JPS6377850A - Fluorine-containing propanenitrile compound - Google Patents
Fluorine-containing propanenitrile compoundInfo
- Publication number
- JPS6377850A JPS6377850A JP22156386A JP22156386A JPS6377850A JP S6377850 A JPS6377850 A JP S6377850A JP 22156386 A JP22156386 A JP 22156386A JP 22156386 A JP22156386 A JP 22156386A JP S6377850 A JPS6377850 A JP S6377850A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- liquid crystal
- formula
- fluorine
- reaction
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 12
- 239000011737 fluorine Substances 0.000 title claims description 12
- -1 propanenitrile compound Chemical class 0.000 title claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 10
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 abstract description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000282373 Panthera pardus Species 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical compound C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】 ［ａ業上の利用分野］ 本発明は、新規な含フッ素化合物に関するものである。[Detailed description of the invention] [Field of use in business a] The present invention relates to a novel fluorine-containing compound.
詳しくは、液晶組成物の成分として使用することができ
る新規な含フッ素プロパンニトリル系化合物に関するも
のである。Specifically, the present invention relates to a novel fluorine-containing propanenitrile compound that can be used as a component of a liquid crystal composition.
［発明の背景コ
液晶化合物が電気光学表示装置に利用されて以来、数多
くの液晶物賃が合成され、ネマチック液晶またはネマチ
ック−コレステリック液晶がねじれネマチックモード表
示素子、コレステリック−ネマチック相転８現象利用表
示素子、またはゲスト・ホスト効果利用表示素子などに
広く利用され、またカイラルス゛メタチックＣ？夜晶を
イ吏用した液晶表示も検討さ打ている。[Background of the Invention] Since liquid crystal compounds were used in electro-optical display devices, many liquid crystal compounds have been synthesized, and nematic liquid crystals or nematic-cholesteric liquid crystals are used to create twisted nematic mode display elements, displays using the cholesteric-nematic phase change phenomenon, etc. It is widely used in display devices that utilize the guest-host effect. A liquid crystal display using night crystals is also being considered.
これら液晶化合物には、水分、空気、光、熱等に対して
安定であることが要求され、また室温で液晶状態である
のは勿論のこと、低温から高温までのできるだけ広い温
度範囲で液晶状態を示し、速い応答速度を示すものが望
まれる。These liquid crystal compounds are required to be stable against moisture, air, light, heat, etc., and are not only in a liquid crystal state at room temperature, but also in a liquid crystal state over a wide temperature range from low to high temperatures. , and a fast response speed is desired.
［発明の構成］
本発明は、かかる要求を満たす液晶組成物を与える新規
化合物を提供することをその目的とするものである。[Structure of the Invention] An object of the present invention is to provide a novel compound that provides a liquid crystal composition that satisfies such requirements.
即ち、本発明は、一般式［エコ （式中、Ｒはアルキル二を示す。） で表わされる含フッ素プロパンニトリル系化合物、 を要旨とするものである。That is, the present invention is based on the general formula [Eco (In the formula, R represents alkyl di.) A fluorine-containing propanenitrile compound represented by The main points are as follows.
本発明の含フッ素プロパンニトリル系化合物は、適当な
公知の液晶化合物と組み合せて使用することができ、低
粘性で高速応答を示す液晶組成物として使用することが
できる。The fluorine-containing propanenitrile compound of the present invention can be used in combination with an appropriate known liquid crystal compound, and can be used as a liquid crystal composition that exhibits low viscosity and high-speed response.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の含フッ素プロパンニトリル系化合物は前記一般
式［ＩＩで示されるものであって、その置換基Ｒはアル
キル基を示すが、好ましくは、Ｒは炭素数１〜８のアル
キル基を示す。The fluorine-containing propanenitrile compound of the present invention is represented by the above general formula [II, in which the substituent R represents an alkyl group, and preferably R represents an alkyl group having 1 to 8 carbon atoms.
このような本発明の含フッ素プロパンニトリル系化合物
は、例えば、次の■〜■の反応による合成法で得ること
が・できる。Such a fluorine-containing propanenitrile compound of the present invention can be obtained, for example, by a synthetic method using the following reactions (1) to (2).
■ ［ＩＶ ｊ ＋ ［Ｖ］ □
ｎ
（なお、一般式［ＩＩ ］、［ｒＶ］〜［■コにおける
Ｒは、前記一般式［ＩＩにおけると同意義を示す。）
上記■の反応は、例えば、ジメチルホルムアミド、Ｎ−
メチルピロリドン等の有機溶媒中、銅粉の存在下、例え
ば１００〜２００℃の温度で行うことができる。■ [IV j + [V] □ n (In addition, R in the general formulas [II], [rV] to [■ has the same meaning as in the general formula [II]). , dimethylformamide, N-
It can be carried out in an organic solvent such as methylpyrrolidone in the presence of copper powder at a temperature of, for example, 100 to 200°C.
