JP5910387B2 - Method for producing hydroxy compound - Google Patents

Description

  The present invention also relates to a method for producing a corresponding hydroxy compound by hydrocracking an ether compound having a hydroxymethyl group using the hydrocracking catalyst.

  If the ether compound is a cyclic ether, the hydroxy compound produced by the hydrocracking catalyst of the present invention can produce the corresponding diol compound. The obtained diol compound is a useful compound as, for example, a polymer raw material such as polyester, polycarbonate, or polyurethane, a resin additive, a raw material for intermediates of medical and agricultural chemicals, various solvents, and the like.

  Conventionally, as a hydrocracking catalyst capable of producing a corresponding hydroxy compound by hydrocracking an ether compound having a hydroxymethyl group, for example, at least one selected from the group consisting of rhodium, rhenium, molybdenum and tungsten A catalyst comprising a metal of the above (for example, see Patent Document 1), a catalyst in which platinum or ruthenium is supported on a support such as alumina (for example, see Patent Document 2), or a copper-chromium catalyst (for example, see Patent Document 2). )It has been known.

JP 2009-046417 A JP 2003-183200 A

Organic Synthesis Col. Vol.3, 693 pages (1955)

  However, it has been difficult to say that any of the above proposed catalysts provides a reaction rate, yield, and selectivity that satisfy industrial production. In particular, when maintaining a high conversion rate, problems such as sequential hydrocracking and low molecular weight cracking reactions reduce the selectivity of the target hydroxy compound, and use of harsh reaction conditions and toxic catalysts. There was also a problem such as being forced. Therefore, it has been desired to provide an industrially suitable hydrocracking catalyst that solves such problems and a method for producing a hydroxy compound using the catalyst.

  The problem to be solved by the present invention is that hydrogen that can be applied to industrial production that solves the above-mentioned problems and gives a hydroxy compound from an ether compound having a hydroxymethyl group at a high reaction rate and in a high yield and high selectivity. The object is to provide a catalyst for chemical decomposition.

The subject of the present invention is
(A) a metal compound containing any of the metals of Groups 3 to 11 of the periodic table;
Selected from the group consisting of (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table and (C) a high-valent metal compound containing any of metals of Groups 8 to 11 of the periodic table After mixing at least one metal compound, an amine compound is present when hydrolyzing an ether compound having a hydroxymethyl group in the presence of a hydrogen source using a catalyst obtained by reducing the resulting mixture. It solves by the manufacturing method of the hydroxy compound characterized by making it produce.

  According to the present invention, it is possible to provide a hydrocracking reaction that can hydrolyze an ether compound having a hydroxymethyl group to give a corresponding hydroxy compound with high reaction rate and high yield.

(Catalyst for hydrocracking)
The hydrocracking catalyst of the present invention is
(A) a metal compound containing any of the metals of Groups 3 to 11 of the periodic table;
Selected from the group consisting of (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table and (C) a high-valent metal compound containing any of metals of Groups 8 to 11 of the periodic table After mixing at least one metal compound, the obtained mixture is reduced.

In addition, (A) a metal compound containing any of the metals in Groups 3 to 11 of the periodic table;
Selected from the group consisting of (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table and (C) a high-valent metal compound containing any of metals of Groups 8 to 11 of the periodic table At least one metal compound,
What is obtained by reducing the resulting mixture after mixing the amine compound can also be used as the hydrocracking catalyst of the present invention.

(A) Metal compound containing any of metals in Group 3 to Group 11 of the periodic table (hereinafter sometimes simply referred to as metal compound)
Examples of the metal of the metal compound containing any of Group 3 to Group 11 metals used in the present invention include scandium, yttrium, lanthanum, cerium, neodymium, samarium, ytterbium, lutetium, titanium, zirconium, and hafnium. , Vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, etc., preferably lanthanum, Ytterbium, zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium, cobalt, rhodium, iridium, palladium, platinum, copper, gold, more preferably ruthenium, rhodium, iridium, Is gold.

