JP3300712B2 - Method for producing optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one - Google Patents
Method for producing optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-oneInfo
- Publication number
- JP3300712B2 JP3300712B2 JP36039792A JP36039792A JP3300712B2 JP 3300712 B2 JP3300712 B2 JP 3300712B2 JP 36039792 A JP36039792 A JP 36039792A JP 36039792 A JP36039792 A JP 36039792A JP 3300712 B2 JP3300712 B2 JP 3300712B2
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- JP
- Japan
- Prior art keywords
- dimethyl
- phenyl
- dioxolan
- optically active
- mixture
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、D−(−)−あるいは
L−(+)−マンデル酸およびそれらのエステル並びに
アミドの中間体として有用な光学活性な2,2−ジメチ
ル−5−フェニル−1,3−ジオキソラン−4−オンの
製造法に関する。The present invention relates to an optically active 2,2-dimethyl-5-phenyl useful as an intermediate of D-(-)-or L-(+)-mandelic acid and their esters and amides. The present invention relates to a method for producing -1,3-dioxolan-4-one.
【0002】[0002]
【従来の技術】マンデル酸の光学活性体を得る方法とし
ては、ベンゾイルギ酸を原料に用いる不斉還元およびベ
ンズアルデヒドを原料に用いる不斉シアノヒドリン反応
などが知られているが、高価な触媒が必要であり、工業
的には適していない。一方、光学分割により、光学活性
なマンデル酸を得る方法としては、α−フェネチルアミ
ン[特開昭55−147236号またはJ.Amer.Chem.So
c.,55,411(1933)]、エフェドリン[J.Amer.Chem.Soc.,
51,1906(1929)]あるいはシンコニン[J.Chem.Soc.,964
(1899)]を用いるジアステレオマ−分割法が知られてい
るが、いずれの方法も分割効率が悪く、工業的方法とし
ては難点があった。また、(±)−2−アミノ−1−ブ
タノールと(±)−マンデル酸との塩を用い、どちらか
一方の光学活性体の塩を交互に優先晶出させる方法[特
開昭56−123936号]あるいは(±)−マンデル
酸のピペリジン塩またはN−メチルシクロヘキシルアミ
ン塩においてどちらか一方の光学活性体の塩を交互に優
先晶出させる方法[特開昭56−122329号]が知
られているが、これらの方法では収量が少ないうえ、煩
雑な操作を必要とする。2. Description of the Related Art As a method for obtaining an optically active form of mandelic acid, asymmetric reduction using benzoylformic acid as a raw material and asymmetric cyanohydrin reaction using benzaldehyde as a raw material are known, but an expensive catalyst is required. Yes, not industrially suitable. On the other hand, as a method for obtaining optically active mandelic acid by optical resolution, α-phenethylamine [JP-A-55-147236 or J. Amer.
c., 55 , 411 (1933)], ephedrine [J. Amer. Chem. Soc.,
51 , 1906 (1929)] or cinchonine [J. Chem. Soc., 964
(1899)], the diastereomer separation method is known, but all of these methods have poor separation efficiency and have disadvantages as an industrial method. Also, a method in which a salt of (±) -2-amino-1-butanol and (±) -mandelic acid is used to alternately preferentially crystallize one of the salts of the optically active substance [JP-A-56-123936] Or a method of alternately preferentially crystallizing one of the optically active salts in the piperidine salt of (±) -mandelic acid or the N-methylcyclohexylamine salt [JP-A-56-122329] is known. However, these methods have low yields and require complicated operations.
【0003】[0003]
【発明が解決しようとする課題】本発明の目的は、光学
活性なマンデル酸およびその誘導体の中間体として有用
な、光学活性な2,2−ジメチル−5−フェニル−1,3
−ジオキソラン−4−オンを高収率で安価に製造する方
法を提供することにある。An object of the present invention is to provide an optically active 2,2-dimethyl-5-phenyl-1,3 useful as an intermediate of optically active mandelic acid and its derivatives.
-To provide a method for producing dioxolan-4-one in high yield and at low cost.
