JPH04266883A - Method for separating isomer - Google Patents
Method for separating isomerInfo
- Publication number
- JPH04266883A JPH04266883A JP2842291A JP2842291A JPH04266883A JP H04266883 A JPH04266883 A JP H04266883A JP 2842291 A JP2842291 A JP 2842291A JP 2842291 A JP2842291 A JP 2842291A JP H04266883 A JPH04266883 A JP H04266883A
- Authority
- JP
- Japan
- Prior art keywords
- dioxolane
- compound
- trans
- formula
- stereoisomers
- 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
- 238000000034 method Methods 0.000 title description 18
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 16
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 150000002012 dioxanes Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 24
- 150000000093 1,3-dioxanes Chemical class 0.000 abstract description 10
- 125000004429 atom Chemical group 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000470 constituent Chemical group 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000002876 beta blocker Substances 0.000 description 2
- 229940097320 beta blocking agent Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000000185 1,3-diols Chemical class 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical group C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- BOHGAOWOIJMTPZ-UHFFFAOYSA-N 1,3-dioxolan-4-ylmethanol Chemical compound OCC1COCO1 BOHGAOWOIJMTPZ-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- -1 phosphoryl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は１，３ −ジオキソラン
又は１，３ −ジオキサン誘導体の立体異性体の分離法
に関するものであり、本発明の異性体分離方法は医薬を
中心とするファインケミストリーの分野で利用すること
ができる。[Field of Industrial Application] The present invention relates to a method for separating stereoisomers of 1,3-dioxolane or 1,3-dioxane derivatives. It can be used in the field.
【０００２】0002
【従来の技術及び発明が解決しようとする課題】１，３
−ジオキソラン及び１，３ −ジオキサン誘導体は、
各々１，２ −及び１，３ −ジオールの保護された化
合物として、医薬を中心とする各種ファインケミカルの
中間体として、工業的に重要な位置を占める。しかし、
通常の化学合成では異性体の混合物となることが多く、
特に光学異性体は１：１の混合物、いわゆるラセミ体と
なる。言うまでもなく、殆どの使用目的において純品と
して用いることが望ましいが、これらを分離する良い方
法がなかった。例をあげれば、下記一般式（１）[Prior art and problems to be solved by the invention] 1, 3
-dioxolane and 1,3-dioxane derivatives are
As protected compounds of 1,2- and 1,3-diols, they occupy an industrially important position as intermediates for various fine chemicals, mainly pharmaceuticals. but,
Normal chemical synthesis often results in a mixture of isomers.
In particular, optical isomers form a 1:1 mixture, a so-called racemate. Needless to say, for most purposes it is desirable to use pure products, but there has been no good way to separate them. For example, the following general formula (1)
【０００３】0003
【化１】[Chemical formula 1]
【０００４】で表される光学活性な２，２ −ジメチル
−１，３ −ジオキソラン−４−メタノールは、β−遮
断剤など、各種の光学活性体より成る医薬の中間体とし
て利用価値の高いものである。このラセミ体はグリセリ
ンから安価に導くことができるが、良い分割法がないた
め、光学活性体はマンノースからの多段階化学処理、あ
るいはラセミ体からの生物学的分割（特開昭６３−９４
９８６ 号） 等の方法で調製している。しかし、これ
らの方法は多段階の製造工程を経るためコストが高い、
光学異性体の一方しか得られない、光学純度が不十分で
あるなどの問題があった。この例からも分るように、１
，３−ジオキソラン及び１，３ −ジオキサン誘導体の
、光学異性体を含む立体異性体を効率的に分割できる方
法が求められていた。The optically active 2,2-dimethyl-1,3-dioxolane-4-methanol represented by [0004] has high utility value as an intermediate for pharmaceuticals composed of various optically active substances, such as β-blockers. It is. This racemic form can be obtained inexpensively from glycerin, but since there is no good resolution method, the optically active form can be obtained by multi-step chemical treatment from mannose or by biological resolution from the racemic form (Japanese Patent Application Laid-Open No. 63-94
No. 986). However, these methods are expensive due to the multi-step manufacturing process.
There were problems such as only one of the optical isomers being obtained and the optical purity being insufficient. As you can see from this example, 1
, 3-dioxolane and 1,3-dioxane derivatives, there has been a need for a method that can efficiently resolve stereoisomers, including optical isomers.