■の反応は、例えば、エタノール等のアルコール系溶媒
中、亜鉛の存在下、例えば７０℃〜１００℃の温度で行
うことができる。The reaction (2) can be carried out, for example, in an alcoholic solvent such as ethanol in the presence of zinc at a temperature of, for example, 70°C to 100°C.
■の反応は、例えば、アセトン等のケトン系溶媒中、例
えば−１Ｏ℃〜５０℃で過マンガン酸カリウムで酸化す
ることにより行うことができる。The reaction (2) can be carried out, for example, by oxidizing with potassium permanganate at -10°C to 50°C in a ketone solvent such as acetone.
■の反応は、例えば、ベンゼン、トルエン等の芳香族系
溶媒、四塩化炭素、クロロホルム等の塩素系溶媒、ジオ
キサン、テトラヒドロフラン等のエーテル系溶媒等の有
機溶媒存在下又はこれらの溶媒の不存在下、塩化チオニ
ル等のクロル化剤により、例えば５０〜１０ｆ１℃の反
応温度で行うことができる。The reaction (2) is carried out in the presence of organic solvents such as aromatic solvents such as benzene and toluene, chlorine solvents such as carbon tetrachloride and chloroform, and ether solvents such as dioxane and tetrahydrofuran, or in the absence of these solvents. The reaction can be carried out using a chlorinating agent such as , thionyl chloride, etc., at a reaction temperature of, for example, 50 to 10°C.
■の反応は、例えば、ジエチルエーテル、ジオキサン又
はテトラヒドロフラン等のエーテル系溶媒等の有機溶媒
の存在下又は不存在下、アンモニア等により、例えば−
１０℃〜１００℃の反応温度で行うことができる。The reaction (2) is carried out using, for example, -
It can be carried out at a reaction temperature of 10°C to 100°C.
■の反応は、例えば、五酸化リン等の脱水剤により、例
えば１００〜２５０℃の反応温度で行うことができる。The reaction (2) can be carried out using a dehydrating agent such as phosphorus pentoxide at a reaction temperature of, for example, 100 to 250°C.
本発明の含フッ素プロパンニトリル系化合物を使用して
液晶組成物を形成させる場合、適当な公知の液晶化合物
と組み合せて使用することができるが、かかる公知の液
晶化合物としては、′エステル系、ジエステル系、アゾ
キシ系、アゾ系、シッフ系、ピリミジン系、ビフェニル
系、フェニルシクロヘキサン系、シクロへキシルシクロ
ヘキサン系、ビシクロオクタン系、ジオキサン系あるい
は、ベンゼン環、シクロヘキサン環より成る多環化合物
系等のものが挙げられる。更に、本発明の化合物を用い
て液晶組成物を形成する場合、公知の二色性色素あるい
は減粘剤等の添加剤を併用することもできる。When forming a liquid crystal composition using the fluorine-containing propanenitrile compound of the present invention, it can be used in combination with an appropriate known liquid crystal compound. Examples include azoxy, azo, Schiff, pyrimidine, biphenyl, phenylcyclohexane, cyclohexylcyclohexane, bicyclooctane, dioxane, and polycyclic compounds consisting of benzene and cyclohexane rings. Can be mentioned. Furthermore, when forming a liquid crystal composition using the compound of the present invention, additives such as known dichroic dyes or thinners can also be used in combination.
［実施例］
次に、本発明を実施例により具体的に説明するが、本発
明は、その要旨を超えない限り以下の実施例に限定され
るものではない。[Examples] Next, the present invention will be specifically explained using Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例１
３−（Ｐ−（４−１−ランス−ｎ−プロピルシクロヘキ
シル）−フェニル）−テトラフルオロブロパンニトリル
反応に先立って硫酸銅１００ｇを温水３５０ｍｕに溶か
し、室温にした後、亜鉛３５ｇをゆフくりと加えた。こ
れにより、銅が沈殿してくる。これを水２００ａｌずつ
で５回デカンテーションして洗浄し、５％希塩酸１００
ｍｊ２で残フている亜鉛を溶かして除き、沈殿銅を得た
。Example 1 Prior to the 3-(P-(4-1-lanse-n-propylcyclohexyl)-phenyl)-tetrafluoropropanenitrile reaction, 100 g of copper sulfate was dissolved in 350 mu of warm water, and after bringing the temperature to room temperature, 35 g of zinc was added. I added slowly. This causes copper to precipitate. This was washed by decantation five times with 200 al of water, and then washed with 100 al of 5% diluted hydrochloric acid.
The remaining zinc was dissolved and removed in mj2 to obtain precipitated copper.
