WO2002002493A1 - Process for producing tertiary alcohol having adamantane skeleton - Google Patents
Process for producing tertiary alcohol having adamantane skeleton Download PDFInfo
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- WO2002002493A1 WO2002002493A1 PCT/JP2001/005572 JP0105572W WO0202493A1 WO 2002002493 A1 WO2002002493 A1 WO 2002002493A1 JP 0105572 W JP0105572 W JP 0105572W WO 0202493 A1 WO0202493 A1 WO 0202493A1
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- adamantane
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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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Definitions
- the present invention relates to a method for efficiently producing a tertiary alcohol having an adamantine skeleton from a substituted or unsubstituted 2-adamantanone in high yield.
- tertiary alcohols can be produced by using ethyllithium without producing reduced forms, but the reagents are expensive and difficult to handle, which is dangerous.
- cerium chloride in the reaction of a ketone with a Grignard reagent can suppress an abnormal reaction such as formation of a reduced form.
- an abnormal reaction such as formation of a reduced form.
- isopropylation of disopropyl ketone is performed using a Grignard reagent and coexistence of cerium chloride
- the formation of the adduct can be significantly reduced from 3% to 52% compared to the case without using dihycerium chloride.
- the present invention solves the above-mentioned problems of the prior art, and when a substituted or unsubstituted 2-adamantanone is alkylated to produce a tertiary alcohol, the production of a reduced form can be significantly suppressed; It is an object of the present invention to provide a method capable of efficiently producing an adduct at a high yield at a low cost.
- the present invention provides a compound represented by the general formula (I):
- R represents an alkyl group having 210 carbon atoms having i3 hydrogen
- Y represents a hydrogen atom, a halogen atom, an alkyl group having 110 carbon atoms, an alkoxy group having 110 carbon atoms, a ketal group, It represents a silyl group or a trisubstituted amino group
- n represents an integer of 15.
- R represents an alkyl group having 2 to 10 carbon atoms having 8 hydrogen atoms
- X represents a halogen atom.
- the present invention is to produce a tertiary alcohol having an adamantane skeleton represented by the above general formula (I).
- R represents 2 carbon atoms derived from the Grignard reagent.
- Re represents an alkyl group having 3 to 10 hydrogens, for example, an ethyl group or a propyl group
- Y represents a hydrogen atom or various substituents, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms (eg, , A methyl group, an ethyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.), a ketal group (a dimethyl ketal group, etc.), a silyl group (a trimethylsilyl group, etc.), or a 3-substituted amino. Group (trimethylamino group, etc.).
- tertiary alcohol represented by the general formula (I) examples include 2-ethylamidamantane-1-ol, 1-methyl-12-ethylethylamantane-1-ol, 1 -Methyl-2-propylpropylamantane-1-ol, 1-methyl-1-butylethylamantane-1-ol, 1,3-dimethyl-2-ethylethylamantatan-1-ol, 1,3-dimethyl-2 —Butyl adamantane 1-2-ol, 1-chloro-2-ethyl ethyl amantane 1-ol, 1-trimethylsilyl-12-ethyl ethyl adamantane 1-2-ol, and the like.
- an adamantane skeleton represented by the general formula (I) is provided.
- the tertiary alcohol is a substituted or unsubstituted 2-adamantanone compound represented by the general formula ( ⁇ ).
- R represents a hydrogen-containing alkyl group having 2 to 10 carbon atoms
- X represents a halogen atom.
- the magnesium compound represented by the general formula (111) is an ordinary Grignard reagent.
- Examples of the dimethylmagnesium compound include dimethylmagnesium, getylmagnesium, and dibutylmagnesium.
- the magnesium compound is used in an amount of 1 to 10 equivalents, preferably 1 equivalent, to 1 equivalent of the substituted or unsubstituted 2-adamantanone compound of the general formula ( ⁇ ). Used in an amount of ⁇ 5 equivalents. Use of magnesium compounds in excess of 10 equivalents is economically disadvantageous and meaningless.
- rare earth halides include lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, pium chloride, gadmium chloride, terbium chloride, dysprosium chloride, pormium chloride, and erbium chloride.
- Ytterbium chloride, lutetium chloride, and corresponding bromides and iodides can be used alone or in combination of two or more. It is also possible to use a mixed rare earth (an unpurified halide containing a large amount of cerium and lanthanum obtained from a rough stone).
- rare earth halides are used in an amount of 0.01 to 50 equivalents, preferably 0.1 to 10 equivalents, per equivalent of the magnesium compound. If the amount used is less than 0.01 equivalent, the effect of improving the yield cannot be exhibited, and even if it exceeds 50 equivalents, it is only economically disadvantageous.
- the reaction between the compound of the general formula (II) and the magnesium compound in the presence of a rare earth halide is carried out at normal pressure in a solvent used for a usual Grignard reagent. At a temperature of about 10 ° C. to about room temperature for 0.5 to 10 hours.
- a solvent for example, tetrahydrofuran, getyl ether, 1 , 41-dioxane, etc.
- Example 2 The same operation as in Example 1 was carried out except that cerium chloride was not used, and the product was analyzed. As a result, the yield of 2-ethyladamantan-1-ol was 31%. Industrial applicability
- a tertiary alcohol having an adamantane skeleton can be industrially produced efficiently from 2-adamantanone or substituted 1-adamantanone at low cost, and in that case, the formation of reduced forms is remarkably suppressed.
- the yield of tertiary alcohol can be dramatically improved.
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Abstract
A process for producing a tertiary alcohol having an adamantane skeleton which comprises reacting optionally substituted 2-adamantanone with a Grignard reagent in the presence of a rare earth halide. By the process in which optionally substituted 2-adamantanone is alkylated to produce a tertiary alcohol, the addition product can be efficiently produced in high yield while almost perfectly inhibiting the generation of reduction products.
Description
明 細 書 ァダマンタン骨格を有する第三級アルコールの製造方法 技術分野 Description Method for producing tertiary alcohol having adamantane skeleton
本発明は、 置換又は非置換 2—ァダマンタノンからァダマン夕ン骨格を有する 第三級ァルコ一ルを高収率で効率よく製造する方法に関する。 背景技術 The present invention relates to a method for efficiently producing a tertiary alcohol having an adamantine skeleton from a substituted or unsubstituted 2-adamantanone in high yield. Background art
近年、 ァダマン夕ノン誘導体は、 種々の分野に用途展開が図られており、 2— ェチルァダマンタノールもレジスト原料としての開発が進められている。 In recent years, applications of the adaman non-derivatives have been developed in various fields, and development of 2-ethyl adamantanol as a resist material has been promoted.
従来、 ァダマン夕ノン誘導体のアルキル化において、 グリニャール試薬等のマ グネシゥム化合物を用いると、 目的とするアルキル化物の他に還元ァルコ一ルが 主に生成する。 例えば、 2—ァダマンタノンでェチルダリニヤ一ル試薬を反応さ せると、 主にケトン自身の嵩高さのため.、 2—ェチルァダマン夕ノールの他にァ ダマン夕ノンが還元された 2—ァダマンタノ一ルが多量に生成することが知られ ている 〔 2—ェチルァダマンタノール収率 40%： J. Am. Chem. Soc.Vol. 9. No. 1 3、 4 24 8〜 4634頁 （ 1 972) 〕 。 Conventionally, when a magnesium compound such as a Grignard reagent is used in the alkylation of an adaman-nonone derivative, reduced alcohol is mainly produced in addition to the intended alkylated product. For example, when 2-ethylamantanone reacts with etildarinyl reagent, mainly because of the bulkiness of the ketone itself. [Yield of 2-ethylethylamantanol 40%: J. Am. Chem. Soc. Vol. 9. No. 13, 424-8-4634 (1972)] .
また、 ェチルリチウムを使用することにより還元体を生成することなく第三級 アルコールを製造することができるが、 試薬が高価でかつ取り扱いが困難で危険 である。 Also, tertiary alcohols can be produced by using ethyllithium without producing reduced forms, but the reagents are expensive and difficult to handle, which is dangerous.
