JP2001181216A - Method for producing optically active unsaturated hydrocarbons or their halogenated compounds - Google Patents
Method for producing optically active unsaturated hydrocarbons or their halogenated compoundsInfo
- Publication number
- JP2001181216A JP2001181216A JP36922599A JP36922599A JP2001181216A JP 2001181216 A JP2001181216 A JP 2001181216A JP 36922599 A JP36922599 A JP 36922599A JP 36922599 A JP36922599 A JP 36922599A JP 2001181216 A JP2001181216 A JP 2001181216A
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- Japan
- Prior art keywords
- optically active
- compound
- group
- unsaturated hydrocarbon
- halogen
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学活性な不飽和
炭化水素類又はそのハロゲン置換化合物の製造法に関す
るものであり、これらの化合物は医薬や農薬を中心とす
るファインケミストリーの分野で高い利用価値を有する
ものである。The present invention relates to a process for producing an optically active unsaturated hydrocarbon or a halogen-substituted compound thereof, and these compounds are highly utilized in the field of fine chemistry mainly for pharmaceuticals and agricultural chemicals. It has value.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】光学活
性な不飽和炭化水素類又はそのハロゲン置換化合物は、
近年、医薬や農薬を中心とする各種ファインケミカルの
合成原料として工業的に重要な化合物となっており、光
学活性体を容易に得る方法が求められていた。しかし、
通常の化学合成においては、光学異性体の等量混合物、
いわゆるラセミ体を与え、光学活性体を得るには通常か
なり困難を伴う。BACKGROUND OF THE INVENTION Optically active unsaturated hydrocarbons or halogen-substituted compounds thereof are:
In recent years, it has become an industrially important compound as a raw material for synthesizing various fine chemicals, mainly pharmaceuticals and agricultural chemicals, and a method for easily obtaining an optically active substance has been demanded. But,
In normal chemical synthesis, an equal mixture of optical isomers,
It is usually quite difficult to give a so-called racemate and obtain an optically active form.
【０００３】従来、光学活性な不飽和炭化水素類の合成
は容易ではなく、報告例が少ない。例えば、光学活性な
３−フェニルシクロヘキセンは８ステップを経て合成さ
れている。また、一般的な光学活性な不飽和炭化水素類
を入手する方法としては各種の光学活性な金属触媒を使
用した不斉合成法が挙げられるが、代表的な例として、
（ａ）光学活性なニッケル系触媒を用いた不斉合成によ
る方法[J.Chem.Soc.,Chem. Commun.(1980),(20),937; T
etrahedron(1986),42(7),2043; Organometallics(199
1),10(10),3425]、（ｂ）モリブデン−タングステン錯
体を触媒として用いた光学活性な不飽和炭化水素類の閉
環反応による方法[WO9524366]、（ｃ）光学活性なリン
系触媒を用いた不斉合成反応による方法[J.Org.Chem.(1
985),50(10),1781]などが知られている。Hitherto, the synthesis of optically active unsaturated hydrocarbons has not been easy and there have been few reports. For example, optically active 3-phenylcyclohexene is synthesized through eight steps. In addition, examples of a method for obtaining general optically active unsaturated hydrocarbons include an asymmetric synthesis method using various optically active metal catalysts.
(A) Asymmetric synthesis using an optically active nickel-based catalyst [J. Chem. Soc., Chem. Commun. (1980), (20), 937; T
etrahedron (1986), 42 (7), 2043; Organometallics (199
1), 10 (10), 3425], (b) a method by a ring-closing reaction of an optically active unsaturated hydrocarbon using a molybdenum-tungsten complex as a catalyst [WO9524366], (c) an optically active phosphorus-based catalyst. Method by the asymmetric synthesis reaction used [J. Org.
985), 50 (10), 1781].
【０００４】しかし、これらの方法では合成工程が長い
例や高価な金属錯体触媒を使用する例、毒性の極めて高
い化合物を使用する例など、いずれも光学活性な不飽和
炭化水素類を生産する方法として好ましくない。[0004] However, in these methods, a method for producing an optically active unsaturated hydrocarbon, such as an example in which the synthesis step is long, an example in which an expensive metal complex catalyst is used, an example in which an extremely toxic compound is used, and the like. Is not preferred.
【０００５】また、光学活性な不飽和炭化水素類のハロ
ゲン置換化合物を入手するための方法はあまり知られて
おらず、僅かにラセミ体を光学活性な固定相を用いたガ
スクロマトグラフィーにより分離するなどの方法が知ら
れているにすぎない。しかし、光学活性なハロゲン化不
飽和脂肪族炭化水素類を大量に生産する方法としては好
ましくない。[0005] Further, a method for obtaining a halogen-substituted compound of an optically active unsaturated hydrocarbon is not well known, and a slightly racemic compound is separated by gas chromatography using an optically active stationary phase. Such methods are only known. However, it is not preferable as a method for producing optically active halogenated unsaturated aliphatic hydrocarbons in large quantities.
【０００６】上記の問題に対処して、本発明が解決しよ
うとする課題は、医薬や農薬を中心とする各種ファイン
ケミカルの合成原料として重要な化合物である光学活性
な不飽和炭化水素類又はそのハロゲン置換化合物を容易
に得る方法を提供することである。[0006] In view of the above-mentioned problems, an object of the present invention is to provide an optically active unsaturated hydrocarbon or a halogen thereof, which is an important compound as a raw material for synthesizing various fine chemicals, mainly pharmaceuticals and agricultural chemicals. An object is to provide a method for easily obtaining a substituted compound.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記の課題
を解決するため、鋭意研究を重ねた結果、本発明に至っ
た。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.
【０００８】すなわち、本発明は、不飽和炭化水素類又
はそのハロゲン置換化合物のラセミ体と、光学活性な酒
石酸誘導体とを混合して、不飽和炭化水素類又はそのハ
ロゲン置換化合物の光学活性体と光学活性な酒石酸誘導
体との包接化合物を形成させ、この包接化合物から不飽
和炭化水素類又はそのハロゲン置換化合物の光学活性体
を分離して得ることを特徴とする、光学活性な不飽和炭
化水素類又はそのハロゲン置換化合物の製造法である。That is, the present invention relates to a method of mixing a racemate of an unsaturated hydrocarbon or a halogen-substituted compound thereof with an optically active tartaric acid derivative to form an optically active form of an unsaturated hydrocarbon or a halogen-substituted compound thereof. Forming an clathrate compound with an optically active tartaric acid derivative and separating the clathrate from an optically active form of an unsaturated hydrocarbon or a halogen-substituted compound thereof to obtain an optically active unsaturated carbon This is a method for producing hydrogens or halogen-substituted compounds thereof.
【０００９】[0009]
【発明の実施の形態】本発明において、不飽和炭化水素
類として、シクロヘキセン誘導体、ノルボルネン誘導
体、あるいは下記の式（１）又は（２）で表される化合
物が挙げられるが、必ずしもこれらに限定されるもので
はなく、ここで用いられる光学活性な酒石酸誘導体であ
るホスト化合物と包接化合物を形成するものであればい
かなるものでもよい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of unsaturated hydrocarbons include cyclohexene derivatives, norbornene derivatives, and compounds represented by the following formulas (1) or (2), but are not necessarily limited thereto. Instead, any compound may be used as long as it forms an inclusion compound with the host compound which is the optically active tartaric acid derivative used here.
【００１０】[0010]
【化６】 Embedded image
【００１１】シクロヘキセン誘導体の具体例として、下
記の式（６）〜（９）で表される化合物が挙げられ、ノ
ルボルネン誘導体の具体例として、下記の式（10）で表
される化合物が挙げられる。Specific examples of the cyclohexene derivative include compounds represented by the following formulas (6) to (9). Specific examples of the norbornene derivative include a compound represented by the following formula (10). .
【００１２】[0012]
【化７】 Embedded image
【００１３】また、不飽和炭化水素類のハロゲン置換化
合物として、下記の式（３）で表される化合物が挙げら
れる。The halogen-substituted compounds of unsaturated hydrocarbons include compounds represented by the following formula (3).