【0004】[0004]
【課題を解決するための手段】上記課題を解決するた
め、本発明者らは鋭意研究を行った結果、2,2−ジメ
チル−5−フェニル−1,3−ジオキソラン−4−オン
がラセミ混合物であり、優先晶出可能な物質であること
を見出した。また、2,2−ジメチル−5−フェニル−
1,3−ジオキソラン−4−オンの光学活性体を溶媒に
溶解または溶融させた中に、ラセミ化促進剤を加えると
容易にラセミ化が起こることも見出した。これらの知見
に基づき検討を重ねた結果、ラセミ化と優先晶出を同時
に進行させることにより、2,2−ジメチル−5−フェ
ニル−1,3−ジオキソラン−4−オンのラセミ混合物
から目的の光学活性体を高収率で得る方法を見出した。Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, it has been found that 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one is a racemic mixture. And found that the substance can be preferentially crystallized. Also, 2,2-dimethyl-5-phenyl-
It has also been found that racemization easily occurs when a racemization accelerator is added to a solution in which a 1,3-dioxolan-4-one optically active substance is dissolved or melted in a solvent. As a result of repeated studies based on these findings, it was found that racemization and preferential crystallization proceed at the same time to obtain the target optical compound from a racemic mixture of 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one. A method for obtaining the active substance in high yield was found.
【0005】以下、本発明を製造ルートにしたがって詳
細に説明する。Hereinafter, the present invention will be described in detail according to a manufacturing route.
【0006】[0006]
【0007】本発明方法は、式[2]の化合物であるラ
セミ体あるいは一方の光学活性体が他方の光学活性体よ
り過剰に存在する混合物を、ラセミ化促進剤の存在下、
溶融状態あるいは溶解状態にさせた後、過冷却状態でい
ずれか一方の光学活性体を種晶として添加することによ
り、目的の光学活性体(式[3a]または式[3b]で
表わされる化合物)を優先晶出させる。原料に用いる式
[2]の2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オンは、たとえば、ジャーナル・オブ・
オーガニック・ケミストリー、55,5878-5881(1990)に記
載されており、マンデル酸から高収率で得ることができ
る。ラセミ化優先晶出法によって得られた光学活性な
2,2−ジメチル−5−フェニル−1,3−ジオキソラン
−4−オン(式[3a]または[3b]の化合物)はジ
ャーナル・オブ・ケミカル・ソシアティ・パーキン・ト
ランスアクションI2223-2228(1984)に記載されてい
るように、光学活性なマンデルアミドおよびハロスタチ
ンに容易に導くことができる。また、光学活性なマンデ
ル酸またはマンデル酸エステル(式[4a]、[4
b]、[5a]または式[5b]で表わされる化合物)
[Rはエステル残基を示す。]も高収率で得ることがで
きる。The process of the present invention comprises the step of reacting a racemic compound of the formula [2] or a mixture in which one optically active substance is present in excess of the other optically active substance in the presence of a racemization accelerator.
After being brought into a molten state or a dissolved state, one of the optically active substances is added as a seed crystal in a supercooled state to obtain a target optically active substance (compound represented by the formula [3a] or [3b]) Is preferentially crystallized. 2,2-Dimethyl-5-phenyl-1,3-dioxolan-4-one of the formula [2] used as a raw material is, for example, a journal of
Organic chemistry, 55 , 5878-5881 (1990) and can be obtained in high yield from mandelic acid. The optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one (compound of the formula [3a] or [3b]) obtained by the racemization preferential crystallization method is described in Journal of Chemicals. -Can be easily led to optically active mandelamide and halostatin, as described in Sociati Parkin Transaction I2223-2228 (1984). Further, optically active mandelic acid or mandelic acid ester (formula [4a], [4
b], [5a] or a compound represented by the formula [5b])
[R represents an ester residue. ] Can also be obtained in high yield.
【0008】この反応に使用される溶媒としては、式
[2]の化合物が適切な溶解度を示すもの、たとえば、
石油エーテル、ベンジン、リグロイン、n−ヘキサンお
よびシクロヘキサンなどのような脂肪族炭化水素類;塩
化メチレン、ジクロロエタン、クロロホルム、四塩化炭
素およびクロロベンゼンなどのようなハロゲン化炭化水
素類;ジエチルエーテル、ジイソプロピルエーテル、ジ
ブチルエーテル、テトラヒドロフランおよびジオキサン
などのようなエーテル類;ベンゼンおよびトルエンなど
のような芳香族炭化水素類;酢酸エチルおよび酢酸ブチ
ルなどのようなエステル類;イソプロパノールおよびシ
クロヘキサノールなどのような二級アルコール類;tert
-ブタノールおよびtert-アミルアルコールなどのような
三級アルコール類;アセトン、メチルエチルケトン、メ
チルイソブチルケトンおよびシクロペンタノンなどのよ
うなケトン類;アセトニトリルのようなニトリル類;
N,N−ジメチルホルムアミドのようなアミド類;並び
にジメチルスルホキシドのようなスルホキシド類および
これらの混合溶媒などを挙げることができるが、特に脂
肪族炭化水素類と上述の溶媒との混合溶媒が好ましい。[0008] As the solvent used in this reaction, those in which the compound of the formula [2] shows appropriate solubility, for example,
Aliphatic hydrocarbons such as petroleum ether, benzine, ligroin, n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; diethyl ether, diisopropyl ether; Ethers such as dibutyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene and toluene; esters such as ethyl acetate and butyl acetate; secondary alcohols such as isopropanol and cyclohexanol. Tert
Tertiary alcohols such as -butanol and tert-amyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; nitriles such as acetonitrile;
Examples thereof include amides such as N, N-dimethylformamide; sulfoxides such as dimethylsulfoxide; and a mixed solvent thereof. A mixed solvent of an aliphatic hydrocarbon and the above-mentioned solvent is particularly preferable.
【0009】ラセミ化促進剤としては、トリエチルアミ
ン、1,8−ジアザビシクロ[5.4.0]−7−ウン
デセン(DBU)、1,5−ジアザビシクロ[4.3.
0]ノン−5−エン(DBN)、1,4−ジアザビシク
ロ[2,2,2]オクタンおよびN−メチルピペラジンな
どのような有機塩基;tert-ブトキシカリウムのような
アルカリ金属アルコキシド;並びにテトラブチルアンモ
ニウムフルオリドのような有機溶媒に可溶な四級アンモ
ニウム塩などが挙げられる。また、ラセミ化促進剤の使
用量は、原料である式[2]の化合物に対して0.1-10重
量%で十分である。As racemization accelerators, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.
0] non-5-ene (DBN), organic bases such as 1,4-diazabicyclo [2,2,2] octane and N-methylpiperazine; alkali metal alkoxides such as potassium tert-butoxy; and tetrabutyl Examples include quaternary ammonium salts soluble in organic solvents such as ammonium fluoride. Further, the amount of the racemization accelerator used is sufficient to be 0.1 to 10% by weight based on the compound of the formula [2] as the raw material.
【0010】種晶の添加量および粒度は特に限定されな
いが、通常溶液中のラセミ体に対し0.1-10重量%程度の
結晶を砕いた粉末を、そのまま用いるかあるいは予め同
じ溶媒系に懸濁したものを用いる。操作温度も特に制限
はなく、溶媒の沸点まで可能であるが、用いる溶媒に対
する式[2]の化合物の溶解度にしたがって、安定過飽
和溶液が得られるように調整するのが好ましい。The amount and the particle size of the seed crystal are not particularly limited, but usually, a powder obtained by crushing crystals of about 0.1 to 10% by weight based on the racemic form of the solution is used as it is or suspended in the same solvent system in advance. Use something. The operating temperature is not particularly limited, and can be up to the boiling point of the solvent. However, it is preferable to adjust the temperature according to the solubility of the compound of the formula [2] in the solvent to be used so as to obtain a stable supersaturated solution.
【0011】[0011]
【実施例】つぎに、本発明化合物の製造例を、具体的に
参考例および実施例を挙げて説明するが、本発明は、こ
れらに限定されるものではない。なお、光学純度におけ
る%e.e.は鏡像異性体過剰率である。EXAMPLES Next, Production Examples of the compound of the present invention will be described specifically with reference to Reference Examples and Examples, but the present invention is not limited thereto. In addition,% ee in optical purity is an enantiomeric excess.
【0012】実施例1 (±)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オン14.27gをn−ヘキサン14.3mlおよび
イソプロピルエーテル14.3mlの混合液に加熱溶解させ
る。この溶液に32℃で1,8−ジアザビシクロ[5.
4.0]−7−ウンデセン1.07gを添加し、ついで27℃
で(−)−2,2−ジメチル−5−フェニル−1,3−ジ
オキソラン−4−オン[[α]D=-82.7°(21.5℃,C=1.
0,CHCl3)]の結晶0.43gを加える。得られた混合物を26
℃で1時間攪拌した後、4時間を要して20℃まで、つい
で3時間を要して10℃まで徐々に冷却する。析出する結
晶を濾取し、氷冷下で酢酸エチル50mlに加えて溶解さ
せ、水50mlで洗浄する。有機層を分取し、水洗後、硫酸
マグネシウムで乾燥させる。減圧下に溶媒を留去すれ
ば、淡黄色の(−)−2,2−ジメチル−5−フェニル
−1,3−ジオキソラン−4−オンの粗結晶12.17gを得
る。添加した種晶分を除いた収率は、82.3%である。 [α]D=-74.8°(21.5℃,C=1.0,CHCl3) 光学純度90.4
%e.e. なお、上記の粗結晶11.61gをイソプロピルアルコール1
3.0mlより再結晶すれば、無色針状晶の(−)−2,2−
ジメチル−5−フェニル−1,3−ジオキソラン−4−
オン10.16gを得る。 融点;70.4-72.3℃ [α]D=-82.6°(21.5℃,C=1.0,CHCl3) 光学純度99.9
%e.e. IR(KBr)νC=O;1809cm-1 Example 1 14.27 g of (±) -2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one is dissolved by heating in a mixed solution of 14.3 ml of n-hexane and 14.3 ml of isopropyl ether. This solution was added to 1,8-diazabicyclo [5.
4.0] -7-undecene (1.07 g) and then 27 ° C
And (-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one [[α] D = -82.7 ° (21.5 ° C., C = 1.
0, CHCl 3 )]. 26 of the resulting mixture
After stirring at 1 ° C. for 1 hour, the mixture is gradually cooled to 20 ° C. over 4 hours, and then to 10 ° C. over 3 hours. The precipitated crystals are collected by filtration, dissolved in 50 ml of ethyl acetate under ice cooling, and washed with 50 ml of water. The organic layer is separated, washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain pale yellow (-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one as crude crystals (12.17 g). The yield excluding the added seed crystal is 82.3%. [Α] D = -74.8 ° (21.5 ° C, C = 1.0, CHCl 3 ) Optical purity 90.4
% Ee In addition, 11.61 g of the above-mentioned crude crystals was added to isopropyl alcohol 1
When recrystallized from 3.0 ml, colorless needles of (-)-2,2-
Dimethyl-5-phenyl-1,3-dioxolan-4-
You get 10.16g on. Melting point: 70.4-72.3 ° C [α] D = -82.6 ° (21.5 ° C, C = 1.0, CHCl 3 ) Optical purity 99.9
% Ee IR (KBr) ν C = O ; 1809cm -1
【0013】実施例2 (+)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オンを種晶として用い、(±)−2,2
−ジメチル−5−フェニル−1,3−ジオキソラン−4
−オン10.00gを実施例1と同様に処理すれば、淡黄色の
(+)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オンの粗結晶8.57gを得る。添加した種
晶分を除いた収率は、82.7%である。 [α]D=+75.3°(18.0℃,C=1.0,CHCl3) 光学純度89.5
%e.e. この粗結晶8.00gをイソプロピルアルコール10.0mlより
再結晶すれば、無色針状晶の(+)−2,2−ジメチル
−5−フェニル−1,3−ジオキソラン−4−オン6.69g
を得る。 融点;70.0-72.3℃ [α]D=+83.7°(18.0℃,C=1.0,CHCl3) 光学純度99.
5%e.e. IR(KBr)νC=O;1809cm-1 Example 2 Using (+)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one as a seed crystal, (±) -2,2
-Dimethyl-5-phenyl-1,3-dioxolan-4
When 10.00 g of -one was treated in the same manner as in Example 1, 8.57 g of pale yellow (+)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one as crude crystals was obtained. The yield excluding the added seed crystal is 82.7%. [Α] D = + 75.3 ° (18.0 ° C, C = 1.0, CHCl 3 ) Optical purity 89.5
% Ee 8.00 g of the crude crystals are recrystallized from 10.0 ml of isopropyl alcohol to give 6.69 g of (+)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one as colorless needles.
Get. Melting point: 70.0-72.3 ° C [α] D = + 83.7 ° (18.0 ° C, C = 1.0, CHCl 3 ) Optical purity 99.
