JP5158325B2 - Process for producing chain aliphatic diol - Google Patents

Description

  The present invention relates to a novel process for producing a chain aliphatic diol. The chain aliphatic diol of the present invention is useful as a monomer raw material and additive for polyester resins and polyurethane resins, and an intermediate for raw materials for medicines and agricultural chemicals.

  In recent years, chain aliphatic diols have attracted attention as monomer raw materials and additives for polyester resins and polyurethane resins. In any case, it is used as a monomer raw material or an additive having 6 or more carbon atoms and having a chain-structured aliphatic hydrocarbon in the skeleton and having two hydroxyl groups.

  For example, decanediol having 10 carbon atoms is produced through the production of sebacic acid by alkali melting of castor oil (see, for example, Non-Patent Document 1).

  However, there are problems such as an alkali melting process that is difficult to handle due to severe reaction conditions, and that it is difficult to convert to a diol because of an intermediate of a dicarboxylic acid structure.

1999 Fine Chemical Yearbook, page 361 (CMC)

  The present invention has been made in view of the above-mentioned problems, and the purpose thereof is easily available, and is a chain aliphatic diol useful as an intermediate for a polyester resin monomer raw material, a polyurethane resin additive, and a medical and agrochemical raw material. It is to provide a manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found a novel method for producing a chain aliphatic diol, and have completed the present invention. That is, the present invention relates to a novel method for producing a chain aliphatic diol having 9 to 12 carbon atoms.

  Hereinafter, the present invention will be described in detail.

  The novel method for producing a C9-12 chain aliphatic diol of the present invention comprises a step of producing a dihydroxyalkadiene by hydroxylating a dihalogenoalkadiene represented by the following general formula (1), and a dihydroxyalkadiene: It consists of hydrogenating the diene.

（式中、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表し、ｎは３〜６の整数を表す。）
本発明の製造方法で製造される炭素数９〜１２の鎖状脂肪族ジオールは、具体的には炭素数９の鎖状脂肪族ジオールとして１，９−ノナンジオール、３，７−ノナンジオール、３，９−ノナンジオールおよびこれらの混合物、炭素数１０の鎖状脂肪族ジオールとして１，１０−デカンジオール、３，８−デカンジオール、３，１０−デカンジオールおよびこれらの混合物、炭素数１１の鎖状脂肪族ジオールとして１，１１−ウンデカンジオール、３，９−ウンデカンジオール、３，１１−ウンデカンジオールおよびこれらの混合物、炭素数１２の鎖状脂肪族ジオールとして１，１２−ドデカンジオール、３，１０−ドデカンジオール、３，１２−ドデカンジオールおよびこれらの混合物等があげられる。

(In formula, X represents a chlorine atom, a bromine atom, or an iodine atom each independently, and n represents the integer of 3-6.)
The chain aliphatic diol having 9 to 12 carbon atoms produced by the production method of the present invention is specifically 1,9-nonanediol, 3,7-nonanediol as a chain aliphatic diol having 9 carbon atoms, 3,9-nonanediol and mixtures thereof, 1,10-decanediol, 3,8-decanediol, 3,10-decanediol and mixtures thereof as chain aliphatic diols having 10 carbon atoms, 11 carbon atoms 1,11-undecanediol, 3,9-undecanediol, 3,11-undecanediol and mixtures thereof as chain aliphatic diol, 1,12-dodecanediol as chain aliphatic diol having 12 carbon atoms, 3, Examples thereof include 10-dodecanediol, 3,12-dodecanediol, and mixtures thereof.

  Examples of the dihalogenoalkadiene represented by the general formula (1) used in the production method of the present invention include 1,9-dichloro-2,7-nonadiene and 1,9-dibromo-2,7-nonadiene. 1,9-diiodo-2,7-nonadiene, 1-bromo-9-chloro-2,7-nonadiene, 1-bromo-9-iodo-2,7-nonadiene, 1-chloro-9-iodo-2 , 7-nonadiene, 1,10-dichloro-2,8-decadiene, 1,10-dibromo-2,8-decadiene, 1,10-diiodo-2,8-decadiene, 1-bromo-10-chloro-2 , 8-decadiene, 1-bromo-10-iodo-2,8-decadiene, 1-chloro-10-iodo-2,8-decadiene, 1,11-dichloro-2,9-undecadiene, 1,11-dibromo -2, -Undecadiene, 1,11-diiodo-2,9-undecadiene, 1-bromo-11-chloro-2,9-undecadiene, 1-bromo-11-iodo-2,9-undecadiene, 1-chloro-11-iodo -2,9-undecadiene, 1,12-dichloro-2,10-dodecadiene, 1,12-dibromo-2,10-dodecadiene, 1,12-diiodo-2,10-dodecadiene, 1-bromo-12-chloro -2,10-dodecadiene, 1-bromo-12-iodo-2,10-dodecadiene, 1-chloro-12-iodo-2,10-dodecadiene and the like. Among these, 1,9-dichloro-2,7-nonadiene and 1,10-dichloro-2,8-decadiene, in which both Xs in the general formula (1) are chlorine atoms, can be produced easily and efficiently. 1,11-dichloro-2,9-undecadiene, 1,12-dichloro-2,10-dodecadiene, 1,9-dibromo-2,7-, wherein X in the general formula (1) is a bromine atom Nonadiene, 1,10-dibromo-2,8-decadiene, 1,11-dibromo-2,9-undecadiene, 1,12-dichloro-2,10-dodecadiene, X in the above general formula (1) is both iodine 1,9-diiodo-2,7-nonadiene, 1,10-diiodo-2,8-decadiene, 1,11-diiodo-2,9-undecadiene, 1,12-diene as atoms 1,9-dichloro-, wherein X in the general formula (1) is both a chlorine atom because of its high stability and easy availability of raw materials. 2,7-nonadiene, 1,10-dichloro-2,8-decadiene, 1,11-dichloro-2,9-undecadiene and 1,12-dichloro-2,10-dodecadiene are more preferred.

The dihalogenoalkadiene represented by the general formula (1) used in the production method of the present invention is 1,4-dihalogeno-2-butene represented by the following general formula (2) and the following general formula (3). Can be simply and efficiently produced by carrying out a ring-opening cross-metathesis reaction in the presence of a metathesis reaction catalyst .

