JPH02235828A - Optically active 2-fluoro-2-methyl-1-alkanols and preparation thereof - Google Patents
Optically active 2-fluoro-2-methyl-1-alkanols and preparation thereofInfo
- Publication number
- JPH02235828A JPH02235828A JP5605889A JP5605889A JPH02235828A JP H02235828 A JPH02235828 A JP H02235828A JP 5605889 A JP5605889 A JP 5605889A JP 5605889 A JP5605889 A JP 5605889A JP H02235828 A JPH02235828 A JP H02235828A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- fluoro
- amine
- optically active
- 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
Links
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001412 amines Chemical class 0.000 abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methyl-1-butanol Substances CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 9
- -1 ( -)-2-fluoro-2,3-dimethyl-1-hexanol Chemical compound 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKHRYHIXUNLSPK-UHFFFAOYSA-N 2-fluoro-2-methylhexan-1-ol Chemical compound CCCCC(C)(F)CO OKHRYHIXUNLSPK-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- ZTCDEKMURLCFQJ-UHFFFAOYSA-N 2-butyl-2-methyloxirane Chemical compound CCCCC1(C)CO1 ZTCDEKMURLCFQJ-UHFFFAOYSA-N 0.000 description 3
- VGBLYDUUNHKAEC-UHFFFAOYSA-N 2-fluoro-2-methyldodecan-1-ol Chemical compound FC(CO)(CCCCCCCCCC)C VGBLYDUUNHKAEC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 1
- CFUSADRNVKTODB-UHFFFAOYSA-N 2-(2,2-dimethylbutyl)-2-methyloxirane Chemical compound CCC(C)(C)CC1(C)CO1 CFUSADRNVKTODB-UHFFFAOYSA-N 0.000 description 1
- WZHRVCOCPMCGEA-UHFFFAOYSA-N 2-(2,2-dimethylpropyl)-2-methyloxirane Chemical compound CC(C)(C)CC1(C)CO1 WZHRVCOCPMCGEA-UHFFFAOYSA-N 0.000 description 1
- FNSDYJBAZKKTPR-UHFFFAOYSA-N 2-fluoro-2,3-dimethylbutan-1-ol Chemical compound CC(C)C(C)(F)CO FNSDYJBAZKKTPR-UHFFFAOYSA-N 0.000 description 1
- POWAXQIZAJQFBA-UHFFFAOYSA-N 2-fluoro-2,4-dimethylpentan-1-ol Chemical compound CC(C)CC(C)(F)CO POWAXQIZAJQFBA-UHFFFAOYSA-N 0.000 description 1
- JTADSDIQROXXJS-UHFFFAOYSA-N 2-fluoro-2-methylbutan-1-ol Chemical compound CCC(C)(F)CO JTADSDIQROXXJS-UHFFFAOYSA-N 0.000 description 1
- YDMVNLGIKJVQFF-UHFFFAOYSA-N 2-fluoro-2-methyldecan-1-ol Chemical compound CCCCCCCCC(C)(F)CO YDMVNLGIKJVQFF-UHFFFAOYSA-N 0.000 description 1
- YJTPLTLMROFLHU-UHFFFAOYSA-N 2-fluoro-2-methylhexadecan-1-ol Chemical compound FC(CO)(CCCCCCCCCCCCCC)C YJTPLTLMROFLHU-UHFFFAOYSA-N 0.000 description 1
- MXNQSLJMQFNXRI-UHFFFAOYSA-N 2-fluoro-2-methylnonan-1-ol Chemical compound FC(CO)(CCCCCCC)C MXNQSLJMQFNXRI-UHFFFAOYSA-N 0.000 description 1
- KFGKCNVTICEZTA-UHFFFAOYSA-N 2-fluoro-2-methyloctan-1-ol Chemical compound CCCCCCC(C)(F)CO KFGKCNVTICEZTA-UHFFFAOYSA-N 0.000 description 1
- YHMGBYXCLWMGPX-UHFFFAOYSA-N 2-fluoro-2-methylpentadecan-1-ol Chemical compound CCCCCCCCCCCCCC(C)(CO)F YHMGBYXCLWMGPX-UHFFFAOYSA-N 0.000 description 1
- UCLKDKHIDQBUJE-UHFFFAOYSA-N 2-fluoro-2-methylpentan-1-ol Chemical compound CCCC(C)(F)CO UCLKDKHIDQBUJE-UHFFFAOYSA-N 0.000 description 1
- UGBACKGVRKBBSF-UHFFFAOYSA-N 2-fluoro-2-methyltetradecan-1-ol Chemical compound FC(CO)(CCCCCCCCCCCC)C UGBACKGVRKBBSF-UHFFFAOYSA-N 0.000 description 1
- XFSUAXAXHFINFP-UHFFFAOYSA-N 2-fluoro-2-methylundecan-1-ol Chemical compound FC(CO)(CCCCCCCCC)C XFSUAXAXHFINFP-UHFFFAOYSA-N 0.000 description 1
- NWUFFHCAVDQKNN-UHFFFAOYSA-N 2-heptyl-2-methyloxirane Chemical compound CCCCCCCC1(C)CO1 NWUFFHCAVDQKNN-UHFFFAOYSA-N 0.000 description 1
- ZGTIKXQPNJWGLR-UHFFFAOYSA-N 2-methyl-2-(3-methylbutyl)oxirane Chemical compound CC(C)CCC1(C)CO1 ZGTIKXQPNJWGLR-UHFFFAOYSA-N 0.000 description 1
- JATXAMXFNMUGBL-UHFFFAOYSA-N 2-methyl-2-propan-2-yloxirane Chemical compound CC(C)C1(C)CO1 JATXAMXFNMUGBL-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-butylamine Natural products CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N n-hexyl alcohol Natural products CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin 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】
上の１
本発明は、医薬、農薬、或いは液晶化合物等の機能性材
料などを製造するための中間体として利用される光学活
性な２−フルオロ−２−メチル−１−アルカノール類及
びこの化合物を製造する方法に関する。Detailed Description of the Invention [1] The present invention relates to optically active 2-fluoro-2-methyl-1 which is used as an intermediate for producing functional materials such as pharmaceuticals, agricultural chemicals, or liquid crystal compounds. - Concerning alkanols and methods for producing these compounds.
災来二ユ丘
２−フルオロ−２−メチル−１−アルカノール類の合成
方法としては、２−メチル−１．２−エボキシアルカン
にジイソプ口ビルエチルアミン及びテトラブチルアンモ
ニウムフルオライド或いは水の存在下に四フッ化ケイ素
を作用させる方法が、既に提案されている［清水真、吉
岡宏輔，テトラヘドロン レターズ（Ｔｅｔｒａｈｅｄ
ｏ−ｒｏｎ ＬｅＬｔｅｒｓ），２９，ｐ４１０１（１
９８８）］。しかし、この化合物はラセミ体であり、光
学活性な化合物は未だ得られていない。ところで、特異
な生理活性や機能を有する医薬や農薬、さらには強誘電
性液晶等の開発のための原料として，この種の化合物の
光学活性体の安価で大量の提供が望まれていた．しかし
、光学活性体をラセミ体からの光学分割等で得る方法は
、未だその手段も確立されておらず、またコストが非常
に高くつくものと予想される．
よ と る
本発明者は、かかる現状に鑑み、鋭意研究を進めた結果
、光学活性な２−メチル−１，２ーエボキシアルカンに
アミンーフッ化水素錯体、または四フッ化ケイ素を作用
させると、驚くべきことにラセミ化することなく、光学
活性な２−フルオロー２−メチル−１−アルカノールを
得ることができることを見い出した。本発明は、かかる
知見に基づきなされたもので、本発明の目的は、新規な
化合物である２−フルオロ−２−メチルーｌ−アルカノ
ール類及びこの先学活性体、さらにはこれらの化合物の
、安価で、しかも簡易な製造方法を提案することにある
．
るための
本発明は、次式（１）
ＣＨ，
Ｒ−Ｃ”−ＣＨ，Ｏ Ｈ （ Ｉ）一
Ｆ
（式中Ｒは炭素中２乃至１６個のアルキル基を、Ｃ８は
光学活性が誘起された不斉炭素を表わす）で示される新
規な光学活性な２−フルオロ−２−メチル−１−アルカ
ノール類、及び次式（ｎ）ＣＨ，
Ｏ
（式中Ｒは炭素中２乃至１６個のアルキル基を、Ｃｘは
光学活性が誘起された不斉炭素を表わす）で示される光
学活性なエボキシドにアミンーフッ化水素錯体または四
フッ化ケイ素を作用させる前記２−フルオロー２−メチ
ル−１−アルカノール類を製造することからなるもので
ある。As a method for synthesizing 2-fluoro-2-methyl-1-alkanols, diisobylethylamine and tetrabutylammonium fluoride are added to 2-methyl-1,2-epoxyalkane in the presence of water. A method of using silicon tetrafluoride has already been proposed [Makoto Shimizu, Kosuke Yoshioka, Tetrahedron Letters]
o-ron LeLters), 29, p4101 (1
988)]. However, this compound is a racemate, and an optically active compound has not yet been obtained. Incidentally, there has been a desire to provide inexpensive, large quantities of optically active forms of this type of compound as raw materials for the development of medicines and agricultural chemicals with unique physiological activities and functions, as well as for the development of ferroelectric liquid crystals. However, methods for obtaining optically active forms by optical resolution, etc. from racemic forms have not yet