JPH0532649A - Production of optically active benzyl glycidyl ether - Google Patents
Production of optically active benzyl glycidyl etherInfo
- Publication number
- JPH0532649A JPH0532649A JP3280952A JP28095291A JPH0532649A JP H0532649 A JPH0532649 A JP H0532649A JP 3280952 A JP3280952 A JP 3280952A JP 28095291 A JP28095291 A JP 28095291A JP H0532649 A JPH0532649 A JP H0532649A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- glycidyl ether
- benzyloxy
- benzyl glycidyl
- formula
- 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
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- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は光学活性ベンジルグリシ
ジルエーテルの製法に関する。この化合物は、例えば光
学活性天然物等の合成の有用な中間体として知られてい
る（高野ら、Ｊ．Ｓｙｎ．Ｏｒｇ．Ｃｈｅｍ．Ｊｐ
ｎ．，４７，８１３（１９８９））。FIELD OF THE INVENTION The present invention relates to a method for producing an optically active benzyl glycidyl ether. This compound is known as a useful intermediate for the synthesis of, for example, optically active natural products (Takano et al., J. Syn. Org. Chem. Jp.
n. , 47, 813 (1989)).
【０００２】[0002]
【従来の技術】従来、光学活性ベンジルグリシジルエー
テルの製造経路としては、光学活性３−ベンジルオキシ
−１，２−プロパンジオールの１級水酸基をモノトシル
化した後、これを塩基処理してエポキシ化する方法が知
られている（高野ら、Ｈｅｔｅｒｏｃｙｃｌｅｓ，１
６，３８１（１９８１））。しかし、この方法において
は、モノトシル化の際に２級水酸基のトシル化された化
合物がわずかながら生成し、これが続く塩基処理によっ
て得られる光学活性ベンジルグリシジルエーテルの光学
純度を低下させる原因となっていた。2. Description of the Related Art Conventionally, as a production route of optically active benzyl glycidyl ether, the primary hydroxyl group of optically active 3-benzyloxy-1,2-propanediol is monotosylated and then treated with base to be epoxidized. Methods are known (Takano et al., Heterocycles, 1
6, 381 (1981)). However, in this method, a small amount of a compound tosylated with a secondary hydroxyl group is produced during monotosylation, which causes a decrease in the optical purity of the optically active benzyl glycidyl ether obtained by the subsequent base treatment. .
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の如き
光学純度の低下のない高純度光学活性ベンジルグリシジ
ルエーテルの製法を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a method for producing a highly pure optically active benzyl glycidyl ether, which is free from deterioration of optical purity as in the prior art.
【０００４】[0004]
【課題を解決するための手段】本発明は、光学活性３−
ベンジルオキシ−１，２−プロパンジオールをテトラハ
ロゲノメタン及びトリフェニルホスフィンと有機溶媒中
で反応させて光学活性ハロゲノヒドリン誘導体を得、次
いでこれを塩基処理することを特徴とする光学活性ベン
ジルグリシジルエーテルの製法である。The present invention provides an optically active 3-
Process for producing an optically active benzyl glycidyl ether, characterized in that benzyloxy-1,2-propanediol is reacted with tetrahalogenomethane and triphenylphosphine in an organic solvent to obtain an optically active halogenohydrin derivative, which is then treated with a base. Is.
【０００５】本発明の方法においては、穏やかな中性条
件下で光学活性３−ベンジルオキシ−１，２−プロパン
ジオールは、まず光学活性ハロゲノヒドリン誘導体へ変
換される。この際１級水酸基及び２級水酸基のいずれか
がハロゲンで置換され２種類の光学活性ハロゲノヒドリ
ン誘導体の混合物（光学活性１−ベンジルオキシ−３−
ハロゲノ−２−プロパノール及び光学活性３−ベンジル
オキシ−２−ハロゲノ−１−プロパノール）となるが、
続く塩基処理によりこれらは同一の立体構造をもつ光学
活性ベンジルグリシジルエーテルへ変換される。従っ
て、光学純度の低下が起こらず、極めて高純度の光学活
性ベンジルグリシジルエーテルが得られる。In the process of the present invention, the optically active 3-benzyloxy-1,2-propanediol is first converted into the optically active halogenohydrin derivative under mild neutral conditions. At this time, either the primary hydroxyl group or the secondary hydroxyl group is substituted with halogen, and a mixture of two kinds of optically active halogenohydrin derivatives (optically active 1-benzyloxy-3-
Halogeno-2-propanol and optically active 3-benzyloxy-2-halogeno-1-propanol),
By the subsequent base treatment, these are converted into optically active benzyl glycidyl ether having the same three-dimensional structure. Therefore, the optical purity does not decrease, and an extremely high-purity optically active benzyl glycidyl ether can be obtained.