  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 the metal compound include lanthanum compounds such as lanthanum trichloride, lanthanum tribromide, lanthanum triiodide, lanthanum trinitrate, lanthanum phosphate, dilanthanum trisulfate, and dilanthanum tricarbonate; Ytterbium compounds such as ytterbium, ytterbium tribromide, ytterbium trinitrate, diytterbium trisulfate; zirconium compounds such as zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, zirconium tetranitrate, zirconium disulfate; hafnium tetrachloride, Hafnium compounds such as hafnium tetrabromide, hafnium tetraiodide, hafnium tetranitrate, hafnium disulfate; niobium compounds such as niobium pentachloride, niobium pentabromide, niobium pentaiodide; tantalum pentachloride, tantalum pentabromide, five Tantalum compounds such as tantalum iodide; Molybdenum compounds such as tungsten, molybdenum pentachloride, molybdenum tribromide; tungsten compounds such as tungsten tetrachloride, tungsten hexachloride, tungsten pentabromide; rhenium compounds such as rhenium trichloride, rhenium pentachloride, rhenium triiodide, three Ruthenium compounds such as ruthenium chloride, ruthenium tribromide, ruthenium diammonium pentachloride, ruthenium triammonium hexachloride, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, ruthenium tribromide hexabromide, ruthenium hexabromide dipotassium; Cobalt compounds such as cobalt dichloride, cobalt dibromide, cobalt diiodide, cobalt difluoride, cobalt dinitrate, cobalt oxide, cobalt phosphate, cobalt diacetate; rhodium trichloride, rhodium triammonium chloride, hexachloride Rhodium tripotassium, Rhodium compounds such as rhodium trisodium chloride and rhodium trinitrate; iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, ammonium iridate, hexaammineiridium trichloride, pentaamminechloroiridium dichloride Iridium hexachloride, iridium trichloride, iridium hexachloride, trisodium iridium hexachloride, iridium tetrachloride, diammonium tetrachloride, iridium hexachloride, iridium hexachloride, dipotassium hexachloride, iridium hexachloride, iridium hexachloride Compound: Nickel compound such as nickel dichloride, nickel dibromide, nickel diiodide; palladium dichloride, palladium dibromide, palladium diiodide, palladium diacetate, palladium dinitrate, palladium sulfate, oxidation Palladium compounds such as palladium; platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum dibromide, platinum tetrabromide, platinum hexabromide, platinum diiodide, platinum tetraiodide, platinum diammonium dichloride , Platinum hexachloride diammonium, platinum hexachloride diammonium, platinum diammonium tetrachloride, platinum disodium hexachloride, dipotassium tetrachloride, dipotassium hexachlorochloride, diammonium platinum dibromide, dipotassium tetrabromide tetrabromide Platinum compounds such as diammonium platinum bromide, sodium hexaiodide platinate, potassium hexaiodide platinate, platinum oxide, hexahydroxoplatinate; copper such as copper monochloride, copper dichloride, copper diammonium dichloride Compounds: Gold compounds such as gold monochloride, gold trichloride, tetrachloroauric acid, gold tribromide, gold triiodide, etc., but preferably ruthenium trichloride, cobalt dichloride, trichloride Indium, iridium trichloride, iridium tetrachloride, hexachloroiridate acid, two nickel chloride, palladium dichloride, platinum dichloride, cupric chloride, tetrachloroauric acid.

(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, technotium, 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) ) Rhenium oxides such as potassium acid, sodium tetraoxorhenium (VII), rhenium hexachloride, tripotassium hexachloride, dipotassium hexachloride, rhenium dioxide, rhenium trioxide, dirhenium heptoxide are preferred. Or divanadium pentoxide, potassium trioxovanadate (V), sodium trioxovanadate (V), sodium pyrovanadate, sodium tetraoxotungsten (VI), silicomolybdic acid, tetracosaoxoheptamolybdenum (VI) Ammonium acid, sodium tetraoxomolybdate (VI), ammonium tetraoxorhenium (VII), potassium tetraoxorhenium (VII), dirhenium heptoxide are used.

(C) A high-valent metal compound containing any one of metals in Groups 8 to 11 of the periodic table (hereinafter sometimes simply referred to as a high-valent metal compound)
Examples of the metal of the high valence metal compound containing any of the metals of Group 3 to Group 11 of the periodic table used in the present invention include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, Examples thereof include copper, silver, and gold. Ruthenium, rhodium, iridium, palladium, platinum, and gold are preferable.

  The high valent metal of the present invention refers to a metal having a metal valence of 3 or more.

  The form of the high valence metal compound is not particularly limited, 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 high valence metal compounds individually or in mixture of 2 or more types.