【００１４】[0014]
【化８】 Embedded image
【００１５】（式中、Ｘはフッ素基、クロル基、ブロム
基のうちのいずれかを、Ｒは水素原子、メチル基、エチ
ル基、プロピル基、イソプロピル基、フッ素基、クロル
基、ブロム基のいずれかを示す。） 一方、本発明で用いられるホスト化合物は、不飽和炭化
水素類又はそのハロゲン置換化合物の光学活性体と包接
化合物を形成するもので、分離能、入手のし易さ、取り
扱いのし易さ、後工程の処理などから、好ましくは光学
活性な酒石酸誘導体であり、より好ましくは下記の式
（４）又は（５）で表される光学活性な酒石酸誘導体で
ある。(In the formula, X represents any one of a fluorine group, a chloro group and a bromo group, and R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a fluorine group, a chloro group and a bromo group. On the other hand, the host compound used in the present invention forms an inclusion compound with an optically active substance of an unsaturated hydrocarbon or a halogen-substituted compound thereof, and has a resolving power, easy availability, From the viewpoint of ease of handling and subsequent treatment, an optically active tartaric acid derivative is preferable, and an optically active tartaric acid derivative represented by the following formula (4) or (5) is more preferable.
【００１６】[0016]
【化９】 Embedded image
【００１７】（式中、Ｒ1及びＲ2は同一又は異なって、
水素原子、メチル基又はエチル基を示す。Ａｒはフェニ
ル基、トリル基又はナフチル基を示す。ｎ＝４，５又は
６である。） 特に、上記の式（５）で表される光学活性な酒石酸誘導
体は分離能が高い。また、上記の式（４）及び（５）で
表される光学活性な酒石酸誘導体は光学活性な酒石酸か
ら容易に合成できるので、安価に得られ、さらに再利用
も可能である。(Wherein R 1 and R 2 are the same or different,
Represents a hydrogen atom, a methyl group or an ethyl group. Ar represents a phenyl group, a tolyl group or a naphthyl group. n = 4, 5 or 6. In particular, the optically active tartaric acid derivative represented by the above formula (5) has high separation ability. Further, the optically active tartaric acid derivatives represented by the above formulas (4) and (5) can be easily synthesized from optically active tartaric acid, and thus can be obtained at low cost and can be reused.
【００１８】本発明において、不飽和炭化水素類又はそ
のハロゲン置換化合物の光学活性体と光学活性な酒石酸
誘導体との包接化合物を形成させるためには、いかなる
方法を用いてもよい。例えば、ラセミ体の不飽和炭化水
素類又はそのハロゲン置換化合物と光学活性な酒石酸誘
導体を２：１から１：４のモル比で、必要ならば、加温
下に適切な溶媒に溶解し、冷却、又は溶解度の低い溶媒
を徐々に加えることにより、包接化合物の結晶を得るこ
とができる。また、無溶媒下で混合することによって、
包接化合物が形成することもある。In the present invention, any method may be used for forming an clathrate compound of an optically active unsaturated hydrocarbon or a halogen-substituted compound thereof with an optically active tartaric acid derivative. For example, a racemic unsaturated hydrocarbon or a halogen-substituted compound thereof and an optically active tartaric acid derivative are dissolved in a suitable solvent at a molar ratio of 2: 1 to 1: 4 if necessary while heating, and then cooled. Alternatively, by gradually adding a solvent having low solubility, crystals of the clathrate compound can be obtained. Also, by mixing under no solvent,
Inclusion compounds may form.