（式中、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表す。）

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)

（式中、ｍは０〜３の整数を表す。）
ここで、開環クロスメタセシス反応とは、環状オレフィンと非環状オレフィンを原料に用い、環状オレフィンの開環反応と非環状オレフィンとのクロスメタセシス反応が同時に起こることによりカップリング生成物を与える反応であり、例えば、「第５版 実験化学講座１８ 有機化合物の合成ＶＩ 金属を用いる有機合成」（日本化学会編・丸善株式会社）第３１１頁、第３２２頁に記載されている。

(In the formula, m represents an integer of 0 to 3.)
Here, the ring-opening cross-metathesis reaction is a reaction in which a cyclic olefin and an acyclic olefin are used as raw materials, and a ring-opening reaction of the cyclic olefin and a cross-metathesis reaction with the acyclic olefin occur simultaneously to give a coupling product. Yes, for example, “Fifth Edition Experimental Chemistry Course 18 Synthesis of Organic Compounds VI Organic Synthesis Using Metals” (edited by Chemical Society of Japan, Maruzen Co., Ltd.), pages 311 and 322.

  In the ring-opening cross-metathesis reaction, 1,4-dihalogeno-2-butene and ethylene are produced by the metathesis reaction between allyl halides, and the desired metathesis reaction between the 1,4-dihalogeno-2-butene and the cyclic olefin is performed. The formation of dihalogenoalkadienes is considered. Examples of 1,4-dihalogeno-2-butene include 1,4-dichloro-2-butene, 1,4-dibromo-2-butene, 1,4-diiodo-2-butene, and 1-chloro-4. -Bromo-2-butene, 1-chloro-4-iodo-2-butene, 1-bromo-4-iodo-2-butene and the like.

  In the ring-opening cross metathesis reaction, a metathesis reaction catalyst is usually used. The metathesis reaction catalyst is a transition metal compound of Groups 4 to 9 of the periodic table, and any catalyst that undergoes the ring-opening cross-metathesis reaction between the allyl halide and the cyclic olefin may be used. For example, (i) a catalyst based on a combination of a transition metal compound and an alkylating agent or Lewis acid that functions as a promoter, (ii) a transition metal-carbene complex catalyst, (iii) a transition metal compound supported on a support Examples of solid catalysts include, for example, “Fifth Edition Experimental Chemistry Course 18 Synthesis of Organic Compounds VI Organic Synthesis Using Metals” (edited by Chemical Society of Japan, Maruzen Co., Ltd.), pages 313 to 314, “Catalyst Course” Volume 8 (Industrial Catalysis Reaction 2) Industrial Catalysis Reaction I ”(Catalyst Society, Kodansha Scientific) The catalysts listed on pages 70-71 are used. It can be.

The transition metal compound in the catalyst (i) is not particularly limited as long as it retains high catalytic activity and stability. For example, titanium compounds such as TiCl ₄ and TiBr ₄ ; VOCl ₃ , vanadium compounds such as VOBr ₃ ; niobium compounds such as NbBr ₅ , NbCl ₅ and Nb (OEt) ₅ ; tantalum compounds such as TaBr ₅ , TaCl ₅ , Ta (OMe) ₅ and Ta (OBu) ₅ ; MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , MoOF _{4 and} other molybdenum compounds; WBr ₂ , WCl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WF ₄ , WF _{4 WI 2, WOBr 4, WOCl 4} , WOF 4, WCl 4 (OC 6 H 4 Cl 2) 2, W ( _O) tungsten compounds such as _{6; CH 3 ReO 3, ReCl} 5, ReCl (CO) rhenium compounds such as _{5, RuBr 3, RuCl 3,} Ru 3 (CO) ruthenium compounds such as _12; RhCl _3, etc. Rhodium compounds; iridium compounds such as IrCl _{3 and the} like.

  The alkylating agent or Lewis acid that functions as a co-catalyst in the catalyst (i) is not particularly limited as long as it can exhibit high catalytic activity. For example, trimethylaluminum, triethylaluminum, Isobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride, di-n-butylaluminum monochloride, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane , Organoaluminum compounds such as isobutylaluminoxane; tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, teto Butyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, Organotin compounds such as butyltin trichloride and butyltin tribromide; Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium Organomagnesium compounds such as bromide, n-propylmagnesium bromide, t-butylmagnesium chloride, arylmagnesium chloride; Organic zinc compounds such as tilzinc; Organic sodium compounds such as cyclopentyl sodium; trimethylboron, triethylboron, tri-n-butylboron, triphenylboron, tris (perfluorophenyl) boron, N, N-dimethylanilinium And organic boron compounds such as tetrakis (perfluorophenyl) borate and trityltetrakis (perfluorophenyl) borate; and organic antimony compounds such as triphenylantimony.

  Furthermore, alcohols such as methanol and ethanol, phenols and the like may be added as a third component to the extent that the ring-opening cross-metathesis reaction is not affected.

The transition metal (ii) - The carbene complex catalyst is not particularly limited as long as it can exhibit a high catalytic activity, for _{^{example, W (N-2,6-Pr}} i 2 C 6 H 3 ^{_{) (CHBu t) (OBu t}} ) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 ^{_{C 6 H 3) (CHBu t}} ) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, W (N- ^{_{2,6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF ₃ ) ₂ ) Tungsten-carbene complexes such as ₂ ; Mo (N-2) ^{_{, 6-Pr i 2 C 6}} H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, Mo ^{_{(N-2,6-Pr i 2}} C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) ^{_{(OBu t) 2, Mo (}} N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3 _{) (CHCMe 2 Ph) (OCMe} (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (BIPHEN), Mo (N-2,6-Pr ^{_{i 2 C 6 H 3) (}} CHCMe 2 Ph) (BINO) (THF) , etc. Molybdenum - carbene ^{complexes, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2-Bu t C 6 H ₄ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , Re (CBu ^t ) (CHBu ^t ) Rhenium-carbene complexes such as (O-2,6-Me ₂ C ₆ H ₃ ) ₂ ; benzylidene (1,3-dimesityl-2-imidazolidineylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesityl-2-imidazolidineylidene) (3-methyl-2-buteneylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1 3-Dimesityl-2-octahydrobenzimidazolylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-bis (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride , Benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4) , 5-Tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphos ) Ruthenium dichloride, benzylidene (1,3-dimesityl-2-imidazolidine ylidene) pyridine ruthenium dichloride, benzylidene bis (1,3-dicyclohexyl-2-imidazolidine ylidene) ruthenium dichloride, benzylidene bis (1,3 -Diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride, (1,3-dimesitylmimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1, 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidenerutheniumdi Chloride, benzylidene-bis (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-2-imidazolidineylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride, tricyclohexylphosphine (o-isopropoxyphenylmethylene) ruthenium Examples thereof include ruthenium-carbene complexes such as dichloride, (3-methyl-2-buteneylidene) bis (tricyclopentylphosphine) ruthenium dichloride, and (3-methyl-2-buteneylidene) bis (tricyclohexylphosphine) ruthenium dichloride.

Here, in the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl −3,3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. Respectively.