一方、 ケトン類とグリニャール試薬との反応の際に、 塩化セリウムを共存させ ると、 還元体の生成等の異常な反応を抑制しうることが知られている。 例えば、 ジィソプロピルケトンのィソプロピル化を、 グリ二ヤール試薬を用いて行う場合 に、 塩化セリウムを共存させると、 付加体の生成を塩ィヒセリウムを用いない場合 の 3%から 5 2%まで大幅に向上することができるが、 還元体をある程度 （ 3 1
o/o) 生成する [Tetrahedron Lett. ： Vo l. 2 6 . No. 3 9 4 7 6 3 4 7 6 6 頁 （ 1 9 8 5 ) 〕 On the other hand, it is known that the presence of cerium chloride in the reaction of a ketone with a Grignard reagent can suppress an abnormal reaction such as formation of a reduced form. For example, when isopropylation of disopropyl ketone is performed using a Grignard reagent and coexistence of cerium chloride, the formation of the adduct can be significantly reduced from 3% to 52% compared to the case without using dihycerium chloride. Can be improved, but the reductant to some extent (3 1 o / o) Generated [Tetrahedron Lett .: Vol. 26. No. 3 9 4 7 6 3 4 7 6 6 (1998)]
発明の開示 Disclosure of the invention
本発明は、 上記の従来技術の問題点を解消し、 置換又は非置換 2—ァダマンタ ノンをアルキル化し、 第三級アルコールを製造する場合に、 還元体の生成を著し く抑えることができ、付加体を高収率で効率よく安価に製造しうる方法を提供す ることを目的とする。 The present invention solves the above-mentioned problems of the prior art, and when a substituted or unsubstituted 2-adamantanone is alkylated to produce a tertiary alcohol, the production of a reduced form can be significantly suppressed; It is an object of the present invention to provide a method capable of efficiently producing an adduct at a high yield at a low cost.
本発明者は、 鋭意研究の結果、 置換又は非置換 1―ァダマンタノンとグリ二ャ —ル試薬との反応の際に希土類ハロゲン化物を共存させると、 還元体の生成を著 しく抑えうることを見出し、 本発明を完成した。 As a result of intensive studies, the present inventors have found that the coexistence of a rare earth halide in the reaction of a substituted or unsubstituted 1-adamantanone with a Grignard reagent can significantly suppress the formation of the reduced form. The present invention has been completed.
すなわち、 本発明は、 一般式 （ I ) That is, the present invention provides a compound represented by the general formula (I):
〔式中、 Rは炭素数 2 1 0の i3水素を有するアルキル基を示し、 Yは水素原子 , ハロゲン原子， 炭素数 1 1 0のアルキル基， 炭素数 1 1 0のアルコキシ基 ， ケタール基， シリル基又は 3置換アミノ基を示し、 nは 1 5の整数を示す。 〕 で表されるァダマンタン化合物の第三級アルコールを製造する際に、 一般式 （ I I ) [In the formula, R represents an alkyl group having 210 carbon atoms having i3 hydrogen, Y represents a hydrogen atom, a halogen atom, an alkyl group having 110 carbon atoms, an alkoxy group having 110 carbon atoms, a ketal group, It represents a silyl group or a trisubstituted amino group, and n represents an integer of 15. When producing the tertiary alcohol of the adamantane compound represented by the general formula (II)
RMgX (III) RMgX (III)
〔式中、 Rは) 8水素を有する炭素数 2〜 10のアルキル基を示し、 Xはハロゲン 原子を示す。 〕 で表されるマグネシウムィヒ合物又はジアルキルマグネシウム化合 物と、 希土類ハロゲン化物の存在で反応させることを特徴とする一般式 （I) で 表されるァダマンタン骨格を有する第三級アルコールの製造方法を提供するもの である。 発明を実施するための最良の形態 [Wherein, R represents an alkyl group having 2 to 10 carbon atoms having 8 hydrogen atoms, and X represents a halogen atom. A method for producing a tertiary alcohol having an adamantane skeleton represented by the general formula (I), wherein the tertiary alcohol is reacted with a magnesium hydride compound or a dialkylmagnesium compound represented by the formula (I): It provides BEST MODE FOR CARRYING OUT THE INVENTION
本発明は、 前記の一般式 （I) で表されるァダマンタン骨格を有する第三級ァ ルコ一ルを製造するものであるが、 一般式 （I) において Rはグリニャール試薬 に由来する炭素数 2〜1 0の3水素を有するアルキル基、 例えば、 ェチル基， プ 口ピル基などを示し、 Yは水素原子又は各種の置換基、 例えば、 ハロゲン原子， 炭素数 1〜1 0のアルキル基 （例えば、 メチル基， ェチル基等） ， 炭素数 1〜1 0のアルコキシ基 （例えば、 メトキシ基， エトキシ基等） ， ケタール基 （ジメチ ルケタール基等） ， シリル基 （卜リメチルシリル基等） 又は 3置換ァミノ基 （ト リメチルアミノ基等） を示す。 The present invention is to produce a tertiary alcohol having an adamantane skeleton represented by the above general formula (I). In the general formula (I), R represents 2 carbon atoms derived from the Grignard reagent. Represents an alkyl group having 3 to 10 hydrogens, for example, an ethyl group or a propyl group; Y represents a hydrogen atom or various substituents, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms (eg, , A methyl group, an ethyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.), a ketal group (a dimethyl ketal group, etc.), a silyl group (a trimethylsilyl group, etc.), or a 3-substituted amino. Group (trimethylamino group, etc.).