been established, and the cost is expected to be extremely high. In view of the current situation, the inventors of the present invention have carried out intensive research, and as a result, they were surprised to find that when an amine-hydrogen fluoride complex or silicon tetrafluoride is applied to an optically active 2-methyl-1,2-epoxyalkane. It has been found that optically active 2-fluoro-2-methyl-1-alkanol can be obtained without racemization. The present invention has been made based on this knowledge, and an object of the present invention is to obtain novel compounds such as 2-fluoro-2-methyl-l-alkanols and their previously activated forms, as well as inexpensive and inexpensive compounds. , and to propose a simple manufacturing method. The present invention has the following formula (1) CH, RC"-CH, OH (I)-F (wherein R is an alkyl group of 2 to 16 carbon atoms, and C8 is an alkyl group induced by optical activity. Novel optically active 2-fluoro-2-methyl-1-alkanols represented by The above-mentioned 2-fluoro-2-methyl-1-alkanols in which an amine-hydrogen fluoride complex or silicon tetrafluoride is applied to an optically active epoxide represented by an alkyl group (Cx represents an asymmetric carbon having induced optical activity) It consists of manufacturing.
本発明の光学活性な２−フルオロ−２−メチル−１−ア
ルカノールとしては、（−）−２−フルオロー２−メチ
ル−１−ブタノール、（−）−２−フルオロー２−メチ
ル−１−ペンタノール、（−）−２−フルオロー２，３
−ジメチル−１−ブタノール、（−）−２−フルオロ−
２−メチル−１〜ヘキサノール、（−）−２−フルオロ
ー２，３−ジメチルーｌ−ベンタノール、（−）−２−
フルオロ〜２，４−ジメチル−１−ペンタノール、（−
）−２−フルオロー２−メチル−１−ヘブタノール、（
−）−２−フルオロー２，３−ジメチル−１−ヘキサノ
ール、（一）−２−フルオロ−２，４−ジメチル−１−
ヘキサノール、（−）−２−フルオロー２，５−ジメチ
ル−１−ヘキサノール、（−）−２−フルオロー２．４
．４−トリメチルーｌ−ペンタノール、（−）−２−フ
ルオロー２−メチル−１−オクタノール、（−）−２〜
フルオロ−２，４−ジメチル−１−ヘプタノール、（−
）−２−フルオロ−２，６−ジメチル−１−ヘブタノー
ル、（−）−２−フルオロー２−メチル−１一ノナノー
ル、（一）−２−フルオロ−２．４．４−トリメチル−
１−ヘキサノール、（−）−２−フルオロー２−メチル
−１一デカノール、（−）−２−フルオロー２−メチル
ー１ーウンデカノール、（−）−２−フルオロー２−メ
チル−１−ドデカノール、（一）−２−フルオロー２一
メチルーｌ一トリデカノール、（−）−２−フルオロ−
２−メチル−１−テトラデカノール、（−）−２−フル
オロー２−メチル−１−ペンタデカノール、（−）−２
−フルオロー２−メチル−１−ヘキサデカノール、（−
）−２−フルオロー２−メチル−１−ヘブタデカノール
等、並びに（＋）の上記アルカノール類を例示しつる。The optically active 2-fluoro-2-methyl-1-alkanol of the present invention includes (-)-2-fluoro-2-methyl-1-butanol and (-)-2-fluoro-2-methyl-1-pentanol. , (-)-2-fluoro2,3
-dimethyl-1-butanol, (-)-2-fluoro-
2-Methyl-1-hexanol, (-)-2-fluoro-2,3-dimethyl-1-bentanol, (-)-2-
Fluoro-2,4-dimethyl-1-pentanol, (-
)-2-fluoro-2-methyl-1-hebutanol, (
-)-2-fluoro-2,3-dimethyl-1-hexanol, (1)-2-fluoro-2,4-dimethyl-1-
Hexanol, (-)-2-fluoro 2,5-dimethyl-1-hexanol, (-)-2-fluoro 2.4
．． 4-trimethyl-l-pentanol, (-)-2-fluoro-2-methyl-1-octanol, (-)-2~
Fluoro-2,4-dimethyl-1-heptanol, (-
)-2-fluoro-2,6-dimethyl-1-hebutanol, (-)-2-fluoro-2-methyl-1-nonanol, (1)-2-fluoro-2.4.4-trimethyl-
1-hexanol, (-)-2-fluoro-2-methyl-1-decanol, (-)-2-fluoro-2-methyl-1-undecanol, (-)-2-fluoro-2-methyl-1-dodecanol, (1) -2-fluoro-2-methyl-l-tridecanol, (-)-2-fluoro-
2-Methyl-1-tetradecanol, (-)-2-fluoro-2-methyl-1-pentadecanol, (-)-2
-fluoro-2-methyl-1-hexadecanol, (-
)-2-fluoro-2-methyl-1-hebutadecanol, and (+) of the above alkanols are exemplified.