  As the high valence metal compound, at least one compound selected from the group consisting of a high valence metal oxide, a hydroxy metal, and a hydroxy metal acid salt is preferably used. For example, ruthenium dioxide, ruthenium trioxide, ruthenium tetroxide, potassium perruthenate, perruthenic acid (tetrapropylammonium), perruthenic acid (tetrabutylammonium), dipotassium tetraoxoruthenium (VI), tetraoxoruthenium (VI) High-valent metal oxides such as disodium acid, trihydroxy iron (III), tetrahydroxyruthenium (IV), tetrahydroxyosmium (IV), trihydroxycobalt (III), hexahydroxyrhodium (III) Trisodium acid, hexahydro Sirodium (III) tripotassium, disodium hexahydroxyrhodium (IV), dipotassium hexahydroxyrhodium (IV), disodium hexahydroxyiridium (IV), dipotassium hexahydroxyiridium (IV), hexahydroxy Disodium palladium (IV), dipotassium hexahydroxypalladium (IV), hexahydroxyplatinum (IV) acid, disodium hexahydroxyplatinum (IV), dipotassium hexahydroxyplatinate (IV), trihydroxygold ( III) hydroxymetals and hydroxymetalates such as ruthenium tetroxide, potassium perruthenate, perruthenic acid (tetrapropylammonium), dipotassium tetraoxoruthenium (VI) Tetraoxoruthenium (VI) disodium, tetrahydroxyruthenium (IV), trisodium hexahydroxyrhodium (III), tripotassium hexahydroxyrhodium (III), disodium hexahydroxyrhodium (IV), hexahydroxyrhodium (IV) Dipotassium acid, hexahydroxyiridium (IV) disodium, hexahydroxyiridium (IV) dipotassium, hexahydroxypalladium (IV) disodium, hexahydroxypalladium (IV) dipotassium, hexahydroxyplatinum (IV) acid, hexahydroxyplatinum (IV) disodium, hexahydroxyplatinic acid (IV) dipotassium, trihydroxygold (III), more preferably ruthenium tetroxide, potassium perruthenate , Perruthenic acid (tetrapropylammonium), tetraoxoruthenium (VI) dipotassium, tetraoxoruthenium (VI) disodium, tetrahydroxyruthenium (IV), hexahydroxyrhodium (III) trisodium, hexahydroxy Dipotassium iridium (IV), dipotassium hexahydroxypalladium (IV), hexahydroxyplatinum (IV) acid, disodium hexahydroxyplatinum (IV), and trihydroxygold (III) are used. These high-valent metal compounds may be hydrates or adducts of organic compounds, or may be supported on a carrier.

  In the production of the hydrocracking catalyst of the present invention, first, a metal compound, a high-valent metal 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 high-valent metal compound is preferably employed.

  More specifically, after adding a metal compound and a high-valent metal compound to a solvent (for example, water) to form a solution (for example, an aqueous solution), the obtained solution is preferably 60 to 200 ° C., More 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 the high-valent metal 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 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. .

  The hydrocracking catalyst obtained by the reduction treatment may be isolated once by, for example, filtration and washing, and can be used as it is for the production of a hydroxy compound.

  The hydrogenation reaction catalyst 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 above mixture. The carrier used is preferably a porous carrier. Specifically, for example, silica, alumina, silica alumina (aluminosilicate), ceria, magnesia, calcia, titania, silica titania (titanosilicate). Zirconia and 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 hydroxy compound from an ether compound having a hydroxymethyl group.

(Production of hydroxy compounds)
A hydroxy compound can be produced by contacting an ether compound having a hydroxymethyl group with a hydrocracking catalyst in the presence of an amine compound in the presence of a hydrogen source. Examples of the ether compound include a cyclic or chain ether compound, and a five-membered ether compound, a six-membered ether compound, or a dialkyl ether compound is preferable.

(Production of 5-membered cyclic ether compound having a hydroxymethyl group)
When the ether compound is a five-membered ring ether compound, 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, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R bonded to adjacent carbon. ¹ and R ² , R ² and R ³ may be bonded to each other to form a ring.

Represents a single bond or a double bond. )
A hydrocracking catalyst and an ether compound having a hydroxymethyl group represented by the general formula (2) are brought into contact with each other in the presence of an amine compound.

(Wherein R ¹ , R ² , R ³ and

Is as defined above. )
It becomes manufacture of the hydroxy compound shown by these. In addition, the hydroxy compound shown by General formula (2) is a 1, 5-diol compound.

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.

R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group has the same meaning as that represented by R ¹ above. Note that R ¹ , R ² , R ^3, and R ⁴ bonded to adjacent carbons may be bonded to each other to form a ring (eg, a cyclohexane ring). In addition,

Represents a single bond or a double bond.