【００１９】包接化合物から不飽和炭化水素類又はその
ハロゲン置換化合物の光学活性体を取得する方法は、い
かなる方法であってもよい。例えば、包接化合物を加熱
することにより不飽和炭化水素類又はそのハロゲン置換
化合物の光学活性体と光学活性な酒石酸誘導体とを分離
する方法、包接化合物をカラムクロマトグラフィー処理
することにより不飽和炭化水素類又はそのハロゲン置換
化合物の光学活性体と光学活性な酒石酸誘導体とを分離
する方法、包接化合物中の不飽和炭化水素類又はそのハ
ロゲン置換化合物の光学活性体をメタノールやアセトン
など他の化合物に置換することによって不飽和炭化水素
類又はそのハロゲン置換化合物の光学活性体を得る方法
などがある。The method for obtaining an optically active compound of an unsaturated hydrocarbon or a halogen-substituted compound thereof from the clathrate may be any method. For example, a method of separating an optically active substance of an unsaturated hydrocarbon or a halogen-substituted compound thereof from an optically active tartaric acid derivative by heating an inclusion compound, and a method of separating an unsaturated hydrocarbon by column chromatography of an inclusion compound. A method for separating an optically active form of hydrogens or a halogen-substituted compound thereof from an optically active tartaric acid derivative, and the use of an unsaturated hydrocarbon or an optically active form of the halogen-substituted compound in an inclusion compound with another compound such as methanol or acetone To obtain an optically active compound of an unsaturated hydrocarbon or a halogen-substituted compound thereof.
【００２０】また、包接化合物の段階で再結晶を繰り返
すか、又は包接化合物から不飽和炭化水素類又はそのハ
ロゲン置換化合物の光学活性体を分離した後、再度、光
学活性な酒石酸誘導体を用いて包接化合物を形成させる
ことによって、得られる不飽和炭化水素類又はそのハロ
ゲン置換化合物の光学活性体の光学純度を向上させるこ
とも可能である。Further, recrystallization is repeated at the stage of the clathrate compound, or an optically active compound of an unsaturated hydrocarbon or a halogen-substituted compound thereof is separated from the clathrate compound, and then an optically active tartaric acid derivative is used again. By forming the clathrate compound by heating, it is also possible to improve the optical purity of the optically active isomer of the obtained unsaturated hydrocarbon or its halogen-substituted compound.
【００２１】[0021]
【作用】本発明の方法が不飽和炭化水素類又はそのハロ
ゲン置換化合物の光学活性体の製造に適している理由は
明確ではないが、本発明で用いられる光学活性な酒石酸
誘導体が、不飽和炭化水素類又はそのハロゲン置換化合
物と相互作用し易い大きさと極性を持っており、包接化
合物を形成し易いものと考えられる。さらに、光学活性
な酒石酸誘導体の立体構造によって、不飽和炭化水素類
又はそのハロゲン置換化合物の光学異性体の一方のみと
選択的に包接化合物を形成するものと考えられる。The reason why the method of the present invention is suitable for the production of an optically active substance of an unsaturated hydrocarbon or a halogen-substituted compound thereof is not clear, but the optically active tartaric acid derivative used in the present invention may be an unsaturated hydrocarbon. It has a size and polarity that easily interacts with hydrogens or a halogen-substituted compound thereof, and is considered to easily form an inclusion compound. Further, it is considered that an inclusion compound is selectively formed only with one of the optical isomers of unsaturated hydrocarbons or a halogen-substituted compound thereof depending on the stereostructure of the optically active tartaric acid derivative.
【００２２】[0022]
【実施例】以下、実施例によって本発明をさらに具体的
に説明するが、本発明はこれらに限定されるものではな
い。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００２３】実施例１ 下記の式（11）で表される酒石酸誘導体の（Ｒ，Ｒ）−
（−）体(3.00ｇ、6.1mmol)と上記式(６)で表される３
−メチルシクロヘキセンのラセミ体(0.58ｇ、6.1mmol)
をジエチルエーテル15mlに溶解した後、12時間放置する
と、２：１包接結晶2.34ｇが得られた。得られた包接結
晶を減圧蒸留(20mmHg、120℃)することにより、光学活
性な（−）−３−メチルシクロヘキセン0.16ｇが53％の
収率で得られた。純品との比旋光度比較により得られた
光学活性な（−）−３−メチルシクロヘキセンの光学純
度を測定したところ、16％e.e.であった。同様の操作を
更に２回繰り返した結果、得られた光学活性な（−）−
３−メチルシクロヘキセンの光学純度は75％e.e.まで上
昇した。Example 1 (R, R)-of a tartaric acid derivative represented by the following formula (11)
(−)-Isomer (3.00 g, 6.1 mmol) and 3 represented by the above formula (6)
-Racemic methylcyclohexene (0.58 g, 6.1 mmol)
Was dissolved in 15 ml of diethyl ether and left for 12 hours to obtain 2.34 g of 2: 1 clathrate crystals. By distilling the obtained clathrate crystals under reduced pressure (20 mmHg, 120 ° C.), 0.16 g of optically active (−)-3-methylcyclohexene was obtained with a yield of 53%. The optical purity of the optically active (−)-3-methylcyclohexene obtained by comparing the specific rotation with the pure product was 16% ee. As a result of repeating the same operation two more times, the obtained optically active (-)-
The optical purity of 3-methylcyclohexene increased to 75% ee.