The transition metal compound in the solid catalyst (iii) is not particularly limited as long as it has high stability. For example, V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , MoO ₂ , oxides such as MoO ₃ , WO ₃ , Re ₂ O ₇ , ReO ₃ , CH ₃ ReO ₇ , RuO ₂ , Rh ₂ O ₃ , Ir ₂ O ₃ ; MoS ₃ , MoS ₂ , WS ₂ , Re ₂ sulfides such as S _7, and the like. Further, the carrier is not particularly limited. For example, Al ₂ O ₃ , SiO ₂ , TiO ₂ , MgO, ZrO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , SiO _2- Al ₂ O _{3 and the} like.

  These metathesis reaction catalysts can be used alone or in combination of two or more. Of these, a transition metal-carbene complex catalyst is preferably used because of its high catalytic activity and excellent handling safety, and ruthenium-carbene complexes are more preferably used.

  The hydroxylation reaction in the step of producing dihydroxyalkadiene by hydroxylating the dihalogenoalkadiene represented by the general formula (1) is, for example, a hydrolysis reaction using a base and water, or a silver salt such as silver nitrate or silver acetate. For example, “Fifth Edition Experimental Chemistry Course 14 Synthesis of Organic Compounds II Alcohol / Amine” (edited by the Chemical Society of Japan, Maruzen Co., Ltd.) ) From page 93 to page 95. Among these reactions, a hydrolysis reaction using a base and water is preferably used because it can be easily and efficiently hydroxylated.

  In the method of hydroxylating by hydrolysis reaction using a base and water, the base used is not particularly limited, for example, lithium formate, sodium formate, potassium formate, rubidium formate, cesium formate, magnesium formate, calcium formate, Strontium formate, barium formate, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate and other carboxylic acid alkali salts, lithium hydroxide, sodium hydroxide, potassium hydroxide , Rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate Inorganic bases such as um, calcium carbonate, strontium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate Kind.

  Regarding the charging ratio of dihalogeno alkadiene and base, the amount of base is 2 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of dihalogeno alkadiene.

  As for the charging ratio of dihalogeno alkadiene and water, the amount of water is preferably 2 or more with respect to 1 mol of dihalogeno alkadiene, and water can be used as a solvent.

  In the method of hydroxylating by a hydrolysis reaction using a silver salt such as silver nitrate or silver acetate, the silver salt used is not particularly limited. For example, silver nitrate, silver carbonate, silver acetate, silver benzoate, silver salicylate, Examples thereof include silver trifluoroacetate and silver p-toluenesulfonate.

  As for the charging ratio of dihalogeno alkadiene and silver salt, the amount of base is 2 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of dihalogeno alkadiene.

  As for the charging ratio of dihalogeno alkadiene and water, the amount of water is preferably 2 or more with respect to 1 mol of dihalogeno alkadiene, and water can be used as a solvent.

  The step of producing dihydroxyalkadiene by hydroxylating dihalogenoalkadiene can be carried out using a phase transfer catalyst if necessary in order to promote hydroxylation efficiently.

  The phase transfer catalyst is not particularly limited. For example, tetramethylammonium hydroxide, tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium hydroxide, tetraethylammonium fluoride, tetraethyl Ammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium fluoride De, tetra Tylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, methyltriethylammonium hydroxide, methyltriethylammonium fluoride, methyltriethylammonium chloride, methyltriethylammonium bromide, methyltriethylammonium iodide, trioctylammonium hydroxide, tri Octylammonium fluoride, trioctylammonium chloride, trioctylammonium bromide, trioctylammonium iodide, benzylcetyldimethylammonium hydroxide, benzylcetyldimethylammonium fluoride, benzylcetyldimethylammonium chloride, benzylcetyldimethylammonium bromide, benzylce Dimethyldimethylammonium iodide, benzyldimethylphenylammonium hydroxide, benzyldimethylphenylammonium fluoride, benzyldimethylphenylammonium chloride, benzyldimethylphenylammonium bromide, benzyldimethylphenylammonium iodide, benzyldimethylstearylammonium hydroxide, benzyldimethylstearylammonium Fluoride, benzyldimethylstearylammonium chloride, benzyldimethylstearylammonium bromide, benzyldimethylstearylammonium iodide, benzyldimethyltetradecylammonium hydroxide, benzyldimethyltetradecylammonium fluoride, benzyldimethyltetradecylammonium Chloride, benzyldimethyltetradecylammonium bromide, benzyldimethyltetradecylammonium iodide, N-benzylquinidinium hydroxide, N-benzylquinidinium fluoride, N-benzylquinidinium chloride, N-benzylquinidinium bromide N-benzylquinidinium iodide, benzyltributylammonium hydroxide, benzyltributylammonium fluoride, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium iodide, (3-chloro-2-hydroxypropyl) trimethylammonium Hydroxide, (3-chloro-2-hydroxypropyl) trimethylammonium fluoride, (3-chloro-2-hydride) Xylpropyl) trimethylammonium chloride, (3-chloro-2-hydroxypropyl) trimethylammonium bromide, (3-chloro-2-hydroxypropyl) trimethylammonium iodide, n-decyltrimethylammonium hydroxide, n-decyltrimethylammonium fluoride N-decyltrimethylammonium chloride, n-decyltrimethylammonium bromide, n-decyltrimethylammonium iodide, dichloromethylenedimethyliminium hydroxide, dichloromethylenedimethyliminium fluoride, dichloromethylenedimethyliminium chloride, dichloromethylenedimethyli Minium bromide, dichloromethylenedimethyliminium iodide, diethyl distearyl ammonium Hydroxide, diethyl distearyl ammonium fluoride, diethyl distearyl ammonium chloride, diethyl distearyl ammonium bromide, diethyl distearyl ammonium iodide, dodecyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium fluoride, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide , Dodecyltrimethylammonium iodide, hexadecyltrimethylammonium hydroxide, hexadecyltrimethylammonium fluoride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium iodide, phenyltriethylammonium hydroxide, Quaternary ammonium compounds such as phenyltriethylammonium fluoride, phenyltriethylammonium chloride, phenyltriethylammonium bromide, phenyltriethylammonium iodide, 12-crown-4-ether, 15-crown-5-ether, 18-crown- 6-ether, 24-crown-8-ether, dibenzo-15-crown-5-ether, dibenzo-18-crown-6-ether, dibenzo-21-crown-7-ether, dibenzo-24-crown-8- Ether, dibenzo-30-crown-10-ether, 4'-acetylbenzo-15-crown-5-ether, 4'-aminobenzo-15-crown-5-ether, 2- (allyloxymethyl) -18-crown -6 Ether, 1-aza-12-crown-4-ether, 1-aza-15-crown-5-ether, 1-aza-18-crown-6-ether, benzo-12-crown-4-ether, benzo- 15-crown-5-ether, benzo-18-crown-6-ether, bis (1,4-phenylene) -34-crown-10-ether, 4'-bromobenzo-15-crown-5-ether, 4 ' -Bromobenzo-18-crown-6-ether, 4'-carboxybenzo-15-crown-5-ether, 15-crown-4 [4- (2,4-dinitrophenylazo) phenol, 4,10-diaza- 15-crown-5-ether, 4,13-diaza-18-crown-6-ether, N, N′-dibenzyl-4,13-diaza-18 Crown-6-ether, dicyclohexano-18-crown-6-ether, 2- (hydroxymethyl) -15-crown-5-ether, 4'-methoxycarbonylbenzo-15-crown-5-ether, 4 ' -Nitrobenzo-15-crown-5-ether, N'-phenylaza-15-crown-5-ether, 1,4,7,10-tetraazacyclododecane, 1,4,7,10-tetraazacyclododecanetetrahydro Chloride, 1,4,8,12-tetraazacyclopentadecane, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetrathiacyclotetradecane, 1,4,7-triazacyclo Nonanetrihydrochloride, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7-to Crown ethers such as lithiacyclononane, tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetraphenyl Phosphonium chloride, tributylhexadecylphosphonium chloride, ethyltriphenylphosphonium chloride, allyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, allyltriphenylphosphonium iodide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenyl Suphonium iodide, bromomethyltriphenylphosphonium chloride, 3-bromopropyltriphenylphosphonium chloride, cinnamyltriphenylphosphonium chloride, cyanomethyltri-n-butylphosphonium chloride, cyclopropyltriphenylphosphonium chloride, 4-ethoxybenzyltri Examples thereof include phosphonium compounds such as phenylphosphonium chloride. Among these phase transfer catalysts, quaternary ammonium compounds are preferably used because they can be used efficiently and economically.