【０００６】本発明は、下記スキームに従って進行す
る。下記スキームにおいて、Ｐｈはフェニル基、Ｘはハ
ロゲン原子をそれぞれ表わし、＊の符号はその炭素原子
が不斉炭素原子であることを示す。The present invention proceeds according to the following scheme. In the scheme below, Ph represents a phenyl group, X represents a halogen atom, and the symbol * indicates that the carbon atom is an asymmetric carbon atom.
【０００７】[0007]
【化１】 [Chemical 1]
【０００８】上記スキームにおいて、まず光学活性３−
ベンジルオキシ−１，２−プロパンジオール（Ｉ）をテ
トラハロゲノメタン及びトリフェニルホスフィンと有機
溶媒中で反応させて光学活性ハロゲノヒドリン誘導体混
合物（ＩＩ−１及びＩＩ−２）に変換する。テトラハロ
ゲノメタンとしては四フッ化炭素、四塩化炭素、四臭化
炭素等が挙げられるが、特に四塩化炭素と四臭化炭素が
好ましい。反応に際して、テトラハロゲノメタン及びト
リフェニルホスフィンの割合は、原料の光学活性３−ベ
ンジルオキシ−１，２−プロパンジオールに対して、そ
れぞれ１〜１．５当量がよく、特に高収率を得るために
は、それぞれ１．０２〜１．１５当量が好ましい。有機
溶媒としては非プロトン性の溶媒が用いられ、例えばク
ロロホルム、塩化メチレン、テトラヒドロフラン、エチ
ルエーテル等が好ましい。In the above scheme, the optically active 3-
Benzyloxy-1,2-propanediol (I) is converted to an optically active halogenohydrin derivative mixture (II-1 and II-2) by reacting with tetrahalogenomethane and triphenylphosphine in an organic solvent. Examples of the tetrahalogenomethane include carbon tetrafluoride, carbon tetrachloride and carbon tetrabromide, with carbon tetrachloride and carbon tetrabromide being particularly preferred. In the reaction, the ratio of tetrahalogenomethane and triphenylphosphine is preferably 1 to 1.5 equivalents, respectively, with respect to the optically active 3-benzyloxy-1,2-propanediol as a raw material, in order to obtain a particularly high yield. Is preferably 1.02 to 1.15 equivalents. An aprotic solvent is used as the organic solvent, and for example, chloroform, methylene chloride, tetrahydrofuran, ethyl ether and the like are preferable.
【０００９】上記反応において、反応温度は０〜５０℃
の範囲で行われるが、特に１０〜４０℃で行うと進行も
穏やかで収率も良いので好ましい。この温度範囲では、
反応は５〜８０時間で終了する。反応に際して、光学活
性３−ベンジルオキシ−１，２−プロパンジオール、テ
トラハロゲノメタン及びトリフェニルホスフィンの添加
はどのような順序で加えてもよいが、前二者を混合した
中にトリフェニルホスフィンを加えるのがよい。In the above reaction, the reaction temperature is 0 to 50 ° C.
However, it is preferable to carry out the heating at 10 to 40 ° C. since the progress is mild and the yield is good. In this temperature range,
The reaction is completed in 5 to 80 hours. In the reaction, the optically active 3-benzyloxy-1,2-propanediol, tetrahalogenomethane and triphenylphosphine may be added in any order, but triphenylphosphine may be added to the mixture of the former two. Good to add.
【００１０】なお、上記原料の光学活性３−ベンジルオ
キシ−１，２−プロパンジオールは、このものの高純度
なものとしては高野らの方法（Ｈｅｔｅｒｏｃｙｃｌｅ
ｓ，１６，３８１（１９８１））によって得ることがで
きる。The optically active 3-benzyloxy-1,2-propanediol, which is the above-mentioned raw material, is a highly pure product of the method of Takano et al. (Heterocycle).
s, 16, 381 (1981)).