【００２４】[0024]
【化１０】 Embedded image
【００２５】実施例２ 実施例１と同様、上記の式(11)で表される酒石酸誘導体
の（Ｒ，Ｒ）−（−）体を用いて、上記の式（１）、
（２）、（７）、（８）、（９）、（10）で表される不
飽和炭化水素類のラセミ体から各々、光学活性体を得
た。結果を表１に示した。光学活性体の純品がないもの
に関しては旋光度（[α]D ）で示した。Example 2 In the same manner as in Example 1, using the (R, R)-(−)-form of the tartaric acid derivative represented by the above formula (11),
Optically active substances were obtained from the racemic unsaturated hydrocarbons represented by (2), (7), (8), (9) and (10). The results are shown in Table 1. The optically active substance without pure product was indicated by optical rotation ([α] D ).
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例３ 上記の式（11）で表される酒石酸誘導体の（Ｒ，Ｒ）−
（−）体(3.02ｇ、6.2mmol)と下記式（12）で表される
３−クロル−１−ブテンのラセミ体(0.54ｇ、6.0mmol)
をジエチルエーテル15ml中に溶解した。溶解後、４℃で
一晩放置して、包接化合物の結晶2.25ｇを得た。得られ
た包接結晶を減圧蒸留(20mmHg、120℃)することによ
り、光学活性な３−クロル−１−ブテン0.16ｇが得られ
た。同様の操作を更に２回繰り返した結果、得られた光
学活性な３−クロル−１−ブテンの光学純度は56％e.e.
まで上昇した。Example 3 (R, R)-of the tartaric acid derivative represented by the above formula (11)
Racemic (0.54 g, 6.0 mmol) of the (-) form (3.02 g, 6.2 mmol) and 3-chloro-1-butene represented by the following formula (12)
Was dissolved in 15 ml of diethyl ether. After dissolution, the mixture was allowed to stand at 4 ° C. overnight to obtain 2.25 g of inclusion compound crystals. The obtained clathrate crystals were distilled under reduced pressure (20 mmHg, 120 ° C.) to obtain 0.16 g of optically active 3-chloro-1-butene. As a result of repeating the same operation twice more, the optical purity of the obtained optically active 3-chloro-1-butene was 56% ee.
Up.
【００２８】[0028]
【化１１】 Embedded image
【００２９】[0029]
【発明の効果】本発明により、簡単な操作で、不飽和炭
化水素類又はそのハロゲン置換化合物の光学活性体が分
離できるようになった。また、本発明に用いる光学活性
な酒石酸誘導体は安価で入手が容易であり、かつ、繰り
返し使用できる。この結果、高い光学純度を有する光学
活性な不飽和炭化水素類又はそのハロゲン置換化合物を
大量かつ安価に得る製造を可能にするものである。According to the present invention, an optically active compound of an unsaturated hydrocarbon or a halogen-substituted compound thereof can be separated by a simple operation. Further, the optically active tartaric acid derivative used in the present invention is inexpensive, easily available, and can be used repeatedly. As a result, it is possible to produce an optically active unsaturated hydrocarbon having a high optical purity or a halogen-substituted compound thereof in a large amount at low cost.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 13/45 Ｃ０７Ｃ 13/45 17/395 17/395 21/02 21/02 // Ｃ０７Ｍ 7:00 Ｃ０７Ｍ 7:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C07C 13/45 C07C 13/45 17/395 17/395 21/02 21/02 // C07M 7:00 C07M 7:00
Claims (6)
化合物のラセミ体と、光学活性な酒石酸誘導体とを混合
して、不飽和炭化水素類又はそのハロゲン置換化合物の
光学活性体と光学活性な酒石酸誘導体との包接化合物を
形成させ、この包接化合物から不飽和炭化水素類又はそ
のハロゲン置換化合物の光学活性体を分離して得ること
を特徴とする、光学活性な不飽和炭化水素類又はそのハ
ロゲン置換化合物の製造法。A mixture of a racemate of an unsaturated hydrocarbon or a halogen-substituted compound thereof and an optically active tartaric acid derivative to form an optically active form of an unsaturated hydrocarbon or a halogen-substituted compound thereof and an optically active tartaric acid. Forming an inclusion compound with a derivative, and separating and obtaining an optically active form of an unsaturated hydrocarbon or a halogen-substituted compound thereof from the inclusion compound, wherein the optically active unsaturated hydrocarbon or A method for producing a halogen-substituted compound.
