WO2005090273A1 - Method for producing alcohol compound - Google Patents

Method for producing alcohol compound Download PDF

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Publication number
WO2005090273A1
WO2005090273A1 PCT/JP2005/005110 JP2005005110W WO2005090273A1 WO 2005090273 A1 WO2005090273 A1 WO 2005090273A1 JP 2005005110 W JP2005005110 W JP 2005005110W WO 2005090273 A1 WO2005090273 A1 WO 2005090273A1
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group
bicyclo
bis
dicarboxylate
methyl
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PCT/JP2005/005110
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French (fr)
Japanese (ja)
Inventor
Kazuyuki Tanaka
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Sumitomo Chemical Company, Limited
Dainippon Sumitomo Pharma Co., Ltd.
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Publication of WO2005090273A1 publication Critical patent/WO2005090273A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a method for producing an alcohol compound.
  • a 1 represents a cyclic hydrocarbon group which may be crosslinked, and A 2 and A 3 each represent the same or different and represent a single bond or an alkylene group having 11 to 12 carbon atoms.
  • R represents a lower alkyl group, and Y represents a hydrogen atom or a group represented by COR.
  • a method of reacting an ester compound represented by the formula (1) with lithium aluminum hydride is known (for example, Patent Document 1, Non-Patent Document 1).
  • lithium aluminum hydride is a water-inhibiting reagent that requires careful handling, it is necessary to strictly control the water content in the reaction system, and it is a by-product in post-treatment after the reaction. The operation of removing the aluminum compound is also complicated, and it cannot be said that the production method is necessarily satisfactory industrially.
  • Patent Document 1 Japanese Patent No. 2800953
  • Non-Patent Document 1 J. Am. Chem. So, 75, 4780 (1953)
  • Non-Patent Document 2 J. Am. Chem. Soc., 78, 2582 (1956)
  • the present inventor has developed a method for producing an alcohol compound from the ester compound represented by the formula (1) more industrially and advantageously using a reagent that is easy to handle.
  • a borohydride compound such as sodium borohydride
  • the reduction reaction proceeded easily, and the desired alcoholic conjugate was obtained. They have found that they can be obtained, leading to the present invention.
  • a borohydride compound is reacted with a borohydride compound in an organic solvent in the presence of methanol. Equation (2) characterized by
  • an alcohol compound can be easily produced using a borohydride compound which is easy to handle, and post-treatment after the reaction is also easy. This is an advantageous manufacturing method.
  • ester compound (1) In Esuterui ⁇ compound represented (hereinafter, abbreviated as ester compound (1).) Compounds of, A 1 is rack A represents an optionally bridged cyclic hydrocarbon group, and A 2 and A 3 are the same or different and each represents a single bond or an alkylene group having 11 to 12 carbon atoms. R represents a lower alkyl group; Y represents a hydrogen atom or a group represented by COR.
  • cyclic hydrocarbon group which may be crosslinked examples include, for example, cyclopropane-1,1, -diyl group, cyclopropane-1,2_diyl group, cyclobutane-1,1,1-diyl group, cyclobutane-1,2_ Diyl group, cyclobutane-1,3_diyl group, cyclopentane_1,1_diyl group, cyclopentane-1,2_diyl group, cyclopentane-1,3_diyl group, cyclohexane-1,1,1- Diinole, cyclohexane-1,2, diyl, cyclohexane-1,3, diyl, cyclohexane-1,4-diinole, cycloheptane-1,1, diyl, cycloheptane-1 , 2-Diynole, cycloheptane_1,3_diyl,
  • Divalent saturated or unsaturated 317-membered ring Hydride groups such as bicyclo [1.1.1] pentane-2,2-diyl group, bicyclo [1.1.1] pentane-2,4-diynole group, bicyclo [2.1.1] hexane 2,3-diyl group, bicyclo [2.1.1] hexa 2-ene-5,5-diyl group, bicyclo mouth [2.2.1] heptane-2,3_diyl group, bicyclo [2.2] .1] Hepta_2_ene-5,6-diyl group, bicyclo [2.2.2] octane-1,2,3-diyl group, bicyclo [2.2.2] octa_2-ene-1,5,6 —Ginole group, bicyclo [4.1.1] octane-1,3,4—Diyl group, bicyclo [4.1.1] octane-1,5, —G
  • Examples of the alkylene group having 1 to 2 carbon atoms include a methylene group, a 1,2-ethylene group, and a 1,1-ethylene group.
  • Examples of lower alkyl groups include methyl, ethyl, ⁇ -propyl, isopropyl, ⁇ -butyl, isobutyl, sec-butyl, tert-butylinole, n-pentyl, and n-hexyl groups.
  • Examples of the group represented by _C ⁇ R include a methoxycarbonyl group and an ethoxycarbonyl group.
  • n-propoxycarbonyl group isopropoxycarbonyl group, n-butoxycarbinole group, n-pentyloxycarbonyl group, n-xyloxycarbonyl group and the like.
  • Examples of the strong ester compound (1) include, for example, cyclopropane-1-methyl carboxylate, cyclopropane-111-ethyl ruvonate, cyclopropane_1-isopropyl rubonate, cyclopropane-111-rubonic acid n -Butyl, cyclopropane, n -butyric acid, n-xynole, 1- (methoxycarbonylmethyl) cyclopropane, 1_ (1-methoxycarbonylethyl) cyclopropane, 1_ (2-methoxycarbonylethylenole) cyclopropane, Methyl cyclopropane-1,1-dicarboxylate, ethyl 1,1-dicarboxylate, cyclopropane-1,1-dicarboxylate, n-butyl cyclopropane-1,1-dicarboxylate, 1,1-dicarboxylic cycloprop
  • Cyclopentane-111-Methyl Rubonate 1- (Methoxycarbonylmethyl) cyclopentane, Cyclopentane-1,1-dicarboxylate, Cyclopentane-1-1,1-Dicarboxylate, 1,1_ Bis (methoxycarbonylmethinole) cyclopentane, cyclopentane-methyl 1,2-dicarboxylate, cyclopentane_1,2-dicarboxylate, 1,2_bis (methoxycanolebonylmethinole) cyclopentane, cyclopentane Methyl 1,3-dicarboxylate, cyclopentane-1,3-dicarboxylate, 1,3_bis (methoxycarboninolemethynole) cyclopentane, cyclohexane_1_methyl carboxylate, 1- (methoxycarbonitrile Rumethinole) cyclohexane, cyclohexane,
  • Examples of the borohydride compound include alkali metal borohydride compounds such as lithium borohydride, sodium borohydride, and potassium borohydride; Examples thereof include alkaline earth metal borohydride compounds, such as zinc borohydride, and more preferred are alkali metal borohydride compounds, and more preferred are lithium borohydride and sodium borohydride.
  • borohydride compound a commercially available compound may be used, or a compound produced according to a known method such as a reaction between a borate ester and sodium hydride may be used. Is also good.
  • the amount of the borohydride compound to be used is as follows: In the case of (1), the amount is usually 0.5 to 10 times, preferably 0.5 to 5 times, more preferably 0.5 to 2 times the molar amount of the esterified conjugate (1). In the case of the ester compound (1) in which Y is a group represented by —COR, the ester compound (1) is usually used in a molar amount of usually 120 to 20 times, preferably 1 to 10 times, and more preferably 1 to 10 times. 4 mole times.
  • the organic solvent is not particularly limited as long as it is inert to the reaction.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • ethers such as getyl ether, diisopropyl ether, methyl tert-butyl ether, and tetrahydrofuran
  • a single solvent or a mixed solvent such as an alcoholic solvent having 3 or more carbon atoms such as isopropanol and tert-butanol is used. It is 50 times by weight, preferably 110 times by weight, more preferably 110 times by weight.
  • the organic solvent may be previously mixed with at least one selected from the esterified compound (1), the borohydride compound and the methanol solvent.
  • the reaction between the ester compound (1) and the borohydride compound is carried out in the presence of methanol, and the amount of methanol to be used is usually about 110 to 10 times the molar amount of the borohydride compound. Is 1 to 5 mole times, more preferably 1.5 to 3 mole times.
  • the reaction temperature is usually in the range of -10 to 150 ° C, preferably in the range of 0 to 100 ° C, and more preferably in the range of 0 to 80 ° C.
  • reaction solution After completion of the reaction, for example, the obtained reaction solution is mixed with an aqueous solution of a mineral acid such as hydrochloric acid or sulfuric acid, and then, if necessary, an organic solvent insoluble in water is added to carry out extraction treatment. Is concentrated to obtain the formula (2)
  • alcohol compound (2) The ability to take out the alcoholic compound represented by (hereinafter abbreviated as alcohol compound (2)).
  • the alcohol compound (2) taken out may be further purified by ordinary purification means such as recrystallization, distillation, column chromatography and the like.