【００１１】上記反応によって得られた光学活性ハロゲ
ノヒドリン誘導体は、上記スキームのようにＩＩ−１及
びＩＩ−２の混合物であるが、これをこのまま用いる
か、あるいはそれぞれに単離して続く塩基処理による閉
環反応に供せられる。いずれの場合も高収率で高純度の
光学活性ベンジルグリシジルエーテルを得ることができ
る。用いられる塩基としては有機塩基及び無機塩基があ
るが収率の点で無機塩基が好ましい。無機塩基として
は、例えば水酸化ナトリウム、水酸化カリウム、水酸化
リチウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウ
ム等が好ましく用いられる。使用量は光学活性ハロゲノ
ヒドリン誘導体に対して４〜２０当量の範囲が収率及び
反応時間の点で好ましい。The optically active halogenohydrin derivative obtained by the above reaction is a mixture of II-1 and II-2 as shown in the above scheme, which is used as it is or is isolated from each of them and subjected to the ring closure by the subsequent base treatment. It is subjected to the reaction. In any case, a high-yield and highly pure optically active benzyl glycidyl ether can be obtained. The base used includes an organic base and an inorganic base, but the inorganic base is preferable in terms of yield. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and the like are preferably used. The amount used is preferably in the range of 4 to 20 equivalents with respect to the optically active halogenohydrin derivative in terms of yield and reaction time.
【００１２】反応は有機溶媒又は有機溶媒と水の混合溶
媒中で行われるが、収率の点で前者が好ましい。有機溶
媒としては、エチルエーテル、テトラヒドロフラン、ｎ
−ヘキサン、塩化メチレン、クロロホルム等が挙げられ
る。反応は０〜６０℃の範囲で行われるが、収率の点で
５〜４０℃の範囲が好ましい。この温度範囲では、反応
は３０分〜１０時間で終了する。The reaction is carried out in an organic solvent or a mixed solvent of an organic solvent and water, and the former is preferred in terms of yield. As the organic solvent, ethyl ether, tetrahydrofuran, n
-Hexane, methylene chloride, chloroform and the like. The reaction is carried out in the range of 0 to 60 ° C, preferably 5 to 40 ° C in terms of yield. In this temperature range, the reaction is completed in 30 minutes to 10 hours.
【００１３】本発明においては、原料として光学活性
（Ｒ）−３−ベンジルオキシ−１，２−プロパンジオー
ルを用いた場合は、光学活性（Ｓ）体のハロゲノヒドリ
ン誘導体を経て光学活性（Ｓ）−ベンジルグリシジルエ
ーテルが得られ、光学活性（Ｓ）−３−ベンジルオキシ
−１，２−プロパンジオールを用いた場合は、光学活性
（Ｒ）体のハロゲノヒドリン誘導体を経て光学活性
（Ｒ）−べンジルグリシジルエーテルがそれぞれ高収率
及び高純度で得られる。In the present invention, when optically active (R) -3-benzyloxy-1,2-propanediol is used as a raw material, the optically active (S) -form is passed through the optically active (S) form of the halogenohydrin derivative. When benzyl glycidyl ether is obtained and optically active (S) -3-benzyloxy-1,2-propanediol is used, the optically active (R) -isomer is passed through the optically active (R) -form halogenohydrin derivative. Glycidyl ether is obtained in high yield and high purity, respectively.
【００１４】[0014]
実施例１
光学活性（Ｒ）−３−ベンジルオキシ−１，２−プロパ
ンジオール１．００ｇ（５．４９ｍ ｍｏｌ、＞９８％
ｅｅ）と四臭化炭素２．０１ｇ（６．０６ｍｍｏｌ）を
塩化メチレン６ｍｌに溶かして０℃にして撹拌し、その
中にトリフェニルホスフィン１．５９ｇ（６．０６ｍ
ｍｏｌ）の塩化メチレン９ｍｌ溶液を滴下してさらに室
温で５３時間撹拌した。反応後、反応混合物を水洗した
後無水硫酸マグネシウムで乾燥し溶媒を減圧留去した。Example 1 1.00 g (5.49 mmol,> 98%) of optically active (R) -3-benzyloxy-1,2-propanediol.
ee) and 2.01 g (6.06 mmol) of carbon tetrabromide were dissolved in 6 ml of methylene chloride and stirred at 0 ° C., and 1.59 g (6.06 m of triphenylphosphine) was stirred therein.
