JPH0446251B2 - - Google Patents
Info
- Publication number
- JPH0446251B2 JPH0446251B2 JP59011810A JP1181084A JPH0446251B2 JP H0446251 B2 JPH0446251 B2 JP H0446251B2 JP 59011810 A JP59011810 A JP 59011810A JP 1181084 A JP1181084 A JP 1181084A JP H0446251 B2 JPH0446251 B2 JP H0446251B2
- Authority
- JP
- Japan
- Prior art keywords
- methylbutyl
- fluoro
- trans
- formula
- chiral
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- -1 methylbutyl Chemical group 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 235000015096 spirit Nutrition 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- HTRNHWBOBYFTQF-UHFFFAOYSA-N 4-bromo-2-fluoro-1-phenylbenzene Chemical group FC1=CC(Br)=CC=C1C1=CC=CC=C1 HTRNHWBOBYFTQF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGKVXIBFPYXSNI-MEELFCDTSA-N C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F DGKVXIBFPYXSNI-MEELFCDTSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YFNHOTZVDNNLFV-UHFFFAOYSA-N 2-(4-ethylcyclohexyl)acetyl chloride Chemical compound CCC1CCC(CC(Cl)=O)CC1 YFNHOTZVDNNLFV-UHFFFAOYSA-N 0.000 description 1
- QCAZNOJAHCFLHI-UHFFFAOYSA-N 2-fluoro-4-(2-methylbutyl)-1-phenylbenzene Chemical group FC1=CC(CC(C)CC)=CC=C1C1=CC=CC=C1 QCAZNOJAHCFLHI-UHFFFAOYSA-N 0.000 description 1
- GIWWLDRRWWDXJH-UHFFFAOYSA-N 2-methylbutyl benzenesulfonate Chemical compound CCC(C)COS(=O)(=O)C1=CC=CC=C1 GIWWLDRRWWDXJH-UHFFFAOYSA-N 0.000 description 1
- XHMZENXYLCHKOB-XPUGBJAQSA-N C(C)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F Chemical group C(C)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F XHMZENXYLCHKOB-XPUGBJAQSA-N 0.000 description 1
- VXLYKCROFRHQKJ-JTKSQVOZSA-N C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F Chemical compound C(C)[C@@H]1CC[C@H](CC1)CCC1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F VXLYKCROFRHQKJ-JTKSQVOZSA-N 0.000 description 1
- OWKNWDVPECHYTQ-FMWDMEFWSA-N C(CCC)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F Chemical group C(CCC)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F OWKNWDVPECHYTQ-FMWDMEFWSA-N 0.000 description 1
- OXMZZKBMFGEIKR-XYPYZODXSA-N C(CCC)[C@@H]1CC[C@H](CC1)CC(=O)Cl Chemical compound C(CCC)[C@@H]1CC[C@H](CC1)CC(=O)Cl OXMZZKBMFGEIKR-XYPYZODXSA-N 0.000 description 1
- DUIRJSKQHQTETN-FJUZFHEGSA-N C(CCCCCC)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F Chemical group C(CCCCCC)[C@@H]1CC[C@H](CC1)CC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)CC(CC)C)F DUIRJSKQHQTETN-FJUZFHEGSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】
従来キラルなネマチツク材料として公知の液晶
材料は、一般に、１種もしくはそれ以上のキラル
なネマトゲニツク化合物から成り、前記化合物は
液晶相を形成する性質又は形成する傾向を示す光
学的に活性な化合物である。これらの材料は、例
えば所謂“相転移”効果の如き適当な効果を利用
する種々の電気光学装置に使用され得る。また、
これらの材料は、各波長の放射の温度に依存する
選択反射を含む種々の温度感知装置に使用され得
る。前記の如き温度感知装置の場合、選択的反射
が可視スペクトル領域で生じるのが好ましい。DETAILED DESCRIPTION OF THE INVENTION Liquid crystal materials, conventionally known as chiral nematic materials, generally consist of one or more chiral nematogenic compounds, said compounds exhibiting an optical property or tendency to form a liquid crystal phase. It is a chemically active compound. These materials can be used in various electro-optical devices making use of appropriate effects, such as the so-called "phase transition" effect. Also,
These materials can be used in a variety of temperature sensing devices, including temperature-dependent selective reflection of each wavelength of radiation. In the case of temperature sensing devices such as those described above, selective reflection preferably occurs in the visible spectral region.
本発明のキラルなネマトゲニツク化合物の製造
に使用するのに適当な新規なフルオロビフエニル
は、式
Ｒ−R1 ［］
［式中、Ｒは、２，３，2′又は3′位の少なくと
も１箇所にフツ素置換基を有する４−ビフエニル
基を表わし、またR1は光学的に活性な（＋）−２
−メチルブチル基（＋）・−CH2CH（CH3）
CH2CH3を表わす］
を有し、単一の光学活性異性体である。 The novel fluorobiphenyls suitable for use in the preparation of the chiral nematogenic compounds of the present invention have the formula represents a 4-biphenyl group having a fluorine substituent at the position, and R 1 is an optically active (+)-2
-Methylbutyl group (+)・-CH 2 CH (CH 3 )
CH 2 CH 3 ] and is a single optically active isomer.
（＋）−は、ポジテイブな光学回転角度を示す
光学的な活性基を示す。 (+)- represents an optically active group exhibiting a positive optical rotation angle.
フツ素は２又は2′−位にある（R1は４位にあ
る）のが好ましい。 Preferably, the fluorine is in the 2 or 2'-position (R 1 is in the 4-position).
側位がフツ素化された４−アルキルビフエニル
類は公知であるが、該化合物の末端のアルキル基
が光学的に活性な中心を含むキラル基である化合
物は未知であつた。 Although 4-alkylbiphenyls having fluorinated side positions are known, compounds in which the terminal alkyl group is a chiral group containing an optically active center have not been known.
本発明は、キラルなネマチツク液晶材料に使用
するのに適当なキラルなネマトゲニツク化合物の
製造に式の化合物を使用することにも係る。 The invention also relates to the use of compounds of formula for the preparation of chiral nematogenic compounds suitable for use in chiral nematic liquid crystal materials.
式のビフエニルから製造され得るキラルなネ
マトゲニツク化合物として、式
（式中、R2はｎ−アルキルであり、Ｘ及びＹ
はＨ及びＦから選択されＸ及びＹの少なくとも一
方はＦである）
を有する化合物が例示される。 As a chiral nematogenic compound that can be prepared from biphenyl of formula (wherein R 2 is n-alkyl, X and Y
is selected from H and F, and at least one of X and Y is F).
式の化合物から合成された液晶化合物は、予
期せぬ優れた性質、例えば以下に示す如く室温で
光を選択的に反射し得る性質を有する。 The liquid crystal compound synthesized from the compound of the formula has unexpectedly excellent properties, such as the ability to selectively reflect light at room temperature as shown below.
式の化合物は、下記のルートで製造され得
る。 Compounds of formula may be prepared by the following route.
Ｒ−Br
↓
Ｒ−MgBr
↓
Ｒ−R1
［式中、Ｒ及びR1は前記に定義したとおりで
ある。］
前記した式及びの化合物の製造及び性質を
以下実施例を以つて説明する。 R-Br ↓ R-MgBr ↓ R-R 1 [wherein R and R 1 are as defined above. ] The preparation and properties of the compounds of the above formulas will be explained below with reference to Examples.
実施例中に使用した記号の意味は、次の通りで
ある。 The meanings of symbols used in the examples are as follows.
glc＝気液クロマトグラフイー
bp＝沸点
mp＝融点
Ch−Ｉ＝キラルなネマチツク−等方性液体転
移温度
Ｓ−Ch＝スメクチツク−キラルなネマチツク
転移温度
Ｋ−Ch＝結晶性固体−キラルなネマチツク転
移温度
実施例 １
（＋）−１−（トランス−４−ｎ−ブチルシクロ
ヘキシル）−２−［2′−フルオロ−4′−（２−メ
チルブチル）−４−ビフエニルイル］エタンの
製造：
ステツプ １
（＋）−２−フルオロ−４−（２−メチルブチ
ル）−ビフエニルの予備製造：
４−ブロモ−２−フルオロビフエニル（90ｇ）
のテトラヒドロフラン（90ml）溶液10mlを、窒素
下でマグネシウム屑9.6ｇ及びテトラヒドロフラ
ン20mlに添加した。ヨウ素の単結晶を添加後、加
温し反応を開始せしめた。４−ブロモ−２−フル
オロビフエニル溶液の残部を30分間に亘つて添加
した。 glc=gas-liquid chromatography bp=boiling point mp=melting point Ch-I=chiral nematic-isotropic liquid transition temperature S-Ch=smectic-chiral nematic transition temperature K-Ch=crystalline solid-chiral nematic transition Temperature Example 1 Preparation of (+)-1-(trans-4-n-butylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)-4-biphenylyl]ethane: Step 1 (+ Preparation of )-2-fluoro-4-(2-methylbutyl)-biphenyl: 4-bromo-2-fluorobiphenyl (90 g)
10 ml of a solution of 100 ml in tetrahydrofuran (90 ml) was added to 9.6 g of magnesium dust and 20 ml of tetrahydrofuran under nitrogen. After adding a single crystal of iodine, the mixture was heated to initiate a reaction. The remainder of the 4-bromo-2-fluorobiphenyl solution was added over 30 minutes.
１時間還流加熱後、グリニヤール試薬の溶液を
25℃に冷却した。２−メチルブチルフエニル−ス
ルフオネート（150ｇ）のテトラヒドロフラン
（140ml）溶液10mlを反応混合物に添加後、更に塩
化第一銅３ｇを添加した。フエニルスルフオネー
ト溶液の残部を40分間に亘つて添加した。生じた
グレー／グリーン反応混合物の温度は45℃に上昇
しており、これを１時間沸騰するまで加熱した。
室温まで冷却後、20容量％の塩酸溶液2.5を加
え、生成物をジクロロメタン（２×500ml）で抽
出した。有機層を水洗し（２×500ml）、無水硫酸
ナトリウム15ｇで乾燥し、溶媒を蒸発させると、
有機の液体残留物が得られた。冷却すると残留物
から白色固体が晶出した。過後残留物（88.6
ｇ）を真空（0.5トル）で分別蒸溜すると、無色
の液体65ｇが得られた。このものの純度はglcに
よると98.8％であつた。bpは0.5トルで120℃であ
つた。旋光度は＋14.62゜（溶媒）であつた。 After heating under reflux for 1 hour, the Grignard reagent solution was
Cooled to 25°C. 10 ml of a solution of 2-methylbutylphenyl-sulfonate (150 g) in tetrahydrofuran (140 ml) was added to the reaction mixture followed by a further 3 g of cuprous chloride. The remainder of the phenyl sulfonate solution was added over 40 minutes. The temperature of the resulting gray/green reaction mixture had risen to 45°C and it was heated to boiling for 1 hour.
After cooling to room temperature, 2.5 ml of 20% by volume hydrochloric acid solution was added and the product was extracted with dichloromethane (2 x 500 ml). The organic layer was washed with water (2 x 500 ml), dried over 15 g of anhydrous sodium sulfate, and the solvent was evaporated.
An organic liquid residue was obtained. A white solid crystallized from the residue upon cooling. Residue after filtration (88.6
Fractional distillation of g) in vacuo (0.5 Torr) gave 65 g of a colorless liquid. The purity of this product was 98.8% according to GLC. bp was 0.5 Torr and 120°C. The optical rotation was +14.62° (solvent).