  The amount of the phase transfer catalyst used is 0.00001 to 10 mol, preferably 0.0001 to 2 mol, more preferably 0.0001 to 0.5 mol, per 1 mol of dihalogenoalkadiene.

  The step of producing dihydroxyalkadiene by hydrolyzing dihalogenoalkadiene can be carried out without a solvent, but can also be carried out using an organic solvent. Although it does not specifically limit as an organic solvent used when performing using an organic solvent, For example, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane etc. Aliphatic hydrocarbons; Cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, decahydronaphthalene and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; methanol, ethanol, n Alcohols such as propanol, isopropanol, n-butanol and tert-butanol; ethers such as ethyl ether, tetrahydrofuran, dioxane, diglyme and triglyme; ketones such as acetone, methyl ethyl ketone and cyclohexanone; es such as methyl acetate and ethyl acetate Le acids; N- methylpyrrolidone, dimethylformamide, amides such as dimethylacetamide; dimethylsulfoxide; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, halogenated hydrocarbons such as tetrachloroethane and the like. These organic solvents can be used alone or in combination of two or more. Among these organic solvents, alcohols, ethers, ketones, amides, dimethyl sulfoxide and the like are preferable because they can be efficiently hydrolyzed, and ethers are more preferable.

There is no restriction | limiting in particular in the reaction temperature of the process of hydroxylating dihalogeno alkadiene and manufacturing dihydroxy alkadiene, For example, it is 0-300 degreeC, Preferably it is 0-200 degreeC. The reaction pressure is not particularly limited, but is usually 1 to 100 kg / cm ² in absolute pressure, preferably 1 to 50 kg / cm ² . In addition, the reaction time depends on the temperature and the substrate concentration of the raw material and cannot be generally determined, but is usually 1 minute to 50 hours. The atmosphere during the reaction is not particularly limited, but it is desirable to perform the reaction while avoiding air. For example, the reaction is preferably performed in an inert gas atmosphere such as nitrogen, argon, or helium.

  There is no particular limitation on the process for producing dihydroxyalkadiene by hydroxylating the dihalogenoalkadiene represented by the general formula (1) of the present invention. The raw material dihalogenoalkadiene, base, water, and if necessary A batch transfer system in which a phase transfer catalyst and, if necessary, an organic solvent or the like are charged into a reaction apparatus to carry out a hydroxylation reaction, or a raw material dihalogenoalkadiene, base, water, and a phase transfer catalyst if necessary and a solvent if necessary Etc. can be carried out either continuously, while continuously supplying unreacted raw materials and reaction liquid.

  After completion of the reaction, dihydroxyalkadiene can be recovered by a known separation method such as distillation. The dihalogenoalkadiene as a raw material can be recovered by a known separation method, for example, a method such as distillation and reused as a raw material.

  The dihydroxyalkadiene obtained by the hydroxylation reaction as described above is hydrogenated to produce a chain aliphatic diol. The hydrogenation reaction in the step of producing a chain aliphatic diol by hydrogenating dihydroxydecadiene is not particularly limited as long as the hydrogenation reaction can proceed efficiently, for example, hydrogenation The reaction is carried out with hydrogen in the presence of a reaction catalyst. Here, the hydrogenation reaction catalyst is a catalyst comprising a transition metal of Groups 6 to 11 of the periodic table, and specifically, chromium, molybdenum, tungsten, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium. Metal catalysts such as osmium, iridium and platinum can be used.

  The hydrogenation reaction catalyst may be of any form as long as the hydrogenation reaction proceeds. For example, any of a solid catalyst and a metal complex catalyst can be used. The solid catalyst includes (i) a solid catalyst prepared from a transition metal compound, and (ii) a solid catalyst having a transition metal compound supported on a support, and any solid catalyst can be used. The solid catalyst and the metal complex catalyst are described, for example, in “Catalytic hydrogenation reaction” (Tokyo Kagaku Dojin), pages 15 to 54.

  The solid catalyst prepared from the transition metal compound (i) is not particularly limited as long as it retains high catalytic activity and stability. For example, Raney nickel catalyst, Urushibara nickel catalyst, boride Nickel catalyst, nickel formate catalyst, nickel-phosphorus catalyst, nickel sulfide catalyst, Raney cobalt catalyst, Raney copper catalyst, Raney iron catalyst, molybdenum oxide catalyst, tungsten oxide catalyst, molybdenum trisulfide catalyst, ruthenium hydroxide catalyst, ruthenium black catalyst, dioxide Ruthenium catalyst, rhodium hydroxide catalyst, rhodium black catalyst, rhodium oxide catalyst, rhodium-platinum oxide catalyst, palladium oxide catalyst, palladium hydroxide catalyst, palladium black catalyst, platinum oxide catalyst, platinum black catalyst, osmium black catalyst, iridium black Examples include a catalyst and a rhenium black catalyst.

  The solid catalyst having the transition metal compound supported on the carrier (ii) is not particularly limited as long as it retains high catalytic activity and stability. For example, molybdenum, tungsten, iron, cobalt, Examples include nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum metal, oxide, hydroxide, sulfide and the like. The carrier is not particularly limited, and examples thereof include activated carbon, alumina, silica, titania, magnesia, zirconia, calcium carbonate, barium sulfate, and silica-alumina.