本発明の一般式 （I) で表される第三級アルコールの具体例としては、 2—ェ チルァダマンタン一 1一オール， 1—メチル一 2—ェチルァダマンタン一 2—ォ —ル， 1ーメチルー 2—プロピルァダマンタン一 2—オール， 1—メチル一2— プチルァダマンタン一 1—オール， 1， 3一ジメチルー 2—ェチルァダマンタン 一 2—オール， 1 , 3—ジメチルー 2—ブチルァダマンタン一 2—オール， 1— クロロー 2—ェチルァダマンタン一 1—オール， 1一トリメチルシリル一 2—ェ チルァダマンタン一 2—オールなどが挙げられる。 Specific examples of the tertiary alcohol represented by the general formula (I) according to the present invention include 2-ethylamidamantane-1-ol, 1-methyl-12-ethylethylamantane-1-ol, 1 -Methyl-2-propylpropylamantane-1-ol, 1-methyl-1-butylethylamantane-1-ol, 1,3-dimethyl-2-ethylethylamantatan-1-ol, 1,3-dimethyl-2 —Butyl adamantane 1-2-ol, 1-chloro-2-ethyl ethyl amantane 1-ol, 1-trimethylsilyl-12-ethyl ethyl adamantane 1-2-ol, and the like.
本発明の方法においては、 前記一般式 （I) で表されるァダマンタン骨格を有
する第三級アルコールは、前記一般式 （Π ) で表される置換又は非置換 2—ァダ マンタノン化合物を一般式 （Π Ι) In the method of the present invention, an adamantane skeleton represented by the general formula (I) is provided. The tertiary alcohol is a substituted or unsubstituted 2-adamantanone compound represented by the general formula (Π).
R M g X ( I I I) R M g X (I I I)
〔式中、 Rは 水素を有する炭素数 2〜 1 0のアルキル基を示し、 Xはハロゲン 原子を示す。 〕 で表されるマグネシウム化合物又はジアルキルマグネシウム化合 物と、 希土類ハロゲン化物の存在で反応させることによって製造される。 [Wherein, R represents a hydrogen-containing alkyl group having 2 to 10 carbon atoms, and X represents a halogen atom. And a dialkylmagnesium compound represented by the following formula: in the presence of a rare earth halide.
前記一般式 （111)で表されるマグネシウム化合物は、 通常のグリニャール試薬 である。 また、 ジァルキルマグネシゥム化合物としては、 例えば、 ジメチルマグ ネシゥム， ジェチルマグネシウム， ジブチルマグネシウムなどが挙げられる。 マグネシウム化合物は、 一般式 （Π ) の置換又は非置換 2—ァダマンタノン化 合物 1当量に対して 1〜 1 0当量、 好ましくは！〜 5当量の量で用いる。 マグネ シゥム化合物を 1 0当量を超えて使用しても経済的に不利益なだけで無意味であ る。 The magnesium compound represented by the general formula (111) is an ordinary Grignard reagent. Examples of the dimethylmagnesium compound include dimethylmagnesium, getylmagnesium, and dibutylmagnesium. The magnesium compound is used in an amount of 1 to 10 equivalents, preferably 1 equivalent, to 1 equivalent of the substituted or unsubstituted 2-adamantanone compound of the general formula (Π). Used in an amount of ~ 5 equivalents. Use of magnesium compounds in excess of 10 equivalents is economically disadvantageous and meaningless.
