Development of fluorinated ferroelectric liquid crystals through an enzymatic reaction.

通过酶促反应开发氟化铁电液晶。

• 批准号: 07554066
• 负责人: ITOH Toshiyuki
• 金额: $ 1.22万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07554066/
• 关键词: synnthesis; optically active; tirfluoromethylcarbinol; ferroelectirc liquid crystal; lipase-catalyzed reaction; resolution of racemic compounds; enantioselective acylation; フッ素官能基; キラル化合物; トリフルオロメチルカルビノール; リパーゼ; 不斉アシル化反応

Ferroelectric liquid crystals (FLC) are known to be important high-speed switching devices, and their response time strongly depends on the magnitude of spontaneous polarization. A recent study revealed that chiral FLC compounds which involve optically active 1,1,1-trifluoro-2-alkanols possess remarkable characteristics of a wide temperature range of Sc^<**> phase, a large spontaneous polarization, and a short responsetime. Becausethe target compounds are FLC compounds, large scale preparation is particularly desired. Candida antarctica-lipase (CAL) -catalyzed esterification in hexane using vinyl acetate as acyl donor was successfully utilized for optical resolution of racemic 1,1,1-trifluoro-2-alkanols to provide corresponding (S) -acetates in an optically pure state. Five types of optically pure alkanols, i.e.1,1,1-trifluoro-2-octanol, 1,1,1-trifluoro-2-nonanol, 1,1,1-trifluoro-2-decanol, 1,1,1-trifluoro-2-undecanol, and 1,1,1-trifluoro-8-benzylo-2-octanol, were thus obtained by the … More CAL-catalyzed acylation.Antiferroelectric liquid crystal (AFLCs) compounds, which possess a chiral bis (trifluoromethyl) alkanediol moiety, are also known to be important high-speed switching devices. Enantioselective hydrolysis of diacetates of bis (trifluoromethyl) alkanediols has been demonstrated. CAL was chosen from among commercial enzymes as the one most able to enantioselectively hydrolyze the acetyl group of diacetates giving five types of optically pure diols and diacetates. Among compounds obtained by CAL-catalyzed reaction, 1,4-bis (1,1,1-trifluoro-2-dodecanyl) benzene has been successfuly converted to a new AFLCs compound.The lipase-catalyzed reaction can be used in a large scale preparation, the present method therefore affords a valuable method of preparing optically pure 1,1,1-trifluoro-2-alkanols and bis (trifluoromethyl) alkanediols. Key compounds for making ferroelectric and antiferroelectric liquid crystals were thus developed via an enzymaticreaction as a key reaction. Less

铁电液晶是一种重要的高速开关器件，其响应时间强烈地依赖于自发极化的大小。最近的一项研究表明，含有光学活性的1，1，1-三氟-2-烷醇的手性FLC化合物具有Sc相温度范围宽、自发极化大、响应时间短等显著特点。由于目标化合物为FLC类化合物，因此大规模制备尤为必要。利用南极假丝酵母脂肪酶(CAL)催化的乙酸乙烯酯为酰基供体的正己烷酯化反应，成功地拆分了外消旋1，1，1-三氟-2-烷醇，得到了光学纯度较高的(S)-乙酸酯。通过…，得到了5种光学纯的烷醇：1，1，1-三氟-2-辛醇、1，1，1-三氟-2-壬醇、1，1，1-三氟-2-癸醇、1，1，1-三氟-2-十一醇和1，1，1-三氟-8-苄基-2-辛醇具有手性双(三氟甲基)烷二醇部分的反铁电液晶(AFLC)化合物也是重要的高速开关器件。研究了双(三氟甲基)烷基二醇二乙酸酯的不对称水解反应。在商业酶中，CaL被选为最能对二乙酸酯的乙酰基进行对映选择性水解的酶，得到了五种光学纯的二元醇和二乙酸酯。在CAL催化反应得到的化合物中，1，4-二(1，1，1-三氟-2-十二烷基)苯已成功地转化为一种新的AFLC化合物，脂肪酶催化反应可用于大规模制备，为制备光学纯的1，1，1-三氟-2-烷醇和双(三氟甲基)烷二醇提供了一种有价值的方法。因此，通过酶促反应作为关键反应，开发了用于制造铁电和反铁电液晶的关键化合物。较少

项目成果

Nakamura,K. ; Matsuda,T. ; Itoh,T. ; Ohno,A.: "Different Stereochemistry for the Reduction of Trifluoromethyl Ketones and Methyl Ketones Catalyzed" Tetrahedron Letters. 37-32. 5727-5730 (1996)

中村，K.

Hamada,H. ; Shiromoto,M. ; Funahashi,M. ; Itoh,T. ; Nakamura,K.: "Efficient Synthesis of Optically Pure 1,1,1-Trifluoro-2-alkanols through Lipase-Catalyzed Acylation in Organic Media" The Jornal of Organic Chemistry. 61・7. 2332-2336 (1996)

Hamada，H.；Funahashi，M.；Itoh，T.：“通过脂肪酶催化酰化有效合成光学纯 1,1,1-三氟-2-烷醇” “有机化学杂志。61・7.2332-2336（1996）

Itoh,T. ; Takagi,Y. ; Tsukube,H.: "Review : Synthesis of Chiral Building Blocks for Organic Synthesis via Lipase-Catalyzed Reaction ; New Method of Enhancing Enzymatic Reaction Enatioselectivity" J.Molecular Catalysis B : Enzymatic. (in press). (1997)

伊藤，T.

H.Hamada, M.Shiromoto, M.Funahashi, T.Itoh, and K.Nakamura: "Efficient Synthesis of Optically Pure 1,1,1-Trifluoro-2-alkanols through Lipase-Catalyzed Acylation in Organic Media" J.Org.Chem.61. 2332-2336 (1996)

H.Hamada、M.Shiromoto、M.Funahashi、T.Itoh 和 K.Nakamura：“通过脂肪酶催化酰化在有机介质中高效合成光学纯 1,1,1-三氟-2-烷醇”J.Org

Itoh,T. ; Takagi,Y. ; Tsukube,H.: "Review : Synthesis of Chiral Building Blocks for Organic Synthesis via Lipase-Catalyzed Reaction ; New Method of Enhancing Enzymatic Reaction Enantioselectivity" J.Molecular Catalysis B : Enzymatic. 3・6. 261-270 (1997)

Itoh, T.；Tsukube, H.：“综述：通过脂肪酶催化反应进行有机合成的手性结构单元的合成；增强酶反应对映选择性的新方法”J.分子催化 B：酶促。 6. 261-270（1997）