The metal complex catalyst is not particularly limited as long as it retains high catalytic activity and stability. For example, dichlorotris (triphenylphosphine) ruthenium (II), dicarbonyldichlorobis ( Triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium (I), di-μ-chlorobis (cyclooctadiene) dirhodium (I), trans-hydridocarbonyltris (triphenylphosphine) rhodium (I), di-μ -Chlorodichlorobis (pentamethylcyclopentadienyl) dirhodium (III), hexadecacarbonyl hexarhodium, trans-chlorocarbonyl bis (triphenylphosphine) iridium (I), hydridotris (triphenylphosphine) dichloroi Lidium (III), dichlorobis (triphenylphosphine) palladium (II), dodecacarbonyltriosmium (0), cis-dichlorobis (triphenylphosphine) platinum (II), hexacarbonylchromium, benzene-tricarbonylchromium (0), Examples thereof include pentacyanocobalt (II), octacarbonyl dicobalt (0), and η ³ -allyltris (trimethoxyphosphine) cobalt.

  Of these hydrogenation reaction catalysts, it is preferable to use a solid catalyst from the viewpoint of easy handling and safety, and more preferably, a solid catalyst Raney nickel catalyst or Raney prepared from the transition metal compound (i). Cobalt catalyst, Raney copper catalyst, Raney iron catalyst, etc., or solid catalyst supported nickel activated carbon catalyst, supported nickel alumina catalyst, supported nickel silica catalyst, supported palladium activated carbon catalyst, supported by the above-mentioned (ii) carrier supported by transition metal compound Palladium alumina catalyst, supported palladium silica catalyst, supported ruthenium activated carbon catalyst, supported ruthenium alumina catalyst, supported ruthenium silica catalyst, supported rhodium activated carbon catalyst, supported rhodium alumina catalyst, supported rhodium silica catalyst, supported rhenium activated carbon catalyst, supported rhenium alumina catalyst, supported Rhenium Siri Catalyst, supported platinum activated carbon catalyst, supported platinum alumina catalyst, supported platinum silica catalyst, supported iridium activated carbon catalyst, supported iridium alumina catalyst, supported iridium silica catalyst or the like is used.

  The amount of the hydrogenation catalyst used depends on the reaction conditions and the substrate concentration of the raw material and cannot be determined in general. Usually, the catalyst metal is 0.000001 to 1 mol, preferably 0, per 1 mol of dihydroxyalkadiene. The amount is 0.0001 to 0.5 mol, more preferably 0.00001 to 0.2 mol.

  The hydrogenation reaction can be performed in a solvent or without a solvent. Examples of such a solvent include, but are not limited to, water; aromatic hydrocarbons such as benzene, toluene and xylene; methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like. Alcohols such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide; ethers such as ethyl ether, tetrahydrofuran, dioxane, diglyme, and triglyme. Furthermore, these solvents can be used alone or in combination of two or more.

There is no restriction | limiting in particular in the temperature in a hydrogenation reaction, For example, it is -20-300 degreeC, Preferably it is 0-200 degreeC. The reaction pressure is not particularly limited, but is usually 0.01 to 300 kg / cm ² in absolute pressure, preferably 1 to 150 kg / cm ² . The reaction time depends on the temperature and the substrate concentration of the raw material and cannot be determined in general, but is usually 1 minute to 100 hours. The hydrogenation reaction can be performed by diluting with an inert gas such as nitrogen, argon or helium.

  There are no particular restrictions on the method of the hydrogenation reaction. The raw material dihydroxyalkadiene, the hydrogenation catalyst, and, if necessary, a batch system in which a solvent is charged into the reactor at once, dihydroxyalkadiene, and if necessary, a solvent, etc. It can be carried out in either a fixed bed or a continuous bed in which the unreacted raw material and the reaction solution are continuously drawn out while being continuously supplied. The reaction state is not particularly limited, and the reaction can be performed in a liquid phase or a gas phase, and further in a gas-liquid mixed state.

  After completion of the reaction, a chain aliphatic diol can be obtained by a known separation method such as distillation. In addition, the raw material dihydroxyalkadiene can be recovered by a known separation method, such as distillation, and reused as a raw material.

  The chain aliphatic diol of the present invention can be suitably used as a monomer raw material and additive for polyester resins and polyurethane resins and an intermediate for raw materials for medical and agricultural chemicals.

  The present invention provides an efficient method for producing a chain aliphatic diol having 9 to 12 carbon atoms, which is useful as an intermediate for polyester raw materials and additives for polyurethane resins and intermediates for raw materials for pharmaceuticals and agricultural chemicals. And is very useful industrially.

  Examples of the present invention are shown below, but the present invention is not limited to these examples.

  The measurement methods used in the examples are shown below.

<Gas chromatographic analysis>
Tetradecane was added as an internal standard to the reaction solution, and 0.4 μl of the reaction solution was injected into a gas chromatograph (GC-1700 manufactured by Shimadzu Corporation) equipped with a TC-1 column (trade name) manufactured by GL Sciences, and analysis was performed.

^<1 H- nuclear magnetic resonance (hereinafter, referred to as NMR) measurement>
¹ H-NMR measurement was performed using a nuclear magnetic resonance apparatus (trade name JNMGX400, manufactured by JEOL Ltd.).

<GC-MS measurement>
The measurement was performed using a gas chromatograph mass spectrometer (GC part; manufactured by Hewlett-Packard, trade name HP6890, MS part; manufactured by JEOL, trade name JMS-700).

Synthesis example 1
(1,3 dimesityl-2-imidazolidine ylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride (Aldrich, trade name ^{Hoveyda-Grubbs} Catalyst 2 nd Generation) and 6.8 mg (10.9Myumol) and dichloromethane 20ml Place in a 50 ml Schlenk tube. Next, 2.11 g (31.0 mmol) of cyclopentene was added, and 1.54 g (12.3 mmol) of 1,4-dichloro-2-butene (cis isomer: trans isomer = 36: 64) was further added. The Schlenk tube was heated to 40 ° C. in an oil bath and stirred for 3 hours to perform a ring-opening cross metathesis reaction. After completion of the reaction, the Schlenk tube was cooled to obtain a reaction solution.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. The obtained liquid was subjected to vacuum distillation (40 ° C., 4 mmHg to separate a colorless transparent liquid).

¹ H-NMR and GC-MS measurement of the obtained liquid was performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on one methylene group in the middle of the three methylene groups in the center of the carbon chain at δ 1.46 to 1.55 ppm (m), δ 2.00 to 2.10 ppm (m) is the peak based on two methylene groups adjacent to the double bond among the three methylene groups in the center of the carbon chain, and δ 4.06 ppm (d) is the carbon-terminated terminal adjacent to the chlorine atom. A peak based on four hydrogen atoms at the double bond site was observed at δ 5.60-5.75 ppm (m), a peak based on two methylene groups.

