JPH0267237A - Production of optically active 1,1,1-trifluoro-2-alkanol - Google Patents
Production of optically active 1,1,1-trifluoro-2-alkanolInfo
- Publication number
- JPH0267237A JPH0267237A JP21853688A JP21853688A JPH0267237A JP H0267237 A JPH0267237 A JP H0267237A JP 21853688 A JP21853688 A JP 21853688A JP 21853688 A JP21853688 A JP 21853688A JP H0267237 A JPH0267237 A JP H0267237A
- Authority
- JP
- Japan
- Prior art keywords
- trifluoro
- alkanol
- optically active
- diastereomer
- acid
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 230000003287 optical effect Effects 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- PUANNVQABXUYKU-VXGBXAGGSA-N (1r,2r)-2-benzamidocyclohexane-1-carboxylic acid Chemical compound OC(=O)[C@@H]1CCCC[C@H]1NC(=O)C1=CC=CC=C1 PUANNVQABXUYKU-VXGBXAGGSA-N 0.000 claims description 7
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- -1 alkyl Grignard reagent Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、光学活性なｌ、ｌ、ｌ−トリフルオロ−２−
アルカノールの製造法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides optically active l,l,l-trifluoro-2-
This relates to a method for producing alkanol.
光学活性な１，ｌ−トリフルオロ−２−アルカノールは
強誘電性液晶化合物の合成原料として有用な化合物であ
る０強誘電性液晶化合物は光学活性であることが必須で
あり、このため光学純度の高い化合物を効率良く得るこ
とが重要である。Optically active 1,l-trifluoro-2-alkanol is a compound useful as a raw material for the synthesis of ferroelectric liquid crystal compounds.It is essential for ferroelectric liquid crystal compounds to be optically active, and for this reason, optical purity is important. It is important to efficiently obtain high-quality compounds.
［従来の技術］
従来、（±）−１，ｌ、１−トリフルオロ−２−アルカ
ノールは、トリフルオロ酢酸とアルキルグリニヤール試
薬から得られる１、１．１−トリフルオロアルカノンを
還元することにより以下のようにして合成される。[Prior Art] Conventionally, (±)-1,l,1-trifluoro-2-alkanol is produced as follows by reducing 1,1,1-trifluoroalkanone obtained from trifluoroacetic acid and an alkyl Grignard reagent. It is synthesized as follows.
しかしながら、この方法ではラセミ体のトリフルオロア
ルカノールしか得られない。However, this method only yields racemic trifluoroalkanols.
また、２−アセトキシ−１，１，１−トリフルオロアル
カンを酵素により不斉加水分解し、光学活性体を得る方
法（ヤン テン リン［ＪｅｎｑＴａｉｎ Ｌｉｎ］お
よび山崎、北爪「ジャーナル オンオーガニック シン
セシス（Ｊｏｕｒｎｏｌ ｏｆ Ｏｒｇａｎ−ｉｃ
５ｙｎｔｈｅｓｉｓ ） Ｊ ３２１１〜コ２１
コ頁、 Ｖｏｌ、５２． Ｎｏ。In addition, a method of asymmetrically hydrolyzing 2-acetoxy-1,1,1-trifluoroalkane with an enzyme to obtain an optically active substance (JenqTain Lin and Yamazaki, Kitazume, "Journal of Organic Synthesis") Organic
5ynthesis) J 3211~ko21
Cop., Vol. 52. No.
Ｉｓ、 １９８７年）も知られているが、製造条件が微
妙な為、工業的には有効な方法であるとはいえない、す
なわち、強誘電性液晶化合物の開発に利用するためには
、光学純度の高い化合物を効率よく製造することができ
る方法でなければならない。Is, 1987), but it cannot be said to be an industrially effective method because the manufacturing conditions are delicate. The method must be able to efficiently produce a highly pure compound.
