JPH01157929A - Production of optically active 2-fluorobutanoic acid - Google Patents
Production of optically active 2-fluorobutanoic acidInfo
- Publication number
- JPH01157929A JPH01157929A JP31410087A JP31410087A JPH01157929A JP H01157929 A JPH01157929 A JP H01157929A JP 31410087 A JP31410087 A JP 31410087A JP 31410087 A JP31410087 A JP 31410087A JP H01157929 A JPH01157929 A JP H01157929A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- acid
- fluorobutanoic
- fluorobutanoic acid
- solvent
- 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
- GCSPSGQVZXMPKU-UHFFFAOYSA-N 2-fluorobutanoic acid Chemical compound CCC(F)C(O)=O GCSPSGQVZXMPKU-UHFFFAOYSA-N 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002253 acid Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 13
- 230000003287 optical effect Effects 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- ZICDZTXDTPZBKH-UHFFFAOYSA-N 2-(4-methylphenyl)-1-phenylethanamine Chemical compound C1=CC(C)=CC=C1CC(N)C1=CC=CC=C1 ZICDZTXDTPZBKH-UHFFFAOYSA-N 0.000 abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 Water Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003947 ethylamines Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LWCDSJZGNUDNCO-IHWYPQMZSA-N (z)-2-fluorobut-2-enoic acid Chemical compound C\C=C(/F)C(O)=O LWCDSJZGNUDNCO-IHWYPQMZSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- BLYSPQXGKZNMJA-UHFFFAOYSA-N 2-fluorobutan-1-ol Chemical compound CCC(F)CO BLYSPQXGKZNMJA-UHFFFAOYSA-N 0.000 description 1
- IXHWZHXLJJPXIS-UHFFFAOYSA-N 2-fluorobutane Chemical compound CCC(C)F IXHWZHXLJJPXIS-UHFFFAOYSA-N 0.000 description 1
- RUJHATQMIMUYKD-UHFFFAOYSA-N 2-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C(CCN)=CC=CC2=C1 RUJHATQMIMUYKD-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WISBVPAFDHAZAM-UHFFFAOYSA-N n-[2-(4-methylphenyl)ethyl]aniline Chemical compound C1=CC(C)=CC=C1CCNC1=CC=CC=C1 WISBVPAFDHAZAM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 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２−フルオロブタン酸の製造法に関し
、詳しくは強誘電性液晶化合物の合成原料として有用な
光学活性な２−フルオロブタン酸の製造方法に関するも
のである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing optically active 2-fluorobutanoic acid, and more particularly, to a method for producing optically active 2-fluorobutanoic acid, which is useful as a raw material for the synthesis of ferroelectric liquid crystal compounds. The present invention relates to a manufacturing method.
［従来の技術］
従来、（±）−２−フルオロブタン酸の製造法としては
、１，２−エポキシブタンを原料とじてフッ化水素を作
用させて２−フルオロブタノールとし、これを酸化する
ことにより合成する方法か知られている。[Prior Art] Conventionally, the method for producing (±)-2-fluorobutanoic acid involves using 1,2-epoxybutane as a raw material, reacting hydrogen fluoride with it to form 2-fluorobutanol, and oxidizing this. A method of synthesis is known.
しかしながら、この方法ではラセミ体の２−フルオロブ
タン酸しか得られない。However, this method only yields racemic 2-fluorobutanoic acid.
また、アミノ酸に亜硝酸を作用させ、続いてフッ化水素
ピリジンを作用させて合成する方法［オラーおよびウェ
ルフェ、シンセシス（５ｙｎｔｈｅｓｉｓ）、 １９７
４． ６５２頁］も知られているが、この方法により光
学活性な２−フルオロブタン酸か得られたという報告は
ない。In addition, a method of synthesizing amino acids by reacting nitrous acid with hydrogen fluoride pyridine [Oler and Welfe, Synthesis, 197]
4. 652] is also known, but there is no report that optically active 2-fluorobutanoic acid was obtained by this method.
光学活性な２−フルオロブタン酸の合成法としては、２
−フルオロクロトン酸に酵素を作用させる方法［ハシモ
トおよびシモン、アンゲヴアンテヘミー（Ａｎｇｅｗａ
ｎｄｔｅ Ｃｈｅｍｉｅ） 、 ８７巻、１１１頁。As a method for synthesizing optically active 2-fluorobutanoic acid, 2
- A method of causing an enzyme to act on fluorocrotonic acid [Hashimoto and Simon, Angewand Chemie]
ndte Chemie), vol. 87, p. 111.