一方、上記化合物の製造方法の発明では、出発物質とし
て光学活性を有する２−メチル−１，２−エボキシアル
カンを用いるが、この化合物としては、（−）−２−メ
チル−１，２−エボキシブタン、（−）−２−メチル−
１．２−エポキシベンタン、（−）−２．３−ジメチル
−１，２−エボキシブタン、（−）−２−メチル−１，
２−エボキシヘキサン、（−）−２．３−ジメチル−１
．２−エボキシペンタン、（−）−２１４−ジメチル−
１，２−エボキシベンタン、（−）−２−メチル−１．
２−エボキシへブタン、（−）−２．３−ジメチル−１
，２ーエボキシヘキサン、（−）−２．４−ジメチル−
１，２−エボキシヘキサン、（−）−２．５−ジメチル
−１，２−エボキシヘキサン、（−）−２．４．４−ト
リメチル−１，２−エボキシペンタン、（−）−２−メ
チル−１，２−エボキシオクタン、（−）−２，４−ジ
メチル−１．２−エボキシへブタン、（−）−２．６−
ジメチル−１．２−エボキシへブタン、（−）一２−メ
チル−１，２−エボキシノナン、（−）−２．４，４−
トリメチル−１，２−エボキシヘキサン、（一）−２−
メチル−１．２−エボキシデカン、（−）−２−メチル
−１，２−エボキシウンデカン、（−）−２−メチル−
１．２−エボキシドデカン、（一）−２−メチル−１．
２−エボキシトリデカン、（−）−２−メチル−１．２
−エボキシテトラデカン、（一）−２−メチル−１．２
−エボキシペンタデカン、（−）−２−メチル−１．２
−エボキシヘキサデカン、（−）−２−メチル−１．２
−エボキシヘプタデカン等、並びに（＋）の上記エボキ
シド類を例示しつる。On the other hand, in the invention of the method for producing the above compound, optically active 2-methyl-1,2-epoxyalkane is used as a starting material; , (-)-2-methyl-
1,2-epoxybentane, (-)-2,3-dimethyl-1,2-epoxybutane, (-)-2-methyl-1,
2-Eboxyhexane, (-)-2,3-dimethyl-1
．． 2-Eboxypentane, (-)-214-dimethyl-
1,2-Eboxybentane, (-)-2-methyl-1.
2-Eboxyhebutane, (-)-2,3-dimethyl-1
, 2-Eboxyhexane, (-)-2,4-dimethyl-
1,2-Eboxyhexane, (-)-2.5-dimethyl-1,2-epoxyhexane, (-)-2.4.4-trimethyl-1,2-epoxypentane, (-)-2-methyl -1,2-Eboxyoctane, (-)-2,4-dimethyl-1,2-epoxyhebutane, (-)-2.6-
Dimethyl-1,2-epoxyhebutane, (-)-2-methyl-1,2-epoxynonane, (-)-2.4,4-
Trimethyl-1,2-epoxyhexane, (1)-2-
Methyl-1,2-eboxydecane, (-)-2-methyl-1,2-eboxyundecane, (-)-2-methyl-
1.2-Eboxydodecane, (1)-2-methyl-1.
2-Eboxytridecane, (-)-2-methyl-1.2
-Eboxytetradecane, (1)-2-methyl-1.2
-Eboxypentadecane, (-)-2-methyl-1.2
-Eboxyhexadecane, (-)-2-methyl-1.2
-Eboxyheptadecane, etc., as well as (+) the above-mentioned eboxides.