【０００５】[0005]
【課題を解決するための手段】本発明者は１，３ −ジ
オキソラン及び１，３ −ジオキサン誘導体の立体異性
体を分離することの重要性を考え、鋭意検討を行なった
結果、ｔｒａｎｓ −１，２ −二置換環状化合物との
クラスレート化合物形成を利用することにより、上記立
体異性体の分離が効果的に達成されることを見出し、本
発明に到達した。[Means for Solving the Problems] The present inventor considered the importance of separating stereoisomers of 1,3-dioxolane and 1,3-dioxane derivatives, and as a result of intensive studies, trans -1, The inventors have discovered that the separation of the stereoisomers can be effectively achieved by utilizing the formation of a clathrate compound with a 2-disubstituted cyclic compound, and have arrived at the present invention.
【０００６】即ち本発明は、１，３ −ジオキソラン又
は１，３ −ジオキサン誘導体の立体異性体の混合物を
ｔｒａｎｓ−１，２ −二置換環状化合物を用いて分
離することを特徴とする異性体分離法を提供するもので
ある。That is, the present invention is an isomer separation method characterized in that a mixture of stereoisomers of 1,3-dioxolane or 1,3-dioxane derivatives is separated using a trans-1,2-disubstituted cyclic compound. It provides law.
【０００７】本発明にいう１，３ −ジオキソラン又は
１，３ −ジオキサン誘導体とは、各々、次の式（Ｉ）
又は（ＩＩ）[0007] The 1,3-dioxolane or 1,3-dioxane derivative referred to in the present invention is represented by the following formula (I).
or (II)
【０００８】[0008]
【化２】[Case 2]
【０００９】で示される骨格を有し、少なくとも４−位
以上の位置に１個以上の置換基を有し、立体異性体を有
するものである。この４−位以上の位置の置換基の数、
種類には特に制限はない。また２−位の炭素は、いかな
る構造をとっても良いが、以下に示すような構造が一般
的である。It has the skeleton shown below, has one or more substituents at least at the 4-position and above, and has stereoisomers. The number of substituents at the 4-position and above,
There are no particular restrictions on the type. Further, the carbon at the 2-position may have any structure, but the structure shown below is common.
【００１０】0010
【化３】[Chemical formula 3]
【００１１】一方、４位以上の位置の置換基はいかなる
ものが何個結合していても良いが、例えば■ アルキ
ル基（置換基、不飽和結合を持っていても良い）中でも
重要性の高いものは−ＣＨ２ＯＲ３， −ＣＨ２ＮＨＲ
３ （Ｒ３はＨ 、アルキル基、アリール基、アシル基
、ホスホニル基、ホスホリル基又はスルホニル基であり
、置換基、不飽和結合を有しても良い。）■ アリー
ル基（置換基をもっていても良い）■アシル基、カルボ
キシル基、アルコキシカルボニル基等が重要である。中
でも工業的有用性の高い化合物は、２，２ −ジメチル
−１，３ −ジオキソラン−４−メタノール及びそのメ
タノール残基のアルコール性プロトンを芳香族基で置換
したものであり、これらは各種光学活性化合物、例えば
β−遮断剤と呼ばれる一連の医薬を合成するための中間
体となる。On the other hand, any number of substituents at the 4th or higher positions may be bonded, but for example: -CH2OR3, -CH2NHR
3 (R3 is H, an alkyl group, an aryl group, an acyl group, a phosphonyl group, a phosphoryl group, or a sulfonyl group, and may have a substituent or an unsaturated bond.)■ Aryl group (which may have a substituent) ) ■ Acyl groups, carboxyl groups, alkoxycarbonyl groups, etc. are important. Among them, compounds with high industrial utility are 2,2-dimethyl-1,3-dioxolane-4-methanol and those in which the alcoholic proton of the methanol residue is substituted with an aromatic group, and these have various optical activities. It serves as an intermediate for the synthesis of compounds such as a series of drugs called β-blockers.
【００１２】本発明にいうｔｒａｎｓ −１，２ −二
置換環状化合物とは、次の式（ＩＩＩ）で示される化合
物である。The trans-1,2-disubstituted cyclic compound referred to in the present invention is a compound represented by the following formula (III).