１９７５年］、および光学活性なキャピラリーカラムで
（±）−２−フルオロブタン酸を分割する方法［ワタへ
およびギル−アブ、ジャーナル オツ７クロマトグラフ
ィ−（Ｊｏｕｒｎａｌ ｏｆ Ｃｈｒｏｍａｔｏｇｒａ
ｐｈｙ）、 ３８１巻、２３５頁、 １９８５年］が知
られている。1975], and a method for resolving (±)-2-fluorobutanoic acid in an optically active capillary column [Watahe and Gil-Ab, Journal of Chromatography.
phy), vol. 381, p. 235, 1985].
しかしながら、これらの方法では光学活性な２−フルオ
ロブタン酸を効率よく得ることはできない。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、工業的に効率よく製造できる方法で
なければならない。However, optically active 2-fluorobutanoic acid cannot be efficiently obtained by these methods. That is,
In order to use this method for the development of ferroelectric liquid crystal compounds, it is necessary to use a method that can industrially and efficiently produce compounds with high optical purity.
［発明が解決しようとする問題点］
本発明の目的は、上記の問題点を改善し、光学活性な２
−フルオロブタン酸を工業的に効率よく製造する方法を
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
- To provide a method for industrially and efficiently producing fluorobutanoic acid.
［問題点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２−フルオロブタン酸を得るため鋭
意検討した結果、（±）−２−フルオロブタン酸に光学
活性なｌ−フェニル−２−（ｐ−トリル）エチルアミン
を作用させ、生成したジアステレオマー塩を、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２−フルオロブタン酸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 [Operation] As a result of intensive studies to obtain optically active 2-fluorobutanoic acid, the present inventors found that (±)-2-fluorobutanoic acid has an optically active l - Optically active 2-fluorobutanoic acid is produced in high yield and high optical purity by a method of reacting phenyl-2-(p-tolyl)ethylamine and optically resolving the generated diastereomer salt based on the difference in solubility in the solvent. We discovered that it can be manufactured using
すなわち、本発明は、（±）−２−フルオロブタン酸に
光学活性なｌ−フェニル−２−（ｐ−トリル）エチルア
ミンを作用させて得られるジアステレオマー塩の溶媒に
対する溶解度差を利用して（±）−２−フルオロブタン
酸を光学分割することを特徴とする光学活性２−フルオ
ロブタン酸の製造法に係わるものである。That is, the present invention utilizes the difference in solubility in a solvent of diastereomeric salts obtained by reacting optically active l-phenyl-2-(p-tolyl)ethylamine with (±)-2-fluorobutanoic acid. The present invention relates to a method for producing optically active 2-fluorobutanoic acid, which is characterized by optically resolving (±)-2-fluorobutanoic acid.
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.
先ず、適当な溶媒に、（±）−２−フルオロブタン酸と
光学活性なｌ−フェニル−２−（ｐ−トリル）エチルア
ミンを加え加熱溶解する。First, (±)-2-fluorobutanoic acid and optically active l-phenyl-2-(p-tolyl)ethylamine are added to a suitable solvent and dissolved by heating.
ここで用いる溶媒としては、目的のジアステレオマー塩
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適当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 desired diastereomeric salt, i.e.
Water, or alcohols such as methanol, ethanol, or 2-propanol, or ketones such as acetone or methyl ethyl ketone, or esters such as methyl acetate or ethyl acetate, or aromatic hydrocarbons such as benzene, toluene, or xylene. Suitable examples include carbon halides such as methylene chloride, 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 as a mixture in an appropriate ratio, if necessary.
ここで用いられる光学活性なｌ−フェニル−２−（ｐ−
トリル）エチルアミンの量は、特に限定されるものでは
ないが、（±）−２−フルオロブタン９１モルに対し、
０．５から１．１モル量が好適である。The optically active l-phenyl-2-(p-
The amount of tolyl)ethylamine is not particularly limited, but for 91 mol of (±)-2-fluorobutane,
0.5 to 1.1 molar amounts are preferred.
このようにして得られた過飽和溶液を徐冷して難溶性の
ジアステレオマー塩を析出させる。この際、上記過飽和
溶液に難溶性塩である（＋）−２−フルオロブタン酸・
（＋）−１−フェニル−２−（ｐ−）−リル）エチルア
ミン塩、または（−）−２−フルオロブタン酸・ （−
）−１−フェニル−２−（ｐ−）リル）エチルアミン塩
を少量接種して析出させてもよい。得られた結晶は、ろ
過分離した後、必要であれば再結晶した後、常法通りの
方法でジアステレオマー塩を分解する。The supersaturated solution thus obtained is slowly cooled to precipitate the sparingly soluble diastereomeric salt. At this time, (+)-2-fluorobutanoic acid, which is a sparingly soluble salt in the supersaturated solution,
(+)-1-phenyl-2-(p-)-lyl)ethylamine salt, or (-)-2-fluorobutanoic acid (-
)-1-phenyl-2-(p-)lyl)ethylamine salt may be inoculated in a small amount for precipitation. After the obtained crystals are separated by filtration and recrystallized if necessary, the diastereomeric salts are decomposed by a conventional method.
すなわち、ジアステレオマー塩に等モル以上の無機酸（
例えば、塩酸、硫酸等）を加えて塩を分解する０次いで
、適当な有機溶媒を用いて抽出することにより光学活性
な（＋）−または（−）−２−フルオロブタン酸を得る
ことができる。In other words, the diastereomeric salt contains at least the same molar amount of inorganic acid (
For example, hydrochloric acid, sulfuric acid, etc.) are added to decompose the salt.Next, optically active (+)- or (-)-2-fluorobutanoic acid can be obtained by extraction using an appropriate organic solvent. .
ここで用いる有機溶媒としては、エーテル、塩化メチレ
ン、クロロホルムなどがあげられる。Examples of the organic solvent used here include ether, methylene chloride, and chloroform.
このジアステレオマー塩に対する無機酸添加に先立ち、
等モル以上のアルカリ（例えば、水酸化ナトリウム、水
酸化カリウム等）を加える方法で、光学分割剤である１
−フェニル−２−（ｐ−トリル）エチルアミンを有機溶
媒で抽出して回収することがてきるが、２−フルオロブ
タン酸を遊離させ抽出除去した後の水層に、等モル以上
のアルカリを加える方法でも光学分割剤の回収は可能で
ある。Prior to the addition of an inorganic acid to this diastereomeric salt,
This method involves adding more than the same mole of alkali (e.g., sodium hydroxide, potassium hydroxide, etc.) to 1, which is an optical resolving agent.
-Phenyl-2-(p-tolyl)ethylamine can be extracted and recovered with an organic solvent, but after liberating and extracting 2-fluorobutanoic acid, an aqueous layer containing at least the same molar amount of alkali is added. It is also possible to recover the optical resolution agent using this method.
又、光学分割剤の（＋）一体と（−）一体を適当に選ら
ぶことにより、（＋）−または（−）−２−フルオロブ
タン酸を任意に得ることが可能てある。Furthermore, by appropriately selecting the (+) and (-) parts of the optical resolution agent, it is possible to obtain (+)- or (-)-2-fluorobutanoic acid as desired.
上記の方法により得られる光学活性な２−フルオロブタ
ン酸は、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。強誘電性液晶化合物は光学活性であること
か必須であり、このため、本発明の方法により製造され
る化合物の２−フルオロブタン酸が光学活性であること
は、強誘電性液晶化合物の合成原料として重要なポイン
トである。Optically active 2-fluorobutanoic acid obtained by the above method is a compound useful as a raw material for the synthesis of ferroelectric liquid crystal compounds. It is essential for a ferroelectric liquid crystal compound to be optically active. Therefore, the fact that 2-fluorobutanoic acid, which is a compound produced by the method of the present invention, is optically active means that it is a raw material for the synthesis of a ferroelectric liquid crystal compound. This is an important point.
［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。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
（＋）−ｉ−フェニル−２−（ｐ−トリル）エチルアミ
ン（以下、（、）−ＰＴＥと略記する） ｉｏ、３８ｇ
（４９，２腸Ｍ）と（±）−２−フルオロブタン酸６．
５２ｇ（６１，５ｍＭ）を、アセトン−メタノール（２
：１）の混合溶媒１８ｓＪに加え、加熱溶解した後に冷
蔵庫内に一晩静置した。析出した納品をろ別することに
より（、）−ＰＴＥ ・（＋）−２−フルオロブタン酸
塩９．７．４ｇを得た。これを当該混合溶媒を用いて４
回再結晶することにより精製・（＋）−ＰＴＥ・（＋）
−２−フルオロブタン酸塩２．７１ｇ（３，５５■−）
を得た。融点１８２〜１８４℃、［α］ ＜：＋ｓ”
’ ＋ １９７．３’ （ｃＯ，９５１； ＭｅＯＨ）
、用いた（±）−２−フルオロブタン酸中の（＋）一体
に対する収率は、２７．８％であった・
この塩を１Ｍ水酸化ナトリウム水溶液に溶解させ、エー
テルで（＋）−ＰＴＥを抽出除去し、次に、この水層に
濃塩酸をｐｉｌｌになるまで加えてから。Example 1 (+)-i-phenyl-2-(p-tolyl)ethylamine (hereinafter abbreviated as (,)-PTE) io, 38 g
(49,2-M) and (±)-2-fluorobutanoic acid6.