また、 希土類ハロゲン化物としては、 塩ィヒランタン， 塩化セリウム， 塩化プラ セオジム， 塩化ネオジム， 塩化プロメチウム， 塩化サマリウム， 塩化ユウ口ピウ ム， 塩化ガドリゥム， 塩化テルビウム， 塩化ジスプロシウム， 塩化ポルミゥム， 塩化エルビウム， 塩化ツリウム， 塩化イッテルビウム， 塩化ルテチウム、 さらに これらに対応する臭化物， 沃化物などを単独であるいは二種以上を併せて使用す ることができる。 また、混合希土 （原石から得られるセリウムやランタンを多く 含む精製前のハロゲン化物） を用いることもできる。 Examples of rare earth halides include lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, pium chloride, gadmium chloride, terbium chloride, dysprosium chloride, pormium chloride, and erbium chloride. , Ytterbium chloride, lutetium chloride, and corresponding bromides and iodides can be used alone or in combination of two or more. It is also possible to use a mixed rare earth (an unpurified halide containing a large amount of cerium and lanthanum obtained from a rough stone).
これらの希土類ハロゲン化物は、 マグネシウム化合物 1当量に対して 0 . 0 1 〜5 0当量、 好ましくは 0 . 1〜 1 0当量の量で使用される。 この使用量が 0 . 0 1当量未満であると、 収率向上の効果が発揮できず、 5 0当量を超えて使用し ても、 経済的に不利益なだけである。 These rare earth halides are used in an amount of 0.01 to 50 equivalents, preferably 0.1 to 10 equivalents, per equivalent of the magnesium compound. If the amount used is less than 0.01 equivalent, the effect of improving the yield cannot be exhibited, and even if it exceeds 50 equivalents, it is only economically disadvantageous.
本発明において、 希土類ハロゲン化物の存在での一般式 （I I ) の化合物と前記 マグネシゥム化合物との反応は、 通常のグリニヤ一ル試薬に用いる溶媒中で常圧
で一 5 0° (：〜 1 0 O ；、 好ましくは一 1 0°C〜室温付近の温度で 0. 5〜 1 0時 間で行う。 溶媒としては、 例えば、 テトラヒドロフラン， ジェチルェ一テル， 1 ， 4一ジォキサンなどが用いられる。 次に、 実施例に基づいて本発明をさらに具体的に説明するが、 本発明はこれに よつて制限されるものではない。 In the present invention, the reaction between the compound of the general formula (II) and the magnesium compound in the presence of a rare earth halide is carried out at normal pressure in a solvent used for a usual Grignard reagent. At a temperature of about 10 ° C. to about room temperature for 0.5 to 10 hours. As a solvent, for example, tetrahydrofuran, getyl ether, 1 , 41-dioxane, etc. Next, the present invention will be described more specifically based on Examples, but the present invention is not limited thereto.
実施例 1 Example 1
5 0m lの三つ口フラスコを減圧乾燥した後、 このフラスコに無水塩化セリゥ ム 1. 9 g (テトラヒドロフラン 1 0m l中 7. 5ミ リモル、 2—ァダマンタノ ン 1当量に対して 1. 5当量） を仕込み、 氷浴下、 ェチルマグネシウムクロライ ド 7. 5m l ( 7. 5ミリモル、 テトラヒドロフラン 1 リッ トル中 1モル、 ァダ マン夕ノン 1当量に対して 1. 5当量） を加え、 1時間攪拌する。 次に、 同じく 氷浴下にテトラヒドロフランに溶かした 2—ァダマンタノン 1 0m l (含有ァダ マンタノン量は 5ミリモル） を 1 0分かけて滴下した。 滴下終了後、 2時間後に 1 0重量％酢酸水溶液で反応を終了させ、 へキサン抽出後、 抽出液をガスクロマ トグラフィ一で分析したところ、 2—ェチルァダマンタン一 2一オールが収率 9 9%で生成し、 還元体はわずか 1 %しか生成しなかった。 After drying a 50 ml three-necked flask under reduced pressure, 1.9 g of anhydrous cerium chloride (7.5 mmol in 10 ml of tetrahydrofuran, 1.5 equivalent to 1 equivalent of 2-adamantanone) was added to the flask. ), And 7.5 ml of ethyl magnesium chloride (7.5 mmol, 1 mol in 1 liter of tetrahydrofuran, 1.5 equivalents per 1 equivalent of non-adamantane) was added in an ice bath. Stir for 1 hour. Next, 10 ml of 2-adamantanone (containing 5 mmol of adamantanone) dissolved in tetrahydrofuran was added dropwise over 10 minutes in the same ice bath. Two hours after the completion of the dropwise addition, the reaction was terminated with a 10% by weight aqueous solution of acetic acid. After extraction with hexane, the extract was analyzed by gas chromatography. At 9%, only 1% of the reductant was formed.