(9 mol) methylene chloride solution was added dropwise, and the mixture was further stirred at room temperature for 53 hours. After the reaction, the reaction mixture was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
【００１５】上記処理によって得られた残渣４．１２ｇ
をテトラヒドロフラン３０ｍｌに溶かし、０℃で水酸化
カリウム２．４２ｇ（４３．１ｍ ｍｏｌ）を加えて室
温で６時間撹拌した。反応後、反応混合物にエチルエー
テルを加えて水洗し、さらに飽和食塩水で洗浄した後、
無水硫酸マグネシウムで乾燥し、溶媒を減圧下で留去し
た。4.12 g of the residue obtained by the above treatment
Was dissolved in 30 ml of tetrahydrofuran, 2.42 g (43.1 mmol) of potassium hydroxide was added at 0 ° C., and the mixture was stirred at room temperature for 6 hours. After the reaction, ethyl ether was added to the reaction mixture and the mixture was washed with water and further washed with saturated saline,
It was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure.
【００１６】上記処理によって得られた残渣をシリカゲ
ルカラムクロマトグラフィー（ｎ−ヘキサン：エチルエ
ーテル＝８：１）によって精製し、油状の光学活性
（Ｓ）−ベンジルグリシジルエーテル７４８ｍｇ（収率
８３％、＞９８％ｅｅ）を得た。
〔α〕Ｄ（３１℃）−１０．６１°（ｃ＝５．３６、メタノール）
スペクトルデータは、総て文献値（高野ら、Ｈｅｔｅｒ
ｏｃｙｃｌｅｓ，３１，１７１５（１９９０））と一致
した。The residue obtained by the above treatment was purified by silica gel column chromatography (n-hexane: ethyl ether = 8: 1) to obtain 748 mg of optically active (S) -benzyl glycidyl ether as an oil (yield 83%,> 98% ee) was obtained. [Α] D (31 ° C.)-10.61 ° (c = 5.36, methanol) All spectral data are literature values (Takano et al., Heter.
Cycles, 31, 1715 (1990)).
【００１７】実施例２
トリフェニルホスフィン２．８９ｇ（１１．０ｍ ｍｏ
ｌ）四塩化炭素２５ｍｌに溶かし、３７時間還流した後
室温まで冷却し、減圧下に溶媒を留去した。得られた残
渣を塩化メチレン２５ｍｌに溶かし、０℃で光学活性
（Ｒ）−３−ベンジルオキシ−１，２−プロパンジオー
ル１．００ｇ（５．４９ｍ ｍｏｌ、＞９８％ｅｅ）の
塩化メチレン５ｍｌの溶液に滴下してさらに室温で１１
時間撹拌した。反応後、反応混合物を飽和炭酸水素ナト
リウム水溶液及び飽和食塩水で洗浄した後、無水硫酸マ
グネシウムで乾燥し、減圧下で溶媒を留去した。Example 2 2.89 g (11.0 m mo) of triphenylphosphine
l) It was dissolved in 25 ml of carbon tetrachloride, refluxed for 37 hours, cooled to room temperature, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 25 ml of methylene chloride, and at 0 ° C., 1.00 g (5.49 mmol,> 98% ee) of optically active (R) -3-benzyloxy-1,2-propanediol was added to 5 ml of methylene chloride. Add it dropwise to the solution and add it at room temperature for 11
Stir for hours. After the reaction, the reaction mixture was washed with a saturated sodium hydrogen carbonate aqueous solution and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
【００１８】上記処理によって得られた残渣４．４５ｇ
をテトラヒドロフラン２０ｍｌに溶かし、水酸化カリウ
ム２．５０ｇ（４４．５ｍ ｍｏｌ）を加えて室温で２
時間撹拌した。反応後、反応混合物にエチルエーテルを
加え、水洗及び飽和食塩水で洗浄後、無水硫酸マグネシ
ウムで乾燥し、溶媒を減圧下で留去した。4.45 g of the residue obtained by the above treatment
Was dissolved in 20 ml of tetrahydrofuran, 2.50 g (44.5 mmol) of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours.
Stir for hours. After the reaction, ethyl ether was added to the reaction mixture, washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
【００１９】上記処理によって得られた残渣をシリカゲ
ルカラムクロマトグラフィー（ｎ−ヘキサン：エチルエ
ーテル＝８：１）によって精製し、油状の光学活性
（Ｓ）−ベンジルグリシジルエーテル７９４ｍｇ（収率
８８％、＞９８％ｅｅ）を得た。
〔α〕Ｄ（３０℃）−１０．２８°（ｃ＝５．２３、メタノール）
スペクトルデータは総て実施例１によって得られた光学
活性（Ｓ）−ベンジルグリシジルエーテルと一致した。The residue obtained by the above treatment was purified by silica gel column chromatography (n-hexane: ethyl ether = 8: 1), and 794 mg of optically active (S) -benzyl glycidyl ether was obtained as oil (yield 88%,> 98% ee) was obtained. [Α] D (30 ° C.) -10.28 ° (c = 5.23, methanol) All the spectral data were in agreement with the optically active (S) -benzyl glycidyl ether obtained according to Example 1.
【００２０】実施例３
光学活性（Ｒ）−３−ベンジルオキシ−１，２−プロパ
ンジオールの代りに光学活性（Ｓ）−３−ベンジルオキ
シ−１，２−プロパンジオール（＞９８％ｅｅ）を用い
た以外は実施例１と同様に行って光学活性（Ｒ）−ベン
ジルグリシジルエーテルを得た（収率８２％、＞９８％
ｅｅ）。
〔α〕Ｄ（３１℃）＋１０．４０°（ｃ＝５．０６、メタノール）Example 3 Instead of optically active (R) -3-benzyloxy-1,2-propanediol, optically active (S) -3-benzyloxy-1,2-propanediol (> 98% ee) was used. Optically active (R) -benzyl glycidyl ether was obtained in the same manner as in Example 1 except that it was used (yield: 82%,> 98%).
ee). [Α] D (31 ° C) + 10.40 ° (c = 5.06, methanol)
【００２１】実施例４
光学活性（Ｒ）−３−ベンジルオキシ−１，２−プロパ
ンジオールの代りに光学活性（Ｓ）−３−ベンジルオキ
シ−１，２−プロパンジオール（＞９８％ｅｅ）を用い
た以外は実施例２と同様に行って光学活性（Ｒ）−ベン
ジルグリシジルエーテルを得た（収率８７％、＞９８％
ｅｅ）。
〔α〕Ｄ（３０℃）＋１０．３３°（ｃ＝５．５０、メタノール）Example 4 Instead of optically active (R) -3-benzyloxy-1,2-propanediol, optically active (S) -3-benzyloxy-1,2-propanediol (> 98% ee) was used. Optically active (R) -benzyl glycidyl ether was obtained in the same manner as in Example 2 except that it was used (yield 87%,> 98%).
ee). [Α] D (30 ° C.) + 10.33 ° (c = 5.50, methanol)
【００２２】実施例５
光学活性（Ｒ）−３−ベンジルオキシ−１，２−プロパ
ンジオール１．００ｇ（５．４９ｍ ｍｏｌ、＞９８％
ｅｅ）と四臭化炭素２．０１ｇ（６．０６ｍｍｏｌ）を
塩化メチレン６ｍｌに溶かして０℃にして撹拌し、その
中にトリフェニルホスフィン１．５９ｇ（６．０６ｍ
ｍｏｌ）の塩化メチレン９ｍｌ溶液を滴下してさらに室
温で５３時間撹拌した。反応後、反応混合物を水洗した
後無水硫酸マグネシウムで乾燥し溶媒を減圧留去した。Example 5 1.00 g (5.49 mmol,> 98%) of optically active (R) -3-benzyloxy-1,2-propanediol
ee) and 2.01 g (6.06 mmol) of carbon tetrabromide were dissolved in 6 ml of methylene chloride and stirred at 0 ° C., and 1.59 g (6.06 m of triphenylphosphine) was stirred therein.