［発明が解決しようとする課題］
本発明の目的は、上記の問題点を改善し、光学活性な１
，１−トリフルオロ−２−アルカノールを工業的に効率
良く、高光学純度で製造する方法を提供することにある
。[Problems to be Solved by the Invention] The purpose of the present invention is to improve the above-mentioned problems and to provide an optically active monomer.
, 1-trifluoro-2-alkanol industrially and efficiently with high optical purity.
［課題を解決するための手段］および［作用］本発明者
等は、光学活性なｌ、ｌ、ｌ−トリフルオロ−２−アル
カノールを得る為、鋭意検討した結果、（±）−ｉ、ｌ
、ｉ−トリフルオロ−２−アルカノールに光学活性なト
ランス−２−ベンズアミドシクロヘキサンカルボン酸を
作用させ、生成したジアステレオマーのエステルを溶媒
に対する溶解度の差により光学分割する方法により、光
学活性なｌ、ｌ、１−トリフルオロ−２−アルカノール
を高収率、かつ高光学純度で製造できることを見出した
。[Means for Solving the Problems] and [Action] The present inventors have conducted intensive studies to obtain optically active l,l,l-trifluoro-2-alkanol, and have found that (±)-i,l
, i-trifluoro-2-alkanol is reacted with optically active trans-2-benzamidocyclohexanecarboxylic acid, and the resulting diastereomeric esters are optically resolved based on the difference in solubility in the solvent, thereby producing optically active l, It has been found that 1,1-trifluoro-2-alkanol can be produced in high yield and with high optical purity.
即ち、本発明は、（±）−１，ｌ、ｌ−トリフルオロ−
２−アルカノールに光学活性なトランス−２−ベンズア
ミドシクロヘキサンカルボン酸を作用させることを特徴
とする下記−形式（１）％式％（１）
（式中、Ｒは炭素原子数が４〜８である直鎖状アルキル
基、Ｃ１は不斉炭素原子を示す）で表わされる光学活性
１，１．１−トリフルオロ−２−アルカノールの製造法
である。That is, the present invention provides (±)-1,1,1-trifluoro-
The following formula (1) % formula % (1) (wherein, R has 4 to 8 carbon atoms This is a method for producing an optically active 1,1.1-trifluoro-2-alkanol represented by a linear alkyl group (C1 represents an asymmetric carbon atom).
以下、本発明の実施態様を順を追って説明する。Hereinafter, embodiments of the present invention will be described in order.
光学活性なトランス−２−ベンズアミドシクロヘキサン
カルボン酸に塩化チオニルを作用させ酸塩化物とした後
、（±）−１，ｌ、ｌ−トリフルオロ−２−アルカノー
ルと反応させジアステレオマーのエステルとする。ここ
で用いられる光学活性なトランス−２−ベンズアミドシ
クロヘキサンカルボン酸の量は、（±）−１，ｌ、１−
トリフルオロ−２−アルカノールに対し、等モル量以上
であれば特に限定されるものではないが、１．０〜１．
２倍モル量が好適である。Optically active trans-2-benzamidocyclohexanecarboxylic acid is reacted with thionyl chloride to form an acid chloride, and then reacted with (±)-1,l,l-trifluoro-2-alkanol to form a diastereomeric ester. . The amount of optically active trans-2-benzamidocyclohexanecarboxylic acid used here is (±)-1,1,1-
There is no particular limitation as long as the amount is equal to or more than the equivalent molar amount relative to trifluoro-2-alkanol, but 1.0 to 1.
A double molar amount is preferred.
このようにして得られたジアステレオマーのエステルを
溶媒に加熱溶解させ、過飽和溶液とした後、徐冷して難
溶性基のジアステレオマーのエステルを析出させる。The diastereomeric ester thus obtained is heated and dissolved in a solvent to form a supersaturated solution, and then slowly cooled to precipitate the diastereomeric ester of the poorly soluble group.