上記光学活性を有するエボキシド類は微生物を利用して
、相当するα−オレフィンを酸化することにより調製で
きる（特公昭６１−２２９５８号公報参照）．
また、この製造の際に用いるアミンーフッ化水素錯体は
、アミン中に無水フッ化水素を滴下、混合することによ
り、容易に調製することができる。この錯体のアミンと
フッ化水素の割合は、これらの化合物の混合比を調整す
ることにより容易に行え、一旦調製したアミンーフッ化
水素錯体でも、再びアミンかフッ化水素を添加すること
により、その比を容易に変えることができる。また、こ
の錯体はアミンとフッ化水素酸を混合し、減圧下、水を
留去することによっても調製できる。Eboxides having the above-mentioned optical activity can be prepared by oxidizing the corresponding α-olefin using microorganisms (see Japanese Patent Publication No. 61-22958). Further, the amine-hydrogen fluoride complex used in this production can be easily prepared by dropping anhydrous hydrogen fluoride into the amine and mixing it. The ratio of amine and hydrogen fluoride in this complex can be easily adjusted by adjusting the mixing ratio of these compounds, and even if the amine-hydrogen fluoride complex is once prepared, the ratio can be adjusted by adding amine or hydrogen fluoride again. can be easily changed. This complex can also be prepared by mixing an amine and hydrofluoric acid and distilling off water under reduced pressure.
さらに、アミンーフッ化水素錯体に代えて、四フッ化ケ
イ素を作用させても良い。この四フッ化ケイ素を作用さ
せる場合は，アミン及びテトラブチルアンモニウムフル
オライド又は水の存在下に反応を行うことが、反応を円
滑に進行させる上で、特に好ましい。しかし、この方法
は、アミンーテトラブチルアンモニウムフルオライドを
添加した系ではボリマーが生成するため、またアミンー
水系では反応混合物がゲル状となり、生成物の分離回収
操作が煩雑となる場合があるのであまり好ましくない．
尚、上記アミンーフッ化水素錯体及び四フツ化ケイ素を
作用させる際に存在させるアミンとしては、プロビルア
ミン、イソプロビルアミン、プチルアミン、イソブチル
アミン、ＳｅＣ−プチルアミン、ｔｅｒｔ−プチルアミ
ン、ジエチルアミン、ジプロビルアミン、ジイソブ口ビ
ルアミン、ジブチルアミン、ジーｓｅｅ−プチルアミン
、トリエチルアミン、トリブロビルアミン、トリブチル
アミン、ヘキシルアミン、ジヘキシルアミン、トリヘキ
シルアミン、ヘブチルアミン、オクチルアミン、ｔｅｒ
ｔ−オクチルアミン、ジオクチルアミン、デシルアミン
、オクタデシルアミン、ビリジン、メラミン等を例示し
うる．
上記のエボキシド類とアミンーフッ化水素錯体或いは四
フッ化ケイ素との反応は、そのまま無溶媒で行ってもよ
いし、また、クロロホルム、塩化メチレン、四塩化炭素
、ジエチルエーテル、酢酸エチル、アセトン、ヘキサン
、ベンゼン、アセトニトリルなどの有機溶媒中で行って
も良い．
また、コノ反応は、−２０” 〜１３０℃の広範囲の温
度で行うことができ、最適な反応温度は、実際に使用す
るアミンーフッ化水素錯体、アミンの種類および溶媒の
種類等に応じて決めるとよい。Furthermore, silicon tetrafluoride may be used instead of the amine-hydrogen fluoride complex. When this silicon tetrafluoride is used, it is particularly preferable to carry out the reaction in the presence of an amine and tetrabutylammonium fluoride or water in order to allow the reaction to proceed smoothly. However, this method is not recommended because a polymer is produced in a system in which amine-tetrabutylammonium fluoride is added, and the reaction mixture becomes gel-like in an amine-water system, making the separation and recovery operation of the product complicated. I don't like it. The amines to be present when the amine-hydrogen fluoride complex and silicon tetrafluoride are allowed to act include probylamine, isopropylamine, butylamine, isobutylamine, SeC-butylamine, tert-butylamine, diethylamine, diprobylamine, Diisobutylamine, dibutylamine, di-see-butylamine, triethylamine, tribubylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, hebutylamine, octylamine, ter
Examples include t-octylamine, dioctylamine, decylamine, octadecylamine, pyridine, and melamine. The reaction between the above-mentioned eboxides and the amine-hydrogen fluoride complex or silicon tetrafluoride may be carried out directly without a solvent, or may be carried out using chloroform, methylene chloride, carbon tetrachloride, diethyl ether, ethyl acetate, acetone, hexane, It may also be carried out in an organic solvent such as benzene or acetonitrile. In addition, the cono reaction can be carried out at a wide range of temperatures from -20" to 130°C, and the optimal reaction temperature is determined depending on the amine-hydrogen fluoride complex, the type of amine, the type of solvent, etc. actually used. good.
また、反応時間は反応温度に応じて０．５〜３０時間の
範囲で適宜選定される。Moreover, the reaction time is appropriately selected in the range of 0.5 to 30 hours depending on the reaction temperature.
さらに、上記のエボキシド類に対するアミンーフッ化水
素錯体の使用量はアミン量で０．５〜１０当量の範囲で
、四フッ化ケイ素の使用量は５〜１０当量の範囲で適宜
選定することが適当である。また、四フツ化ケイ素を用
いる場合のアミンの添加量は、原料のエポキシドに対し
て０．５〜１０当量、テトラブチルアンモニウムフルオ
ライド或いは水の添加量は１〜４当量の範囲から適宜選
定することが好ましい。Furthermore, it is appropriate to select the amount of the amine-hydrogen fluoride complex used in the range of 0.5 to 10 equivalents in terms of amine amount and the amount of silicon tetrafluoride to be used in the range of 5 to 10 equivalents relative to the above-mentioned eboxides. be. In addition, when silicon tetrafluoride is used, the amount of amine added is appropriately selected from the range of 0.5 to 10 equivalents relative to the raw material epoxide, and the amount of tetrabutylammonium fluoride or water added is selected from the range of 1 to 4 equivalents. It is preferable.
上記により反応を行った後、当該反応生成物について相
分離、抽出、蒸留、カラムクロマトグラフィー等の手法
により、光学活性な２−フルオロー２−メチル−１−ア
ルカノールを分離して精製する。After carrying out the reaction as described above, the reaction product is purified by separating optically active 2-fluoro-2-methyl-1-alkanol by techniques such as phase separation, extraction, distillation, and column chromatography.
以上の本発明の化合物は、ヒドロキシ基を結合子として
各種の化合物と反応させ、新たな機能を有する医薬や農
薬、或いは液晶化合物等を合成することができる。The above-described compounds of the present invention can be reacted with various compounds using a hydroxy group as a bonding agent to synthesize medicines, agricultural chemicals, liquid crystal compounds, etc. having new functions.
以下、実施例により本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
ス』【勇」２
ジイソプロビルアミンーフツ化水素［（ｉ−Ｐｒ），Ｎ
Ｈ・４８Ｆ）錯体２，７ ｇ（１ ５ｍｍｏｌ）に、水
浴上で、（−）−２−メチル−１．２−エボキシヘキサ
ン１．１ ４ ｇ （ １ ０ｍｍｏｌ）を滴下した。``S''[Yu'' 2 Diisoprobylamine-hydrogen fluoride [(i-Pr), N
1.14 g (10 mmol) of (-)-2-methyl-1,2-epoxyhexane was added dropwise to 2.7 g (15 mmol) of the H.48F) complex on a water bath.
滴下終了後、室温で１．５時間撹拌した後、反応液を氷
水３０ｍαにあけ、エーテル３０ｍ２で抽出した。After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours, and then the reaction solution was poured into 30 mα of ice water and extracted with 30 m2 of ether.
エーテル層を、５％濃度の炭素ナトリウム水溶液及び水
で洗浄した後、無水硫酸ナトリウムで乾燥した。エーテ
ルを留去した後、減圧蒸留（クーゲラ− ７０〜８０℃
／ １ ２ ｍｍＨｇ）し、０．３５ｇの（−）−２−
フルオロー２−メチル−１−ヘキサノールを得た。収率
は２６％、ガスクロマトグラフィーによる純度は９３％
、比旋光度〔α］♂は−０．７’ （ｃ＝２．０， Ｃ
ＨＣＩ，）であった。The ether layer was washed with a 5% aqueous sodium carbon solution and water, and then dried over anhydrous sodium sulfate. After distilling off the ether, vacuum distillation (Kugeler 70~80℃)
/ 12 mmHg) and 0.35 g of (-)-2-
Fluoro-2-methyl-1-hexanol was obtained. Yield: 26%, purity by gas chromatography: 93%
, the specific optical rotation [α]♂ is -0.7' (c=2.0, C
HCI,).