  • Pentane 1,3-bis (2-hydroxyethynole) cyclopentane
  • Example 1
  • dimethyl trans-1,2-cyclohexanedicarboxylate 5.0 g, tert-butanol 25.2 g And 3.81 g of sodium borohydride, and then the internal temperature was adjusted to 35 ° C. At the same temperature, 9.6 g of methanol was added dropwise over 2 hours, and the mixture was stirred and reacted at the same temperature for 3 hours. After 35.4 g of a 10% by weight aqueous hydrochloric acid solution was added dropwise, 30.6 g of water was added and the mixture was concentrated.
  • an alcohol compound can be industrially advantageously produced from the ester mixture represented by the formula (1) using a reagent that is easy to handle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a method for producing an alcohol compound represented by the following formula (2): HOH2C-A2-A1-A3-Q (2) (wherein A1, A2 and A3 are as defined below; and Q represents a hydrogen atom when Y defined below is an hydrogen atom or represents a hydroxymethyl group when Y is a group expressed as -CO2R), wherein an ester compound represented by the following formula (1): RO2C-A2-A1-A3-Y (1) (wherein A1 represents a cyclic hydrocarbon group which may be crosslinked; A2 and A3 may be the same or different and respectively represent a single bond or an alkylene group having 1-2 carbon atoms; R represents a lower alkyl group; and Y represents a hydrogen atom or a group expressed as -CO2R) is reacted with a borohydride compound in an organic solvent in the presence of methanol.

Description

明 細 書  Specification
アルコール化合物の製造方法  Method for producing alcohol compound
技術分野  Technical field
[0001] 本発明はアルコール化合物の製造方法に関する。  The present invention relates to a method for producing an alcohol compound.
背景技術  Background art
[0002] 1 , 2—ビス（ヒドロキシメチル）シクロへキサン、 1 , 2—ビス（ヒドロキシメチノレ）— 4—シク 口へキセン等の架橋されてレ、てもよレ、環状炭化水素基を有するアルコール化合物は 、例えば医薬合成中間体として有用であり（例えば特許文献 1参照。）、その製造方 法としては、式（1)  [0002] 1,2-bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxymethynole) -4-cyclohexene, etc. The alcohol compound is useful, for example, as a pharmaceutical synthesis intermediate (for example, see Patent Document 1).
R〇2C ^ A2— A1— A3— Y (1) R〇 2 C ^ A 2 — A 1 — A 3 — Y (1)
(式中、 A1は架橋されていてもよい環状炭化水素基を表わし、 A2および A3は、それぞ れ同一または相異なって、単結合または炭素数 1一 2のアルキレン基を表わす。 Rは 低級アルキル基を表わし、 Yは水素原子または一 CO Rで示される基を表わす。 ) で示されるエステルィヒ合物と水素化リチウムアルミニウムと反応させる方法が知られて いる（例えば特許文献 1、非特許文献 1参照。）。し力 ながら、水素化リチウムアルミ 二ゥムは取扱いに注意を要する禁水性の試薬であるため、反応系内の水分管理を 厳密に行う必要があり、また、反応後の後処理において副生するアルミニウム化合物 の除去操作も煩雑であり、必ずしも工業的に十分満足し得る製造方法とは言えなか つた。 (In the formula, A 1 represents a cyclic hydrocarbon group which may be crosslinked, and A 2 and A 3 each represent the same or different and represent a single bond or an alkylene group having 11 to 12 carbon atoms. R represents a lower alkyl group, and Y represents a hydrogen atom or a group represented by COR.) A method of reacting an ester compound represented by the formula (1) with lithium aluminum hydride is known (for example, Patent Document 1, Non-Patent Document 1). However, since lithium aluminum hydride is a water-inhibiting reagent that requires careful handling, it is necessary to strictly control the water content in the reaction system, and it is a by-product in post-treatment after the reaction. The operation of removing the aluminum compound is also complicated, and it cannot be said that the production method is necessarily satisfactory industrially.
[0003] 一方、水素化リチウムアルミニウムに比べて取扱いの容易な水素化ホウ素ナトリウム を、塩化アルミニウムとともに用いる方法も知られている（例えば非特許文献 2参照。） が、反応後の後処理において、除去操作が煩雑なアルミニウム化合物を副生するた め、必ずしも工業的に十分満足し得るものではなかった。  [0003] On the other hand, a method is known in which sodium borohydride, which is easier to handle than lithium aluminum hydride, is used together with aluminum chloride (for example, see Non-Patent Document 2). Since the removal operation produces a by-product of a complicated aluminum compound, it has not always been industrially satisfactory.
特許文献 1：特許第 2800953号公報  Patent Document 1: Japanese Patent No. 2800953
非特許文献 1 :J. Am. Chem. So ， 75, 4780 (1953)  Non-Patent Document 1: J. Am. Chem. So, 75, 4780 (1953)
非特許文献 2 :J. Am. Chem. Soc. , 78, 2582 (1956)  Non-Patent Document 2: J. Am. Chem. Soc., 78, 2582 (1956)
発明の開示 発明が解決しょうとする課題 Disclosure of the invention Problems the invention is trying to solve
[0004] このような状況のもと、本発明者は、取扱いが容易な試剤を用いて、前記式（1)で 示されるエステル化合物からアルコール化合物をより工業的に有利に製造する方法 を開発すべく検討したところ、水素化ホウ素ナトリウム等の水素化ホウ素化合物を用 レ、、メタノールの存在下に反応を行うことにより、容易に還元反応が進行し、 目的とす るアルコールィ匕合物を得ることができることを見出し、本発明に至った。 課題を解決するための手段 [0004] Under such circumstances, the present inventor has developed a method for producing an alcohol compound from the ester compound represented by the formula (1) more industrially and advantageously using a reagent that is easy to handle. When the reaction was carried out in the presence of methanol using a borohydride compound such as sodium borohydride, the reduction reaction proceeded easily, and the desired alcoholic conjugate was obtained. They have found that they can be obtained, leading to the present invention. Means for solving the problem
[0005] すなわち本発明は、式（1) [0005] That is, the present invention relates to formula (1)
R02C ^ A2— A1— A3— Y (1) R0 2 C ^ A 2 — A 1 — A 3 — Y (1)
(式中、 A1は架橋されていてもよい環状炭化水素基を表わし、 A2および A3は、それぞ れ同一または相異なって、単結合または炭素数 1一 2のアルキレン基を表わす。 Rは 低級アルキル基を表わし、 Yは水素原子または一 C〇 Rで示される基を表わす。 ) で示されるエステルイ匕合物と水素化ホウ素化合物とを、有機溶媒中、メタノールの存 在下に反応させることを特徴とする式（2) (In the formula, A 1 represents a cyclic hydrocarbon group which may be crosslinked, and A 2 and A 3 each represent the same or different and represent a single bond or an alkylene group having 11 to 12 carbon atoms. R represents a lower alkyl group, and Y represents a hydrogen atom or a group represented by C〇R.) A borohydride compound is reacted with a borohydride compound in an organic solvent in the presence of methanol. Equation (2) characterized by
HOH2C ^ A2— A1— AJ— Q (2) HOH 2 C ^ A 2 — A 1 — A J — Q (2)
(式中、 A1, A2および A3は上記と同一の意味を表わし、 Qは、 Yが水素原子のときに 水素原子を、 Yが _C〇 Rで示される基のときにヒドロキシメチル基を表わす。） で示されるアルコール化合物の製造方法を提供するものである。 (Wherein A 1 , A 2 and A 3 have the same meanings as above, Q is a hydrogen atom when Y is a hydrogen atom, and a hydroxymethyl group when Y is a group represented by _C〇R The present invention provides a method for producing an alcohol compound represented by the formula:
発明の効果  The invention's effect
[0006] 本発明によれば、取扱いが容易な水素化ホウ素化合物を用いて、簡便にアルコー ル化合物を製造することができ、また反応後の後処理も容易であるため、工業的によ り有利な製造方法である。  According to the present invention, an alcohol compound can be easily produced using a borohydride compound which is easy to handle, and post-treatment after the reaction is also easy. This is an advantageous manufacturing method.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0007] 式（1) [0007] Expression (1)
R02C ^ A2— A1— A3— Y (1) R0 2 C ^ A 2 — A 1 — A 3 — Y (1)
で示されるエステルイ匕合物（以下、エステル化合物（1)と略記する。）の式中、 A1は架 橋されていてもよい環状炭化水素基を表わし、 A2および A3は、それぞれ同一または 相異なって、単結合または炭素数 1一 2のアルキレン基を表わす。 Rは低級アルキル 基を表わし、 Yは水素原子または一 CO Rで示される基を表わす。 In Esuterui匕合compound represented (hereinafter, abbreviated as ester compound (1).) Compounds of, A 1 is rack A represents an optionally bridged cyclic hydrocarbon group, and A 2 and A 3 are the same or different and each represents a single bond or an alkylene group having 11 to 12 carbon atoms. R represents a lower alkyl group; Y represents a hydrogen atom or a group represented by COR.
2  2
架橋されていてもよい環状炭化水素基としては、例えばシクロプロパン一 1， 1—ジィ ル基、シクロプロパン— 1， 2_ジィル基、シクロブタン— 1 , 1_ジィル基、シクロブタン— 1 , 2_ジィル基、シクロブタン— 1， 3_ジィル基、シクロペンタン _1， 1_ジィル基、シク 口ペンタン— 1 , 2_ジィル基、シクロペンタン— 1， 3_ジィル基、シクロへキサン— 1 , 1- ジィノレ基、シクロへキサン一 1 , 2_ジィル基、シクロへキサン一 1 , 3_ジィル基、シクロ へキサン— 1， 4—ジィノレ基、シクロヘプタン—1 , 1—ジィル基、シクロヘプタン— 1 , 2- ジィノレ基、シクロヘプタン _1， 3_ジィル基、 3—シクロペンテン— 1， 2_ジィル基、 4_ シクロへキセン一 1 , 2_ジィル基、 4—シクロヘプテン一 1， 2_ジィル基等の二価の飽和 もしくは不飽和の三一七員環の環状炭化水素基、例えばビシクロ [1. 1. 1]ペンタン —2, 2—ジィル基、ビシクロ [1 · 1. 1]ペンタン—2, 4—ジィノレ基、ビシクロ [2. 1. 1]へ キサン一 2, 3—ジィル基、ビシクロ [2· 1. 1]へキサー 2—ェンー 5, 5—ジィル基、ビシク 口 [2· 2. 1]ヘプタン— 2, 3_ジィル基、ビシクロ [2· 2. 1]ヘプタ _2_ェンー 5, 6—ジ ィル基、ビシクロ [2. 2. 2]オクタン一 2, 3_ジィル基、ビシクロ [2. 2. 2]ォクタ _2—ェ ン一 5, 6—ジィノレ基、ビシクロ [4. 1. 1]オクタン一 3, 4—ジィル基、ビシクロ [4. 1. 1] オクタン一 2, 5_ジィル基、ビシクロ [4. 1. 1]オクタン一 7, 7_ジィル基、ビシクロ [4. 1. 1]ォクタ _2—ェン _7, 7—ジィル基、ビシクロ [4. 1. 1]ォクタ _3—ェン _7, 7—ジィ ル基、ビシクロ [3· 2. 1]オクタン一 3, 3_ジィル基、ビシクロ [3. 2. 1]オクタン一 6, 7 —ジィル基、ビシクロ [3· 2. 1]ォクタ _2—ェン -6, 7_ジィル基、ビシクロ [3· 2. 1]ォ クタ _6—ェン—2, 3_ジィル基、ビシクロ [3. 2. 2]ノナン— 3， 3_ジィル基、ビシクロ [3 . 2. 2]ノナン _2， 4—ジィノレ基、ビシクロ [3. 2. 2]ノナン一6, 7—ジィル基、ビシクロ [ 3. 2. 2]ノナ— 2—ェン— 6， 7—ジィル基、ビシクロ [3. 2. 2]ノナ— 6—ェン— 2， 3—ジィ ル基、 5—ォキサビシクロ [1. 1. 1]ペンタン— 2, 2_ジィル基、 6—ォキサビシクロ [2. 1. 1]へキサン _2， 3_ジィル基、 6—ォキサビシクロ [2. 1. 1]へキサ _2—ェン—5, 5 —ジィル基、 7—ォキサビシクロ [2. 2. 1]ヘプタン— 2， 3_ジィル基、 7_ォキサビシク 口 [2. 2. 1]ヘプタ一 2—ェン _5， 6—ジィノレ基、 8—ォキサビシクロ [4. 1. 1]オクタン一 3, 4—ジィル基、 8—ォキサビシクロ [4· 1. 1]オクタン一 2, 5—ジィル基、 8—ォキサビ シクロ [4. 1. 1]オクタン一 7, 7_ジィル基、 8—ォキサビシクロ [3· 2. 1]オクタン一 3, 3_ジィル基、 8—ォキサビシクロ [3. 2. 1]オクタン— 6, 7_ジィル基、 8—ォキサビシク 口 [3. 2. 1]ォクタ— 6—ェン一 2， 3_ジィル基等の酸素原子、炭素数 1一 3の低級アル キレン基等で架橋された二価の環状炭化水素基等が挙げられる。 Examples of the cyclic hydrocarbon group which may be crosslinked include, for example, cyclopropane-1,1, -diyl group, cyclopropane-1,2_diyl group, cyclobutane-1,1,1-diyl group, cyclobutane-1,2_ Diyl group, cyclobutane-1,3_diyl group, cyclopentane_1,1_diyl group, cyclopentane-1,2_diyl group, cyclopentane-1,3_diyl group, cyclohexane-1,1,1- Diinole, cyclohexane-1,2, diyl, cyclohexane-1,3, diyl, cyclohexane-1,4-diinole, cycloheptane-1,1, diyl, cycloheptane-1 , 2-Diynole, cycloheptane_1,3_diyl, 3-cyclopentene-1,2_diyl, 4_cyclohexene-1,1,2_diyl, 4-cycloheptene-1,1,2_diyl, etc. Divalent saturated or unsaturated 317-membered ring Hydride groups such as bicyclo [1.1.1] pentane-2,2-diyl group, bicyclo [1.1.1] pentane-2,4-diynole group, bicyclo [2.1.1] hexane 2,3-diyl group, bicyclo [2.1.1] hexa 2-ene-5,5-diyl group, bicyclo mouth [2.2.1] heptane-2,3_diyl group, bicyclo [2.2] .1] Hepta_2_ene-5,6-diyl group, bicyclo [2.2.2] octane-1,2,3-diyl group, bicyclo [2.2.2] octa_2-ene-1,5,6 —Ginole group, bicyclo [4.1.1] octane-1,3,4—Diyl group, bicyclo [4.1.1] octane-1,5, -Diyl group, bicyclo [4.1.1] octane-1,7 7_diyl group, bicyclo [4.1.1] octa_2_7,7-diyl group, bicyclo [4.1.1] octa_3-3-ene_7,7-diyl group, bicyclo [3 · 2.1] Octane-1,3,3-diyl group, bicyclo [3.2.1] Octane-1,6,7—Diyl group, bicyclo [3.2.1] Kuta_2-ene-6,7_diyl group, bicyclo [3.2.1] octa_6_ene-2,3_diyl group, bicyclo [3.2.2] nonane-3,3_diyl Group, bicyclo [3.2.2] nonane_2,4-diinole group, bicyclo [3.2.2] nonane-1,6,7-diyl group, bicyclo [3.2.2] non-2-ene 6,7-diyl group, bicyclo [3.2.2] nona-6-ene-2,3-diyl group, 5-oxabicyclo [1.1.1] pentane-2,2_diyl group, 6 —Oxabicyclo [2.1.1] hexane_2,3_diyl group, 6-oxabicyclo [2.1.1] hexa_2_2-ene-5,5-diyl group, 7-oxabicyclo [2.2. 1] Heptane-2,3_diyl group, 7_oxabisik mouth [2.2.1] Hepta-1 2-ene_5, 6-dinole group, 8-oxabicyclo [4.1.1] octane-1 3,4-diyl group, 8-oxabicyclo [4.1.1] octane-2,5-diyl group, 8-oxabicyclo [4.1.1] octane-1,7,7-diyl group, 8-oxabicyclo [ 3.2.1] octane-3,3_diyl group, 8-oxabicyclo [3.2.1] octane-6,7_diyl group, 8-oxabisik mouth [3.2.1] octa-6-e And oxygen atoms such as 1,2,3-diyl groups, and divalent cyclic hydrocarbon groups cross-linked by lower alkylene groups having 13 to 13 carbon atoms.
[0009] 炭素数 1一 2のアルキレン基としては、例えばメチレン基、 1， 2_エチレン基、 1， 1_ エチレン基が挙げられる。低級アルキル基としては、例えばメチル基、ェチル基、 η- プロピル基、イソプロピル基、 η—ブチル基、イソブチル基、 sec—ブチル基、 tert—ブ チノレ基、 n—ペンチル基、 n—へキシル基等の炭素数 1一 6のアルキル基が挙げられる 。 _C〇 Rで示される基としては、例えばメトキシカルボニル基、エトキシカルボニル基[0009] Examples of the alkylene group having 1 to 2 carbon atoms include a methylene group, a 1,2-ethylene group, and a 1,1-ethylene group. Examples of lower alkyl groups include methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butylinole, n-pentyl, and n-hexyl groups. And an alkyl group having 1 to 6 carbon atoms. Examples of the group represented by _C〇R include a methoxycarbonyl group and an ethoxycarbonyl group.
、 n—プロポキシカルボニル基、イソプロポキシカルボニル基、 n—ブトキシカルボ二ノレ 基、 n—ペンチルォキシカルボニル基、 n キシルォキシカルボニル基等が挙げられ る。 And n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbinole group, n-pentyloxycarbonyl group, n-xyloxycarbonyl group and the like.
[0010] 力かるエステル化合物（1)としては、例えばシクロプロパン一 1_カルボン酸メチル、 シクロプロパン一 1一力ルボン酸ェチル、シクロプロパン _1一力ルボン酸イソプロピル、 シクロプロパン一 1一力ルボン酸 n—ブチル、シクロプロパン一 1一力ルボン酸 n キシ ノレ、 1—(メトキシカルボニルメチル）シクロプロパン、 1_ (1ーメトキシカルボニルェチル )シクロプロパン、 1_ (2—メトキシカルボ二ルェチノレ）シクロプロパン、シクロプロパン一 1 , 1ージカルボン酸メチル、シクロプロパン一 1, 1ージカルボン酸ェチル、シクロプロパ ンー 1, 1ージカルボン酸イソプロピル、シクロプロパン一 1 , 1ージカルボン酸 n—ブチル 、シクロプロパン一 1, 1—ジカルボン酸 n キシル、 1 , 1_ビス（メトキシカルボニルメ チノレ）シクロプロパン、シクロプロパン一 1 , 2—ジカルボン酸メチル、シクロプロパン一 1 , 2—ジカルボン酸ェチル、シクロプロパン一 1， 2—ジカルボン酸イソプロピル、シクロプ 口パン一 1， 2—ジカルボン酸 n—ブチル、シクロプロパン一 1， 2—ジカルボン酸 n キ シル、 1 , 2_ビス（メトキシカルボニルメチル）シクロプロパン、シクロブタン一 1_カルボ ン酸メチル、 1—(メトキシカルボニルメチル）シクロブタン、シクロブタン— 1， 1—ジカル ボン酸メチル、シクロブタン一 1 , 1—ジカルボン酸ェチル、シクロブタン一 1 , 2—ジカル ボン酸メチル、 1， 2_ビス（メトキシカルボニルメチル）シクロブタン、シクロブタン一 1， 3 ージカルボン酸メチル、 1, 3—ビス（メトキシカルボニルメチル）シクロブタン、 Examples of the strong ester compound (1) include, for example, cyclopropane-1-methyl carboxylate, cyclopropane-111-ethyl ruvonate, cyclopropane_1-isopropyl rubonate, cyclopropane-111-rubonic acid n -Butyl, cyclopropane, n -butyric acid, n-xynole, 1- (methoxycarbonylmethyl) cyclopropane, 1_ (1-methoxycarbonylethyl) cyclopropane, 1_ (2-methoxycarbonylethylenole) cyclopropane, Methyl cyclopropane-1,1-dicarboxylate, ethyl 1,1-dicarboxylate, cyclopropane-1,1-dicarboxylate, n-butyl cyclopropane-1,1-dicarboxylate, 1,1-dicarboxylic cyclopropane n Xyl, 1, 1-bis (methoxycarbonylmethylen) cyclopropane, Lopropane-1,2-dimethyl carboxylate, cyclopropane-1,2-diethyl carboxylate, cyclopropane-1,1,2-dicarboxylate, cyclopropane 1,2-dicarboxylate n-butyl, cyclopropane-1 1,2-dicarboxylate n-oxyl, 1,2-bis (methoxycarbonylmethyl) cyclopropane, cyclobutane-1-methyl 1-carbonate, 1- (methoxycarbonylmethyl) cyclobutane, cyclobutane-methyl 1,1-dicarboxylate , Cyclobutane-1,1,1-dicarboxylate, cyclobutane-1,2-dimethyl carbonate, 1,2_bis (methoxycarbonylmethyl) cyclobutane, cyclobutane-1,3 Methyl dicarboxylate, 1,3-bis (methoxycarbonylmethyl) cyclobutane,
[0011] シクロペンタン一 1一力ルボン酸メチル、 1—(メトキシカルボニルメチル）シクロペンタン 、シクロペンタン—1, 1—ジカルボン酸メチル、シクロペンタン一 1 , 1—ジカルボン酸ェ チル、 1， 1_ビス（メトキシカルボ二ルメチノレ）シクロペンタン、シクロペンタン— 1， 2—ジ カルボン酸メチル、シクロペンタン _1， 2—ジカルボン酸ェチル、 1 , 2_ビス（メトキシカ ノレボニルメチノレ）シクロペンタン、シクロペンタン一 1， 3—ジカルボン酸メチル、シクロ ペンタン— 1 , 3—ジカルボン酸ェチル、 1 , 3_ビス（メトキシカルボニノレメチノレ）シクロぺ ンタン、シクロへキサン _1_カルボン酸メチル、 1—(メトキシカルボ二ルメチノレ）シクロ へキサン、シクロへキサン一 1， 1—ジカルボン酸メチル、シクロへキサン一 1， 2—ジカノレ ボン酸メチル、シクロへキサン一 1， 3—ジカルボン酸メチル、シクロへキサン一 1， 4—ジ カルボン酸メチル、 1 , 2_ビス（メトキシカルボニルメチル）シクロへキサン、 1 , 4_ビス (メトキシカルボ二ルメチノレ）シクロへキサン、シクロヘプタン一 1_カルボン酸メチル、 1 —(メトキシカルボ二ルメチノレ）シクロヘプタン、シクロヘプタン一 1, 1ージカルボン酸メ チル、シクロヘプタン一 1 , 2—ジカルボン酸メチル、 1 , 2—ビス（メトキシカルボ二ルメチ ノレ）シクロヘプタン、シクロヘプタン一 1 , 3—ジカルボン酸メチル、 1 , 3_ビス（メトキシカ ノレボニルメチル）シクロヘプタン、 3—シクロペンテン一 1_カルボン酸メチル、 2—シクロ ペンテン _1_カルボン酸メチル、 3—シクロペンテン一 1 , 2—ジカルボン酸メチル、 4一 シクロへキセン一 1 , 2—ジカルボン酸メチル、 4—シクロヘプテン—1, 2—ジカルボン酸 メチル、 [0011] Cyclopentane-111-Methyl Rubonate, 1- (Methoxycarbonylmethyl) cyclopentane, Cyclopentane-1,1-dicarboxylate, Cyclopentane-1-1,1-Dicarboxylate, 1,1_ Bis (methoxycarbonylmethinole) cyclopentane, cyclopentane-methyl 1,2-dicarboxylate, cyclopentane_1,2-dicarboxylate, 1,2_bis (methoxycanolebonylmethinole) cyclopentane, cyclopentane Methyl 1,3-dicarboxylate, cyclopentane-1,3-dicarboxylate, 1,3_bis (methoxycarboninolemethynole) cyclopentane, cyclohexane_1_methyl carboxylate, 1- (methoxycarbonitrile Rumethinole) cyclohexane, cyclohexane-1-methyl 1,1-dicarboxylate, cyclohexane-1-1,2-dicano Methyl levonate, methyl cyclohexane-1,3-dicarboxylate, methyl cyclohexane-1,4-dicarboxylate, 1,2_bis (methoxycarbonylmethyl) cyclohexane, 1,4_bis ( Methoxycarbenylmethynole) cyclohexane, cycloheptane-1-methyl carboxylate, 1— (Methoxycarbenylmethynole) cycloheptane, cycloheptane-1-methyl 1,1-dicarboxylate, Methyl cycloheptane 1,1,2-dicarboxylate , 1,2-bis (methoxycarbonylmethyl) cycloheptane, cycloheptane-1,3-dimethyl carboxylate, 1,3_bis (methoxycanolebonylmethyl) cycloheptane, 3-cyclopentene-1-methyl carboxylate, 2 —Cyclopentene_1_methyl carboxylate, 3-cyclopentene-1-methyl 1,2-dicarboxylate, 4-cyclo Hexene one 1, 2-dicarboxylic acid methyl, 4-cycloheptene-1,2-dicarboxylic acid methyl,
[0012] ビシクロ [1. 1. 1]ペンタン一 2, 2—ジカルボン酸メチル、ビシクロ [1 · 1. 1]ペンタン一 2, 4—ジカルボン酸メチル、ビシクロ [2. 1. 1]へキサン一 2, 3—ジカルボン酸メチル、 ビシクロ [2. 1. 1]へキサ— 2—ェン— 5, 5—ジカルボン酸メチル、ビシクロ [2. 2. 1]へ プタン一 2, 3—ジカルボン酸メチル、ビシクロ [2. 2. 1]ヘプタ— 2—ェンー 5， 6—ジカノレ ボン酸メチル、ビシクロ [2. 2. 2]オクタン一 2, 3—ジカルボン酸メチル、ビシクロ [2. 2 . 2]ォクタ _2_ェン— 5, 6—ジカルボン酸メチル、ビシクロ [4. 1. 1]オクタン— 3, 4_ ジカルボン酸メチル、ビシクロ [4. 1. 1]オクタン一 2, 5—ジカルボン酸メチル、ビシク 口 [4. 1. 1]オクタン一 7, 7—ジカルボン酸メチル、ビシクロ [4. 1. 1]ォクタ一 2—ェン一 7, 7—ジカルボン酸メチル、ビシクロ [4. 1. 1]ォクタ _3_ェンー 7， 7—ジカルボン酸メ チル、ビシクロ [3· 2. 1]オクタン一 3, 3—ジカルボン酸メチル、ビシクロ [3. 2. 1]オタ タン一 6, 7—ジカルボン酸メチル、ビシクロ [3. 2. 1]ォクタ— 2_ェンー 6, 7—ジカルボ ン酸メチル、ビシクロ [3. 2. 1]ォクタ— 6_ェンー 2, 3—ジカルボン酸メチル、 [0012] Bicyclo [1.1.1] pentane-1,2,2-dicarboxylate, bicyclo [1.1.1] pentane 1,2,4-dicarboxylate, bicyclo [2.1.1] hexane Methyl 2,3-dicarboxylate, bicyclo [2.1.1] hexa-2-ene-5,5-dimethyl carboxylate, bicyclo [2.2.1] Heptane-methyl 2,3-dicarboxylate , Bicyclo [2.2.1] hept-2-ene-5,6-methyldicanolebonate, bicyclo [2.2.2] octane-1,2,3-dicarboxylate, bicyclo [2.2.2] octa 2,2-methyl-5,6-dicarboxylate, bicyclo [4.1.1] octane-3,4_methyl dicarboxylate, bicyclo [4.1.1] octane-1,5-methyldicarboxylate, bisic [4.1.1] Octane-1 7,7-methyldicarboxylate, bicyclo [4.1.1] Octa-1-ene7,7-dimethyl methyl, bicyclo [4.1.1] Octa_3 __En 7, 7-dicarboxylic Sanme Methyl, bicyclo [3.2.1] octane-1,3-dicarboxylate, bicyclo [3.2.1] otatan-1,6,7-methyl dicarboxylate, bicyclo [3.2.1] octa-2 Methyl 6,7-dicarboxylate, bicyclo [3.2.1] octa-6,2-methyl 2,3-dicarboxylate,
[0013] ビシクロ [3. 2. 2]ノナン一 3， 3—ジカルボン酸メチル、ビシクロ [3. 2. 2]ノナン一 2， 4 —ジカルボン酸メチル、ビシクロ [3. 2. 2]ノナン一 6， 7—ジカルボン酸メチル、ビシクロ [3. 2. 2]ノナ— 2—ェンー 6， 7—ジカルボン酸メチル、ビシクロ [3. 2. 2]ノナー 6—ェン -2, 3—ジカルボン酸メチル、 5—ォキサビシクロ [1. 1. 1]ペンタン一 2， 2—ジカルボン 酸メチル、 6—ォキサビシクロ [2. 1. 1]へキサン一 2， 3—ジカルボン酸メチル、 6—ォキ サビシクロ [2. 1. 1]へキサ— 2_ェンー 5， 5—ジカルボン酸メチル、 7—ォキサビシクロ [ 2. 2. 1]ヘプタン— 2， 3—ジカルボン酸メチル、 7—ォキサビシクロ [2. 2. 1]ヘプタ— 2 —ェン _5, 6—ジカルボン酸メチル、 8—ォキサビシクロ [4. 1. 1]オクタン— 3, 4—ジカ ルボン酸メチル、 8—ォキサビシクロ [4. 1. 1]オクタン一 2， 5—ジカルボン酸メチル、 8 —ォキサビシクロ [4· 1. 1]オクタン一 7, 7—ジカルボン酸メチル、 8—ォキサビシクロ [3 . 2. 1]オクタン一 3, 3—ジカルボン酸メチル、 8—ォキサビシクロ [3. 2. 1]オクタン— 6 , 7—ジカルボン酸メチル、 8—ォキサビシクロ [3· 2. 1]ォクタ— 6_ェンー 2, 3—ジカル ボン酸メチル等が挙げられる。  [0013] Bicyclo [3.2.2] nonane-methyl 3,3-dicarboxylate, bicyclo [3.2.2] Nonane 1, 2, 4-methyl methyl dicarboxylate, bicyclo [3.2.2] Nonane 6 , 7-Methyl dicarboxylate, Bicyclo [3.2.2] non-2-methyl-6,7-dicarboxylate, Bicyclo [3.2.2] Nonomer 6-ene-2,3-Dimethyl carboxylate, 5-Oxabicyclo [1.1.1] pentane-1,2,2-dicarboxylate, 6-oxabicyclo [2.1.1] Hexane-1,2,3-dicarboxylate, 6-oxabicyclo [2.1] 1] hexa-2-methyl-5,5-dicarboxylate, 7-oxabicyclo [2.2.1] heptane-methyl 2,3-dicarboxylate, 7-oxabicyclo [2.2.1] hepta-2 —Ene _5,6-methyl dicarboxylate, 8-oxabicyclo [4.1.1] octane—methyl 3,4-dicarboxylate, 8-oxabicyclo [4.1.1] o Methane 1,5-dicarboxylate, 8-oxabicyclo [4.1.1] octane-1,7,7-dicarboxylate, 8-oxabicyclo [3.2.1] octane-1,3,3-dicarboxylate, 8-Oxabicyclo [3.2.1] octane-6,7-dicarboxylate, 8-Oxabicyclo [3.2.1] octa-6_en-2-3,3-dicarbonate methyl and the like.
[0014] 力かるエステルイ匕合物（1)の中には、不斉炭素を有し、光学異性体が存在する化 合物も存在するが、光学異性体が存在するエステル化合物の場合、いずれかの光 学異性体単独を用いてもょレ、し、光学異性体の任意の混合物を用いてもょレ、。  [0014] Among the powerful esteri conjugates (1), there are compounds having an asymmetric carbon and having an optical isomer, but in the case of an ester compound having an optical isomer, These optical isomers may be used alone, or any mixture of optical isomers may be used.
[0015] 水素化ホウ素化合物としては、例えば水素化ホウ素リチウム、水素化ホウ素ナトリウ ム、水素化ホウ素カリウム等の水素化ホウ素アルカリ金属化合物、例えば水素化ホウ 素カルシウム、水素化ホウ素マグネシウム等の水素化ホウ素アルカリ土類金属化合 物、例えば水素化ホウ素亜鉛等が挙げられ、水素化ホウ素アルカリ金属化合物が好 ましぐ水素化ホウ素リチウム、水素化ホウ素ナトリウムがより好ましい。  [0015] Examples of the borohydride compound include alkali metal borohydride compounds such as lithium borohydride, sodium borohydride, and potassium borohydride; Examples thereof include alkaline earth metal borohydride compounds, such as zinc borohydride, and more preferred are alkali metal borohydride compounds, and more preferred are lithium borohydride and sodium borohydride.
[0016] 力、かる水素化ホウ素化合物は、通常市販されているものを用いてもよいし、例えば ホウ酸エステルと水素化ナトリウムとの反応等の公知の方法に準じて製造したものを 用いてもよい。  As the borohydride compound, a commercially available compound may be used, or a compound produced according to a known method such as a reaction between a borate ester and sodium hydride may be used. Is also good.
[0017] 力、かる水素化ホウ素化合物の使用量は、 Υが水素原子であるエステルイ匕合物（1) の場合には、当該エステルイ匕合物（1)に対して、通常 0. 5— 10モル倍、好ましくは 0 . 5— 5モル倍、より好ましくは 0. 5— 2モル倍である。 Yがー CO Rで示される基である エステル化合物（1)の場合は、当該エステル化合物（1)に対して、通常 1一 20モル 倍、好ましくは 1一 10モル倍、より好ましくは 1一 4モル倍である。 [0017] The amount of the borohydride compound to be used is as follows: In the case of (1), the amount is usually 0.5 to 10 times, preferably 0.5 to 5 times, more preferably 0.5 to 2 times the molar amount of the esterified conjugate (1). In the case of the ester compound (1) in which Y is a group represented by —COR, the ester compound (1) is usually used in a molar amount of usually 120 to 20 times, preferably 1 to 10 times, and more preferably 1 to 10 times. 4 mole times.
[0018] 有機溶媒としては、反応に不活性なものであればよぐ例えばトルエン、キシレン等 の芳香族炭化水素系溶媒、例えばジェチルエーテル、ジイソプロピルエーテル、メチ ノレ tert—ブチルエーテル、テトラヒドロフラン等のエーテル系溶媒、例えばイソプロパ ノール、 tert—ブタノール等の炭素数 3以上のアルコール系溶媒等の単独もしくは混 合溶媒が挙げられ、その使用量は、エステル化合物（1)に対して、通常 0. 5— 50重 量倍、好ましくは 1一 20重量倍、より好ましくは 1一 10重量倍である。力、かる有機溶媒 は、予めエステルイ匕合物（1)、水素化ホウ素化合物およびメタノール力 選ばれる少 なくとも一つと混合しておいてもよい。  The organic solvent is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbon solvents such as toluene and xylene, for example, ethers such as getyl ether, diisopropyl ether, methyl tert-butyl ether, and tetrahydrofuran A single solvent or a mixed solvent such as an alcoholic solvent having 3 or more carbon atoms such as isopropanol and tert-butanol is used. It is 50 times by weight, preferably 110 times by weight, more preferably 110 times by weight. The organic solvent may be previously mixed with at least one selected from the esterified compound (1), the borohydride compound and the methanol solvent.
[0019] エステル化合物（1)と水素化ホウ素化合物との反応は、メタノールの存在下に実施 され、メタノールの使用量は、水素化ホウ素化合物に対して、通常 1一 10モル倍、好 ましくは 1一 5モル倍、より好ましくは 1. 5— 3モル倍である。  [0019] The reaction between the ester compound (1) and the borohydride compound is carried out in the presence of methanol, and the amount of methanol to be used is usually about 110 to 10 times the molar amount of the borohydride compound. Is 1 to 5 mole times, more preferably 1.5 to 3 mole times.
[0020] 本反応は、例えば有機溶媒とエステル化合物（1)と水素化ホウ素化合物との混合 物中に、メタノールを加える方法、有機溶媒と水素化ホウ素化合物との混合物中に、 エステル化合物（1)とメタノーノレを別々に、もしくは混合して加える方法、エステルイ匕 合物（1)と有機溶媒とメタノールとの混合物中に、水素化ホウ素化合物を加える方法 等により実施される。メタノールを加える際は、連続的もしくは間欠的に滴下すること が好ましい。  [0020] In this reaction, for example, a method of adding methanol to a mixture of an organic solvent, an ester compound (1) and a borohydride compound, a method of adding an ester compound (1) to a mixture of an organic solvent and a borohydride compound, ) And methanol are separately or mixed, and a borohydride compound is added to a mixture of the esterified compound (1), an organic solvent and methanol. When adding methanol, it is preferable to drop the mixture continuously or intermittently.
[0021] 反応温度は、通常—10— 150°Cの範囲、好ましくは 0 100°Cの範囲、より好ましく は 0 80°Cの範囲である。  [0021] The reaction temperature is usually in the range of -10 to 150 ° C, preferably in the range of 0 to 100 ° C, and more preferably in the range of 0 to 80 ° C.
[0022] 反応終了後、例えば得られた反応液と、例えば塩酸、硫酸等の鉱酸水溶液を混合 した後、必要に応じて水に不溶の有機溶媒を加えて抽出処理し、得られる有機層を 濃縮処理することにより、式（2) After completion of the reaction, for example, the obtained reaction solution is mixed with an aqueous solution of a mineral acid such as hydrochloric acid or sulfuric acid, and then, if necessary, an organic solvent insoluble in water is added to carry out extraction treatment. Is concentrated to obtain the formula (2)
HOH2C ^ A2— A1— AJ— Q (2) HOH 2 C ^ A 2 — A 1 — A J — Q (2)
(式中、 A1, A2および A3は上記と同一の意味を表わし、 Qは、 Yが水素原子のときに 水素原子を、 Yがー CO Rで示される基のときにヒドロキシメチル基を表わす。） で示されるアルコールィヒ合物（以下、アルコール化合物（2)と略記する。）を取り出す こと力 Sできる。取り出したアルコール化合物（2)は、例えば再結晶、蒸留、カラムクロ マトグラフィ等の通常の精製手段によりさらに精製してもよい。 (Wherein A 1 , A 2 and A 3 have the same meanings as above, and Q represents when Y is a hydrogen atom. A hydrogen atom represents a hydroxymethyl group when Y is a group represented by —CO R. ) The ability to take out the alcoholic compound represented by (hereinafter abbreviated as alcohol compound (2)). The alcohol compound (2) taken out may be further purified by ordinary purification means such as recrystallization, distillation, column chromatography and the like.
[0023] 力、くして得られるアルコール化合物（2)としては、例えば 1—(ヒドロキシメチル）シクロ As the alcohol compound (2) thus obtained, for example, 1- (hydroxymethyl) cyclo
. (2—ヒドロキシェチル）シクロプロパン、 1_ (3—ヒドロキシプロピル）シクロ  . (2-Hydroxyethyl) cyclopropane, 1_ (3-hydroxypropyl) cyclo
Figure imgf000009_0001
Figure imgf000009_0001
ペンタン、 1, 3—ビス（2—ヒドロキシェチノレ）シクロペンタン、  Pentane, 1,3-bis (2-hydroxyethynole) cyclopentane,
[0024] 1—(ヒドロキシメチル）シクロへキサン、 1_ (2—ヒドロキシェチル）シクロへキサン、 1, 1 [0024] 1- (hydroxymethyl) cyclohexane, 1_ (2-hydroxyethyl) cyclohexane, 1, 1
キサン、 1 , 2_ビス（2—ヒドロキシェチノレ）シクロへキサン、 1 , 4_ビス（2—ヒドロキシェ チノレ）シクロへキサン、 1—(ヒドロキシメチノレ）シクロヘプタン、 1_ (2—ヒドロキシェチル )シクロヘプタン、 1， 1_ビス（ヒドロキシメチル）シクロヘプタン、 1 , 2_ビス（ヒドロキシ メチル）シクロヘプタン、 1， 2—ビス（2—ヒドロキシェチル）シクロヘプタン、 1， 3—ビス（ ヒドロキシメチル）シクロヘプタン、 1 , 3_ビス（2—ヒドロキシェチル）シクロヘプタン、 1 —(ヒドロキシメチノレ）_3—シクロペンテン、 1—(ヒドロキシメチノレ）_2—シクロペンテン、 1 , 2—ビス（ヒドロキシメチノレ）— 3—シクロペンテン、 1 , 2—ビス（ヒドロキシメチル）—4— シクロへキセン、 1， 2—ビス（ヒドロキシメチル）—4—シクロヘプテン、 [0025] 2, 2_ビス（ヒドロキシメチノレ)一ビシクロ [1 · 1. 1]ペンタン、 2, 4_ビス（ヒドロキシメチ ノレ）一ビシクロ [1 · 1. 1]ペンタン、 2, 3_ビス（ヒドロキシメチル）一ビシクロ [2· 1. 1]へ キサン、 5, 5_ビス（ヒドロキシメチノレ）一ビシクロ [2· 1. 1]へキサー 2—ェン、 2, 3_ビス (ヒドロキシメチル）—ビシクロ [2. 2. 1]ヘプタン、 5， 6_ビス（ヒドロキシメチル）—ビシク 口 [2. 2. 1]ヘプタ— 2—ェン、 2， 3—ビス（ヒドロキシメチル）—ビシクロ [2. 2. 2]ォクタ ン、 5， 6—ビス（ヒドロキシメチル）—ビシクロ [2. 2. 2]ォクタ— 2—ェン、 3, 4—ビス（ヒド 口キシメチル）—ビシクロ [4. 1. 1]オクタン、 2， 5_ビス（ヒドロキシメチル）—ビシクロ [4 . 1. 1]オクタン、 7， 7—ビス（ヒドロキシメチル）一ビシクロ [4. 1. 1]オクタン、 7， 7—ビ ス（ヒドロキシメチル）—ビシクロ [4. 1. 1]ォクタ _2_ェン、 7， 7_ビス（ヒドロキシメチル )—ビシクロ [4. 1. 1]ォクタ一 3—ェン、 3， 3—ビス（ヒドロキシメチル）一ビシクロ [3. 2. 1]オクタン、 6, 7_ビス（ヒドロキシメチノレ）一ビシクロ [3. 2. 1]オクタン、 6, 7_ビス（ヒ ドロキシメチノレ）一ビシクロ [3. 2. 1]ォクタ _2_ェン、 2， 3_ビス（ヒドロキシメチル）一ビ シクロ [3. 2. 1]ォクタ一 6—ェン、 1,2-bis (2-hydroxyethynole) cyclohexane, 1,4-bis (2-hydroxyethynole) cyclohexane, 1- (hydroxymethynole) cycloheptane, 1_ (2-hydroxy 1,2-bis (hydroxymethyl) cycloheptane, 1,2-bis (hydroxymethyl) cycloheptane, 1,2-bis (2-hydroxyethyl) cycloheptane, 1,3-bis (Hydroxymethyl) cycloheptane, 1,3_bis (2-hydroxyethyl) cycloheptane, 1- (hydroxymethinole) _3-cyclopentene, 1- (hydroxymethinole) _2-cyclopentene, 1,2-bis ( Hydroxymethinol) —3-cyclopentene, 1,2-bis (hydroxymethyl) -4-cyclohexene, 1,2-bis (hydroxymethyl) -4-cycloheptene, [0025] 2,2_bis (hydroxymethinole) 1-bicyclo [1.1.1] pentane, 2,4_bis (hydroxymethinole) 1-bicyclo [1.1.1] pentane, 2, 3_bis (Hydroxymethyl) 1-bicyclo [2.1.1] hexane, 5, 5_bis (hydroxymethinole) 1-bicyclo [2.1.1] hexyl 2-ene, 2, 3_ bis (hydroxymethyl ) —Bicyclo [2.2.1] heptane, 5, 6_bis (hydroxymethyl) -bicyclo mouth [2.2.1] Hepta-2-ene, 2,3-bis (hydroxymethyl) -bicyclo [ 2.2.2] octane, 5,6-bis (hydroxymethyl) -bicyclo [2.2.2] octa-2-ene, 3,4-bis (hydroxymethyl) -bicyclo [4.1] 1] octane, 2,5_bis (hydroxymethyl) -bicyclo [4.1.1] octane, 7,7-bis (hydroxymethyl) bicyclo [4.1.1] octane, 7,7-bi Su (hi) Droxymethyl) -bicyclo [4.1.1] octa_2_ene, 7,7_bis (hydroxymethyl) -bicyclo [4.1.1] octa-3-ene, 3,3-bis (hydroxymethyl) ) 1-bicyclo [3.2.1] octane, 6,7_bis (hydroxymethinole) 1-bicyclo [3.2.1] octane, 6,7_bis (hydroxymethinole) 1-bicyclo [3.2.1] ] Octa_2_ene, 2,3_bis (hydroxymethyl) -bicyclo [3.2.1] octa-6-ene,
[0026] 3, 3_ビス（ヒドロキシメチル）ビシクロ [3· 2. 2]ノナン、 2, 4_ビス（ヒドロキシメチル)― ビシクロ [3· 2. 2]ノナン、 6, 7—ビス（ヒドロキシメチル)一ビシクロ [3· 2. 2]ノナン、 6 , 7_ビス（ヒドロキシメチノレ）一ビシクロ [3· 2. 2]ノナー 2—ェン、 2, 3_ビス（ヒドロキシメ チル)—ビシクロ [3· 2. 2]ノナ— 6_ェン、 2, 2_ビス（ヒドロキシメチノレ )_5—ォキサビ シクロ [1. 1. 1]ペンタン、 2, 3_ビス（ヒドロキシメチル ) _6—ォキサビシクロ [2· 1. 1] へキサン、 5, 5—ビス（ヒドロキシメチル)—6—ォキサビシクロ [2. 1. 1]へキサー 2—ェ ン、 2, 3—ビス（ヒドロキシメチル）—7—ォキサビシクロ [2· 2. 1]ヘプタン、 5, 6—ビス（ ヒドロキシメチル）_7—ォキサビシクロ [2· 2. 1]ヘプタ _2_ェン、 3, 4_ビス（ヒドロキ シメチノレ）一 8—ォキサビシクロ [4. 1. 1]オクタン、 2， 5—ビス（ヒドロキシメチル）一8—ォ キサビシクロ [4. 1. 1]オクタン、 7， 7_ビス（ヒドロキシメチル）_8—ォキサビシクロ [4. 1. 1]オクタン、 3, 3_ビス（ヒドロキシメチル）_8—ォキサビシクロ [3. 2. 1]オクタン、 6, 7_ビス（ヒドロキシメチノレ）_8—ォキサビシクロ [3. 2. 1]オクタン、 2， 3_ビス（ヒドロ キシメチル)一 8—ォキサビシクロ [3. 2. 1]ォクタ— 6—ェン等が挙げられる。  [0026] 3,3_bis (hydroxymethyl) bicyclo [3.2.2] nonane, 2,4_bis (hydroxymethyl) -bicyclo [3.2.2] nonane, 6,7-bis (hydroxymethyl ) 1-bicyclo [3.2.2] nonane, 6,7_bis (hydroxymethinole) 1-bicyclo [3.2.2] noner 2-ene, 2,3_bis (hydroxymethyl) -bicyclo [ 3.2.2] Nona-6-ene, 2, 2-bis (hydroxymethinole) _5-oxabicyclo [1.1.1] pentane, 2,3_bis (hydroxymethyl) _6-oxabicyclo [2 · 1.1] hexane, 5,5-bis (hydroxymethyl) -6-oxabicyclo [2.1.1] hexa 2-ene, 2,3-bis (hydroxymethyl) -7-oxabicyclo [2 · 2.1] Heptane, 5,6-bis (hydroxymethyl) _7-oxabicyclo [2.2.1] Hepta_2_ene, 3,4_bis (hydroxymethinole) -18-oxabicyclo [4.1.1] octane, 2,5-bis (hydroxymethyl) -18-oxabicyclo [4.1.1] octane, 7,7_bis (hydroxymethyl) _8-oxabicyclo [4.1.1] ] Octane, 3,3_bis (hydroxymethyl) _8-oxabicyclo [3.2.1] octane, 6, 7_bis (hydroxymethinole) _8-oxabicyclo [3.2.1] octane, 2, 3_ Bis (hydroxymethyl) -1-oxabicyclo [3.2.1] octa-6-ene and the like.
[0027] 以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限 定されない。 実施例 1 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1
[0028] (1R， 2R)-1, 2—シクロへキサンジカルボン酸ジメチル 14. 9g、テトラヒドロフラン 4 5gおよび水素化ホウ素ナトリウム 5. 6gを混合後、内温 65°Cに昇温した。同温度で、 メタノーノレ 7. lgを 1時間かけて滴下した後、内温 67°Cで 2時間攪拌、反応させた。 内温 30°Cに冷却した後、 10重量％塩酸水溶液 54. 2gを滴下した。 27重量％水酸 化ナトリウム水溶液を加えて中和処理した後、濃縮処理した。濃縮残渣に、メチルイソ プチルケトン 150gを加えて抽出処理し、得られた有機層を一部濃縮処理し、（1R, 2 ン溶液 31. 7gを得た。収率 97%。  [0028] After mixing 14.9 g of dimethyl (1R, 2R) -1,2-cyclohexanedicarboxylate, 45 g of tetrahydrofuran and 5.6 g of sodium borohydride, the internal temperature was raised to 65 ° C. At the same temperature, 7. lg of methanol was added dropwise over 1 hour, followed by stirring and reaction at an internal temperature of 67 ° C for 2 hours. After cooling to an internal temperature of 30 ° C., 54.2 g of a 10% by weight aqueous hydrochloric acid solution was added dropwise. The mixture was neutralized by adding a 27% by weight aqueous sodium hydroxide solution, and then concentrated. 150 g of methyl isobutyl ketone was added to the concentrated residue for extraction, and the obtained organic layer was partially concentrated to obtain 31.7 g of a (1R, 2 solution). Yield 97%.
実施例 2  Example 2
[0029] trans— 1 , 2—シクロへキサンジカルボン酸ジメチル 5. lg、イソプロノ ノーノレ 25. 3g および水素化ホウ素ナトリウム 3. 79gを混合後、内温 35°Cに調整した。同温度で、メ タノール 9. 6gを 2時間かけて滴下した後、同温度で 5時間攪拌、反応させた。 10重 量％塩酸水溶液 32. 7gを滴下した後、 2N水酸化ナトリウム水溶液 1. 7gをカ卩え、濃 縮処理した。濃縮残渣をメチルイソプチルケトン 100gで 2回抽出処理し、得られた有 機層を合一した後、濃縮処理し、 1 , 2_ビス（ヒドロキシメチル)シクロへキサンの白色 固体 3. 5gを得た。含量： 98. 9重量％、収率： 94%。  [0029] After mixing 5.lg of dimethyl trans-1,2-cyclohexanedicarboxylate, 25.3g of isoprono nore and 3.79g of sodium borohydride, the internal temperature was adjusted to 35 ° C. At the same temperature, 9.6 g of methanol was added dropwise over 2 hours, and the mixture was stirred and reacted at the same temperature for 5 hours. After 32.7 g of a 10% by weight aqueous hydrochloric acid solution was added dropwise, 1.7 g of a 2N aqueous sodium hydroxide solution was added and concentrated. The concentrated residue was extracted twice with 100 g of methyl isobutyl ketone, and the obtained organic layers were combined and concentrated to obtain 3.5 g of 1,2_bis (hydroxymethyl) cyclohexane white solid. Obtained. Content: 98.9% by weight, yield: 94%.