ここで用いる溶媒としては、目的のジアステレオマーの
エステルを析出させるものであれば特に制限はない、す
なわち、水、又はメタノール、エタノール、２−プロパ
ツールなどのアルコール類、又はアセトン、メチルエチ
ルケトンなどのケトン類、又は酢酸メチル或いは酢酸エ
チルなどのエステル類、又はベンゼン、トルエン或いは
キシレンなどの芳香族炭化水素類、又は塩化メチレン、
クロロホルム或いは四塩化炭素などのハロゲン化炭素類
、又はペンタン、ヘキサン或いはシクロヘキサンなどの
飽和脂肪族炭化水素類、およびテトラヒドロフランなど
を好適な例として挙げることができる。これらの溶媒は
、単独でも良いが必要に応じて連出な比率で混合して使
用しても良い。The solvent used here is not particularly limited as long as it can precipitate the ester of the desired diastereomer, i.e., water, alcohols such as methanol, ethanol, 2-propanol, or acetone, methyl ethyl ketone, etc. Ketones, or esters such as methyl acetate or ethyl acetate, or aromatic hydrocarbons such as benzene, toluene, or xylene, or methylene chloride,
Suitable examples include halogenated carbons such as chloroform or carbon tetrachloride, saturated aliphatic hydrocarbons such as pentane, hexane or cyclohexane, and tetrahydrofuran. These solvents may be used alone, or may be used in combination in different proportions, if necessary.
得られた結晶は濾過・分離した後、必要であれば再結晶
した後、メタノールに溶解させ、強塩基と水を加え加熱
還流することにより難溶性塩のジアステレオマーのエス
テルを加水分解する。After the obtained crystals are filtered and separated, and if necessary recrystallized, they are dissolved in methanol, a strong base and water are added, and the diastereomeric ester of the sparingly soluble salt is hydrolyzed by heating and refluxing.
すなわち、エステルに等モル以上の強塩基（水酸化ナト
リウム・、水酸化カリウムなど）を加えてエステルを加
水分解する０次いで、適当な有機溶媒で抽出することに
より光学活性な（＋）−または（−）−１，１，１−ト
リフルオロ−２−アルカノールを得る。光学分割剤であ
るトランス−２−ベンズアミドシクロヘキサンカルボン
酸はｌ。That is, an equimolar amount or more of a strong base (sodium hydroxide, potassium hydroxide, etc.) is added to the ester to hydrolyze the ester. Next, the optically active (+)- or ( -)-1,1,1-trifluoro-2-alkanol is obtained. The optical resolution agent trans-2-benzamidocyclohexanecarboxylic acid is l.
１、ｌ−トリフルオロ−２−アルカノールを抽出除去し
た後の水層に等モル以上の無ａｍ（塩酸。After extracting and removing 1,1-trifluoro-2-alkanol, more than the same mole of ammonium (hydrochloric acid) is added to the aqueous layer.
硫酸等）を加える方法で有機溶媒で抽出して回収するこ
とができる。It can be recovered by extraction with an organic solvent by adding sulfuric acid, etc.).
また、光学分割剤の（＋）一体と（−）一体を適当に選
ぶことにより、（＋）−または（−）−１、ｌ、１−ト
リフルオロ−２−アルカノールを任意に得ることが可能
である。In addition, by appropriately selecting (+) and (-) units of the optical resolution agent, it is possible to arbitrarily obtain (+)- or (-)-1, l, 1-trifluoro-2-alkanol. It is.
以下に本発明で製造できる光学活性１，１．．１−トリ
フルオロ−２−アルカノールを示す。Optical activities 1, 1. which can be produced by the present invention are as follows. ．． Indicates 1-trifluoro-2-alkanol.
Ｆ３
（＋）−または（−）−
ｎ −Ｃ４１１ｓ −ＣＩｔ −ＯＩＩ（＋）−または
（−）−
Ｆ３
ｎ−Ｃ５Ｈ，、−ＣＩｌ−Ｏｆｔ
（＋）−または（−）−
Ｆ３
ｎ −Ｃ、１１、、−ＣＩＩ −ＯＩｆＣＦ。F3 (+)- or (-)- n -C411s -CIt -OII (+)- or (-)- F3 n-C5H,, -CIl-Oft (+)- or (-)- F3 n -C, 11, , -CII-OIfCF.
（＋）−または（） ｎ−Ｃｙｌｌｔ ５−ＣＩ
ｌ−Ｏ１１Ｆ３
（＋）−または（−） −ｎ−ＣａＬｔ−ｅｌｆ−０１
１［実施例］
以下、実施例を示し本発明をさらに具体的に説明する。(+)- or () n-Cyllt 5-CI
l-O11F3 (+)- or (-) -n-CaLt-elf-01
1 [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
１．１．ｌ−トリフルオロ−２−オクタツールの光学分
割
（−）−トランス−２−ベンズアミドシクロヘキサンカ
ルボン酸１．３１１ｇ （５，３ＩＩＭ ）を塩化チオ
ニル５醜Ｐと７０℃で１．５時間反応させ、酸クロリド
とした後、乾燥ベンゼン５ｓｊ）と共沸させ過剰の塩化
チオニルを完全に留去した。これにベンゼン３ｍｌを加
え、攪拌しながら、（±）−１，１，１−トリフルオロ
−２−オクタツール０．９２１ｇ （５ｍＭ）のベンゼ
ン１ｍｌ溶液を滴下し１次いでピリジン０．４４ｇ （
５，５ｍＭ）のベンゼン３ｓＲ溶液を滴下した。６５℃
で６時間反応させた後、水１５膳２を加えピリジン塩酸
塩を溶解させた。過剰のカルボン酸が白色固体として生
じるのてろ過した後、反応溶液をベンゼンで抽出し、ベ
ンゼン層を１Ｍ塩酸、５％炭酸ナトリウム溶液、蒸留水
で順次洗沙した後、無水硫酸マグネシウムで乾燥させ、
溶媒を留去した。Example 1 1.1. Optical resolution of l-trifluoro-2-octatool 1.311 g (5,3IIM) of (-)-trans-2-benzamide cyclohexanecarboxylic acid was reacted with thionyl chloride 5-ugly P at 70°C for 1.5 hours to obtain an acid After converting it into chloride, it was azeotropically distilled with dry benzene (5sj) to completely distill off excess thionyl chloride. 3 ml of benzene was added to this, and while stirring, a solution of 0.921 g (±)-1,1,1-trifluoro-2-octatool (5 mM) in 1 ml of benzene was added dropwise, followed by 0.44 g of pyridine (
A solution of benzene 3sR (5.5mM) was added dropwise. 65℃
After reacting for 6 hours, 15 portions of water (2 portions) were added to dissolve pyridine hydrochloride. Excess carboxylic acid was produced as a white solid and after filtration, the reaction solution was extracted with benzene, and the benzene layer was sequentially washed with 1M hydrochloric acid, 5% sodium carbonate solution, and distilled water, and then dried over anhydrous magnesium sulfate. ,
The solvent was distilled off.
得られたエステルは収量１．９２ｇ （４，６３鳳Ｍ
）、収率９３％であった。The yield of the obtained ester was 1.92 g (4,63 M
), yield was 93%.
このエステルなヘキサン２０ａｌｌに加熱還流により溶
解させた後、放冷、氷冷し、冷凍庫に一晩静置した。生
じた白色固体をろ別し、（−）−トランス−２−ベンズ
アミドシクロヘキサンカルボン酸の（−）−１，１，１
−トリフルオロ−２−オクタツールエステル０．８６５
ｇ （２，０９霞Ｍ）を得た。収率４１．７％、［Ｑ］
、コ’−５２，９″ （ｃ １．０２７ 、
酢酸エチル） ＊ ＣＱ ］ ４３５” −１０３，
８°（ｃ １．０２７ 、酢酸エチル）。The mixture was dissolved in 20 all of this ester hexane by heating under reflux, then allowed to cool, cooled on ice, and left in a freezer overnight. The resulting white solid was filtered and the (-)-1,1,1 of (-)-trans-2-benzamidocyclohexanecarboxylic acid
-Trifluoro-2-octatool ester 0.865
g (2,09 haze M) was obtained. Yield 41.7%, [Q]
, ko'-52,9'' (c 1.027,
ethyl acetate) *CQ] 435" -103,
8° (c 1.027, ethyl acetate).