(9 mol) methylene chloride solution was added dropwise, and the mixture was further stirred at room temperature for 53 hours. After the reaction, the reaction mixture was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
【００２３】上記処理によって得られた残渣をシリカゲ
ルカラムクロマトグラフィー（ｎ−ヘキサン：エチルエ
ーテル＝８：１）によって分離精製し、光学活性（Ｓ）
−１−ベンジルオキシ−３−ブロモ−２−プロパノール
９５１ｍｇ（収率７１％）及び光学活性（Ｓ）−３−ベ
ンジルオキシ−２−ブロモ−１−プロパノール２７９ｍ
ｇ（収率２１％）を得た。The residue obtained by the above treatment was separated and purified by silica gel column chromatography (n-hexane: ethyl ether = 8: 1) to obtain an optical activity (S).
951 mg (71% yield) of -1-benzyloxy-3-bromo-2-propanol and 279 m of optically active (S) -3-benzyloxy-2-bromo-1-propanol.
g (21% yield) was obtained.
【００２４】上記得られた光学活性（Ｓ）−３−ベンジ
ルオキシ−２−ブロモ−１−プロパノールの性状を以下
に示す。
（１）無色油状
（２）〔α〕Ｄ（３１℃）−３．４８°（ｃ＝１．０
６、クロロホルム）
（４）ＩＲ（ｎｅａｔ）νｍａｘ ３４３８ｃｍ−１
（５）１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ：２．２０（ｄ
ｄ，Ｊ＝６．７，６．７Ｈｚ，１Ｈ，ｅｘｃｈａｎｇｅ
ａｂｌｅ ｗｉｔｈ Ｄ２Ｏ）、３．７９（ｄｄ，Ｊ＝
７．３，１０．５Ｈｚ，１Ｈ）、３．８３（ｄｄ，Ｊ＝
５．５，１０．５Ｈｚ，１Ｈ）、３．９１（ｄｄｄ，Ｊ
＝５．５，６．７，１２．２Ｈｚ，１Ｈ）、３．９５
（ｄｄｄ，Ｊ＝５．５，６．７，１２．２Ｈｚ，１
Ｈ）、４．２２（ｍ，１Ｈ）、４．５９（ｓ，２Ｈ）、
７．３５（ｍ，５Ｈ）
（６）ＭＳ（ｍ／ｚ） ２４６，２４４（Ｍ＋），９１
（１００％）
Ｃ１０Ｈ１３Ｏ２ ８１Ｂｒ 計算値２４６．００７
８、分析値２４６．００７２
Ｃ１０Ｈ１３Ｏ２ ７９Ｂｒ 計算値２４４．００９
９、分析値２４４．００７５The optically active (S) -3-benzi obtained above.
The properties of luoxy-2-bromo-1-propanol are as follows.
Shown in.
(1) colorless oil
(2) [α]D(31 ° C) -3.48 ° (c = 1.0
6, chloroform)
(4) IR (neat) νmax 3438 cm-1
(5)1H-NMR (CDClThree) Δ: 2.20 (d
d, J = 6.7, 6.7 Hz, 1H, exchange
available with DTwoO), 3.79 (dd, J =
7.3, 10.5 Hz, 1H, 3.83 (dd, J =
5.5, 10.5Hz, 1H), 3.91 (ddd, J
= 5.5, 6.7, 12.2 Hz, 1H), 3.95
(Ddd, J = 5.5, 6.7, 12.2 Hz, 1
H), 4.22 (m, 1H), 4.59 (s, 2H),
7.35 (m, 5H)
(6) MS (m / z) 246, 244 (M+), 91
(100%)
C10HThirteenOTwo 81Br calculated value 246.007
8, analytical value 246.0072
C10HThirteenOTwo 79Calculated Br value 244.009
9, analytical value 244.0075
【００２５】上記得られた光学活性（Ｓ）−３−ベンジ
ルオキシ−２−ブロモ−１−プロパノール６１ｍｇ
（０．２５ｍ ｍｏｌ）と水酸化カリウム７９ｍｇ
（１．４１ｍｍｏｌ）をテトラヒドロフラン１ｍｌ中室
温で６．５時間撹拌した。反応後、エチルエーテルを加
えて、飽和食塩水で洗浄し、有機層を無水硫酸マグネシ
ウムで乾燥後溶媒を減圧下で留去した。61 mg of the optically active (S) -3-benzyloxy-2-bromo-1-propanol obtained above.
