[go: up one dir, main page]

WO2005090273A1 - Procédé servant à produire un composé alcoolique - Google Patents

Procédé servant à produire un composé alcoolique Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
group
bicyclo
bis
dicarboxylate
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/005110
Other languages
English (en)
Japanese (ja)
Inventor
Kazuyuki Tanaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Sumitomo Pharma Co Ltd
Original Assignee
Sumitomo Pharmaceuticals Co Ltd
Sumitomo Dainippon Pharma Co Ltd
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Pharmaceuticals Co Ltd, Sumitomo Dainippon Pharma Co Ltd, Sumitomo Chemical Co Ltd filed Critical Sumitomo Pharmaceuticals Co Ltd
Publication of WO2005090273A1 publication Critical patent/WO2005090273A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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.

Landscapes

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

Abstract

Il est exposé un procédé servant à produire un composé alcoolique représenté par la formule (2) suivante : HOH2C-A2-A1-A3-Q (2) (dans laquelle A1, A2 et A3 sont tels que définis ci-dessous ; et Q représente un atome d'hydrogène lorsque Y défini ci-dessous est un atome d'hydrogène ou représente un groupe hydroxyméthyle lorsque Y est un groupe représenté par -CO2R), dans lequel on fait réagir un composé ester représenté par la formule (1) suivante : RO2C-A2-A1-A3-Y (1) (dans laquelle A1 représente un groupe hydrocarboné cyclique qui peut être réticulé ; A2 et A3 peuvent être identiques ou différents et représentent respectivement une liaison simple ou un groupe alkylène ayant 1-2 atomes de carbone ; R représente un groupe alkyle inférieur ; et Y représente un atome d'hydrogène ou un groupe représenté par -CO2R) avec un composé borohydrure dans un solvant organique en présence de méthanol.
PCT/JP2005/005110 2004-03-24 2005-03-22 Procédé servant à produire un composé alcoolique Ceased WO2005090273A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-086382 2004-03-24
JP2004086382A JP2005272335A (ja) 2004-03-24 2004-03-24 アルコール化合物の製造方法

Publications (1)

Publication Number Publication Date
WO2005090273A1 true WO2005090273A1 (fr) 2005-09-29

Family

ID=34993606

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/005110 Ceased WO2005090273A1 (fr) 2004-03-24 2005-03-22 Procédé servant à produire un composé alcoolique

Country Status (2)

Country Link
JP (1) JP2005272335A (fr)
WO (1) WO2005090273A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1143455A (ja) * 1997-07-25 1999-02-16 Mitsubishi Chem Corp ハロゲン化アルコールの製造方法
JP2000007595A (ja) * 1998-06-26 2000-01-11 New Japan Chem Co Ltd シクロヘキサンジメタノールの製造方法
WO2001038276A1 (fr) * 1999-11-19 2001-05-31 Ihara Chemical Industry Co., Ltd. Procede de production de derives d'alcanediol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1143455A (ja) * 1997-07-25 1999-02-16 Mitsubishi Chem Corp ハロゲン化アルコールの製造方法
JP2000007595A (ja) * 1998-06-26 2000-01-11 New Japan Chem Co Ltd シクロヘキサンジメタノールの製造方法
WO2001038276A1 (fr) * 1999-11-19 2001-05-31 Ihara Chemical Industry Co., Ltd. Procede de production de derives d'alcanediol

Also Published As

Publication number Publication date
JP2005272335A (ja) 2005-10-06

Similar Documents

Publication Publication Date Title
EP2097431B1 (fr) Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
CA2671932C (fr) Nouveau procede de preparation de benzocyclobutenes fonctionnalises, et application a la synthese de l'ivabradine et de ses sels d'addition a un acide pharmaceutiquement acceptable
CN102725258A (zh) 环己烯1，4-羧化物
Nickon et al. Synthesis and structure proof of C-2 and C-4 monofunctionalized brexanes and brendanes
EP2921229A1 (fr) Catalyseur d'aluminium
Tokuyasu et al. Yingzhaosu A analogues: synthesis by the ozonolysis of unsaturated hydroperoxides, structural analysis and determination of anti-malarial activity
WO2005090273A1 (fr) Procédé servant à produire un composé alcoolique
Ohshima et al. Manganese (III)-based oxidative free-radical reaction of α-allyl-β-keto ester with molecular oxygen
JP5317939B2 (ja) アルコール化合物の製造方法
JP6285825B2 (ja) Ｎ−アシルカルバモイル基及びラクトン骨格を含む化合物の製造方法
JP2014125462A (ja) エポキシド誘導体およびその製造方法
CN111056890B (zh) 一种基于铁催化的酮酸脱羧、脂肪醛脱羰的自由基-自由基偶联反应制备芳基酮的方法
JP2008162946A (ja) （メタ）アクリル酸エステルの製造方法
JP5603041B2 (ja) （ヘテロ）ディールス−アルダー反応用触媒、それを用いたおよびジヒドロピラン化合物およびディールス−アルダー反応付加物の製造方法
JP2008133223A (ja) エキソ型ヒドロキシテトラシクロドデカンカルボン酸類及びその製造方法
JP4942514B2 (ja) （メタ）アクリル酸エステルの製造方法
Gassman et al. Photoinitiated additions of ketones to bicyclo [1.1. 0] butanes. The existence of diverse reaction pathways
JP2004359669A (ja) 多環式ラクトン化合物及び多環式ラクトン構造を有する（メタ）アクリレート化合物、並びにその製造方法
JP2004346007A (ja) ３，３’−ビシクロヘキセニルの製造方法
WO2019197326A1 (fr) Procédé de production de 2-méthyl-4-(2,6,6-triméthyl-1-cyclohexén-1-yl)-2-buténal
JP2005023063A (ja) 新規なラクトン化合物
WO2004060844A1 (fr) Procede de production de composes de carbonyle $g(a),$g(b) insatures
JP5184565B2 (ja) 水系溶媒中での含窒素化合物の製造方法
JP5468869B2 (ja) ラクトン化合物の製造方法
JP2004315465A (ja) ラクトン構造を有する化合物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase