml was added and heated and stirred at 120 ° C. for 30 minutes. After cooling this to room temperature, 0.2 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) was added, concentrated under reduced pressure at 60 ° C., and the residue was dried under reduced pressure at 60 ° C. for 8 hours to obtain a gray powder. 0.21 g of a body (hereinafter also referred to as “Ir—CO ₃ —Re / SiO ₂ ”) was obtained.
In an autoclave equipped with a 50 ml glass inner tube, 25 mg of the previously obtained “Ir—CO ₃ —Re / SiO ₂ ” and 5.00 g of 1,2-diethoxyethane solution (0.250 g of glycerol carbonate (2 Then, after pressurizing with hydrogen gas to 8 MPa, the mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerol carbonate was 39.9%, and the selectivity for 1,3-propanediol was 65.5%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 19 (Synthesis of 1,3-propanediol)
In an autoclave equipped with a 50 ml glass inner tube, iridium tetrachloride 13.9 mg (0.04 mmol), potassium perruthenate 8.5 mg (0.04 mmol), dirhenium heptoxide 10.1 mg (0.02 mmol) And 2 ml of water were added and the mixture was stirred at 120 ° C. for 30 minutes. After cooling this to room temperature, 0.2 g of silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT G-6) was added, concentrated under reduced pressure at 60 ° C., and then the concentrate was dried under reduced pressure at 60 ° C. for 8 hours to give a gray color. 0.21 g of powder (hereinafter also referred to as “Ir—Ru—Re / SiO ₂ ”) was obtained.
In an autoclave equipped with a 50 ml glass inner tube, 25 mg of the previously obtained “Ir—Ru—Re / SiO ₂ ” and 5.00 g of 1,2-diethoxyethane solution (0.250 g of glycerol carbonate (2. 12 mol) contained), and after pressurizing to 8 MPa with hydrogen gas, the mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of glycerin carbonate was 71.0%, and the selectivity for 1,3-propanediol was 62.2%. By-products 1,2-propanediol and glycerin were not produced at all.

Example 20 (Synthesis of 1,3-propanediol)

In an autoclave equipped with a 50 ml glass inner tube, 25 mg of “Rh—Re / SiO ₂ ” obtained in Example 7 and (2,2-dimethyl-1,3-dioxolan-4-yl) methanol 0 Then, 5.00 g of a 1,2-diethoxyethane solution containing .25 g (1.89 mol) was added, and after pressurizing to 8 MPa with hydrogen gas, the mixture was reacted at 180 ° C. for 2 hours with stirring.
After completion of the reaction, the obtained reaction solution was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion rate of (2,2-dimethyl-1,3-dioxolan-4-yl) methanol was 13.3%, and the selectivity of 1,3-propanediol was It was 12.3%. In addition, 81.0% of glycerol as a by-product was produced.

  From the above results, it was found that a 1,3-diol compound was obtained from a dioxolane compound having a hydroxymethyl group with high reaction rate and high selectivity.

  According to the present invention, a dioxolane compound having a hydroxymethyl group can be hydrocracked to give a corresponding 1,3-diol compound with high reaction rate and high yield. The obtained 1,3-diol compound is a useful compound, for example, as a raw material for polyesters, a solvent, an antifreeze or an additive for an adhesive material.

Claims (7)

In the presence of a hydrogen source, general formula (1)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z represents a keto group, a thioketo group, a methylene group or a dimethylmethylene group.

Represents a single bond or a double bond. )
A dioxolane compound having a hydroxymethyl group represented by general formula (2), and a hydrocracking catalyst are brought into contact with each other.

The manufacturing method of the 1, 3-diol compound shown by these. Hydrocracking catalyst
(A) a metal compound containing Group 8 or Group 9 of the periodic table,
And (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
The method for producing a 1,3-diol compound according to claim 1, wherein the catalyst is obtained by reducing the mixture after mixing. Hydrocracking catalyst
(A) a metal compound containing Group 8 or Group 9 of the periodic table,
And (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
After mixing, the resulting mixture is reduced,
(C) a ruthenium oxide compound,
The method for producing a 1,3-diol compound according to claim 2, which is a catalyst obtained by reducing the mixture obtained by mixing the components. Hydrocracking catalyst
(A) a metal compound containing Group 8 or Group 9 of the periodic table,
And (C) a metal oxide containing a metal of Group 5, Group 6 or Group 7 of the Periodic Table,
After mixing, the resulting mixture is reduced,
(D) polyvalent acid salt,
The method for producing a 1,3-diol compound according to claim 2, which is a catalyst obtained by reducing the mixture obtained by mixing the components. Hydrocracking catalyst
(A) a metal compound containing Group 8 or Group 9 of the periodic table,
(B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
And (C) a ruthenium oxide compound,
The method for producing a 1,3-diol compound according to claim 1, wherein the catalyst is obtained by reducing the mixture after mixing. Hydrocracking catalyst
(A) a metal compound containing a metal of Group 8 or 9 of the periodic table,
(B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table,
And (D) a polyvalent acid salt,
The method for producing a 1,3-diol compound according to claim 1, wherein the catalyst is obtained by reducing the mixture after mixing. Dioxolane compounds having a hydroxymethyl group are represented by the general formulas (1a) to (1h)

(Wherein R ¹ has the same meaning as described above.)
The method for producing a 1,3-diol compound according to claim 1, wherein the compound is represented by the formula: