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WO2006025687A1 - Alcools alcoxy chiraux, 1,3-phenylene-bis[4-(4-alcoxy)phenyliminomethyl]benzoates chiraux et procedes de preparation correspondants - Google Patents

Alcools alcoxy chiraux, 1,3-phenylene-bis[4-(4-alcoxy)phenyliminomethyl]benzoates chiraux et procedes de preparation correspondants Download PDF

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WO2006025687A1
WO2006025687A1 PCT/KR2005/002870 KR2005002870W WO2006025687A1 WO 2006025687 A1 WO2006025687 A1 WO 2006025687A1 KR 2005002870 W KR2005002870 W KR 2005002870W WO 2006025687 A1 WO2006025687 A1 WO 2006025687A1
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chemical formula
compound
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Kyung-Tae Kang
Seng-Kue Lee
Sung Heo
Chang-Won Park
Jin-Wook Choi
Myeong-Ki Baek
Sun-Hee Lee
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Dongjin Semichem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to compounds of chiral primary alkoxyalcohols and chiral 1 ,3-phenylene b ⁇ s[4-(4- alkoxy)phenyl ⁇ m ⁇ nomethyl]benzoates, and the processes for their preparation (b) Description of the Related Art Chiral compounds have been widely used in fields of medicinal and agricultural chemical industry Recently, chiral liquid crystal materials were found applicable to liquid crystal display
  • organic materials should have an asymmetric center as a structure unit, and the ferroelectric liquid crystal should be chiral [R B Meyer et al, J Physique Lett 1975, 36, 69]
  • Laid-Open Publication No 1998-042071 disclose novel optically-active alcohols and alkoxy alcohols having trifluoromethyl groups at the asymmetric center
  • these optically-active compounds are secondary alcohols having hydroxyl groups located right on the asymmetric center It was not easy to prepare highly optically pure primary alcohols where the asymmetric carbon and a hydroxyl group of the alcohols are at least one carbon unit apart
  • thermotropic liquid crystal materials employed in liquid crystal displays are mainly rod-like materials Since Niori et al , (J Mater Ch ⁇ rn , 1996, 6, 1231) discovered that achiral banana-shaped (bent-core) molecules possess unusual and interesting properties, much attention has been paid for these materials As a result of the bent shape, a polar order within the smectic layers can be induced and some phases exhibit ferroelectric and antiferroelectric properties although the molecules are a chiral
  • banana-shaped liquid crystal material 1 ,3-phenylene b ⁇ s[4-(4-alkoxy)phenyl ⁇ m ⁇ nomethyl]benzoate with an angle of about 120 °, which is represented by the following formula
  • EP 1 215 195 A1 discloses a banana-shaped liquid crystal material having a diverse skeleton and a different angle in addition to the bisbenzoate structure
  • the banana-shaped liquid crystal materials having no asymmetric center were widely studied
  • the banana-shaped liquid crystal material coming from primary alcohol in which an asymmetric carbon with a methyl substituent is apart from a hydroxyl group of alcohol by one and more carbon unit, is quite rare Since the chiral primary alcohols are not readily available and they cannot be easily synthesized
  • the present inventors have made extensive studies of techniques for easy and cost-effective synthesis of chiral primary alkoxy alcohols
  • the structure of primary chiral alkoxy alcohols were made by replacing one methylene unit (CH 2 ) in the chiral primary alcohols with oxygen It has been found that a novel chiral primary alkoxy alcohol with high optical purity where asymmetric carbon is apart from a hydroxyl group by a long carbon chain, could be synthesized in high yield
  • the object of the present invention is to provide the method of preparing a chiral alkoxy alcohol, and 1 ,3-phenylene b ⁇ s[4-(4-alkoxy)phenyl ⁇ m ⁇ nomethyl] benzoates therefrom DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the present invention provides a chiral alkoxy alcohols represented by Chemical Formula 1 Chemical Formula 1
  • X is H or F
  • m is an integer of 1 to 5
  • n is an integer of 3 to 10
  • p is an integer of 0 or 1
  • * is asymmetric carbon
  • n is an integer of 1 to 5 and n is 3, and when p is 1 , m is 1 and n is an integer of 3 to 10
  • Representative examples of the compounds include, but are not limited to, fSJ-3-(2-butoxy)propan-1-ol, fS / )-3-(2-pentyloxy)propan-1-ol, (S)-3- ⁇ 2- hexyloxy)propan-1 -ol, fS>3-(2-heptyloxy)propan-1-ol, (SJ-3-(2-octyloxy)propan-1 -ol, (S>3-(1-t ⁇ fluoromethyl-1-hexyloxy)propan-1 -ol, fSJ-3-(1-t ⁇ fluoromethyl-1- heptyloxy)propan-1-ol, fSJ-3-(2-methylbutoxy)propan-1-ol, (SJ-4-(2-methyl butoxy)propan-1-o
  • the compound of Chemical Formula 1 can be prepared according to Reaction Scheme 1 , following the sequential steps of a) reacting a secondary alcohol of Chemical Formula 3 with an alkylating agent to form an allyl ether compound of Chemical Formula 4, and b) reacting the allyl ethers compound of Chemical Formula 4 with a borane reagent followed by oxidation Reaction Scheme 1
  • step a) the secondary alcohol of Chemical Formula 3 is reacted in a solvent with an allylating agent in the presence of a base to prepare the allylether compound of Chemical Formula 4
  • allyllic halides are preferred.
  • ethers such as tetrahydrofuran dioxane, 1 2- dimethoxyethane and dimethylformamide and alcohols such as methanol, ethanol, and isopropanol
  • alcohols such as methanol, ethanol, and isopropanol
  • a base such as a metal hydride, a metal hydroxide, a metal alkoxide, etc can be used
  • the alcohols of Chemical Formula 3 may be purchased or prepared
  • the alcohol compound can be prepared by a racemic compound of 2- alkanol using the lipase Novozyme, as illustrated in JP Laid-Open Publication No 1998-004998, or chiral 1-(tr ⁇ fluoromethyl)-1-alkanol can be prepared from a racemic mixture of 1-(t ⁇ fluoromethyl)-1-alkanol using Novozyme
  • step b) the allylether compound of Chemical Formula 4 is then reacted with a borane compound in the presence of a solvent to perform hydroboration and oxidation to prepare the compound of Chemical Formula 1a
  • a solvent to perform hydroboration and oxidation to prepare the compound of Chemical Formula 1a
  • Diborane or borane substituted with functional groups can be used for the hydroboration
  • a dialkylborane bearing a bulky alkyl group can be used to enhance regioselectivity
  • the solvents suitable for the present invention include ethers, or dimethylformamide, a mixed solvent
  • the reaction of step b) is performed at a temperature of ambient temperature to the boiling point of the solvent
  • the compounds of Chemical Formula 1b can be prepared according to the Reaction Scheme 2, a) reacting a primary alcohol of Chemical Formula 5 with a sulfonyl halide to form a compound of Chemical Formula 6, and b) reacting the compound of Chemical Formula 6 with a diol Reaction Scheme 2
  • step a) the primary alcohols of Chemical Formula 5 are reacted with analkanesulfonyl halide in the presence of a solvent and an organic base to prepare the compound of Chemical Formula 6
  • An organic base such as triethylamine or pyridine is preferable
  • alkanesulfonyl ester as a reagent for ethe ⁇ fication, has good leaving group ability p-Toluenesulfonyl halide, methanesulfonyl halide, etc are used
  • Suitable solvents include haloalkanes such as dichloromethane or ethers
  • the alcohols of Chemical Formula 5 may be purchased or prepared following a known technique [J Begmann, C Lofstedt, V D Ivanov, W Francke, 15 European Journal of Organic Chemistry, (16), 3175 - 3179 (2001), B Guintchin, S Bienz, Tetrahedron, 59 (38), 7527 - 7533 (2003)]
  • step b) the compounds of Chemical Formula 6 are reacted with a diol in the presence of a solvent and base to prepare the chiral alkoxy alcohol compound of Chemical Formula 1 b
  • the diol used may be at least one compound selected from the group consisting of propandiol butandiol pentandiol, hexandiol, heptanediol, octanediol nonandiol, and decanediol
  • Bases such as an alkali metal or a metal hydride are preferable Suitable solvents include alcohols, ethers, dimethylformamide, and a mixture solvent
  • the reaction of step b) is performed at a temperature ranging from ambient to the boiling temperature of the solvent
  • the chiral primary alkoxy alcohols can be prepared without affecting optical purity from secondary alcohol with high optical purity
  • the chiral primary alkoxy alcohols prepared by the present invention have a structure of a hydroxyl group and asymmetric carbon divided by an oxyalkyl chain
  • the chiral alkoxyalcohols of Chemical Formula 1 can be used as valuable intermediates for medicinal and agricultural chemistry, and preferably for liquid crystal manufacture More specifically, banana-shaped liquid crystal materials of Chemical
  • Formula 2 type can be prepared using the chiral alkoxy compound of Chemical Formula 1
  • the compound of Chemical Formula 2 is 1,3-phenylene b ⁇ s[4-(4- alkoxy)phenyl ⁇ m ⁇ nomethyl]benzoate
  • R is , in which X is H or F, m is an integer from 1 to 5, n is an integer from 3 to 10, p is an integer of 0 or 1 , and * ⁇ s an asymmetric carbon )
  • the compounds of Chemical Formula 2 include 1 ,3-phenylene b ⁇ s[4- ⁇ 4-[fSJ-3-(2-butoxy)-1 -propoxy] ⁇ phenyl ⁇ m ⁇ nomethyl]benzoate, 1 ,3-phenylene b ⁇ s[4- ⁇ 4-[(SJ-3-(2-pentyloxy)-1-propoxy] ⁇ phenyl ⁇ m ⁇ nomethyl]-benzoate, 1 ,3- phenylene b ⁇ s[4- ⁇ 4-[fSj-3-(2-hexyloxy)-1 -propoxy] ⁇ -phenyl ⁇ m ⁇ nomethyl]benzoate, 1 ,3-phenylene b ⁇ s[4- ⁇ 4-[(S>3-(2-heptyloxy)-1 - propoxy] ⁇ phenyl ⁇ m ⁇ nomethyl]benzoate, 1 ,3-phenylene b ⁇ s[4- ⁇ 4-[fSJ-3-(1 -t ⁇ fluoro
  • the compound of Chemical Formula 2, 1 ,3-phenylene b ⁇ s[4-(4-alkoxy)- phenyhminomethyljbenzoate can be prepared following Reaction Scheme 3, by the steps of, a) reacting a chiral alkoxy alcohol of Chemical Formula 1 with a alkanesulfonyl halide to prepare a compound of Chemical Formula 7, b) halogenating the compound of Chemical Formula 7 to prepare a compound of Chemical Formula 8, c) reacting the compound of Chemical Formula 8 with acetamidophenol of Chemical Formula 9 to prepare an alkoxyacetanilide compound of Chemical Formula 10, d) treating the compound of Chemical Formula 10 with an acid catalyst to prepare an alkoxyaniline compound of Chemical Formula 11 , and e) reacting the alkoxyaniline compound of Chemical Formula 11 with a compound of Chemical Formula 12
  • X' is a halogen atom
  • step a) the chiral alkoxy alcohol of Chemical Formula 1 is reacted with an alkanesulfonyl halide in the presence of a solvent and an organic base to prepare the compounds of Chemical Formula 7
  • Organic base such as triethylamine or pyridine are preferred
  • haloalkanes such as dichloromethane or ethers
  • a sulfo ⁇ yl halide such as p-toluenesulfonyl hahde, methanesulfonyl hahde, etc is used, of which esters acts as a reagent for ethe ⁇ fication because of the good leaving group ability
  • esters acts as a reagent for ethe ⁇ fication because of the good leaving group ability
  • the compounds of Chemical Formula 7 are reacted with a halogenating agent in the presence of a solvent to prepare the alkyl halides of Chemical Formula 8
  • Suitable halogenating agents are alkali metal halides, preferably bromides Any water-miscible solvent such as acetone, methanol, and ethanol, or aceto ⁇ itrile may be used as a solvent
  • the acetamidophenol of Chemical Formula 9 may be either purchased or prepared directly [Kumazawa et al , J Mater Chem , 2004, 14, 157-164]
  • Inorganic bases such as potassium carbonate, potassium hydroxide, sodium carbonate etc can be a suitable base
  • the reaction is performed in of water-miscible solvent
  • Suitable acid catalysts are an inorganic acid such as hydrochloric acid and sulfuric acid, or organic acid such as acetic acid
  • the 1 ,3-phenylene b ⁇ s[4-(4-alkoxy)phenyl ⁇ m ⁇ nomethyl]benzoates of Chemical Formula 2 have a liquid crystal phase, as is the case of carbon derivatives in a Ref Kumazawa et al , J Mater Chem 2004 14, 157-164
  • the compound of the present invention can be used in the field of electronic optics as an important component of liquid crystal material since the compound of the present invention has a low near-ambient phase-transition temperature Moreover, the substitutions of a methylene group with an ether linkage do not change the bonding angle, stereo-configuration, and torsional, as was disclosed in a Ref (J Dale, Tetrahedron, 1974 30, 1683) Therefore, the novel chiral alkoxy alcohols of the present invention can be used as substitutes of known chiral alcohols
  • (S)-2-alkanol was prepared according to the method described in JP Laid- Open Publication No 1998-004998 To a racemic 2-alkanol, vinylpropionate in 2 eq was added, and enantioselective este ⁇ fication was carried out by lipase
  • Each prepared chiral alcohol was benzoylated using benzoyl chloride, and the optical purity of benzoate was determined by performing chiral high performance liquid chromatography [CHIRALCELTM OB-H, IPA-O 05% TEA in hexane] to identify the optical purity of over 99%ee
  • both an (S)- ⁇ somer and an (R)- ⁇ somer can be used as chiral alkoxy alcohols of the present invention
  • an (S)- ⁇ somer was used for convenience purposes After preparing acetate derivatives from two chiral alcohols and racemic alcohol, the optical purity of benzoate was determined by performing chiral high performance liquid chromatography [CHIRALCELTM OB-H, IPA-O 05% TEA in hexane] to identify the optical purity of over 99%ee
  • Step 1) Preparation of allyl ('SJ-2-butyl ether (15) NaH (60% dispersion in mineral oil, 2 95 g, 73 7 mmol) was washed with THF (20 ml x 2) and dimethylformamide (40 ml) was added To the resulting solution was slowly added (S>2-butanol (13, 3 64 g, 49 1 mmol) at 0°C, and the mixture was stirred at room temperature for 1 hour To the solution was added allylbromide (14, 5 95 g, 49 1 mmol) in dimethylformamide (25 ml) The resulting solution was refluxed at 60 ° C for 12 hours The reaction was quenched by adding 1 N HCI (25 ml) The product was extracted with ether (40 ml x 3), and washed with water (25 ml * 3), dried over anhydrous Na 2 SO 4 Solvent was removed to obtain allyl (S)-2-butyl ether (15, 4 77
  • the starting material, fSJ-(-)-2-methyl-1-butanol (>99%ee) of Chemical Formula 17, was purchased from Tokyo Kasei Kogyo Co , Ltd and used as received
  • Step 2 Preparation of fS)-3-(2-methylbutoxy)propan-1-ol f211
  • a THF (25 ml) solution of 1 ,3-propaned ⁇ ol (20, 9 9O g, 132 0 mmol) was added metallic sodium (1 14 g, 49 5 mmol) portionwise and stirred at room temperature
  • tosylate (19, 8 00 g, 33 0 mmol) in THF was added
  • the reaction mixture was stirred overnight at 70-80°C and cooled to room temperature
  • the solution was treated with water (70 ml) and extracted with ether (50 ml * 3)
  • the combined ether extracts were washed with water, dried (Na 2 SO 4 ), and concentrated to give fS)-3-(2-methylbutoxy)propan-1-ol (21) (4 77 g, 99%)
  • Step 2) Preparation of rSH -bromo-5-methyl-4-oxaheptane (24)
  • Step 4) Preparation of (S)-4-r3-(2-butoxy)-1-propoxylan ⁇ l ⁇ ne (26)
  • Step 4) Preparation of (S)-4-f3-(2-methylbutoxy)-1-propoxylan ⁇ l ⁇ ne (31)
  • Step 5 Preparation of 1 ,3-phenylene b ⁇ sr4-f4-r(S)-4 -(2-methylbutoxy)-1- butoxyPphenylimminomethyllbenzoate
  • dichloromethane (100ml) solution of bisaldehyde 12 (1 17 g, 3 1 mmol) and (S)-[4-(2-methylbutoxy)-1-butoxy]an ⁇ l ⁇ ne (1 58 g, 6 2 mmol) was refluxed for 4 hours
  • the reaction mixture was concentrated and recrystallized from ethanol to give the title compound (2 84 g, yield 74%)
  • Optical rotation for compounds of Examples 1-11 was measured with an autopolarimeter (Autopol IV, Rudolph Research Analytical) After adding chloroform to a cell (10 cm), the zero point was carefully adjusted After washing with a sample solution, a sample solution was added to the cell, and the value of optical rotation was recorded at a temperature range of 20 to 26 "C The optical rotation was estimated to have a standard deviation of less than 5% over five times, and the results are arranged in Table 1 Optical purity of each compound is the same as that of each starting material
  • the temperature of heating element in the polarization microscope was calibrated by a standard solution having N-bromosucciimide (NBS) and benzoic acid, and a heating and cooling rate of 1-2 °C/m ⁇ n was maintained
  • NBS N-bromosucciimide
  • benzoic acid a heating and cooling rate of 1-2 °C/m ⁇ n was maintained
  • a sample between glass plates (20 mm x 20 mm * 0 01mm) was placed on the heater and the liquid crystal phase was monitored with a right angle polarizer and observer with the magnification rate of 500
  • Table 2 shows the phase-transition temperature of each compound The nomenclature “Bn phases” (B1-B7) was suggested at the workshop on Banana- shaped Liquid Crystal Chirality by Achiral Molecules, held in Berlin in 1997
  • the chiral alkoxy alcohols of the present invention have asymmetric carbon away from the alcoholic hydroxyl group by oxygen-containing carbon chain These can be used for synthesis of chiral liquid crystal materials, pharmaceuticals, agricultural chemicals, and intermediates of natural product synthesis Moreover, the chiral compound, 1 ,3-phenylene b ⁇ s[4-(4-alkoxy)- phe ⁇ yhminomethyljbenzoate bearing an alkoxy alcohol group as an end group has the same or more satisfactory liquid crystal phase and electric optical property, and a low phase transition temperature, when compared with a known carbon derivative with a chiral alkyl group The emergence of ferroelectricity and antiferroelectricity of them depend on the length of chiral (alkoxy)alkyl terminal group, they can be used as important components in the mixture of smectic liquid crystal materials