5% ee IR (KBr) ν C = O ; 1809cm -1
【0014】実施例3 (±)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オン4.00gを45℃に加熱して溶融状態に
し、これに1,8−ジアザビシクロ[5.4.0]−7
−ウンデセン0.20gを加え、40℃まで冷却する。同温度
で、(−)−2,2−ジメチル−5−フェニル−1,3−
ジオキソラン−4−オン[[α]D=-81.7°(26.0℃,C
=1.0,CHCl3)]の結晶0.10gを加え、30分間を要して35℃
に冷却する。全体に固化した内容物を、さらに10℃まで
1時間を要して冷却後、酢酸エチル50mlに溶解させ、つ
いで氷水50mlを加え、2N塩酸でpH3.0に調整する。有
機層を分取し、水、5%炭酸水素ナトリウム水溶液およ
び水で順次洗浄後、無水硫酸マグネシウムで乾燥させ
る。減圧下に溶媒を留去し、得られた残留物をn−ヘキ
サンで洗浄すれば、淡黄色の(−)−2,2−ジメチル
−5−フェニル−1,3−ジオキソランの粗結晶3.20gを
得る。添加した種晶分を除いた収率は、77.5%である。 [α]D=-61.5°(26.0℃,C=1.0,CHCl3) 光学純度75.3
%e.e. 上記の粗結晶2.00gをイソプロピルアルコール3.00mlよ
り再結晶すれば、無色針状晶の(−)−2,2−ジメチ
ル−5−フェニル−1,3−ジオキソラン−4−オン1.4
6gを得る。 融点;70.0-72.3℃ [α]D=-81.1°(26.0℃,C=1.0,CHCl3) 光学純度99.3
%e.e. IR(KBr)νC=O;1809cm-1 Example 3 4.00 g of (±) -2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one was heated to 45 ° C. to be in a molten state, to which 1,8-diazabicyclo [ 54.0] -7
Add 0.20 g of undecene and cool to 40 ° C. At the same temperature, (-)-2,2-dimethyl-5-phenyl-1,3-
Dioxolan-4-one [[α] D = -81.7 ° (26.0 ° C, C
= 1.0, CHCl 3 )] at 35 ° C over 30 minutes
Cool. The whole solidified content is further cooled to 10 ° C. over 1 hour, dissolved in 50 ml of ethyl acetate, added with 50 ml of ice water, and adjusted to pH 3.0 with 2N hydrochloric acid. The organic layer is separated, washed successively with water, a 5% aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was washed with n-hexane to give 3.20 g of pale yellow (-)-2,2-dimethyl-5-phenyl-1,3-dioxolane crude crystals. Get. The yield excluding the added seed crystal is 77.5%. [Α] D = -61.5 ° (26.0 ° C, C = 1.0, CHCl 3 ) Optical purity 75.3
% Ee The above crude crystals (2.00 g) were recrystallized from isopropyl alcohol (3.00 ml) to give colorless needles of (-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one (1.4%).
Get 6g. Melting point: 70.0-72.3 ° C [α] D = -81.1 ° (26.0 ° C, C = 1.0, CHCl 3 ) Optical purity 99.3
% Ee IR (KBr) ν C = O ; 1809cm -1
【0015】参考例1 (−)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オン(光学純度99.0%e.e.)10.0gをア
セトン20mlおよび水10mlの混合液に懸濁させる。氷冷下
で硫酸5.10gを徐々に滴下した後、混合物を室温で1.5時
間攪拌する。反応混合物に酢酸エチル50mlおよび水50ml
を加え、有機層を分取する。得られた有機層を無水硫酸
マグネシウムで乾燥後、減圧下に溶媒を留去する。得ら
れた残留物をトルエン50mlおよびアセトン5mlの混合液
より再結晶すれば、無色針状晶の(−)−マンデル酸7.
08g(収率89.4%)を得る。 融点;132.6-133.9℃ [α]D=-156.5°(20.0℃,C=1.0,H2O) 光学純度99.9
%e.e.Reference Example 1 10.0 g of (-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one (optical purity 99.0% ee) was suspended in a mixture of 20 ml of acetone and 10 ml of water. Let it. After gradually adding 5.10 g of sulfuric acid under ice-cooling, the mixture is stirred at room temperature for 1.5 hours. 50 ml of ethyl acetate and 50 ml of water are added to the reaction mixture.
And the organic layer is separated. After the obtained organic layer is dried over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure. The obtained residue was recrystallized from a mixture of 50 ml of toluene and 5 ml of acetone to give colorless needles of (-)-mandelic acid 7.