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

(In the formula, R ¹ , R ² and R ³ are as defined above.)
The compound shown by these is mentioned.

  Specific examples of the 5-membered ether compound having a hydroxymethyl group represented by the general formula (1) include, for example, tetrahydrofurfuryl alcohol, 2,3-dihydrofurfuryl alcohol, 4,5-dihydrofurfuryl alcohol, Examples include furyl alcohol, 5-methyltetrahydrofurfuryl alcohol, 5-ethyltetrahydrofurfuryl alcohol, 5-propyltetrahydrofurfuryl alcohol, 5-butyltetrahydrofurfuryl alcohol, 5-pentyltetrahydrofurfuryl alcohol, and the like. Is furfuryl alcohol, 4,5-dihydrofurfuryl alcohol, tetrahydrofurfuryl alcohol, 5-methyltetrahydrofurfuryl alcohol, more preferably tetrahydrofurfuryl alcohol It is.

A hydroxy compound obtained by contacting an ether compound having a hydroxymethyl group represented by the general formula (1) with a hydrocracking catalyst is represented by the above general formula (2) (that is, 1,5-diol). Compound). In the general formula (2), R ¹ , R ² , R ³ and

Is as defined above.

  Specific examples of the hydroxy compounds represented by the general formulas (1a) to (1d) include 1,5-pentanediol, 1-pentene-1,5-diol, 2-pentene-1,5-diol, penta -1,3-diene-1,5-diol, 1,5-hexanediol, 1,5-heptanediol, 1,5-octanediol, 1,5-nonanediol, 1,5-decanediol, etc. Preferably, 1,5-pentanediol, 1-pentene-1,5-diol, 2-pentene-1,5-diol, 1,5-hexanediol, more preferably 1,5-pentanediol is used. Is done.

  Hereinafter, the production of a hydroxy compound characterized by contacting an ether compound having a hydroxymethyl group with a hydrocracking catalyst in the presence of an amine compound in the presence of a hydrogen source is referred to as a reaction of the present invention. Sometimes.

  The reaction of the present invention will be described in more detail. In the ether 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 off to correspond. This is a reaction for obtaining a hydroxy compound.

(Wherein R ¹ , R ² , R ³ 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 ether 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 ether compound having a hydroxymethyl group. 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 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, water; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol , Alcohols such as t-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, etc .; methylene chloride, dichloroethane Emissions, and halogenated hydrocarbons such as chloro cyclohexane, preferably water, hydrocarbons, ethers, more preferably, water, 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 ether compound having a hydroxymethyl group. By setting it as this usage-amount, stirring can be performed rapidly and reaction can be advanced smoothly.

  In the reaction of the present invention, the reaction is carried out in the presence of an amine compound. After mixing the hydrocracking catalyst and the ether compound having a hydroxymethyl group, the amine compound is added to coexist in the reaction, or hydrogenation is performed. The amine compound may be present by any method as long as the amine compound is present in the reaction system during the reaction, such as adding and mixing the amine compound at the time of production of the decomposition catalyst.

  As the amine compound, an amine compound having two or more nitrogen atoms is more preferably used. For example, diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1 Aliphatic diamines such as 1,5-diaminopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane; 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4- Aromatic diamines such as diaminobenzene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene; 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4-aminopiperidine, 2,3-diaminopyridine, 2 4-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2- Heterocyclic amines such as minoquinoline, 3-aminoquinoline, 4-aminoquinoline and the like can be mentioned, and 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane are preferable. 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2-aminopyridine, 3- Aminopyridine and 4-aminopyridine, more preferably 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1 1,4-diaminocyclohexane, 1,2-diaminobenzene are used. In addition, you may use these amine compounds individually or in mixture of 2 or more types.

  The amount of the amine compound to be used is preferably 0.01 to 5.0 mol, more preferably 0.1 to 1 mol of the metal of Group 5, 6 or 7 of the periodic table shown in (B). -1.0 mol. By setting it as this usage-amount, the fall of the selectivity of the target hydroxy compound can be suppressed by the sequential reaction in reaction, or a low molecular weight decomposition reaction.

  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.