上記で得られたエステルをヘキサン：酢酸エチル＝１：
１の混合溶媒５．７ ｍｌで再結晶し、精製エステル０
．６０１ｇ （１，４５ｍＭ）を得た。［α］。２７５
６．４° （ｃ １．００９ 、酢酸エチル） ＊
［Ｑ ］ ｎｉａ”−１０９，５°（ｃ １．００９
、酢酸エチル）。The ester obtained above was mixed with hexane:ethyl acetate=1:
Recrystallize with 5.7 ml of a mixed solvent of 1 to obtain purified ester 0
．． 601g (1.45mM) was obtained. [α]. 275
6.4° (c 1.009, ethyl acetate) *
[Q] nia”-109,5° (c 1.009
,Ethyl acetate).
このエステル０．６０１ｇ （１，４５膳鷺）をメタノ
ール４−２に溶かし、これに水酸化カリウム０．：ｌＯ
ｇを水０．４ ｍｌに溶かしたものを加え、５時間加熱
還流させた。放冷後、減圧下にてメタノールを留去し、
それに水５膳２を加え、エーテル抽出し、エーテル層を
無水硫酸マグネシウムで乾燥した。エーテル留去の後、
減圧蒸留（９０〜１００°Ｃ／ ４７ｍｓｌ１ｇ） Ｌ
／、（−） −１，１，１−トリフルオロ−２−オクタ
ツール０．１８７ｇ （１，０２１Ｍ）を得た。Dissolve 0.601 g (1,45 servings) of this ester in 4-2 methanol and add 0.60 g of potassium hydroxide. :lO
g dissolved in 0.4 ml of water was added, and the mixture was heated under reflux for 5 hours. After cooling, methanol was distilled off under reduced pressure.
Five portions of water and two portions were added thereto, followed by extraction with ether, and the ether layer was dried over anhydrous magnesium sulfate. After ether distillation,
Vacuum distillation (90-100°C/47msl1g) L
0.187 g (1,021 M) of /, (-) -1,1,1-trifluoro-2-octatool was obtained.
初めに用いたアルコールの半量を１００とした収率は４
０．６％＊ ［Ｑ ］ ｏ” −２４，Ｓｏ （ｃ
１．００６ 、工−チル）、［α］ ＜３ｓ” −４６
，０” （ｃ １．００６ 、エーテル）であった。The yield is 4 when half the amount of alcohol used at the beginning is taken as 100.
0.6%* [Q] o” -24, So (c
1.006, engineering-chill), [α] <3s" -46
,0'' (c 1.006, ether).
このようにして得られた（−）−１，１，１−トリフル
オロ−２−オクタツールを４−アセトキシ安息香酸との
エステルに訪導し、光学活性な充填剤を用いたカラムク
ロマトグラフィーにより光学純度を検定したところ、そ
の光学純度は８５％であった。The thus obtained (-)-1,1,1-trifluoro-2-octatool was converted into an ester with 4-acetoxybenzoic acid, and the mixture was subjected to column chromatography using an optically active packing material. When the optical purity was assayed, the optical purity was 85%.
また、上記の操作において、（−）−トランス−２−ベ
ンズアミドシクロヘキサンカルボン酸の代わりに（＋）
−トランス−２−ベンズアミドシクロヘキサンカルボン
酸を用いることにより、（＋）−１，ｌ、１−トリフル
オロ−２−オクタツールを得ることができる。Also, in the above operation, (+) instead of (−)-trans-2-benzamidocyclohexanecarboxylic acid
By using -trans-2-benzamidocyclohexanecarboxylic acid, (+)-1,1,1-trifluoro-2-octatool can be obtained.
［発明の効果］
本発明の方法により、光学活性な（＋）−または（−）
−１，１，１−トリフルオロ−２−アルカノールを効率
良く、また高光学純度で得ることが可能になつた。また
、本発明の方法は工業的に大量生産が可能な方法であり
、得られた光学活性なｌ、１．１−トリフルオロ−２−
アルカノールは強誘電性液晶化合物の合成原料として有
用である。[Effect of the invention] By the method of the present invention, optically active (+)- or (-)
It has become possible to obtain -1,1,1-trifluoro-2-alkanol efficiently and with high optical purity. Moreover, the method of the present invention is a method that allows industrial mass production, and the optically active l,1,1-trifluoro-2-
Alkanols are useful as raw materials for the synthesis of ferroelectric liquid crystal compounds.
Claims (2)
ノールに光学活性なトランス−２−ベンズアミドシクロ
ヘキサンカルボン酸を作用させることを特徴とする下記
一般式（１） ▲数式、化学式、表等があります▼（１） （式中、Ｒは炭素原子数が４〜８である直鎖状アルキル
基、Ｃ＾＊は不斉炭素原子を示す） で表わされる光学活性１，１，１−トリフルオロ−２−
アルカノールの製造法。(1) The following general formula (1) characterized by reacting optically active trans-2-benzamidocyclohexanecarboxylic acid with (±)-1,1,1-trifluoro-2-alkanol ▲Mathematical formula, chemical formula, There are tables, etc. ▼ (1) (In the formula, R is a linear alkyl group having 4 to 8 carbon atoms, and C^* represents an asymmetric carbon atom) Optical activity 1,1,1 -trifluoro-2-
Method for producing alkanol.
ノールに光学活性なトランス−２−ベンズアミドシクロ
ヘキサンカルボン酸を作用させ、生成したジアステレオ
マーのエステルから溶解度の差により難溶性塩のジアス
テレオマーを得た後、該難溶性塩のジアステレオマーを
加水分解して前記一般式（１）で表わされる光学活性１
，１，１−トリフルオロ−２−アルカノールを得る請求
項１記載の製造法。(2) (±)-1,1,1-Trifluoro-2-alkanol is reacted with optically active trans-2-benzamide cyclohexanecarboxylic acid, and the resulting diastereomer ester becomes a poorly soluble salt due to the difference in solubility. After obtaining the diastereomer of the slightly soluble salt, the diastereomer of the poorly soluble salt is hydrolyzed to obtain the optical activity 1 represented by the general formula (1).
2. The method according to claim 1, wherein 1,1-trifluoro-2-alkanol is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21853688A JPH0267237A (en) | 1988-09-02 | 1988-09-02 | Production of optically active 1,1,1-trifluoro-2-alkanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21853688A JPH0267237A (en) | 1988-09-02 | 1988-09-02 | Production of optically active 1,1,1-trifluoro-2-alkanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0267237A true JPH0267237A (en) | 1990-03-07 |
Family
ID=16721467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21853688A Pending JPH0267237A (en) | 1988-09-02 | 1988-09-02 | Production of optically active 1,1,1-trifluoro-2-alkanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0267237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194177A (en) * | 1991-01-30 | 1993-03-16 | Canon Kabushiki Kaisha | Optically active compound, liquid crystal composition, liquid crystal device, display apparatus and display method |
-
1988
- 1988-09-02 JP JP21853688A patent/JPH0267237A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194177A (en) * | 1991-01-30 | 1993-03-16 | Canon Kabushiki Kaisha | Optically active compound, liquid crystal composition, liquid crystal device, display apparatus and display method |
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