JPH01156936A - Production of optical active substance of propargyl alcohol compound - Google Patents
Production of optical active substance of propargyl alcohol compoundInfo
- Publication number
- JPH01156936A JPH01156936A JP28483788A JP28483788A JPH01156936A JP H01156936 A JPH01156936 A JP H01156936A JP 28483788 A JP28483788 A JP 28483788A JP 28483788 A JP28483788 A JP 28483788A JP H01156936 A JPH01156936 A JP H01156936A
- Authority
- JP
- Japan
- Prior art keywords
- propargyl alcohol
- alcohol compound
- brucine
- active substance
- diastereomers
- 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.)
- Granted
Links
- -1 propargyl alcohol compound Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000013543 active substance Substances 0.000 title abstract description 7
- 230000003287 optical effect Effects 0.000 title description 2
- RRKTZKIUPZVBMF-IBTVXLQLSA-N brucine Chemical compound O([C@@H]1[C@H]([C@H]2C3)[C@@H]4N(C(C1)=O)C=1C=C(C(=CC=11)OC)OC)CC=C2CN2[C@@H]3[C@]41CC2 RRKTZKIUPZVBMF-IBTVXLQLSA-N 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 5
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract 3
- 238000012986 modification Methods 0.000 abstract 3
- 239000002994 raw material Substances 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- RRKTZKIUPZVBMF-UHFFFAOYSA-N brucine Natural products C1=2C=C(OC)C(OC)=CC=2N(C(C2)=O)C3C(C4C5)C2OCC=C4CN2C5C31CC2 RRKTZKIUPZVBMF-UHFFFAOYSA-N 0.000 description 4
- 239000003799 water insoluble solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OECPUBRNDKXFDX-UHFFFAOYSA-N 2,2-dimethyl-1-phenylpropan-1-one Chemical compound CC(C)(C)C(=O)C1=CC=CC=C1 OECPUBRNDKXFDX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UIGLAZDLBZDVBL-UHFFFAOYSA-N 1-phenylprop-2-yn-1-ol Chemical compound C#CC(O)C1=CC=CC=C1 UIGLAZDLBZDVBL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プロパルギルアルコール化合物の光学活性体
の製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an optically active form of a propargyl alcohol compound.
ラセミ体の分割は、工業的には光学活性な分割試薬を用
いるジアステレオマー法が一般的である。For resolution of racemates, a diastereomer method using an optically active resolving reagent is generally used industrially.
しかし分割試薬の種類に応じて、ジアステレオマーを形
成するラセミ体ｄ限定されるため、種々光学活性を有す
る分割試薬の開発が望まれている。However, depending on the type of resolving reagent, the racemic form d that forms diastereomers is limited, so there is a desire to develop resolving reagents with various optical activities.
特に、プロパルギルアルコール化合物のラセミ体から、
その光学活性体を製造する方法の提供が望まれていた。In particular, from the racemic form of propargyl alcohol compound,
It has been desired to provide a method for producing the optically active substance.
本発明はプロパルギルアルコール化合物の光学活性体の
新規な製法を提供しようとするものである。The present invention aims to provide a novel method for producing an optically active form of a propargyl alcohol compound.
本発明者らは、上記従来技術の実情に鑑み、プロパルギ
ルアルコール化合物の光学活性体を得るために鋭意研究
を行った結果、次の一般式〔１〕で表されるプロパルギ
ルアルコール化合物の光学活性体の製法を提供すること
に成功したものである。In view of the above-mentioned state of the prior art, the present inventors conducted intensive research to obtain an optically active form of a propargyl alcohol compound, and as a result, the optically active form of a propargyl alcohol compound represented by the following general formula [1] We have succeeded in providing a manufacturing method for this.
Ｘ−Ｃ−ＣミＣＨ・・・ 〔１〕
（りＨ
〔ただし、式中Ｘはフェニル基を示し、Ｒは炭素数３〜
５のアルキル基、またはフェニル基（フェニル基の水素
原子は、ハロゲン原子または低級アルキル基で置換され
ていてもよい。）を示す。〕このプロパルギルアルコー
ル化合物の光学活性体は、前記−数式（１）で表される
プロパルギルアルコール化合物のラセミ体を、有機溶媒
中で！−プルシンと接触させ、得られたジアステレオマ
ーをその溶解度の差を利用して分離した後、そのジアス
テレオマーを分解することによって製造することができ
る。X-C-CmiCH... [1] (RiH [However, in the formula, X represents a phenyl group, and R has 3 to 3 carbon atoms.