実施例 3  Example 3
[0030] trans-1 , 2—シクロへキサンジカルボン酸ジメチル 5 · 0g、 tert—ブチルメチルエー テル 25. 3gおよび水素化ホウ素ナトリウム 3. 78gを混合後、内温 35°Cに調整した。 同温度で、メタノーノレ 9. 6gを 2時間かけて滴下した後、同温度で 4時間攪拌、反応さ せた。 10重量％塩酸水溶液 32. 4gを滴下した後、 2N水酸化ナトリウム水溶液 6. 5g を加え、濃縮処理した。濃縮残渣を酢酸ェチル 100gで 2回抽出処理し、得られた有 機層を合一した後、濃縮処理し、 1 , 2_ビス（ヒドロキシメチル)シクロへキサンの白色 固体 3. 2gを得た。含量： 94. 7重量％、収率： 84%。  After mixing 5.0 g of dimethyl trans-1,2-cyclohexanedicarboxylate, 25.3 g of tert-butylmethyl ether and 3.78 g of sodium borohydride, the internal temperature was adjusted to 35 ° C. At the same temperature, 9.6 g of methanol was added dropwise over 2 hours, and the mixture was stirred and reacted at the same temperature for 4 hours. After dropwise adding 32.4 g of a 10% by weight aqueous hydrochloric acid solution, 6.5 g of a 2N aqueous sodium hydroxide solution was added thereto, followed by concentration treatment. The concentrated residue was extracted twice with 100 g of ethyl acetate, and the obtained organic layers were combined and concentrated to obtain 3.2 g of 1,2-bis (hydroxymethyl) cyclohexane white solid. . Content: 94.7% by weight, yield: 84%.
実施例 4  Example 4
[0031] trans-1 , 2—シクロへキサンジカルボン酸ジメチル 5 · 0g、 tert—ブタノール 25· 2g および水素化ホウ素ナトリウム 3. 81gを混合後、内温 35°Cに調整した。同温度で、メ タノール 9. 6gを 2時間かけて滴下した後、同温度で 3時間攪拌、反応させた。 10重 量％塩酸水溶液 35. 4gを滴下した後、水 30. 6gを加え、濃縮処理した。濃縮残渣 をメチルイソプチルケトン 30gで 2回抽出処理し、得られた有機層を合一した後、濃縮 処理し、 1, 2—ビス（ヒドロキシメチル）シクロへキサンの白色固体 3. lgを得た。含量： 88. 4重量％、収率： 76%。 [0031] dimethyl trans-1,2-cyclohexanedicarboxylate 5.0 g, tert-butanol 25.2 g And 3.81 g of sodium borohydride, and then the internal temperature was adjusted to 35 ° C. At the same temperature, 9.6 g of methanol was added dropwise over 2 hours, and the mixture was stirred and reacted at the same temperature for 3 hours. After 35.4 g of a 10% by weight aqueous hydrochloric acid solution was added dropwise, 30.6 g of water was added and the mixture was concentrated. The concentrated residue was extracted twice with 30 g of methyl isobutyl ketone, and the obtained organic layers were combined and concentrated to give 3.lg of a white solid of 1,2-bis (hydroxymethyl) cyclohexane. Was. Content: 88.4% by weight, yield: 76%.
実施例 5  Example 5
[0032] trans-1, 2—シクロへキサンジカルボン酸ジェチル 5· Og、テトラヒドロフラン 27gお よび水素化ホウ素ナトリウム 3. 3gを混合後、内温 35°Cに調整した。同温度で、メタノ ール 8. 4gを 2時間かけて滴下した後、同温度で 2時間、さらに内温 50°Cで 1時間攪 拌、反応させた。室温まで冷却した後、 10重量％塩酸水溶液 31. lgを滴下し、濃縮 処理した。濃縮残渣に水 50gを加え、メチルイソプチルケトン 30gで 2回抽出処理し、 得られた有機層を合一した後、濃縮処理し、 1, 2—ビス (ヒドロキシメチル)シクロへキ サンの白色固体 3. Ogを得た。含量： 68. 9重量％、収率： 65%。  [0032] Trans-1,2-cyclohexanedicarboxylate 5 · Og, 27g of tetrahydrofuran and 3.3g of sodium borohydride were mixed, and the internal temperature was adjusted to 35 ° C. At the same temperature, 8.4 g of methanol was added dropwise over 2 hours, and the mixture was stirred and reacted at the same temperature for 2 hours and at an internal temperature of 50 ° C for 1 hour. After cooling to room temperature, 31.lg of a 10% by weight aqueous hydrochloric acid solution was added dropwise, followed by concentration treatment. 50 g of water was added to the concentrated residue, and the mixture was extracted twice with 30 g of methyl isobutyl ketone. The obtained organic layers were combined, concentrated, and the 1,2-bis (hydroxymethyl) cyclohexan white A solid 3. Og was obtained. Content: 68.9% by weight, yield: 65%.
産業上の利用可能性  Industrial applicability
[0033] 以上記載したごとぐ本発明の製造方法によれば、取扱の容易な試剤を用いて式（ 1)で示されるエステルィヒ合物からアルコール化合物を工業的有利に製造できる。 [0033] According to the production method of the present invention as described above, an alcohol compound can be industrially advantageously produced from the ester mixture represented by the formula (1) using a reagent that is easy to handle.

Claims

請求の範囲 The scope of the claims
[1] 式 (1)  [1] Expression (1)
R02C ^ A2— A1— A3— Y (1) R0 2 C ^ A 2 — A 1 — A 3 — Y (1)
(式中、 A1は架橋されていてもよい環状炭化水素基を表わし、 A2および A3は、それ ぞれ同一または相異なって、単結合または炭素数 1一 2のアルキレン基を表わす。 R は低級アルキル基を表わし、 Yは水素原子または— CO Rで示される基を表わす。 ) (In the formula, A 1 represents a cyclic hydrocarbon group which may be crosslinked, and A 2 and A 3 each represent the same or different and represent a single bond or an alkylene group having 11 to 12 carbon atoms. R represents a lower alkyl group, and Y represents a hydrogen atom or a group represented by —CO R.)
2  2
で示されるエステルイ匕合物と水素化ホウ素化合物とを、有機溶媒中、メタノールの存 在下に反応させることを特徴とする式（2)  Wherein the esterified compound represented by the formula (1) is reacted with a borohydride compound in an organic solvent in the presence of methanol.
HOH2C ^ A2— A1— AJ— Q (2) HOH 2 C ^ A 2 — A 1 — A J — Q (2)
(式中、
Figure imgf000013_0001
A2および A3は上記と同一の意味を表わし、 Qは、 Yが水素原子のときに 水素原子を、 Yがー CO Rで示される基のときにヒドロキシメチル基を表わす。） (Where
Figure imgf000013_0001
A 2 and A 3 have the same meaning as described above, and Q represents a hydrogen atom when Y is a hydrogen atom, and represents a hydroxymethyl group when Y is a group represented by —COR. )
2  2
で示されるアルコール化合物の製造方法。  A method for producing an alcohol compound represented by the formula:
[2] 水素化ホウ素化合物が、水素化ホウ素アルカリ金属化合物または水素化ホウ素ァ ルカリ土類金属化合物である請求項 1に記載のアルコール化合物の製造方法。 [2] The method for producing an alcohol compound according to claim 1, wherein the borohydride compound is an alkali metal borohydride compound or an alkaline earth metal borohydride compound.
[3] 水素化ホウ素アルカリ金属化合物が、水素化ホウ素ナトリウムである請求項 2に記 載のアルコール化合物の製造方法。 3. The method for producing an alcohol compound according to claim 2, wherein the alkali metal borohydride compound is sodium borohydride.
PCT/JP2005/005110 2004-03-24 2005-03-22 Method for producing alcohol compound WO2005090273A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1143455A (en) * 1997-07-25 1999-02-16 Mitsubishi Chem Corp Production of halogenated alcohol
JP2000007595A (en) * 1998-06-26 2000-01-11 New Japan Chem Co Ltd Production of cyclohexanedimethanol
WO2001038276A1 (en) * 1999-11-19 2001-05-31 Ihara Chemical Industry Co., Ltd. Process for the production of alkanediol derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1143455A (en) * 1997-07-25 1999-02-16 Mitsubishi Chem Corp Production of halogenated alcohol
JP2000007595A (en) * 1998-06-26 2000-01-11 New Japan Chem Co Ltd Production of cyclohexanedimethanol
WO2001038276A1 (en) * 1999-11-19 2001-05-31 Ihara Chemical Industry Co., Ltd. Process for the production of alkanediol derivatives

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