ステツプ 1a2：
（＋）−４−（トランス−４−ｎ−ブチルシクロ
ヘキシル−アセチル）−2′−フルオロ−4′−（２
−メチルブチル）ビフエニルの製造：
（＋）−２−フルオロ−４−（２−メチルブチ
ル）ビフエニル（10ｇ）とトランス−４−ｎ−ブ
チルシクロヘキシルアセチル クロライド（9.4
ｇ）とのジクロロメタン（20ml）中の混合物を、
20分間に亘つて無水塩化アルミニウム（6.1ｇ）
のジクロロメタン（20ml）冷却（５−10℃）攪拌
懸濁液に添加した。添加後反応混合物を23℃に加
温し、17時間攪拌した。生じた溶液を水（200ml）
に添加し、石油スピリツト（bp60−80℃：180ml
＋100ml）で順次抽出した。次いで、有機抽出物
を水洗し（200ml）、無水硫酸ナトリウム（５ｇ）
で乾燥し、蒸発させた。黄色の結晶性残留物
（17.9ｇ）をエタノール（35ml）から25℃で再結
晶すると、生成物が得られた（14.8ｇ、収率85
％）。生成物のmpは71.4−72.1℃であつた。実際
のCH−Ｉは68.5−68.8℃であつた。glcにより、
純度は99.5％であつた。Step 1a2: (+)-4-(trans-4-n-butylcyclohexyl-acetyl)-2'-fluoro-4'-(2
-Methylbutyl)biphenyl production: (+)-2-fluoro-4-(2-methylbutyl)biphenyl (10g) and trans-4-n-butylcyclohexylacetyl chloride (9.4
g) in dichloromethane (20ml),
Anhydrous aluminum chloride (6.1 g) over 20 minutes
dichloromethane (20ml) was added to the cooled (5-10°C) stirred suspension. After the addition, the reaction mixture was warmed to 23°C and stirred for 17 hours. Pour the resulting solution into water (200ml)
and petroleum spirits (bp60-80℃: 180ml
+100 ml). The organic extract was then washed with water (200ml) and anhydrous sodium sulfate (5g).
dried and evaporated. The yellow crystalline residue (17.9 g) was recrystallized from ethanol (35 ml) at 25°C to give the product (14.8 g, yield 85
%). The mp of the product was 71.4-72.1°C. Actual CH-I was 68.5-68.8°C. By glc
The purity was 99.5%.
ステツプ 1b2
（＋）−１−（トランス−４−ｎ−ブチルシクロ
ヘキシル）−２−［2′−フルオロ−4′−（２−メ
チルブチル）−４−ビフエニルイル］エタンの
製造：
前記の如く製造したケトン14.4ｇ、99％ヒドラ
ジン水化物14.4ml、水酸化カリウム7.2ｇ及びジ
ゴール（digol）120mlを、攪拌下125℃で４時間
還流加熱した。こ後、過剰のヒドラジン水化物の
蒸溜により温度は175℃に上昇した。次いで、混
合物を17時間還流加熱し、60℃に冷却し、氷水
（500ｇ）に注いだ。有機生成物を石油スピリツト
（bp60−80℃：２×200ml）で抽出し、抽出物を
水洗し（２×200ml）、無水硫酸ナトリウムで乾燥
した。溶媒を蒸発させると、黄色油状物14.1ｇが
得られた。このものは石油スピリツト（bp60−
80℃：100ml）に溶解し、シリカゲル（20ｇ）上
に塩基性アルミナ（50ｇ）を充填させたカラム上
に吸着させた。石油スピリツト（320ml）で溶出
し、溶媒を蒸発させると、無色の油状物が11.7ｇ
得られた。プロパン−１−オールから−50℃で結
晶化させると、キラルなネマチツク材料9.4ｇ
（収率68％）が得られた。このものの純度はglcで
99.8％であつた。Step 1b2 Preparation of (+)-1-(trans-4-n-butylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)-4-biphenylyl]ethane: Ketone prepared as above 14.4 g of 99% hydrazine hydrate, 7.2 g of potassium hydroxide and 120 ml of digol were heated under reflux at 125° C. for 4 hours with stirring. After this, the temperature rose to 175°C due to distillation of excess hydrazine hydrate. The mixture was then heated at reflux for 17 hours, cooled to 60°C and poured onto ice water (500g). The organic product was extracted with petroleum spirits (bp 60-80°C: 2 x 200 ml), the extract was washed with water (2 x 200 ml) and dried over anhydrous sodium sulfate. Evaporation of the solvent gave 14.1 g of a yellow oil. This is petroleum spirits (bp60−
80°C: 100 ml) and adsorbed onto a column packed with basic alumina (50 g) on silica gel (20 g). Elution with petroleum spirits (320 ml) and evaporation of the solvent yielded 11.7 g of a colorless oil.
Obtained. When crystallized from propan-1-ol at -50°C, 9.4 g of chiral nematic material
(68% yield) was obtained. The purity of this stuff is glc
It was 99.8%.