  The reaction of the present invention is carried out, for example, by a method of mixing an ether compound having a hydroxymethyl group, a hydrogenolysis catalyst, an amine compound and a solvent and reacting them with stirring in the presence of a hydrogen source. The reaction temperature in that case becomes like this. Preferably it is 25-200 degreeC, More preferably, it is 50-150 degreeC, Reaction pressure is preferably normal pressure-20MPa as hydrogen partial pressure, More preferably, it is 0.2-15MPa. By setting the reaction temperature and the reaction pressure, the target hydroxy compound can be obtained with high yield and high selectivity at a high reaction rate without generating a by-product. In order to accelerate the reaction, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like may be present if necessary, and the amount thereof is preferably set to 0.1 mol per 1 mol of the ether compound having a hydroxymethyl group. The amount is 0001 to 0.1 mol, more preferably 0.001 to 0.04 mol.

  The target hydroxy compound is obtained by the reaction of the present invention. This hydroxy compound is obtained from the obtained reaction solution after completion of the reaction, for example, filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography. It can be isolated and purified by general operations such as

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In addition, the abbreviation of the hydrocracking catalyst has the following configuration.
(Metal of a metal compound containing any of metals in Groups 3 to 11 of the periodic table)-(High-valent metal compound containing any of metals in Groups 8 to 11 of the periodic table)-(Period Table 5 Metal Oxide Metals Containing Group, Group 6 or Group 7 Metals) Catalysts

Example 1 (Production of hydrocracking catalyst)
In an autoclave equipped with a 50 ml glass inner tube, iridium trichloride n-hydrate (Ishizu Reagent, 53% iridium content) 22.2 mg (iridium is 0.061 mmol), potassium perruthenium (VII) 19 0.6 mg (0.095 mmol) and 5 ml of water were added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. To the solution once cooled to room temperature, 27.8 mg (0.095 mmol) of potassium tetraoxorhenate (VII) and 2.8 mg (0.047 mmol) of 1,2-diaminoethane were added, and again at 120 ° C. for 30 minutes. Stir with heating. Next, the mixture was pressurized to 8 MPa in a hydrogen atmosphere at room temperature, and heated and stirred at 120 ° C. for 1 hour to reduce the mixture. The obtained solution was cooled to room temperature, the aqueous layer was removed by decantation, and a hydrocracking catalyst (hereinafter also referred to as “Ir-Ru—Re catalyst (1)”) was obtained as a residue.

Example 2 (Synthesis of 1,5-pentanediol)

In the same apparatus as in Example 1, the residue (Ir-Ru-Re catalyst (1)) obtained in Example 1 and 5.00 g (2.45 mmol) of 5% tetrahydrofurfuryl alcohol aqueous solution were put, and hydrogen gas was used at 8 MPa. The mixture was then reacted at 100 ° C. for 2 hours with stirring (1,2-diaminoethane coexists). 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 tetrahydrofurfuryl alcohol was 74.3%, the yield of 1,5-pentanediol was 64.6%, and the selectivity was 87.0. %Met. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 3 (Synthesis of 1,5-pentanediol)
The reaction was carried out in the same manner as in Example 2 except that the reaction temperature in Example 2 was changed to 80 ° C. and the reaction time was changed to 4 hours (1,2-diaminoethane coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 70.8%, the yield of 1,5-pentanediol was 64.5%, and the selectivity was 91.1%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Comparative Example 1 (Production of hydrocracking catalyst and synthesis of 1,5-pentanediol using the catalyst)
Except not using the 1,2-diaminoethane added in Example 1, the catalyst was produced in the same manner as in Example 1, and a hydrocracking catalyst (hereinafter referred to as "Ir-Ru-Re catalyst (2)"). May be referred to as “)”. The catalyst thus obtained was used in place of the catalyst used in Example 2, and the reaction was carried out in the same manner as Example 2 except that the reaction time was 1 hour. As a result, the conversion of tetrahydrofurfuryl alcohol was 74.7%, the yield of 1,5-pentanediol was 59.7%, and the selectivity was 79.9%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 4 (Production of hydrocracking catalyst and synthesis of 1,5-pentanediol using it)
Except that the 1,2-diaminoethane added in Example 1 was replaced with 3.5 mg (0.047 mmol) of 1,3-diaminopropane, the catalyst was produced in the same manner as in Example 1 for hydrocracking. A catalyst (hereinafter sometimes referred to as "Ir-Ru-Re catalyst (3)") was obtained. All the reactions were carried out in the same manner as in Example 2 except that the catalyst thus obtained was used instead of the catalyst used in Example 2 (1,3-diaminopropane coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 89.4%, the yield of 1,5-pentanediol was 72.6%, and the selectivity was 81.2%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 5 (Production of hydrocracking catalyst and synthesis of 1,5-pentanediol using it)
The catalyst was produced in the same manner as in Example 1 except that 1,2-diaminoethane added in Example 1 was replaced with 4.1 mg (0.047 mmol) of 1,4-diaminobutane. Catalyst (hereinafter also referred to as "Ir-Ru-Re catalyst (4)") was obtained. The reaction was carried out in the same manner as in Example 2 except that the catalyst thus obtained was used in place of the catalyst used in Example 2 (1,4-diaminobutane coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 83.7%, the yield of 1,5-pentanediol was 70.0%, and the selectivity was 83.3%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 6 (Production of hydrocracking catalyst and hydrocracking using it)
Except that the 1,2-diaminoethane added in Example 1 was replaced with 4.4 mg (0.047 mmol) of 2-aminopyridine, the catalyst was produced in the same manner as in Example 1, and the hydrocracking catalyst ( Hereinafter, "Ir-Ru-Re catalyst (5)" may be obtained). The reaction was performed in the same manner as in Example 2 except that the catalyst thus obtained was used instead of the catalyst used in Example 2 (2-aminopyridine coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 77.7%, the yield of 1,5-pentanediol was 66.2%, and the selectivity was 85.2%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 7 (Production of hydrocracking catalyst and hydrocracking using the same)
Except that the 1,2-diaminoethane added in Example 1 was replaced with 5.4 mg (0.047 mmol) of 1,4-diaminocyclohexane, the catalyst was produced in the same manner as in Example 1, and hydrocracking was performed. Catalyst (hereinafter also referred to as "Ir-Ru-Re catalyst (6)") was obtained. The reaction was carried out in the same manner as in Example 2 except that the catalyst thus obtained was used in place of the catalyst used in Example 2 (1,4-diaminocyclohexane coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 91.8%, the yield of 1,5-pentanediol was 73.5%, and the selectivity was 80.1%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 8 (Production of hydrocracking catalyst and hydrocracking using the same)
Except that 1,2-diaminoethane added in Example 1 was replaced with 5.4 mg (0.047 mmol) of 1,2-diaminocyclohexane, a catalyst was produced in the same manner as in Example 1 for hydrocracking. A catalyst (hereinafter sometimes referred to as “Ir—Ru—Re catalyst (7)”) was obtained. The reaction was carried out in the same manner as in Example 2 except that the catalyst thus obtained was used in place of the catalyst used in Example 2 (1,2-diaminocyclohexane coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 52.2%, the yield of 1,5-pentanediol was 48.4%, and the selectivity was 92.7%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 9 (Production of hydrocracking catalyst and synthesis of 1,5-pentanediol using it)
Except that 1,2-diaminoethane added in Example 1 was replaced with 5.1 mg (0.047 mmol) of 1,2-diaminobenzene, the catalyst was produced in the same manner as in Example 1, and hydrocracking was performed. Catalyst (hereinafter also referred to as “Ir—Ru—Re catalyst (8)”) was obtained. The reaction was carried out in the same manner as in Example 2 except that the catalyst thus obtained was used instead of the catalyst used in Example 2 (1,2-diaminobenzene coexists). As a result, the conversion of tetrahydrofurfuryl alcohol was 30.6%, the yield of 1,5-pentanediol was 28.8%, and the selectivity was 94.0%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 10 (Production of hydrocracking catalyst)
Silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., CARiACT G-6) 0.50 g and tetraoxoruthenium (VI) dipotassium aqueous solution (manufactured by Furuya Metal Co., Ltd., ruthenium concentration 4.3%) 0.244 g ( An aqueous solution in which 0.104 mmol of ruthenium was dissolved in 0.2 g of water was impregnated and dried at 110 ° C. for 7 hours. Next, an aqueous solution in which 53.0 mg (iridium concentration is 0.104 mmol) of hexachloroiridium acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.104 mmol) was dissolved in 0.4 g of water was impregnated and dried at 110 ° C. for 7 hours. After that, finally, impregnation with 18.4 mg of ammonium tetracosaoxoheptamolybdate (VI) tetrahydrate (molybdenum is 0.104 mmol) in 0.4 g of water and drying at 110 ° C. for 7 hours. It was. This powder was dried at 250 ° C. for 4 hours, and a solid (hereinafter referred to as “Ir—Ru—Mo / SiO ₂ catalyst (1) having 4% iridium, 2.1% ruthenium and 2.0% molybdenum supported on silica was supported. ) ”(Sometimes referred to as“) ”.