5 shows an alkyl group or a phenyl group (the hydrogen atom of the phenyl group may be substituted with a halogen atom or a lower alkyl group). ] This optically active form of a propargyl alcohol compound is a racemic form of a propargyl alcohol compound represented by formula (1) above in an organic solvent! - It can be produced by bringing it into contact with prussin, separating the obtained diastereomers using the difference in solubility, and then decomposing the diastereomers.
本発明の方法により得られるプロパルギルアルコール化
合物の光学活性体は、種々ラセミ体の分割試薬、あるい
は医薬、農薬、香料などの出発原料など、多（の用途を
有している。The optically active form of a propargyl alcohol compound obtained by the method of the present invention has many uses, such as as a reagent for resolving various racemates, or as a starting material for medicines, agricultural chemicals, fragrances, and the like.
本発明の製法につき、詳述する。The manufacturing method of the present invention will be explained in detail.
分割試薬として用いる！−プルシンは、マチン科植物の
種子中など天然に存在し、下記の構造式％式％
！−ブルシンの構造式：
本発明方法において、まず、該ｌ−プルシンを有機溶媒
に溶解する。有機溶媒としては、！−ブルシンを溶解し
得るものであればいずれも有用であるが、なかでもアセ
トン、メタノール、酢酸エチルなどを用いることが好ま
しい。溶媒使用量は、！−プルシンを溶かすのに必要な
量、ないしその量よりやや過剰な量であれば十分である
。Use as a splitting reagent! -Prusin exists naturally in the seeds of plants of the Machinaceae family, and has the following structural formula % formula %! - Structural formula of brucine: In the method of the present invention, first, the l-purucin is dissolved in an organic solvent. As an organic solvent! - Any material that can dissolve brucine is useful, but it is preferable to use acetone, methanol, ethyl acetate, and the like. The amount of solvent used is! -The amount required to dissolve purusin, or an amount slightly in excess of that amount, is sufficient.
次に、！−ブルシンの有機溶媒溶液中に、２−プルシン
とほぼ等モルの前記−数式〔１〕で表されるプロパルギ
ルアルコール化合物のラセミ体を加え、両者を接触させ
る。接触は、１０〜５０゛Ｃの温度、通常室温で、１〜
３０時間行うことが好ましい。next,! - A racemic form of the propargyl alcohol compound represented by formula [1] is added to a solution of brucine in an organic solvent in an amount approximately equimolar to that of 2-purucine, and the two are brought into contact with each other. The contact is carried out at a temperature of 10-50°C, usually at room temperature, for 1-50°C.
It is preferable to carry out the treatment for 30 hours.
この接触によって、ｌ−プルシンとプロパルギルアルコ
ール化合物のｄ−活性体とのジアステレオマー、および
！−プルシンとプロパルギルアルコール化合物の！−活
性体とのジアステレオマーが形成される。この二つのジ
アステレオマーは、有機溶媒に対する溶解度において差
が大きく、どちらか一方のジアステレオマーだけが晶出
するため、例えば濾過、遠心分離などの簡単な操作によ
り両者を容易に分離することができる。なお、有機溶媒
に対する溶解度が小さく、従って有機溶媒から晶出して
くるジアステレオマーは、分割に供するラセミ体の種類
に応じて、プロパルギルアルコール化合物のｄ−活性体
のジアステレオマーであったり、またはプロパルギルア
ルコール化合物のｌ−活性体のジアステレオマーであっ
たりする。This contact results in diastereomers of l-pursin and the d-active form of the propargyl alcohol compound, and! - Prussin and propargyl alcohol compounds! - Diastereomers are formed with the active form. These two diastereomers have a large difference in solubility in organic solvents, and only one diastereomer crystallizes out, so it is not possible to easily separate the two by simple operations such as filtration or centrifugation. can. Note that the diastereomer that has low solubility in organic solvents and therefore crystallizes from the organic solvent may be a diastereomer of the d-active form of the propargyl alcohol compound, or It may be a diastereomer of the l-active form of a propargyl alcohol compound.
このようにして分離された両ジアステレオマーの各々を
、分割試薬を離脱させる通常の操作によって分解するこ
とにより、プロパルギルアルコール化合物のｄ−活性体
と！−活性体とを別々に取得することができる。Both diastereomers separated in this way are decomposed by a normal operation to remove the resolving reagent, thereby producing the d-active form of the propargyl alcohol compound! - the active form can be obtained separately.