【００１３】[0013]
【化４】[C4]
【００１４】式中の環状構造は、原子数３乃至７個より
成るものであり、２個の炭素以外の構成原子は何であっ
ても良い。また該環状構造上に置換基を有しても良い。The cyclic structure in the formula is composed of 3 to 7 atoms, and the constituent atoms other than the two carbon atoms may be any. Further, the cyclic structure may have a substituent.
【００１５】式（ＩＩＩ）中のＲ４は、炭素数３０以下
より成る原子団であり、ヘテロ原子を含んでも良い。R4 in formula (III) is an atomic group consisting of 30 or less carbon atoms, and may contain a hetero atom.
【００１６】本発明に使用するｔｒａｎｓ −１，２
−二置換環状化合物は、式（ＩＩＩ） で示される構造
を有し、分離対象となる１，３ −ジオキソラン又は１
，３ −ジオキサン誘導体とクラスレート化合物を形成
するものであることが望ましい。但し、クラスレート化
合物の作り易さはその化学構造に大きく依存し、好まし
くはＲ４中、あるいは環上に、更に剛直な環状原子団を
含むものである。また、Ｒ４中には、更に、分離対象と
する化合物と相互作用するための極性基を含むことが望
ましい。trans-1,2 used in the present invention
-The disubstituted cyclic compound has a structure represented by formula (III), and the 1,3-dioxolane or 1 to be separated.
, 3-dioxane derivatives to form a clathrate compound. However, the ease with which a clathrate compound can be prepared depends largely on its chemical structure, and preferably contains a more rigid cyclic atomic group in R4 or on the ring. Further, it is desirable that R4 further contains a polar group for interacting with the compound to be separated.
【００１７】分離の対象が光学異性体である場合には、
言うまでもなく、該ｔｒａｎｓ −１，２ −二置換環
状化合物は光学活性体でなければならない。光学活性な
該化合物は、いかなる方法で得ても良いが、酒石酸から
誘導するのが、その容易さと、原料の入手し易さにおい
て、すぐれた方法である（例えば実施例中で用いられて
いる式（ａ）で表される化合物は酒石酸より導かれるも
のである） 。[0017] When the targets of separation are optical isomers,
Needless to say, the trans -1,2-disubstituted cyclic compound must be optically active. The optically active compound may be obtained by any method, but deriving it from tartaric acid is an excellent method in terms of ease of use and availability of raw materials (for example, the method used in the examples). The compound represented by formula (a) is derived from tartaric acid).
【００１８】本発明の方法におけるクラスレート化合物
の製造にはいかなる方法を用いても良い。最も一般的な
方法は分離対象となる化合物と、該環状化合物の適当量
を溶媒に溶解し、温度変化、溶媒蒸発、あるいは貧溶媒
の添加などによってクラスレート化合物を析出させる。
あるいは分離対象となる混合物自体を溶媒として用いる
こともできる。また両者が固体であっても、単に混合に
よってクラスレート化合物を生成する場合もある。また
両成分を無溶媒あるいは溶媒存在下に超高圧をかけて結
晶化させることもでき、このような場合には常圧下とは
異なった結晶を生成することもあり得る。このようにし
て得られた固体が、出発物質とは異なった物理的性状（
融点や結晶形など）を示し、両出発物質を含むものであ
れば、クラスレート化合物を形成していることがわかる
。該クラスレート化合物から、分離対象とする化合物を
回収する方法はいかなるものであっても良いが、最も簡
便なのは、減圧蒸留によって、沸点の低い成分のみを別
の容器に分離することである。こうした操作によって、
目的とする１，３ −ジオキソラン又は１，３ −ジオ
キサン誘導体の中の特定の異性体の含量を高めることが
できる。また、純度をより高めたい場合には、クラスレ
ート化合物の段階で再結晶するのが良い方法であるが、
回収後に再結晶操作を適用できる場合もある。またクラ
スレート化合物の形成によって、不要な異性体を除去す
ることも可能である。Any method may be used to produce the clathrate compound in the method of the present invention. The most common method is to dissolve the compound to be separated and an appropriate amount of the cyclic compound in a solvent, and precipitate the clathrate compound by changing temperature, evaporating the solvent, or adding a poor solvent. Alternatively, the mixture itself to be separated can be used as a solvent. Furthermore, even if both are solids, a clathrate compound may be produced simply by mixing them. Further, both components can be crystallized without a solvent or in the presence of a solvent by applying ultra-high pressure, and in such a case, different crystals may be produced than under normal pressure. The solid obtained in this way has different physical properties (
melting point, crystal form, etc.), and if it contains both starting materials, it is understood that it forms a clathrate compound. Any method may be used to recover the compound to be separated from the clathrate compound, but the simplest method is to separate only the components with a low boiling point into a separate container by vacuum distillation. Through these operations,
The content of a specific isomer in the target 1,3-dioxolane or 1,3-dioxane derivative can be increased. In addition, if you want to further increase the purity, a good method is to recrystallize at the clathrate compound stage.