08 g (89.4% yield) are obtained. Melting point: 132.6-133.9 ° C [α] D = -156.5 ° (20.0 ° C, C = 1.0, H 2 O) Optical purity 99.9
% Ee
【0016】参考例2 (−)−2,2−ジメチル−5−フェニル−1,3−ジオ
キソラン−4−オン(光学純度99.9%e.e.)7.02gをメ
タノール14.0mlに懸濁させる。混合液を15℃に冷却し、
硫酸1.79gを徐々に滴下した後、20℃で30分間攪拌す
る。混合液に塩化メチレン50mlおよび水50mlを順次加
え、飽和炭酸水素ナトリウム溶液でpH7.0に調整する。
有機層を分取し、水洗後、無水硫酸マグネシウムで乾燥
させる。減圧下に溶媒を留去し、得られた残留物をn−
ヘキサン30mlおよびジイソプロピルエーテル9mlの混合
液より再結晶すれば、無色針状晶の(−)−マンデル酸
メチルエステル5.40g(収率89.0%)を得る。 融点;54.7-56.1℃ [α]D=-149.7°(17.5℃,C=1.0,MeOH)Reference Example 2 7.02 g of (-)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one (optical purity 99.9% ee) is suspended in 14.0 ml of methanol. Cool the mixture to 15 ° C,
After slowly adding 1.79 g of sulfuric acid, the mixture is stirred at 20 ° C. for 30 minutes. 50 ml of methylene chloride and 50 ml of water are sequentially added to the mixture, and the mixture is adjusted to pH 7.0 with a saturated sodium hydrogen carbonate solution.
The organic layer is separated, washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure.
Recrystallization from a mixture of 30 ml of hexane and 9 ml of diisopropyl ether gives 5.40 g (yield: 89.0%) of (-)-mandelic acid methyl ester as colorless needles. Melting point: 54.7-56.1 ° C [α] D = -149.7 ° (17.5 ° C, C = 1.0, MeOH)
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−238734(JP,A) CHEMTRACTS−ORAGAN IC CHEMISTRY(1988),1 (2),139−140 Angew.Chem.,Vol. 99,No.12,pp.1323−1325,1987 (58)調査した分野(Int.Cl.7,DB名) C07D 317/34 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-238734 (JP, A) CHEMTRACTS-ORAGAN IC CHEMISTRY (1988), 1 (2), 139-140 Angew. Chem. Vol. 99, no. 12, pp. 1323-1325, 1987 (58) Fields investigated (Int. Cl. 7 , DB name) C07D 317/34 CA (STN) REGISTRY (STN)
Claims (1)
ジオキソラン−4−オンのラセミ体あるいは一方の光学
活性体が他方の光学活性体より過剰に存在する混合物の
過飽和溶液もしくは溶融液にラセミ化促進剤の存在下、
目的の光学活性体の結晶を接種することによって目的の
光学活性体を優先的に晶出させることを特徴とする光学
活性な2,2−ジメチル−5−フェニル−1,3−ジオキ
ソラン−4−オンの製造法。(1) 2,2-dimethyl-5-phenyl-1,3-
In the presence of a racemization accelerator, a racemic dioxolan-4-one or a supersaturated solution or melt of a mixture in which one optically active form is present in excess of the other optically active form,
An optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-characterized by inoculating a crystal of the target optically active substance with preference to crystallize the target optically active substance. On manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP36039792A JP3300712B2 (en) | 1992-12-29 | 1992-12-29 | Method for producing optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP36039792A JP3300712B2 (en) | 1992-12-29 | 1992-12-29 | Method for producing optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06199828A JPH06199828A (en) | 1994-07-19 |
JP3300712B2 true JP3300712B2 (en) | 2002-07-08 |
Family
ID=18469235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP36039792A Expired - Fee Related JP3300712B2 (en) | 1992-12-29 | 1992-12-29 | Method for producing optically active 2,2-dimethyl-5-phenyl-1,3-dioxolan-4-one |
Country Status (1)
Country | Link |
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JP (1) | JP3300712B2 (en) |
-
1992
- 1992-12-29 JP JP36039792A patent/JP3300712B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
---|
Angew.Chem.,Vol.99,No.12,pp.1323−1325,1987 |
CHEMTRACTS−ORAGANIC CHEMISTRY(1988),1(2),139−140 |
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JPH06199828A (en) | 1994-07-19 |
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