Example 11 (Synthesis of 1,5-pentanediol)
In the same apparatus as in Example 1, 25 mg of “Ir—Ru—Mo / SiO ₂ catalyst (1)” obtained in Example 10 and 5.00 g (2.45 mmol) of 5% tetrahydrofurfuryl alcohol aqueous solution and 1,2 -15.6 mg (0.0026 mmol) of 1% aqueous solution of diaminoethane was added, pressurized to 8 MPa with hydrogen gas, and then reacted at 150 ° C for 4 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 tetrahydrofurfuryl alcohol was 40.2%, the yield of 1,5-pentanediol was 31.1%, and the selectivity was 77.4. %Met. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 12 (Synthesis of 1,5-pentanediol)
The reaction was performed in the same manner as in Example 11 except that the amount of 1% aqueous solution of 1,2-diaminoethane used in Example 11 was changed to 7.8 mg (0.0013 mmol). As a result, the conversion of tetrahydrofurfuryl alcohol was 51.2%, the yield of 1,5-pentanediol was 36.6%, and the selectivity was 71.4%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Comparative Example 2 (Synthesis of 1,5-pentanediol)
The reaction was carried out in the same manner as in Example 11 except that 1,2-diaminoethane added in Example 11 was not used and the reaction time was changed to 2 hours. As a result, the conversion of tetrahydrofurfuryl alcohol was 43.5%, the yield of 1,5-pentanediol was 30.5%, and the selectivity was 70.2%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 13 (Production of hydrocracking catalyst)
Silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Co., CARiACT G-6) 0.500 g and tetraoxoruthenium (VI) dipotassium aqueous solution (manufactured by Furuya Metal Co., Ltd., ruthenium concentration 4.3%) 0.244 g ( An aqueous solution in which 0.104 mmol of ruthenium was dissolved in 0.2 g of water was impregnated and dried at 110 ° C. for 7 hours. Next, an aqueous solution in which 53.0 mg (iridium concentration is 0.104 mmol) of hexachloroiridium acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.104 mmol) was dissolved in 0.4 g of water was impregnated and dried at 110 ° C. for 7 hours. I let you. This powder was dried at 250 ° C. for 4 hours, and 570 mg of a solid in which 4% of iridium and 2.1% of ruthenium were supported on silica (hereinafter also referred to as “Ir—Ru / SiO ₂ catalyst (1)”) Got.

Example 14 (Synthesis of 1,5-pentanediol)
In the same apparatus as in Example 1, 25 mg of “Ir—Ru / SiO ₂ catalyst (1)” obtained in Example 13; 1.4 mg (0.0029 mmol) of dirhenium heptoxide; 5% tetrahydrofurfuryl alcohol aqueous solution 5 0.001 g (2.45 mmol) and 15.6 mg (0.0026 mmol) of a 1% aqueous solution of 1,2-diaminoethane were added, pressurized to 8 MPa with hydrogen gas, and reacted at 150 ° C. for 2.5 hours with stirring. I let you. 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 tetrahydrofurfuryl alcohol was 84.5%, the yield of 1,5-pentanediol was 64.6%, and the selectivity was 76.5. %Met. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Comparative Example 3 (Synthesis of 1,5-pentanediol)
The reaction was carried out in the same manner as in Example 14 except that 1,2-diaminoethane added in Example 14 was not used and the reaction time was changed to 2 hours. As a result, the conversion of tetrahydrofurfuryl alcohol was 77.8%, the yield of 1,5-pentanediol was 60.6%, and the selectivity was 77.9%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 15 (Production of hydrocracking catalyst)
Diasope (activated charcoal; Calgon Carbon Japan Co., Ltd.) 0.500 g and tetraoxoruthenium (VI) dipotassium aqueous solution (made by Furuya Metal Co., Ltd., ruthenium concentration 4.3%) 0.244 g (ruthenium is 0.104 mmol) ) Was impregnated with 1.0 g of water and dried at 110 ° C. for 7 hours. Next, an aqueous solution in which 53.0 mg (iridium concentration is 0.104 mmol) of hexachloroiridium acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.104 mmol) was dissolved in 1.0 g of water was impregnated and dried at 110 ° C. for 7 hours. I let you. This powder was dried at 250 ° C. for 4 hours, and 580 mg of a solid (hereinafter sometimes referred to as “Ir-Ru / C catalyst (1)”) in which 4% of iridium and 2.1% of ruthenium were supported on activated carbon was added. Obtained.