ＩＬ伝』エ
ジイソプロビルアミンーフッ化水素錯体３．４ ｇ（
２ ０ ｍｍｏｌ）とクロロホルム２ ０＋ｎＱに、水
浴上で、（−）−２−メチル−１，２−エボキシヘキサ
ン１． １ ４ ｇ（１ ０ｍｍｏｌ）を滴下した。滴
下終了後、室温で２４時間撹拌した後、氷水３０ｍＱに
あけ、クロロホルム層を分離した。水層をエーテル３０
ｍｆｉで抽出し、このエーテル層を前記のクロロホルム
層に合わせ、これを５％濃度の炭素ナトリウム水溶液及
び水で洗浄した後、無水硫酸ナトリウムで乾燥した。エ
ーテルを留去した後、減圧蒸留（クーゲラー７ ０〜８
０ ’Ｃ／ １ ２ｍｍ｝Ｉｇ） Ｌ／、０．２４
ｇ（７）（−）−２−フルオロ−２−メチル−１−ヘキ
サノールを得た。収率は１８％、ガスクロマトグラフィ
ーによる純度は９４％、比旋光度〔α］♂は一〇．７°
（ｃ＝２．０， Ｃ｝ＩＣＩ．）であった。IL Den” Edisoprobylamine-Hydrogen Fluoride Complex 3.4 g (
20 mmol) and chloroform (20+nQ) on a water bath, (-)-2-methyl-1,2-epoxyhexane 1. 14 g (10 mmol) was added dropwise. After the addition was completed, the mixture was stirred at room temperature for 24 hours, poured into 30 mQ of ice water, and the chloroform layer was separated. Water layer with ether 30
The ether layer was extracted with mfi, and the ether layer was combined with the chloroform layer, washed with a 5% aqueous sodium carbonate solution and water, and then dried over anhydrous sodium sulfate. After distilling off the ether, vacuum distillation (Kugeller 70-8
0'C/ 1 2mm}Ig) L/, 0.24
g(7)(-)-2-fluoro-2-methyl-1-hexanol was obtained. The yield was 18%, the purity by gas chromatography was 94%, and the specific optical rotation [α]♂ was 10. 7°
(c=2.0, C}ICI.).
１施亘ユ
ジイソブ口ビルエチルアミン１．２ ９ ｇ（１０ｍｍ
ｏｌ）、水０．７ ２ｇ（４ ０ｍｍｏｌ）、エーテル
６０＋ｎＱの混合物中に、水浴上で、四フッ化ケイ素雰
囲気下（２Ｑ）、（一）−２−メチル−１．２−エポキ
シヘキサン１， １ ４ ｇ（１ ０ｍｍｏｌ）のエー
テル溶液を滴下した。滴下終了後、１．５時間撹拌し、
フッ化カリウム水溶液１５０＋ｎＱを加え、ヘキサンで
抽出した後、無水硫酸ナトリウムで乾燥した。溶媒を留
去した後、減圧蒸留（クーゲラー、７０〜８０℃／１２
ＭＨｇ）し、０．３３ｇの（−）−２−フルオロー２−
メチル−１−ヘキサノールを得た。収率は２５％、ガス
クロマトグラフィーによる純度は９９％、比旋光度〔α
１８は−１．２゜（ｃ＝１．８， Ｃ｝ＩｃＩ．）であ
った。1 application: 1.29 g (10 mm
ol), 0.72 g (40 mmol) of water, 60+nQ of ether on a water bath under an atmosphere of silicon tetrafluoride (2Q), (1)-2-methyl-1,2-epoxyhexane 1, 14 g (10 mmol) of an ether solution was added dropwise. After completion of dropping, stir for 1.5 hours,
After adding 150+nQ of potassium fluoride aqueous solution and extracting with hexane, the mixture was dried over anhydrous sodium sulfate. After distilling off the solvent, vacuum distillation (Kugeller, 70-80℃/12
MHg) and 0.33 g of (-)-2-fluoro-2-
Methyl-1-hexanol was obtained. The yield was 25%, the purity by gas chromatography was 99%, the specific optical rotation [α
18 was -1.2° (c=1.8, C}IcI.).
１ｌ五土
ジイソプ口ビルエチルアミン１．２９ｇ（１０ｍｍｏ
ｌ ）、王一テル６０ＩＩＩＩＩ１テトラブチルアンモ
ニウムフルオライド１モル濃度のテトラヒド口フラン溶
液１ ８ ｍ（ １ ８ｍｍｏｌ）の混合液中に、四フ
ッ化ケイ素雰囲気下（２２）に、５℃より低い温度に保
ちながら、（−）−２−メチル−１，２−エボキシヘキ
サン１ ． １ ４ｇ（ １ ０ｍｍｏｌ）ｚ −テル
溶液４０ｍｌｌを滴下した。滴下終了後、２時間かくは
んし、フッ化カリウム水溶液１５０ｍｌｌ，ヘキサン１
００ｍＱを加えて抽出した。1 liter Goto diisopropyl ethylamine 1.29 g (10 mmo
l), Oichitel 60 III 1 Tetrabutylammonium fluoride in a mixture of 18 m (18 mmol) of a 1 molar tetrahydrofuran solution under a silicon tetrafluoride atmosphere (22) at a temperature lower than 5 °C. (-)-2-methyl-1,2-epoxyhexane while maintaining 1. 14 g (10 mmol) of z-tel solution (40 ml) was added dropwise. After dropping, stir for 2 hours and add 150 ml of potassium fluoride aqueous solution and 1 ml of hexane.