導体、ノルボルネン誘導体、あるいは下記の式（１）又
は（２）で表される化合物である請求項１記載の製造
法。 【化１】 2. The method according to claim 1, wherein the unsaturated hydrocarbon is a cyclohexene derivative, a norbornene derivative, or a compound represented by the following formula (1) or (2). Embedded image
が下記の式（３）で表される化合物である請求項１記載
の製造法。 【化２】 （式中、Ｘはフッ素基、クロル基、ブロム基のうちのい
ずれかを、Ｒは水素原子、メチル基、エチル基、プロピ
ル基、イソプロピル基、フッ素基、クロル基、ブロム基
のいずれかを示す。）3. The method according to claim 1, wherein the halogen-substituted compound of the unsaturated hydrocarbon is a compound represented by the following formula (3). Embedded image (In the formula, X represents any one of a fluorine group, a chloro group, and a bromo group, and R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a fluorine group, a chloro group, or a bromo group. Shown.)
（４）又は（５）で表される化合物である請求項１〜３
のいずれか一項に記載の製造法。 【化３】 （式中、Ｒ1及びＲ2は同一又は異なって、水素原子、メ
チル基又はエチル基を示す。Ａｒはフェニル基、トリル
基又はナフチル基を示す。ｎ＝４，５又は６である。）4. The optically active tartaric acid derivative is a compound represented by the following formula (4) or (5).
The production method according to any one of claims 1 to 4. Embedded image (In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group. Ar represents a phenyl group, a tolyl group or a naphthyl group. N = 4, 5 or 6.)
（６）〜（９）で表される化合物である請求項２記載の
製造法。 【化４】 5. The method according to claim 2, wherein the cyclohexene derivative is a compound represented by the following formulas (6) to (9). Embedded image
で表される化合物である請求項２記載の製造法。 【化５】 6. A norbornene derivative represented by the following formula (10):
The method according to claim 2, which is a compound represented by the formula: Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36922599A JP2001181216A (en) | 1999-12-27 | 1999-12-27 | Method for producing optically active unsaturated hydrocarbons or their halogenated compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36922599A JP2001181216A (en) | 1999-12-27 | 1999-12-27 | Method for producing optically active unsaturated hydrocarbons or their halogenated compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001181216A true JP2001181216A (en) | 2001-07-03 |
Family
ID=18493896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36922599A Pending JP2001181216A (en) | 1999-12-27 | 1999-12-27 | Method for producing optically active unsaturated hydrocarbons or their halogenated compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001181216A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134184A (en) * | 2017-06-16 | 2019-01-04 | 中国科学院上海药物研究所 | Diterpene-kind compound, preparation method and the usage |
-
1999
- 1999-12-27 JP JP36922599A patent/JP2001181216A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134184A (en) * | 2017-06-16 | 2019-01-04 | 中国科学院上海药物研究所 | Diterpene-kind compound, preparation method and the usage |
| CN109134184B (en) * | 2017-06-16 | 2021-03-19 | 中国科学院上海药物研究所 | Diterpenoid compounds, preparation method and application thereof |
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