  As a result of GC-MS measurement, molecular ion peaks were confirmed at m / e 192 and 194 as main components.

  From these results, this liquid was identified as 1,9-dichloro-2,7-nonadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of allyl chloride was 55.3%, and the selectivity of 1,9-dichloro-2,7-nonadiene was 73.3%.

Synthesis example 2
(1,3 dimesityl-2-imidazolidine ylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride (Aldrich, trade name ^{Hoveyda-Grubbs} Catalyst 2 nd Generation) of 6.8mg of (10.9Myumol) 50 ml Schlenk Put in a tube. Next, 18.0 g (220 mmol) of cyclohexene was added, and 1.54 g (12.3 mmol) of 1,4-dichloro-2-butene (cis form: trans form = 36: 64) was further added. The Schlenk tube was heated to 80 ° C. in an oil bath and stirred for 3 hours to perform a ring-opening cross metathesis reaction. After completion of the reaction, the Schlenk tube was cooled to obtain a reaction solution.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. A colorless transparent liquid was separated from the obtained liquid by vacuum distillation (40 ° C., 4 mmHg. From gas chromatographic analysis, the purity of the product was 98%.

¹ H-NMR measurement and GC-MS measurement of the obtained liquid were performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on two methylene groups in the middle of the four methylene groups at the center of the carbon chain at δ1.33 to 1.46 ppm (m), δ2.01 to 2.17 ppm (m) is a peak based on two methylene groups adjacent to the double bond among the four methylene groups in the center of the carbon chain, and δ 4.03 ppm (d) and δ 4.09 ppm (d) are chlorine atoms. A peak based on two methylene groups at the end of the carbon chain adjacent to and a peak based on four hydrogen atoms at the double bond site at δ5.55-5.82 ppm (m) was observed. The peaks at δ 4.03 ppm (d) and δ 4.09 ppm (d) were peaks based on the geometric isomerism structure (cis isomer, trans isomer).

  Further, as a result of GC-MS measurement, molecular ion peaks were confirmed at m / e 206 and 208.

  From these results, this liquid was identified as 1,10-dichloro-2,8-decadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of 1,4-dichloro-2-butene was 18.2%, and the selectivity of 1,10-dichloro-2,8-decadiene was 90.4%. there were.

Synthesis example 3
(1,3 dimesityl-2-imidazolidine ylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride (Aldrich, trade name ^{Hoveyda-Grubbs} Catalyst 2 nd Generation) and 6.8 mg (10.9Myumol) and dichloromethane 20ml Place in a 50 ml Schlenk tube. Next, 2.10 g (22.0 mmol) of cycloheptene was added, and further 1.30 g (10.3 mmol) of 1,4-dichloro-2-butene (cis isomer: trans isomer = 36: 64) was added. The Schlenk tube was heated to 80 ° C. in an oil bath and stirred for 3 hours to perform a ring-opening cross metathesis reaction. After completion of the reaction, the Schlenk tube was cooled to obtain a reaction solution.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. A colorless transparent liquid was separated from the obtained liquid by vacuum distillation (40 ° C., 4 mmHg. From gas chromatographic analysis, the purity of the product was 97%.

¹ H-NMR measurement and GC-MS measurement of the obtained liquid were performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on one methylene group in the middle of the five methylene groups in the middle of the carbon chain at δ 1.12 to 1.23 ppm (m), δ 1.36 to Among the five methylene groups at the center of the carbon chain at 1.46 ppm (m), the peak based on the second two methylene groups from the center, five at the center of the carbon chain at δ2.00 to 2.08 ppm (m) Of the two methylene groups adjacent to the double bond, a peak based on the two methylene groups at the end of the carbon chain adjacent to the chlorine atom at δ 4.03 ppm (d), δ 5.65 A peak based on four hydrogen atoms at the double bond site was observed at 5.77 ppm (m).

  As a result of GC-MS measurement, molecular ion peaks were confirmed at m / e 220 and 222 as the main component.

  From these results, this liquid was identified as 1,11-dichloro-2,9-undecadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of 1,4-dichloro-2-butene was 82.1%, and the selectivity of 1,11-dichloro-2,9-undecadiene was 63.2%. there were.

Synthesis example 4
(1,3 dimesityl-2-imidazolidine ylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride (Aldrich, trade name ^{Hoveyda-Grubbs} Catalyst 2 nd Generation) and 6.8 mg (10.9Myumol) and dichloromethane 20ml Place in a 50 ml Schlenk tube. Next, 2.93 g (26.7 mmol) of cyclooctene was added, and 1.21 g (9.7 mmol) of 1,4-dichloro-2-butene (cis body: trans body = 36: 64) was further added. The Schlenk tube was heated to 80 ° C. in an oil bath and stirred for 3 hours to perform a ring-opening cross metathesis reaction. After completion of the reaction, the Schlenk tube was cooled to obtain a reaction solution.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. A colorless transparent liquid was separated from the obtained liquid by vacuum distillation (40 ° C., 4 mmHg. From gas chromatographic analysis, the purity of the product was 95%.

¹ H-NMR measurement and GC-MS measurement of the obtained liquid were performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on four methylene groups in the middle of the six methylene groups at the center of the carbon chain at δ 1.25 to 1.37 ppm (m), δ 2.05 2.13 ppm (m) is a peak based on two methylene groups adjacent to the double bond among the six methylene groups in the center of the carbon chain, and δ 4.05 ppm (d) is the peak of the carbon chain end adjacent to the chlorine atom. A peak based on two methylene groups and a peak based on four hydrogen atoms at the double bond site were observed at δ 5.65 to 5.78 ppm (m).

  As a result of GC-MS measurement of the reaction solution, molecular ion peaks were confirmed at m / e 234 and 236 for the main component.

  From these results, this liquid was identified as 1,12-dichloro-2,10-dodecadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of 1,4-dichloro-2-butene was 92.5%, and the selectivity of 1,12-dichloro-2,10-dodecadiene was 56.6%. there were.

Example 1
In a 50 ml eggplant flask, 0.15 g of sodium formate, 2 ml of distilled water, 1.5 ml of 1,4-dioxane, and 0.19 g of 1,9-dichloro-2,7-nonadiene obtained in Synthesis Example 1 were replaced with nitrogen. And installed in an oil bath set at 80 ° C. After 3 hours, it was taken out and the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of gas chromatographic analysis, 1,9-dichloro-2,7-nonadiene was converted to 95%, the selectivity for 1,9-dihydroxy-2,7-nonadiene was 18%, 3,7-dihydroxy-1, The selectivity of 8-nonadiene was 8%, and the selectivity of 3,9-dihydroxy-1,7-nonadiene was 19%.