00mQ was added and extracted.
上層を水で洗浄した後、無水硫酸ナトリウムで乾燥した
。溶媒を留去した後、減圧蒸留（クーゲラ− ７０〜８
０℃／ １ ２ ｍｍＨｇ） Ｌ、０．１７ｇの（−）
一フルオロ−２−メチル−１−ヘキサノールを得た。収
率は１５％、ガスクロマトグラフィー純度は９４％、比
旋光度〔α］台は−１ ． ２ （ｃ ＝ １．８，
ＣＨＣＩ， ）であった。The upper layer was washed with water and then dried over anhydrous sodium sulfate. After distilling off the solvent, vacuum distillation (Kugeller 70-8
0℃/12 mmHg) L, 0.17g (-)
Monofluoro-2-methyl-1-hexanol was obtained. The yield was 15%, the purity by gas chromatography was 94%, and the specific optical rotation [α] was -1. 2 (c = 1.8,
CHCI, ).
且ユ勿左呈
本発明の光学活性な２−フルオロ−２−メチル−１−ア
ルカノールは、前述したような種々の有用物質の中間体
として重要な化合物であり、本発明の製造方法によると
光学活性な２−メチル−１，２−エボキシアルカンを出
発物質として用い、安価に、簡便に光学活性な２−フル
オロ−２−メチルーｌ−アルカノールを製造することが
できるという格別の効果を奏する。The optically active 2-fluoro-2-methyl-1-alkanol of the present invention is an important compound as an intermediate for various useful substances as mentioned above, and the optically active 2-fluoro-2-methyl-1-alkanol of the present invention is an important compound as an intermediate for various useful substances as described above. Using active 2-methyl-1,2-epoxyalkane as a starting material, it has the special effect of being able to easily produce optically active 2-fluoro-2-methyl-1-alkanol at low cost.
Claims (2)
は光学活性が誘起された不斉炭素を表わす）で示される
光学活性な２−フルオロ−２−メチル−１−アルカノー
ル類。(1) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group with 2 to 16 carbon atoms, C^*
represents an asymmetric carbon having induced optical activity).
は光学活性が誘起された不斉炭素を表わす）で示される
光学活性なエポキシドにアミン−フッ化水素錯体または
四フッ化ケイ素を作用させることを特徴とする請求項（
１）に記載の光学活性な２−フルオロ−２−メチル−１
−アルカノール類の製造方法。(2) The following formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R represents an alkyl group with 2 to 16 carbon atoms, C^*
represents an asymmetric carbon having induced optical activity) is treated with an amine-hydrogen fluoride complex or silicon tetrafluoride.
Optically active 2-fluoro-2-methyl-1 according to 1)
- A method for producing alkanols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5605889A JP2649572B2 (en) | 1989-03-10 | 1989-03-10 | Optically active 2-fluoro-2-methyl-1-alkanols and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5605889A JP2649572B2 (en) | 1989-03-10 | 1989-03-10 | Optically active 2-fluoro-2-methyl-1-alkanols and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02235828A true JPH02235828A (en) | 1990-09-18 |
| JP2649572B2 JP2649572B2 (en) | 1997-09-03 |
Family
ID=13016482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5605889A Expired - Lifetime JP2649572B2 (en) | 1989-03-10 | 1989-03-10 | Optically active 2-fluoro-2-methyl-1-alkanols and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2649572B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331649A (en) * | 2003-04-17 | 2004-11-25 | Kanto Denka Kogyo Co Ltd | Optically active 2-fluoro-1, 3-diol derivative, and method for producing the same |
| GB2582364A (en) * | 2019-03-21 | 2020-09-23 | Mexichem Fluor Sa De Cv | Methods |
-
1989
- 1989-03-10 JP JP5605889A patent/JP2649572B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331649A (en) * | 2003-04-17 | 2004-11-25 | Kanto Denka Kogyo Co Ltd | Optically active 2-fluoro-1, 3-diol derivative, and method for producing the same |
| JP4568002B2 (en) * | 2003-04-17 | 2010-10-27 | 関東電化工業株式会社 | Optically active 2-fluoro-1,3-diol derivative and method for producing the same |
| GB2582364A (en) * | 2019-03-21 | 2020-09-23 | Mexichem Fluor Sa De Cv | Methods |
| US11897832B2 (en) | 2019-03-21 | 2024-02-13 | Mexichem Fluor S.A. De C.V. | Method for preparing partially fluorinated alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2649572B2 (en) | 1997-09-03 |
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