実施例 2 Example 2
無水塩化セリウムの代わりに塩化ランタン 1. 8 g (テトラヒドロフラン 1 0 m l中 7. 5ミリモル、 2—ァダマンタン 1当量に対して 1. 5当量） を用いた 以外は実施例 1と同様に操作し、 生成物を分析したところ、 2—ェチルァダマン タン一 2—オールが収率 8 1 %で生成した。 還元体は 1 9%であった。 The procedure was as in Example 1, except that 1.8 g of lanthanum chloride (7.5 mmol in 10 ml of tetrahydrofuran, 1.5 equivalents per equivalent of 2-adamantane) was used instead of anhydrous cerium chloride. When the product was analyzed, 2-ethylamantan-2-ol was formed in a yield of 81%. The reduced form was 19%.
比較例 1 Comparative Example 1
塩化セリウムを用いない以外は、実施例 1と同様に操作し、 生成物を分析した ところ、 2ーェチルァダマンタン一 1—オールの収率は 3 1 %であった。
産業上の利用可能性 The same operation as in Example 1 was carried out except that cerium chloride was not used, and the product was analyzed. As a result, the yield of 2-ethyladamantan-1-ol was 31%. Industrial applicability
本発明の方法によれば、 2―ァダマンタノン又は置換 1 -ァダマン夕ノンから ァダマンタン骨格を有する第三級アルコールを工業的に安価に効率よく製造する ことができ、 その際還元体の生成を著しく抑えることができ、 第三級アルコール の収率を飛躍的に向上させることができる。
According to the method of the present invention, a tertiary alcohol having an adamantane skeleton can be industrially produced efficiently from 2-adamantanone or substituted 1-adamantanone at low cost, and in that case, the formation of reduced forms is remarkably suppressed. Thus, the yield of tertiary alcohol can be dramatically improved.
Claims
1. 一般式 （ I ) 1. General formula (I)
〔式中、 Rは炭素数 2〜1 0の 水素を有するアルキル基を示し、 Yは水素原子 ， ハロゲン原子， 炭素数 1〜10のアルキル基， 炭素数 1〜10のアルコキシ基 ， ケタール基， シリル基又は 3置換アミノ基を示し、 nは 1〜5の整数を示す。 〕 で表されるァダマンタン骨格を有する第三級アルコールを製造する際に、 一般 式 （II) [Wherein, R represents an alkyl group having 2 to 10 carbon atoms having hydrogen, Y represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a ketal group, It represents a silyl group or a trisubstituted amino group, and n represents an integer of 1 to 5. When producing a tertiary alcohol having an adamantane skeleton represented by the general formula (II)
〔式中、 Υ及び ηは前記のものを示す。 〕 で表される置換又は非置換 2—ァダマ ンタノン化合物を一般式 (111) [Wherein, Υ and η represent the above. The substituted or unsubstituted 2-adamantanone compound represented by the general formula (111)
RMgX (III) RMgX (III)
〔式中、 Rは) 3水素を有する炭素数 2〜 10のアルキル基を示し、 Xはハロゲン 原子を示す。 〕 で表されるマグネシゥム化合物又はジアルキルマグネシゥム化合 物と、 希土類/、口ゲン化物の存在で反応させることを特徴とする一般式 (I) で 表されるァダマンタン骨格を有する第三級アルコールの製造方法。 [In the formula, R represents an alkyl group having 2 to 10 carbon atoms having 3 hydrogen atoms, and X represents a halogen atom. Of a tertiary alcohol having an adamantane skeleton represented by the general formula (I), characterized by reacting with a magnesium compound or a dialkylmagnesium compound represented by the formula (I): Production method.
2. 希土類ハロゲン化物を、 マグネシウム化合物 1当量に対して 0. 0 1〜50
当量使用する請求項 1記載の製造方法。 2. Rare earth halides are added in an amount of 0.01 to 50 per equivalent of magnesium compound. The production method according to claim 1, wherein an equivalent amount is used.
3 . 希土類ハロゲン化物が、 希土類塩化物である請求項 1記載の製造方法。 3. The method according to claim 1, wherein the rare earth halide is a rare earth chloride.
4 . 一般式 （I I I)で表されるマグネシウム化合物を、 一般式 （I I ) で表される置 換又は非置換 2—ァダマンタノン化合物 1当量に対して 1〜 1 0当量使用する請 求項 1記載の製造方法。 4. Claim 1 wherein the magnesium compound represented by the general formula (III) is used in an amount of 1 to 10 equivalents per equivalent of the substituted or unsubstituted 2-adamantanone compound represented by the general formula (II). Manufacturing method.