Example 2
In a 50 ml eggplant flask, 0.43 g of calcium carbonate, 4 ml of distilled water, 3 ml of 1,4-dioxane, and 1,9-dichloro-2,7-nonadiene obtained in Synthesis Example 1 were replaced with 0.55 g of nitrogen. It was installed in an oil bath set at ° C. After 4 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of gas chromatographic analysis, 1,9-dichloro-2,7-nonadiene was completely converted, and the selectivity for 1,9-dihydroxy-2,7-nonadiene was 35%, 3,7-dihydroxy-1, The selectivity for 8-nonadiene was 20% and the selectivity for 3,9-dihydroxy-1,7-nonadiene was 45%.

  The product was extracted from the reaction solution with diethyl ether and distilled to separate and recover the three types of dihydroxy compounds. As a result, 0.14 g of 1,9-dihydroxy-2,7-nonadiene was obtained.

Example 3
In a 10 ml stainless steel autoclave, take 0.28 g of sodium carbonate, 1 ml of distilled water, 0.040 g of hexadecyltrimethylammonium bromide, 0.38 g of 1,9-dichloro-2,7-nonadiene obtained in Synthesis Example 1, and add nitrogen. And then pressurized to 5 kg / cm ² . It was placed in an oil bath set at 140 ° C., and after 3 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of gas chromatographic analysis, 1,9-dichloro-2,7-nonadiene was completely converted, and 1,9-dihydroxy-2,7-nonadiene had a selectivity of 33%, 3,7-dihydroxy-1, The selectivity for 8-nonadiene was 21% and the selectivity for 3,9-dihydroxy-1,7-nonadiene was 46%.

Example 4
A 50 ml two-necked eggplant flask was charged with 10 ml of ethanol and 0.02 g of 5 wt% Pd / C and 5 mg of sodium hydroxide as a hydrogenation catalyst, and the atmosphere was replaced with nitrogen. Thereafter, hydrogen was supplied to the flask at 15 ml / min, and reduction treatment was performed at 50 ° C. for 2 hours.

  The temperature in the flask was lowered to 27 ° C., and 0.14 g of 1,9-hydroxy-2,7-nonadiene obtained in Example 2 was added. After 20 hours, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1,9-dihydroxy-2,7-nonadiene was completely converted and the selectivity for 1,9-nonanediol was 83%.

Example 5
In a 50 ml eggplant flask, 0.15 g of sodium formate, 2 ml of distilled water, 1.5 ml of 1,4-dioxane, and 0.2 g of 1,10-dichloro-2,8-decadiene obtained in Synthesis Example 2 are taken up with nitrogen. It replaced and installed in the oil bath set to 80 degreeC. After 3 hours, it was taken out and the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,10-dichloro-2,8-decadiene was converted to 93%, the selectivity of 1,10-dihydroxy-2,8-decadiene was 18%, 3,8-dihydroxy-1, The selectivity for 9-decadiene was 7% and the selectivity for 3,10-dihydroxy-1,8-decadiene was 22%.

Example 6
In a 50 ml eggplant flask, 0.35 g of calcium carbonate, 4 ml of distilled water, 3 ml of 1,4-dioxane, and 0.5 g of 1,10-dichloro-2,8-decadiene obtained in Synthesis Example 2 were replaced with nitrogen. And installed in an oil bath set at 80 ° C. After 4 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,10-dichloro-2,8-decadiene was completely converted, and the selectivity for 1,10-dihydroxy-2,8-decadiene was 36%, 3,8-dihydroxy-1, The selectivity for 9-decadiene was 14% and the selectivity for 3,10-dihydroxy-1,8-decadiene was 45%.

  The product was extracted from the reaction solution with diethyl ether and distilled to separate and recover the three types of dihydroxy compounds. As a result, 0.13 g of 1,10-dihydroxy-2,8-decadiene was obtained.

Example 7
In a 10 ml stainless steel autoclave, take 0.27 g of sodium carbonate, 1 ml of distilled water, 0.041 g of hexadecyltrimethylammonium bromide, 0.42 g of 1,10-dichloro-2,8-decadiene obtained in Synthesis Example 2, and add nitrogen. And then pressurized to 5 kg / cm ² . It was placed in an oil bath set at 140 ° C., and after 3 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,10-dichloro-2,8-decadiene was completely converted, and the selectivity of 1,10-dihydroxy-2,8-decadiene was 29%, 3,8-dihydroxy-1, The selectivity for 9-decadiene was 23%, and the selectivity for 3,10-dihydroxy-1,8-decadiene was 48%.

Example 8
A 50 ml two-necked eggplant flask was charged with 10 ml of ethanol and 0.02 g of 5 wt% Pd / C and 5 mg of sodium hydroxide as a hydrogenation catalyst, and the atmosphere was replaced with nitrogen. Thereafter, hydrogen was supplied to the flask at 15 ml / min, and reduction treatment was performed at 50 ° C. for 2 hours.

  The temperature in the flask was lowered to 27 ° C., and 0.13 g of 1,10-hydroxy-2,8-decadiene obtained in Example 6 was added. After 20 hours, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1,10-dihydroxy-2,8-decadiene was completely converted and the selectivity for 1,10-decanediol was 81%.

Example 9
A hydrogenation reaction was performed in the same manner as in Example 8 except that the hydrogenation reaction catalyst was 5 wt% Pt / C 0.02 g manufactured by N.E.

  As a result of gas chromatographic analysis, 1,10-dihydroxy-2,8-decadiene was completely converted, and the selectivity for 1,10-decanediol was 90%.

Example 10
A hydrogenation reaction was performed in the same manner as in Example 8 except that the hydrogenation reaction catalyst was changed to 0.3 g of Raney nickel manufactured by Nikko Rica. As a result of gas chromatographic analysis, 1,10-dihydroxy-2,8-decadiene was completely converted, and the selectivity for 1,10-decanediol was 82%.

Example 11
In a 50 ml eggplant flask, 0.15 g of sodium formate, 2 ml of distilled water, 1.5 ml of 1,4-dioxane, and 0.23 g of 1,11-dichloro-2,9-undecadiene obtained in Synthesis Example 3 were replaced with nitrogen. And installed in an oil bath set at 80 ° C. After 3 hours, it was taken out and the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,11-dichloro-2,9-undecadiene was converted to 90%, selectivity of 1,11-dihydroxy-2,9-undecadiene was 20%, 3,9-dihydroxy-1, The selectivity for 10-undecadiene was 11%, and the selectivity for 3,11-dihydroxy-1,9-undecadiene was 21%.