例えば、濾集した一方のジアステレオマーを水に不溶な
溶媒に溶解させた後、この溶液を鉱酸水溶液と接触させ
ることにより、当該ジアステレオマーを分解することが
できる。また、他方のジアステレオマーを含む濾液は、
場合により有機溶媒を、ある程度蒸発させ濃縮した後、
これに水に不溶な溶媒を加え、次いでこれを鉱酸水溶液
と接触させることにより、当該ジアステレオマーを分解
することができる。For example, one of the diastereomers collected by filtration can be dissolved in a water-insoluble solvent and then brought into contact with an aqueous mineral acid solution to decompose the diastereomer. In addition, the filtrate containing the other diastereomer is
In some cases, after evaporating and concentrating the organic solvent to some extent,
The diastereomer can be decomposed by adding a water-insoluble solvent to the mixture and then contacting it with an aqueous mineral acid solution.
上記分解工程に用いられる水に不溶な溶媒としては、例
えばベンゼン、トルエン、キシレンなどが挙げられ、こ
の溶媒の使用量は分解して得られるプロパルギルアルコ
ール化合物の光学活性体を十分溶解させるに必要な量で
あればよい。Examples of water-insoluble solvents used in the above decomposition step include benzene, toluene, xylene, etc., and the amount of this solvent used is the amount necessary to sufficiently dissolve the optically active form of the propargyl alcohol compound obtained by decomposition. Any amount is fine.
また分割試薬の離脱反応に供される鉱酸水溶液としては
、例えば塩酸、硝酸、硫酸などの水溶液が挙げられ、そ
の濃度には特別の規定はないが、通常１〜３０ｗｔ％の
濃度で使用することができる。In addition, examples of the aqueous mineral acid solution used in the splitting reagent separation reaction include aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid, etc., and although there are no particular regulations regarding the concentration, it is usually used at a concentration of 1 to 30 wt%. be able to.
ジアステレオマーの鉱酸水溶液による分解は、通常１０
〜５０°Ｃの温度で５〜６０分間両者を接触させること
によって行われる。Decomposition of diastereomers with an aqueous mineral acid solution usually takes 10
This is done by contacting the two for 5 to 60 minutes at a temperature of ~50°C.
このようにしてジアステレオマーを分解した後、プロパ
ルギルアルコール化合物のｄ−１または！−活性体は水
に不溶な溶媒、すなわち有機層に移行し、ｌ−ブルシン
は鉱酸水溶液、すなわち水層に移行する。従って、両層
を、例えば分液法によって分離した後、有機層を蒸留す
ることにより、目的物のプロパルギルアルコール化合物
のｄ−１およびｌ−活性体の各々を取得することができ
る。After decomposing the diastereomers in this way, d-1 or! of the propargyl alcohol compound! - The active substance migrates to a water-insoluble solvent, ie, the organic phase, and l-brucine migrates to the mineral acid aqueous solution, ie, the aqueous phase. Therefore, by separating both layers by, for example, a liquid separation method, and then distilling the organic layer, each of the d-1 and l-activated forms of the target propargyl alcohol compound can be obtained.
一方、水層にアルカリ物質を加えて処理することにより
！−プルシンを晶出させ、これを濾集、回収し、再び本
発明の製法の分割試薬として利用することもできる。On the other hand, by adding alkaline substances to the water layer and treating it! - Purusin can be crystallized, collected by filtration, and then used again as a resolving reagent in the production method of the present invention.
なお、本発明方法において、プロパルギルアルコール化
合物の光学活性体の出発原料として用いるラセミ体は、
例えば次式に示す反応に従って、容易に合成することが
できる。In addition, in the method of the present invention, the racemate used as a starting material for the optically active form of the propargyl alcohol compound is:
For example, it can be easily synthesized according to the reaction shown in the following formula.
Ｈ
（ただし、式中ＸおよびＲは前記と同じ意味を有す。）
すなわち、ケトン類とナトリウムアセチリドを液体アン
モニア中、常圧下に反応させた後、反応系を常温に保持
することによってアンモニアを気散させ、次いでラセミ
体として得られたプロパルギルアルコール化合物のナト
リウム塩を加水分解することによって得ることができる
。なおナトリウムアセチリドは、通常ナトリウムアミド
の液体アンモニア溶液中に、アセチレンを通ずることに
よって合成されるので、この反応系にケトン類を加え前
記処理を施すこともできる。H (However, in the formula, X and R have the same meanings as above.) That is, after reacting ketones and sodium acetylide in liquid ammonia under normal pressure, ammonia is removed by maintaining the reaction system at room temperature. It can be obtained by aeration and then hydrolysis of the sodium salt of the propargyl alcohol compound obtained as a racemate. Note that since sodium acetylide is usually synthesized by passing acetylene through a liquid ammonia solution of sodium amide, the above-mentioned treatment can also be performed by adding ketones to this reaction system.