52g (61.5mM) was dissolved in acetone-methanol (2
:1) was added to 18 sJ of the mixed solvent, heated and dissolved, and then left to stand in a refrigerator overnight. The precipitated product was filtered to obtain 9.7.4 g of (,)-PTE.(+)-2-fluorobutanoate. Using this mixed solvent,
Purified by multiple recrystallization・(+)-PTE・(+)
-2-fluorobutanoate 2.71g (3,55■-)
I got it. Melting point 182-184℃, [α] <:+s”
'+197.3'(cO,951; MeOH)
, the yield for the (+) unit in the (±)-2-fluorobutanoic acid used was 27.8%. This salt was dissolved in 1M aqueous sodium hydroxide solution, and the (+)-PTE was dissolved in ether. was extracted and removed, and then concentrated hydrochloric acid was added to this aqueous layer until it became a pill.
エーテルを用いて（＋）−２−フルオロブタン酸を抽出
した。このエーテル溶液を硫酸ナトリウムて乾燥した後
、溶媒を留去しく＋）−２−フルオロブタン酸０．８５
ｇ （８，０２ｍＭ）を得た。用いた（±）−２−フル
オロブタン酸中の（＋）一体に対する収率は２６．１％
であった。(+)-2-fluorobutanoic acid was extracted using ether. After drying this ether solution over sodium sulfate, the solvent was distilled off.
g (8.02mM) was obtained. The yield of (+) monomer in the (±)-2-fluorobutanoic acid used was 26.1%.
Met.
［α］ ５８９２７” ＋ １２．９’″（ｃ １．０
６１．エーテル）。[α] 58927" + 12.9'" (c 1.0
61. ether).
Ｅ ａ ］ ４３．．” ４＋ ２７．２°（ｃ １．
Ｑ６１． エーテル）。E a ] 43. ．． ” 4+ 27.2° (c 1.
Q61. ether).
このようにして得られた（＋）−２−フルオロブタン酸
を光学活性なナフチルエチルアミンとのアミドに誘導し
、これを高速液体クロマトグラフィーにかけて光学純度
を検定したところ、その光学純度は９４．４％であった
。The thus obtained (+)-2-fluorobutanoic acid was induced into an amide with optically active naphthylethylamine, and the optical purity was assayed by high performance liquid chromatography, and the optical purity was 94.4. %Met.
また、上記操作において、（、）−ＰＴＨの代りに（−
）−ＰＴＥを用いることにより、（−）−２−フルオロ
ブタン酸を得ることかできた。Also, in the above operation, instead of (,)-PTH, (-
)-PTE, it was possible to obtain (-)-2-fluorobutanoic acid.
［α］ ４：＋ｓ３４’ ２７．９°（ｃ １．４７
９．エーテル）、光学純度９６．９％であった。[α] 4: +s34' 27.9° (c 1.47
9. ether), and the optical purity was 96.9%.
［発明の効果］
本発明の方法により光学活性な（＋）−または（−）−
２−フルオロブタン酸を効率良く、また高光学純度で得
ることが可能になった。この方法は工業的に大量生産か
可能な方法てあり、また得られた光学活性２−フルオロ
ブタン酸は新しい強誘電性液晶化合物を合成する原料と
しての利用も可能である。[Effect of the invention] Optically active (+)- or (-)-
It has become possible to obtain 2-fluorobutanoic acid efficiently and with high optical purity. This method allows industrial mass production, and the optically active 2-fluorobutanoic acid obtained can also be used as a raw material for synthesizing new ferroelectric liquid crystal compounds.
出願人 山川薬品工業株式会社 ノＩ キャノン株式会社 代理人 渡 辺 徳 廣Applicant: Yamakawa Pharmaceutical Co., Ltd. Canon Co., Ltd. Agent: Hiroshi Watari Hebe
Claims (1)
ル−２−（ｐ−トリル）エチルアミンを作用させて得ら
れるジアステレオマー塩の溶媒に対する溶解度差を利用
して（±）−２−フルオロブタン酸を光学分割すること
を特徴とする光学活性２−フルオロブタン酸の製造法。(±)-2- A method for producing optically active 2-fluorobutanoic acid, which comprises optically resolving fluorobutanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31410087A JPH01157929A (en) | 1987-12-14 | 1987-12-14 | Production of optically active 2-fluorobutanoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31410087A JPH01157929A (en) | 1987-12-14 | 1987-12-14 | Production of optically active 2-fluorobutanoic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01157929A true JPH01157929A (en) | 1989-06-21 |
Family
ID=18049238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31410087A Pending JPH01157929A (en) | 1987-12-14 | 1987-12-14 | Production of optically active 2-fluorobutanoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01157929A (en) |
-
1987
- 1987-12-14 JP JP31410087A patent/JPH01157929A/en active Pending
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