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Abstract

La présente invention concerne des alcools alcoxy chiraux, des 1,3-phénylène-bis[4-(4-alcoxy)phényliminométhyl]benzoates chiraux et des procédés de préparation correspondants. Les alcools alcoxy chiraux de la présente invention peuvent s'utiliser pour synthétiser des matières à cristaux liquides chiraux, des produits pharmaceutiques, des produits chimiques agricoles et des intermédiaires destinés à la synthèse de produits naturels. Etant donné que le composé chiral de 1,3-phénylène-bis[4-(4-alcoxy)phényliminométhyl]benzoate a une température de phase de transition moins élevée et manifeste une ferroélectricité ou une antiferroélectricité qui dépend de la longueur du groupe terminal (alcoxy)alkyle chiral, il peut être utilisé en tant que composant important dans le mélange de cristaux liquides smectiques.
PCT/KR2005/002870 2004-09-02 2005-08-30 Alcools alcoxy chiraux, 1,3-phenylene-bis[4-(4-alcoxy)phenyliminomethyl]benzoates chiraux et procedes de preparation correspondants Ceased WO2006025687A1 (fr)

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KR1020040069990A KR100611931B1 (ko) 2004-09-02 2004-09-02 광학활성 알콕시알콜 화합물, 이로부터 유도되는 광학활성1,3-페닐렌-비스[4-(4-알콕시)페닐이미노메틸]벤조에이트화합물 및 이들의 제조방법
KR10-2004-0069990 2004-09-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013184780A1 (fr) * 2012-06-06 2013-12-12 Unither Virology, Llc Nouveaux iminosucres et leurs applications
CN104105778A (zh) * 2011-12-05 2014-10-15 东进世美肯 用于表现液晶混合物的高速响应特性的不对称弯曲型分子化合物

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US6730371B2 (en) * 2001-04-13 2004-05-04 Mitsubishi Gas Chemical Company, Inc. Optically active compound and liquid crystal composition containing the compound

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US5637256A (en) * 1991-04-24 1997-06-10 University Research Corporation Ferroelectric liquid crystals for nonlinear optics applications
EP0937765A1 (fr) * 1998-02-19 1999-08-25 Mitsubishi Gas Chemical Company, Inc. Composé liquide cristallin ferriélectrique
EP0994097A2 (fr) * 1998-10-12 2000-04-19 Mitsubishi Gas Chemical Company, Inc. Nouveau composé phényl triester et composition de cristaux liquides anti-ferroélectriques le contenant
US6730371B2 (en) * 2001-04-13 2004-05-04 Mitsubishi Gas Chemical Company, Inc. Optically active compound and liquid crystal composition containing the compound
JP2002322113A (ja) * 2001-04-25 2002-11-08 Mitsubishi Chemicals Corp エーテル構造を有する多価アルコールの製造方法

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Title
LEE S K ET AL: "Odd-even behavior of ferroelectricity and antiferroelectricity in two homologous series of bent-core mesogens.", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 127, no. 31, 2005, pages 11085 - 11091 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104105778A (zh) * 2011-12-05 2014-10-15 东进世美肯 用于表现液晶混合物的高速响应特性的不对称弯曲型分子化合物
TWI494417B (zh) * 2011-12-05 2015-08-01 Dongjin Semichem Co Ltd 用於表現液晶混合物的高速響應特性的不對稱彎曲型分子化合物
CN104105778B (zh) * 2011-12-05 2016-10-12 东进世美肯 用于表现液晶混合物的高速响应特性的不对称弯曲型分子化合物
WO2013184780A1 (fr) * 2012-06-06 2013-12-12 Unither Virology, Llc Nouveaux iminosucres et leurs applications
US8921568B2 (en) 2012-06-06 2014-12-30 Unither Virology, Llc Iminosugars and their applications

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