(0.25 mmol) and potassium hydroxide 79 mg
(1.41 mmol) was stirred in 1 ml of tetrahydrofuran at room temperature for 6.5 hours. After the reaction, ethyl ether was added and the mixture was washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
【００２６】上記得られた残渣をシリカゲルカラムクロ
マトグラフィー（ｎ−ヘキサン：エチルエーテル＝８：
１）で精製して油状の光学活性（Ｓ）−ベンジルグリシ
ジルエーテル３６ｍｇ（収率８８％）を得た。
〔α〕Ｄ（３０℃）−１０．９５°（ｃ＝１．１０、メタノール）
スペクトルデータは総て文献値（高野ら、Ｈｅｔｅｒｏ
ｃｙｃｌｅｓ，３１，１７１５（１９９０））と一致し
た。The residue obtained above was subjected to silica gel column chromatography (n-hexane: ethyl ether = 8:
Purification in 1) gave 36 mg of oily optically active (S) -benzyl glycidyl ether (yield 88%). [Α] D (30 ° C.)-10.95 ° (c = 1.10, methanol) All spectral data are literature values (Takano et al., Hetero).
Cycles, 31, 1715 (1990)).
【００２７】上記得られた光学活性（Ｓ）−ベンジルグ
リシジルエーテルの光学純度は、高速液体クロマトグラ
フィー（「キラルセルＯＤ」ダイセル化学工業社製）に
よる分析により９８．１％ｅｅであり、中間体である光
学活性（Ｓ）−３−ベンジルオキシ−２−ブロモ−１−
プロパノールが極めて高い光学純度を持つことが分っ
た。The optical purity of the above-obtained optically active (S) -benzyl glycidyl ether was 98.1% ee as analyzed by high performance liquid chromatography (“Chiralcel OD” manufactured by Daicel Chemical Industries, Ltd.), which was an intermediate. Some optically active (S) -3-benzyloxy-2-bromo-1-
It was found that propanol has an extremely high optical purity.
【００２８】[0028]
【発明の効果】本発明の方法によれば、光学活性天然物
等の製造に有用な中間体である光学活性ベンジルグリシ
ジルエーテルを簡便に、しかも高収率で高純度に製造す
ることができる。According to the method of the present invention, an optically active benzyl glycidyl ether, which is an intermediate useful for the production of optically active natural products and the like, can be easily produced with high yield and high purity.
Claims (2)
プロパンジオールをテトラハロゲノメタン及びトリフェ
ニルホスフィンと有機溶媒中で反応させて光学活性ハロ
ゲノヒドリン誘導体を得、次いでこれを塩基処理するこ
とを特徴とする光学活性ベンジルグリシジルエーテルの
製法。1. Optically active 3-benzyloxy-1,2-
A process for producing an optically active benzyl glycidyl ether, which comprises reacting propanediol with tetrahalogenomethane and triphenylphosphine in an organic solvent to obtain an optically active halogenohydrin derivative, which is then treated with a base.
四塩化炭素である請求項１記載の製法。2. The method according to claim 1, wherein the tetrahalogenomethane is carbon tetrabromide or carbon tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28095291A JP2903805B2 (en) | 1991-07-31 | 1991-07-31 | Preparation of optically active benzyl glycidyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28095291A JP2903805B2 (en) | 1991-07-31 | 1991-07-31 | Preparation of optically active benzyl glycidyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0532649A true JPH0532649A (en) | 1993-02-09 |
| JP2903805B2 JP2903805B2 (en) | 1999-06-14 |
Family
ID=17632193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28095291A Expired - Fee Related JP2903805B2 (en) | 1991-07-31 | 1991-07-31 | Preparation of optically active benzyl glycidyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2903805B2 (en) |
-
1991
- 1991-07-31 JP JP28095291A patent/JP2903805B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2903805B2 (en) | 1999-06-14 |
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