5 . 一般式（ I ) で表されるァダマンタン骨格を有する第三級アルコールが、 1 —ェチルァダマンタン一 2—オール， 1ーメチルー 1ーェチルァダマンタン一 2 —オール， 1 一メチル _ 2—プロピルァダマンタン一 2—オール， 1—メチル一 2—ブチルァダマンタン一 2—オール， 1， 3—ジメチル一 2—ェチルァダマン タン一 2—オール， 1， 3—ジメチルー 2—ブチルァダマンタン一 2—オール， 5. The tertiary alcohol having an adamantane skeleton represented by the general formula (I) is 1-ethyl-amantane-2-ol, 1-methyl-1-ethylethylamantane 1-2-ol, 1-methyl _ 2-Propyl adamantane 1-2-ol, 1-methyl-12-butyl adamantane 1-2-ol, 1,3-Dimethyl-12-ethyl-adamantan 1-2-ol, 1,3-Dimethyl-2-butyl Adamantane 1 2—all,
1一クロロー 2—ェチルァダマンタン一 2—オール又は 1ートリメチルシリルー 2ーェチルァダマンタン一 2—オールである請求項 1記載の製造方法。
2. The production method according to claim 1, wherein the production method is 1-chloro-2-ethyl-adamantan-2-ol or 1-trimethylsilyl-2-ethyl-adamantan-2-ol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000202476A JP4220658B2 (en) | 2000-07-04 | 2000-07-04 | Method for producing tertiary alcohol having adamantane skeleton |
| JP2000-202476 | 2000-07-04 |
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| Publication Number | Publication Date |
|---|---|
| WO2002002493A1 true WO2002002493A1 (en) | 2002-01-10 |
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| PCT/JP2001/005572 WO2002002493A1 (en) | 2000-07-04 | 2001-06-28 | Process for producing tertiary alcohol having adamantane skeleton |
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| JP (1) | JP4220658B2 (en) |
| TW (1) | TWI225857B (en) |
| WO (1) | WO2002002493A1 (en) |
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| WO2008078580A1 (en) * | 2006-12-26 | 2008-07-03 | Idemitsu Kosan Co., Ltd. | Adamantyl ethanol and process for production thereof |
| SG174923A1 (en) * | 2009-03-27 | 2011-11-28 | Mitsui Chemicals Inc | Method for producing optically active alcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617223A (en) * | 1984-06-22 | 1986-01-13 | Sagami Chem Res Center | Preparation of 2-ethynyl-1,2,3,4-tetrahydro-2-naphthol derivative |
| JPH11302211A (en) * | 1998-04-21 | 1999-11-02 | Daicel Chem Ind Ltd | Adamantanol derivative and its production |
| JP2001213826A (en) * | 2000-02-03 | 2001-08-07 | Idemitsu Petrochem Co Ltd | Method for producing 2-alkyl-2-adamantanol |
-
2000
- 2000-07-04 JP JP2000202476A patent/JP4220658B2/en not_active Expired - Fee Related
-
2001
- 2001-06-28 WO PCT/JP2001/005572 patent/WO2002002493A1/en active Application Filing
- 2001-07-03 TW TW090116287A patent/TWI225857B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617223A (en) * | 1984-06-22 | 1986-01-13 | Sagami Chem Res Center | Preparation of 2-ethynyl-1,2,3,4-tetrahydro-2-naphthol derivative |
| JPH11302211A (en) * | 1998-04-21 | 1999-11-02 | Daicel Chem Ind Ltd | Adamantanol derivative and its production |
| JP2001213826A (en) * | 2000-02-03 | 2001-08-07 | Idemitsu Petrochem Co Ltd | Method for producing 2-alkyl-2-adamantanol |
Non-Patent Citations (1)
| Title |
|---|
| IMAMOTO T. ET AL.: "Cerium chloride-promoted nucleophilic addition of Grignard reagents to ketones. An efficient method for the synthesis of tertiary alcohols", TETRAHEDRON LETT., vol. 26, no. 39, 1985, pages 4763 - 4766, XP002947214 * |
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| JP2002020334A (en) | 2002-01-23 |
| TWI225857B (en) | 2005-01-01 |
| JP4220658B2 (en) | 2009-02-04 |
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