生成物の性質は次の通りであつた。 The properties of the product were as follows.
Ｓ−Ch＝６℃，
Ch−Ｉ＝72℃，
ラセン分子ピツチ＝0.23ミクロン
実施例 ２
１−（トランス−４−エチルシクロヘキシル）−
２−［2′−フルオロ−4′−（２−メチルブチル）
−４−ビフエニルイル］エタンの製造：
ステツプ 1a3
４−（トランス−４−エチルシクロヘキシルア
セチル）−2′−フルオロ−4′−（２−メチルブチ
ル）ビフエニルの製造：
出発材料として４−エチルシクロヘキシル ア
セチルクロライドを用いて上記ステツプ1a2を繰
返すと、下記の性質を有する生成物が得られた。 S-Ch=6℃, Ch-I=72℃, helical molecular pitch=0.23 micron Example 2 1-(trans-4-ethylcyclohexyl)-
2-[2'-fluoro-4'-(2-methylbutyl)
-4-Biphenylyl]ethane production: Step 1a3 Production of 4-(trans-4-ethylcyclohexylacetyl)-2'-fluoro-4'-(2-methylbutyl)biphenyl: 4-ethylcyclohexyl acetyl chloride as the starting material. Repeating step 1a2 above using the following steps resulted in a product with the following properties:
m.p.＝40−42℃，
実際のCh−Ｉ＝（27.5℃）
ステツプ 1b3
１−（トランス−４−エチルシクロヘキシル）−
２−［2′−フルオロ−4′−（２−メチルブチル）
−４−ビフエニルイル］エタンの製造：
上記ステツプ1b2を繰返して得られた生成物は
次の性質を有する。 mp=40-42℃, Actual Ch-I=(27.5℃) Step 1b3 1-(trans-4-ethylcyclohexyl)-
2-[2'-fluoro-4'-(2-methylbutyl)
Preparation of -4-biphenylyl]ethane: The product obtained by repeating step 1b2 above has the following properties.
Ｓ−Ch＝−11℃，
Ch−Ｉ＝45℃
実施例 ３
１−（トランス−４−ｎ−ヘプチルシクロヘキ
シル）−２−［2′−フルオロ−4′−（２−メチル
ブチル）−４−ビフエニルイル］エタンの製
造：
ステツプ 1a4
４−（トランス−４−ｎ−ヘプチルシクロヘキ
シルアセチル）−2′−フルオロ−4′−（２−メチ
ルブチル）ビフエニルの製造：
上記ステツプ1a2を繰返して得られた生成物は
次の性質を有する。 S-Ch=-11℃, Ch-I=45℃ Example 3 1-(trans-4-n-heptylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)-4-biphenylyl ]Production of ethane: Step 1a4 Production of 4-(trans-4-n-heptylcyclohexylacetyl)-2'-fluoro-4'-(2-methylbutyl)biphenyl: The product obtained by repeating step 1a2 above is It has the following properties.
Ｋ−Ch＝69.8−70.3℃，
Ch−Ｉ＝74.1−74.3℃
ステツプ 1b4
１−（トランス−４−ｎ−ヘプチルシクロヘキ
シル）−２−［2′−フルオロ−4′−（２−メチル
ブチル）−４−ビフエニルイル］エタンの製
造：
上記ステツプ1b2を繰返して得られた生成物は
次の性質を有する。 K-Ch=69.8-70.3℃, Ch-I=74.1-74.3℃ Step 1b4 1-(trans-4-n-heptylcyclohexyl)-2-[2'-fluoro-4'-(2-methylbutyl)-4 - Preparation of biphenylyl]ethane: The product obtained by repeating step 1b2 above has the following properties.
Ｓ−Ch＝52℃， Ch−Ｉ＝79℃ S-Ch=52℃, Ch−I=79℃
Claims (1)
するのに適した式 Ｒ−R1 ［式中、Ｒは、２，３，2′又は3′位の少なくと
も１箇所にフツ素置換基を有する４−ビフエニル
基を表わし、またR1は光学的に活性な（＋）−２
−メチルブチル基を表わす］ を有し、単一の光学活性異性体であるフルオロビ
フエニル。 ２ Ｒが【式】及び 【式】 から選択される特許請求の範囲第１項に記載のフ
ルオロビフエニル。[Claims] 1 Formula suitable for use in the production of chiral nematogenic compounds R-R 1 [wherein R is a fluorine substituted at at least one of the 2, 3, 2' or 3' positions] represents a 4-biphenyl group having a group, and R 1 is an optically active (+)-2
-representing a methylbutyl group] and is a single optically active isomer. 2. Fluorobiphenyl according to claim 1, wherein R is selected from [Formula] and [Formula].
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838302119A GB8302119D0 (en) | 1983-01-26 | 1983-01-26 | Disubstituted ethanes |
| GB8302119 | 1983-01-26 | ||
| GB8333897 | 1983-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6069046A JPS6069046A (en) | 1985-04-19 |
| JPH0446251B2 true JPH0446251B2 (en) | 1992-07-29 |
Family
ID=10536967
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1180984A Granted JPS6069045A (en) | 1983-01-26 | 1984-01-25 | Disubstituted ethane, liquid crystal material and use for device |
| JP1181084A Granted JPS6069046A (en) | 1983-01-26 | 1984-01-25 | Biphenyls and use for manufacture of liquid crystal compounds |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1180984A Granted JPS6069045A (en) | 1983-01-26 | 1984-01-25 | Disubstituted ethane, liquid crystal material and use for device |
Country Status (2)
| Country | Link |
|---|---|
| JP (2) | JPS6069045A (en) |
| GB (1) | GB8302119D0 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61282328A (en) * | 1985-06-10 | 1986-12-12 | Chisso Corp | Cyclohexane derivative |
| FR2586422B1 (en) * | 1985-08-26 | 1988-01-15 | Commissariat Energie Atomique | MIXTURE OF NEMATIC LIQUID CRYSTALS COMPRISING A 1- (ALKYL CYCLOHEXYL) -2- (ALKYL FLUOROBIPHENYLY) ETHANE |
| JP4526605B2 (en) * | 1996-08-28 | 2010-08-18 | チッソ株式会社 | Tetracyclic compound having lateral halogen substituent and liquid crystal composition |
| US8137583B2 (en) * | 2008-05-29 | 2012-03-20 | Jnc Corporation | Liquid crystal four-ring compound having fluorine, liquid crystal composition, and liquid crystal display device |
| JP2010111686A (en) * | 2009-12-24 | 2010-05-20 | Chisso Corp | Tetracyclic compound having lateral halogen substituent group and liquid crystal composition |
| WO2015016093A1 (en) * | 2013-07-30 | 2015-02-05 | Semiconductor Energy Laboratory Co., Ltd. | Organic compound, liquid crystal composition, liquid crystal element, and liquid crystal display device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025537A (en) * | 1973-06-01 | 1975-03-18 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3042391A1 (en) * | 1980-11-10 | 1982-06-16 | Merck Patent Gmbh, 6100 Darmstadt | FLUORINE CYCLOHEXYLBIPHENYL DERIVATIVES, THESE DIELECTRICS AND ELECTRO-OPTICAL DISPLAY ELEMENT |
| JPS57165326A (en) * | 1981-04-03 | 1982-10-12 | Asahi Glass Co Ltd | Trans-4-alkyl-(4'-fluorobiphenyl-4)cyclohexane |
| JPS59155485A (en) * | 1983-02-22 | 1984-09-04 | Canon Inc | Liquid crystal composition |
| JPS6048945A (en) * | 1983-08-27 | 1985-03-16 | Chisso Corp | Fluorinated cyclohexylbiphenyl |
-
1983
- 1983-01-26 GB GB838302119A patent/GB8302119D0/en active Pending
-
1984
- 1984-01-25 JP JP1180984A patent/JPS6069045A/en active Granted
- 1984-01-25 JP JP1181084A patent/JPS6069046A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025537A (en) * | 1973-06-01 | 1975-03-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6069046A (en) | 1985-04-19 |
| JPS6069045A (en) | 1985-04-19 |
| GB8302119D0 (en) | 1983-03-02 |
| JPH0225894B2 (en) | 1990-06-06 |
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