In some cases, a recrystallization operation can be applied after recovery. It is also possible to remove unwanted isomers by forming clathrate compounds.
【００１９】また該ｔｒａｎｓ −１，２ −二置換環
状化合物による分離は、上記クラスレート化合物を経る
ものとは限らず、例えばこのｔｒａｎｓ −１，２ −
二置換環状化合物を何らかの方法によってカラム充填剤
とし、これを用いてガスあるいは液体クロマトグラフィ
ーを行うなど、様々な実施態様が可能である。Furthermore, the separation using the trans -1,2-disubstituted cyclic compound is not limited to the method using the above-mentioned clathrate compound; for example, the trans -1,2-disubstituted cyclic compound
Various embodiments are possible, such as using a disubstituted cyclic compound as a column packing material by some method and performing gas or liquid chromatography.
【００２０】[0020]
【作用】本発明の方法が、１，３ −ジオキソラン及び
１，３ −ジオキサン誘導体の異性体分離に適している
理由は明らかでないが、本発明で用いられるｔｒａｎｓ
−１，２ −二置換環状化合物が、１，３ −ジオキ
ソラン環又は１，３ −ジオキサン環と相互作用し易い
大きさと極性を持っており、クラスレート化合物を形成
し易いものと考えられる。[Operation] Although it is not clear why the method of the present invention is suitable for isomer separation of 1,3-dioxolane and 1,3-dioxane derivatives, the trans
It is considered that the -1,2-disubstituted cyclic compound has a size and polarity that make it easy to interact with the 1,3-dioxolane ring or the 1,3-dioxane ring, and thus easily forms a clathrate compound.
【００２１】[0021]
【発明の効果】本発明の方法に用いるｔｒａｎｓ −１
，２ −二置換環状化合物は、例えば酒石酸などから簡
単に導くことができ、また繰り返し利用することができ
る。従って本発明は工業的に有用な１，３ −ジオキソ
ラン及び１，３ −ジオキサン誘導体を高い純度で多量
に供給することを可能とするものである。[Effect of the invention] trans -1 used in the method of the present invention
, 2-disubstituted cyclic compounds can be easily derived from, for example, tartaric acid, and can be used repeatedly. Therefore, the present invention makes it possible to supply industrially useful 1,3-dioxolane and 1,3-dioxane derivatives in large quantities with high purity.
【００２２】[0022]
【実施例】以下、実施例によって本発明を具体的に説明
するが、本発明がこれらに限定されるものでないことは
言うまでもない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but it goes without saying that the present invention is not limited thereto.
【００２３】実施例１ 次式（１）Example 1 The following formula (1)
【００２４】[0024]
【化５】[C5]
【００２５】で表される２，２ −ジメチル−１，３−
ジオキソラン−４−メタノールのラセミ体５．５ｇと、
次式（ａ）2,2-dimethyl-1,3- represented by
5.5 g of racemic dioxolane-4-methanol,
The following formula (a)
【００２６】[0026]
【化６】[C6]
【００２７】で表される（−）−ｔｒａｎｓ −１，
２ −二置換環状化合物１０．０ｇとをトルエン２０ｍ
ｌ、ｎ−ヘキサン２０ｍｌに混合し、室温に一日放置し
たところ、無色の針状晶を生成した。これを２回再結晶
し、生成した結晶を濾別し、クラスレート化合物８．５
ｇを得た。
〔α〕Ｄ −５３．０５゜（ｃ＝０．３５２， ＣＨＣ
ｌ３） 。(-)-trans −1,
10.0 g of the 2-disubstituted cyclic compound and 20 m of toluene
When mixed with 20 ml of l,n-hexane and left at room temperature for one day, colorless needle-like crystals were produced. This was recrystallized twice, and the formed crystals were separated by filtration, and the clathrate compound 8.5
I got g. [α]D -53.05° (c=0.352, CHC
l3).