Example 16 (Synthesis of 1,5-pentanediol)
The reaction was conducted in the same manner as in Example 14 except that the catalyst of Example 14 was replaced with 25 mg of “Ir—Ru / C catalyst (1)” and the reaction time was changed to 4 hours. As a result, the conversion of tetrahydrofurfuryl alcohol was 55.0%, the yield of 1,5-pentanediol was 49.9%, and the selectivity was 90.7%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Comparative Example 4 (Synthesis of 1,5-pentanediol)
The reaction was conducted in the same manner as in Example 14 except that 1,2-diaminoethane added in Example 16 was not used and the reaction time was changed to 2.5 hours. As a result, the conversion of tetrahydrofurfuryl alcohol was 46.3%, the yield of 1,5-pentanediol was 40.3%, and the selectivity was 87.0%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

From the above, the hydrocracking catalyst of the present invention, that is,
(A) a metal compound containing any of the metals of Groups 3 to 11 of the periodic table;
Selected from the group consisting of (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table and (C) a high-valent metal compound containing any of metals of Groups 8 to 11 of the periodic table A catalyst obtained by mixing at least one metal compound, and then reducing the resulting mixture, or
(A) a metal compound containing any of the metals of Groups 3 to 11 of the periodic table;
Selected from the group consisting of (B) a metal oxide containing a metal of Group 5, 6 or 7 of the periodic table and (C) a high-valent metal compound containing any of metals of Groups 8 to 11 of the periodic table At least one metal compound,
After the amine compound is mixed, the amine compound is present when the ether compound having a hydroxymethyl group is hydrocracked in the presence of a hydrogen source using a hydrocracking catalyst obtained by reducing the resulting mixture. Thus, it was found that the corresponding hydroxy compound was obtained with high yield and high selectivity at a high reaction rate.

  According to the present invention, an ether compound having a hydroxymethyl group can be hydrocracked to provide a method for producing a hydroxy compound corresponding to a high reaction rate and a high yield. If the ether compound is a cyclic ether, a corresponding diol compound can be produced. The obtained diol compound is a useful compound as, for example, a polymer raw material such as polyester, polycarbonate, or polyurethane, a resin additive, a raw material for intermediates of medical and agricultural chemicals, various solvents, and the like.

Claims (5)

(A) a metal compound containing any of Ru, Rh, Ir and Pt ,
(B) a metal oxide containing any metal of V, Mo, W and Re ,
And (C) ruthenium tetroxide, potassium perruthenate, perruthenic acid (tetrapropylammonium), dipotassium tetraoxoruthenium (VI), disodium tetraoxoruthenium (VI), tetrahydroxyruthenium (IV), hexa Trisodium hydroxyrhodium (III), dipotassium hexahydroxyiridium (IV), dipotassium hexahydroxypalladium (IV), hexahydroxyplatinum (IV) acid, disodium hexahydroxyplatinum (IV) and trihydroxygold A step of mixing at least two metal compounds selected from the group (A) to (C) consisting of a high-valent metal compound containing any of (III) ;
Using a catalyst obtained by step of reducing processing the mixture in the presence of a hydrogen source, any of the following general formula (1a) ~ (1d)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R bonded to adjacent carbon. ¹ and R ² , R ² and R ³ may be bonded to each other to form a ring.)
A step of the ether compound hydrogenolysis shown in,
A method for producing a hydroxy compound comprising:
A method for producing a hydroxy compound , wherein an amine compound is present when the mixture is reduced or when the ether compound is hydrocracked . The method for producing a hydroxy compound according to claim 1, wherein the metal oxide is at least one compound selected from the group consisting of metal oxides and metal peroxide salts. The method for producing a hydroxy compound according to claim 1, wherein the amine compound is an amine compound having two or more nitrogen atoms. The method for producing a hydroxy compound according to any one of claims 1 to 3 , wherein the amine compound having two or more nitrogen atoms is an amine compound having at least one primary amine. The presence of a hydrogen source, wherein the ether compound of the general formula by contacting a hydrocracking catalyst (2)
(Wherein R ¹ , R ² and R ³ are as defined above.
Represents a single bond or a double bond . )
The manufacturing method of the hydroxy compound of any one of Claims 1 thru | or 4 which obtains the hydroxy compound shown by these.