Example 12
In a 50 ml eggplant flask, 0.37 g of calcium carbonate, 4 ml of distilled water, 3 ml of 1,4-dioxane and 1,11-dichloro-2,9-undecadiene obtained in Synthesis Example 3 were replaced with 0.55 g of nitrogen. It was installed in an oil bath set at ° C. After 4 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,11-dichloro-2,9-undecadiene was completely converted, and the selectivity of 1,11-dihydroxy-2,9-undecadiene was 33%, 3,9-dihydroxy-1, The selectivity for 10-undecadiene was 15%, and the selectivity for 3,11-dihydroxy-1,9-undecadiene was 47%.

  The product was extracted from the reaction solution with diethyl ether and distilled to separate and recover the three types of dihydroxy compounds. As a result, 0.14 g of 1,11-dihydroxy-2,9-undecadiene was obtained.

Example 13
In a 10 ml stainless steel autoclave, take 0.28 g of sodium carbonate, 1 ml of distilled water, 0.040 g of hexadecyltrimethylammonium bromide, 0.44 g of 1,11-dichloro-2,9-undecadiene obtained in Synthesis Example 3, and add nitrogen. And then pressurized to 5 kg / cm ² . It was placed in an oil bath set at 140 ° C., and after 3 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,11-dichloro-2,9-undecadiene was completely converted, and the selectivity for 1,11-dihydroxy-2,9-undecadiene was 34%, 3,9-dihydroxy-1, The selectivity for 10-undecadiene was 19% and the selectivity for 3,11-dihydroxy-1,9-undecadiene was 47%.

Example 14
A 50 ml two-necked eggplant flask was charged with 10 ml of ethanol and 0.02 g of 5 wt% Pd / C and 5 mg of sodium hydroxide as a hydrogenation catalyst, and the atmosphere was replaced with nitrogen. Thereafter, hydrogen was supplied to the flask at 15 ml / min, and reduction treatment was performed at 50 ° C. for 2 hours.

  The temperature in the flask was lowered to 27 ° C., and 0.14 g of 1,11-hydroxy-2,9-undecadiene obtained in Example 12 was added. After 20 hours, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1,11-dihydroxy-2,9-undecadiene was completely converted, and the selectivity for 1,11-undecanediol was 82%.

Example 15
In a 50 ml eggplant flask, 0.15 g of sodium formate, 2 ml of distilled water, 1.5 ml of 1,4-dioxane, and 0.23 g of 1,12-dichloro-2,10-dodecadiene obtained in Synthesis Example 4 are taken up with nitrogen. It replaced and installed in the oil bath set to 80 degreeC. After 3 hours, it was taken out and the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,12-dichloro-2,10-dodecadiene was converted to 90%, selectivity of 1,12-dihydroxy-2,10-dodecadiene was 20%, 3,10-dihydroxy-1, The selectivity of 11-dodecadiene was 9%, and the selectivity of 3,12-dihydroxy-1,10-dodecadiene was 22%.

Example 16
In a 50 ml eggplant flask, 0.35 g of calcium carbonate, 4 ml of distilled water, 3 ml of 1,4-dioxane, and 0.5 g of 1,12-dichloro-2,10-dodecadiene obtained in Synthesis Example 4 were replaced with nitrogen. And installed in an oil bath set at 80 ° C. After 4 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of gas chromatographic analysis, 1,12-dichloro-2,10-dodecadiene was completely converted, and the selectivity for 1,12-dihydroxy-2,10-dodecadiene was 35%, 3,10-dihydroxy-1, The selectivity for 11-dodecadiene was 13%, and the selectivity for 3,12-dihydroxy-1,10-dodecadiene was 48%.

  The product was extracted from this reaction solution with diethyl ether and distilled to separate and recover three types of dihydroxy compounds, whereby 0.14 g of 1,12-dihydroxy-2,10-decadiene was obtained.

Example 17
In a 10 ml stainless steel autoclave, 0.27 g of sodium carbonate, 1 ml of distilled water, 0.041 g of hexadecyltrimethylammonium bromide, 0.46 g of 1,12-dichloro-2,10-dodecadiene obtained in Synthesis Example 4 are taken, and nitrogen is added. And then pressurized to 5 kg / cm ² . It was placed in an oil bath set at 140 ° C., and after 3 hours, it was taken out, the temperature was lowered to room temperature, and the reaction solution was recovered.

  As a result of analysis by gas chromatography, 1,12-dichloro-2,10-dodecadiene was completely converted, and the selectivity of 1,12-dihydroxy-2,10-dodecadiene was 28%, 3,10-dihydroxy-1, The selectivity for 11-dodecadiene was 24% and the selectivity for 3,12-dihydroxy-1,10-dodecadiene was 48%.

Example 18
A 50 ml two-necked eggplant flask was charged with 10 ml of ethanol and 0.02 g of 5 wt% Pd / C and 5 mg of sodium hydroxide as a hydrogenation catalyst, and the atmosphere was replaced with nitrogen. Thereafter, hydrogen was supplied to the flask at 15 ml / min, and reduction treatment was performed at 50 ° C. for 2 hours.

  The temperature in the flask was lowered to 27 ° C., and 0.14 g of 1,12-hydroxy-2,10-dodecadiene obtained in Example 16 was added. After 20 hours, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1,12-hydroxy-2,10-dodecadiene was completely converted and the selectivity of 1,12-dodecanediol was 80%.

Claims (7)

By carrying out a ring-opening cross-metathesis reaction of 1,4-dihalogeno-2-butene represented by the following general formula (2) and a cyclic olefin represented by the following general formula (3) in the presence of a metathesis reaction catalyst, It comprises a step of producing a dihalogenoalkadiene represented by the general formula (1), a step of producing a dihydroxyalkadiene by hydroxylating the dihalogenoalkadiene , and a step of hydrogenating the dihydroxyalkadiene. A method for producing a chain aliphatic diol having 9 to 12 carbon atoms.

(In formula, X represents a chlorine atom, a bromine atom, or an iodine atom each independently, and n represents the integer of 3-6.)

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)

(In the formula, m represents an integer of 0 to 3.) 2. The method for producing a chain aliphatic diol according to claim 1, wherein both Xs in the general formula (1) are a chlorine atom, a bromine atom or an iodine atom. The method for producing a chain aliphatic diol according to claim 1 or 2, wherein the step of hydroxylating the dihalogenoalkadiene is a hydrolysis reaction using a base and water. The method for producing a chain aliphatic diol according to any one of claims 1 to 3, wherein the solvent used in the hydrolysis reaction is an ether. The method for producing a chain aliphatic diol according to any one of claims 1 to 3, wherein a phase transfer catalyst is used for the hydrolysis reaction. 6. The process for producing a chain aliphatic diol according to any one of claims 1 to 5, wherein the step of hydrogenating the dihydroxyalkadiene is carried out using hydrogen in the presence of a hydrogenation reaction catalyst. Method. The method for producing a chain aliphatic diol according to claim 6, wherein the hydrogenation reaction catalyst is a solid catalyst.