次に、プロパルギルアルコール化合物ラセミ体の合成例
を示す。Next, an example of synthesis of a racemic propargyl alcohol compound will be shown.
合成例１゜
約−６５°Ｃに保持した液体アンモニア１５００ｍｊｔ
中に、ナトリウムアミド８０ｇを加えた後、アセチレン
ガスを１０００ｍ ／ １ＩＩｉｎの速度で１２０分間
吹き込んだ。得られたナトリウムアセチリド含有液体ア
ンモニア溶液に、ｔ−ブチルフェニルケトン５ＱＯｇを
加え、約−６５°Ｃで１２０分間反応を行った後、反応
液を室温にしアンモニアガスを気散させた。Synthesis Example 1 1500 mjt of liquid ammonia kept at about -65°C
After adding 80 g of sodium amide into the solution, acetylene gas was blown into the solution at a rate of 1000 m/1 II in for 120 minutes. 5QOg of t-butylphenylketone was added to the obtained sodium acetylide-containing liquid ammonia solution, and the reaction was carried out at about -65°C for 120 minutes, and then the reaction solution was brought to room temperature and the ammonia gas was evaporated.
次いで加水分解処理を行った後、蒸留し沸点１１２°Ｃ
（８鵬Ｈｇ）を有する１−ｔ−ブチル−１−フェニルプ
ロパルギルアルコールのラセミ体５０５ ｇを得た。Next, after hydrolysis treatment, it is distilled to a boiling point of 112°C.
505 g of racemic 1-t-butyl-1-phenylpropargyl alcohol having (8 Peng Hg) was obtained.
合成例２〜１３
ｔ−ブチルフェニルケトン５００ ｇの代わりに、第１
表に示す各種フェニルケトン！５００ｇを用いた他は、
合成例１の操作に準じて各種プロパルギルアルコール類
のラセミ体を合成した。Synthesis Examples 2 to 13 Instead of 500 g of t-butylphenyl ketone, the first
Various phenyl ketones shown in the table! Besides using 500g,
Racemic forms of various propargyl alcohols were synthesized according to the procedure of Synthesis Example 1.
合成例１〜１３の結果を、第１表に示す。The results of Synthesis Examples 1 to 13 are shown in Table 1.
第１表
第１表のつづき
次に、本発明方法によるプロパルギルアルコール化合物
の光学活性体の製造の実施例を挙げます。Table 1 Continuation of Table 1 Next, examples of the production of optically active forms of propargyl alcohol compounds by the method of the present invention will be given.
実１１」１
１−プルシン２８ｇをアセトン３００ＭＩｌに溶解させ
た後、前記合成例１によって取得した１−ｔ−ブチル−
１−フェニルプロパルギルアルコールのラセミ体１３ｇ
を加え、室温で２４時間静置した。Fruit 11'' 1 After dissolving 28 g of 1-purusin in 300 MIl of acetone, the 1-t-butyl-
13g of racemic form of 1-phenylpropargyl alcohol
was added and allowed to stand at room temperature for 24 hours.
次いで、晶出した無色プリズム状の！−プルシントｔ
−ｔ−７’チル−１−フェニルプロパルギルアルコール
のｄ−活性体とのジアステレオマー２０．１ｇを濾葉し
た。この濾葉物をベンゼン３０戚に溶解させ、この溶液
に希塩酸水溶液（濃度１００ｇ／１）３０ｄを加え室温
で５分間攪拌を行ってジアステレオマーを分解した。次
に分液法によって、得られたベンゼン溶液を蒸留し、１
−ｔ−ブチル−１−フェニルプロパルギルアルコールの
ｄ−活性体６．５ｇを得た。Next, colorless prismatic crystals began to form! -Purucint t
20.1 g of diastereomer of -t-7' thyl-1-phenylpropargyl alcohol with d-active form was filtered. This filtered material was dissolved in benzene 30, and 30 d of dilute hydrochloric acid aqueous solution (concentration 100 g/1) was added to this solution and stirred at room temperature for 5 minutes to decompose diastereomers. Next, the obtained benzene solution was distilled by a liquid separation method, and 1
6.5 g of d-activated form of -t-butyl-1-phenylpropargyl alcohol was obtained.