【００２８】この結晶を蒸留装置に仕込み、真空ポンプ
で減圧しながら １１０℃に加熱することにより、１．
０４ｇの（＋）−２，２ −ジメチル−１，３ −ジオ
キソラン−４−メタノールを得た。〔α〕Ｄ は＋１１
．３９゜（ｃ＝１．０３， ＣＨ３ＯＨ）であり、文献
値との比較（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．， １０２
， ６３０４（１９８０）） から、光学純度１００
％に相当した。[0028] The crystals were charged into a distillation apparatus and heated to 110°C while reducing the pressure with a vacuum pump.1.
04 g of (+)-2,2-dimethyl-1,3-dioxolane-4-methanol were obtained. [α]D is +11
．． 39° (c=1.03, CH3OH), compared with literature values (J. Am. Chem. Soc., 102
, 6304 (1980)), optical purity 100
%.
【００２９】実施例２ 次式（２）Example 2 The following formula (2)
【００３０】[0030]
【化７】[C7]
【００３１】で表されるスピロ［シクロヘキサン−１，
２’−〔１，３ 〕ジオキソラン−４’−メタノール］
のラセミ体２．０ ｇと、前記式（ａ） で表される（
−）−ｔｒａｎｓ −１，２ −二置換環状化合物３．
０ ｇをトルエン１０ｍｌ、ｎ−ヘキサン１０ｍｌに溶
解し、一昼夜放置し、２．７５ｇの白色粉末を得た。こ
れを再結晶し、１．７８ｇの精製クラスレート化合物を
得た。これを実施例１と同様に、１６５ ℃で分解した
ところ０．２ ｇの（＋）−スピロ［シクロヘキサン−
１，２’−〔１，３ 〕ジオキソラン−４’−メタノー
ル］を得た。Spiro[cyclohexane-1,
2'-[1,3]dioxolane-4'-methanol]
and 2.0 g of racemic body of (
-)-trans -1,2-disubstituted cyclic compound 3.
0 g was dissolved in 10 ml of toluene and 10 ml of n-hexane, and allowed to stand overnight to obtain 2.75 g of white powder. This was recrystallized to obtain 1.78 g of purified clathrate compound. When this was decomposed at 165°C in the same manner as in Example 1, 0.2 g of (+)-spiro[cyclohexane-
1,2'-[1,3]dioxolane-4'-methanol] was obtained.
【００３２】〔α〕Ｄ は＋７．６５゜（ｃ＝０．８１
， ＣＨ３ＯＨ）であり、文献値との比較（Ｒ．Ｒ Ｓ
ｃｈｍｉｄｔｅｔ．ａｌ．， Ｊ．Ｃａｒｂｏｈｙｄｒ
．Ｒｅｓ．， ３，６７（１９８４）） から、光学純
度１００ ％に相当した。[α]D is +7.65° (c=0.81
, CH3OH) and comparison with literature values (R.R S
chmidtet. al. , J. Carbohydr
．． Res. , 3, 67 (1984)), it corresponded to an optical purity of 100%.
Claims (1)
−ジオキサン誘導体の立体異性体の混合物を ｔｒａｎ
ｓ−１，２ −二置換環状化合物を用いて分離すること
を特徴とする異性体分離法。[Claim 1] 1,3-dioxolane or 1,3
- tran a mixture of stereoisomers of dioxane derivatives
An isomer separation method characterized by separation using an s-1,2-disubstituted cyclic compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02842291A JP3210683B2 (en) | 1991-02-22 | 1991-02-22 | Isomer separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02842291A JP3210683B2 (en) | 1991-02-22 | 1991-02-22 | Isomer separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04266883A true JPH04266883A (en) | 1992-09-22 |
| JP3210683B2 JP3210683B2 (en) | 2001-09-17 |
Family
ID=12248224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02842291A Expired - Fee Related JP3210683B2 (en) | 1991-02-22 | 1991-02-22 | Isomer separation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3210683B2 (en) |
-
1991
- 1991-02-22 JP JP02842291A patent/JP3210683B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3210683B2 (en) | 2001-09-17 |
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