一方、！−プルシンと１−ｔ−ブチル−１−フェニルプ
ロパルギルアルコールの！＝活性体とのジアステレオマ
ーを含む濾液に、ベンゼン３０成および希塩酸水溶液（
濃度１００ｇ／ｆ ） ３０ｄを加え、室温で５分間
攪拌を行いジアステレオマーを分解した。次に、分液法
によって分離されたベンゼン溶液を蒸留し、１−ｔ−ブ
チル−１−フェニルプロパルギルアルコールのｌ−活性
体６．８ｇを得た。on the other hand,! -Prusin and 1-t-butyl-1-phenylpropargyl alcohol! =To the filtrate containing the diastereomer with the active form, add 30% benzene and dilute aqueous hydrochloric acid solution (
30d (concentration 100g/f) was added and stirred at room temperature for 5 minutes to decompose diastereomers. Next, the benzene solution separated by the liquid separation method was distilled to obtain 6.8 g of 1-activated form of 1-t-butyl-1-phenylpropargyl alcohol.
亥ｍ二」」−
１−ｔ−ブチル−１−フェニルプロパルギルアルコール
のラセミ体に代えて、前記合成例２〜１３によって取得
した各種ラセミ体を所定量（第２表参照）を用いた他は
、実施例１の操作に準じて！−ブルシンとのジアステレ
オマーを得、次いで各種プロパルギルアルコール化合物
の光学活性体を得た。In place of the racemic form of 1-t-butyl-1-phenylpropargyl alcohol, predetermined amounts (see Table 2) of various racemic forms obtained in Synthesis Examples 2 to 13 were used. , according to the operation of Example 1! -Diastereomers with brucine were obtained, and then optically active forms of various propargyl alcohol compounds were obtained.
実施例１〜１３の結果を、第２表に示す。The results of Examples 1 to 13 are shown in Table 2.
以下余白
〔発明の効果〕
本発明方法によりプロパルギルアルコール化合物の光学
活性体が得られる。この光学活性体は、各種ラセミ体の
分割試薬、或いは医薬、農薬、香料などの出発原料とし
て有用なものである。Margins below [Effects of the Invention] An optically active form of a propargyl alcohol compound can be obtained by the method of the present invention. This optically active substance is useful as a reagent for resolving various racemates, or as a starting material for medicines, agricultural chemicals, fragrances, and the like.
Claims (1)
５のアルキル基、またはフェニル基（フェニル基の水素
原子は、ハロゲン原子または低級アルキル基で置換され
ていてもよい。）を示す。〕で表されるプロパルギルア
ルコール化合物のラセミ体を、有機溶媒中で、ｌ−ブル
シンと接触させてジアステレオマーを調製し、このジア
ステレオマーを、その溶解度の差を利用して分離し、前
記分離されたジアステレオマーの各々を分解することを
特徴とする、プロパルギルアルコール化合物の光学活性
体の製法。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, in the formula, X represents a phenyl group, and R represents a carbon number of 3 to
5 shows an alkyl group or a phenyl group (the hydrogen atom of the phenyl group may be substituted with a halogen atom or a lower alkyl group). ] The racemic form of the propargyl alcohol compound represented by is contacted with l-brucine in an organic solvent to prepare diastereomers, and the diastereomers are separated using the difference in solubility, and the diastereomers are separated using the difference in solubility. A method for producing an optically active form of a propargyl alcohol compound, which comprises decomposing each of the separated diastereomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28483788A JPH01156936A (en) | 1988-11-12 | 1988-11-12 | Production of optical active substance of propargyl alcohol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28483788A JPH01156936A (en) | 1988-11-12 | 1988-11-12 | Production of optical active substance of propargyl alcohol compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57033011A Division JPS58150526A (en) | 1982-03-04 | 1982-03-04 | Optically active propargyl alcohol and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01156936A true JPH01156936A (en) | 1989-06-20 |
| JPH0329773B2 JPH0329773B2 (en) | 1991-04-25 |
Family
ID=17683656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28483788A Granted JPH01156936A (en) | 1988-11-12 | 1988-11-12 | Production of optical active substance of propargyl alcohol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01156936A (en) |
-
1988
- 1988-11-12 JP JP28483788A patent/JPH01156936A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0329773B2 (en) | 1991-04-25 |
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