アンプルに４−（４−トランス−ロープロピルシクロヘ
キシル）−ヨードベンゼン［： ＩＩ ａｌ２．５３９
ｇ（７，７４Ｘ１０””ｍｏＪｌ） 、 ３．４−ジク
ロロ−１−ヨードペルフルオロブタン［ＩＩＩコエコ、
１５３１］ｇ（２，１５ｘ １０−２ｍｏ℃ン、上記沈
殿銅４．９５８６ｇ（７，８ｘ １０′−２ｍｏλ）及
び無水ジメチルホルムアミド８ｍＡを入れ封じ、１３５
℃で２４時間、加熱攪拌した。反応終了後、反応液に水
１００ｍ１Ｌを加え、吸引濾過し、濾過をジエチルエー
テルで抽出 （１５０ｍｆｌｘ ５回）、飽和食塩水
で洗浄（５０ｍｕＸＺ回）、無水硫酸マグネシウムで乾
燥した後、減圧濃縮して油状物を得た。カラムクロマト
グラフィ（シリカゲル；ヘキサン）で不純物を分離し、
１−（：１．４〜ジクロロペルフルオロブチル）−４
−（４−トランス−ロープロピルシクロヘキシル）−ベ
ンゼン［ｒＶａｌと１−（３−ペルフルオロブテニル）
−４−（４−トランス−ロープロピルシクロヘキシル）
−ベンゼン［Ｖ ａｌとの混合物２．２２４５ｇを得た
。4-(4-trans-lopropylcyclohexyl)-iodobenzene [: II al2.539
g (7,74
1531] g (2,15 x 10'-2 mo λ), 4.9586 g of the above precipitated copper (7,8 x 10'-2 mo
The mixture was heated and stirred at ℃ for 24 hours. After the reaction was completed, 100 ml of water was added to the reaction solution, filtered under suction, and the filtrate was extracted with diethyl ether (150 mfl x 5 times), washed with saturated brine (50 mu x Z times), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. An oil was obtained. Separate impurities by column chromatography (silica gel; hexane),
1-(:1.4~dichloroperfluorobutyl)-4
-(4-trans-rhopropylcyclohexyl)-benzene [rVal and 1-(3-perfluorobutenyl)
-4-(4-trans-lopropylcyclohexyl)
- 2.2245 g of a mixture with benzene [Val was obtained.
このイみ造は、下記ＮＭＲ，ＨＩＧＨ↑ＪＡＳＳの結果
により確認した。This imitation was confirmed by the following NMR and HIGH↑JASS results.
’Ｈ−Ｎ Ｍ Ｒδ＝ ７．ＢＯ〜７．０５ （ＤＩ
４Ｈ）（ＣＤＣＩｌｓ／ＴＭＳ） ２．７０〜
０．７９ （ｍ １７１（）Ｅ Ａ Ｍ Ｓ
Ｍ／２ ＰＣＥＬＥＩＪＥＮＴＳＨＩＧ）Ｉ ＭＡ
ＳＳ （７０ｅＶ） ４５４ １．６ Ｃ＋９Ｈ２＋ｈ
Ｃｕ＋ＣＪＺτ４５２ １．４ Ｃｌ、Ｈ２＋Ｆ７ＣＪ
１２３８２ １３．９ Ｃｌ９８２１Ｆ７
２５１ １００ Ｃｌ８Ｈ２１Ｆ２
２０１ ４．７ Ｃｌ５Ｈ２，
１５３４Ｂ、６ Ｃ２ＨｓＦ２
１２７ ２６．２ Ｃ２ＨｓＦ２
（ｉｉ） ［ｒＶａ］＋ ［Ｖａ］ −ｎ
反応（ｉ）で得た［■ａ］と［Ｖ ａｌとの混合物２．
２２５ｇに亜鉛０．９９５ｇ （１，５２ｘ １０−”
ｎｏ立）と９９＊工タノール２０ｍｕを加え、１時間加
熱還流した後、カラムクロマトグラフィ（シリカゲル；
ジクロロメタン）で過剰の亜鉛を取り除き、減圧濃縮し
て、［Ｖ ａｌ２．３７３ｇを得た。'H-N M Rδ=7. BO~7.05 (DI
4H) (CDCIls/TMS) 2.70~
0.79 (m 171()E A M S
M/2 PCELEIJENTSHIG)I MA
SS (70eV) 454 1.6 C+9H2+h
Cu+CJZτ452 1.4 Cl, H2+F7CJ
12382 13.9 Cl9821F7 251 100 Cl8H21F2 201 4.7 Cl5H2, 1534B, 6 C2HsF2 127 26.2 C2HsF2 (ii) [rVa]+ [Va] -n [■a] obtained in reaction (i) and [V al A mixture of 2.
0.995g of zinc in 225g (1,52x 10-”
After adding 20 mu of 99*tanol and heating under reflux for 1 hour, column chromatography (silica gel;
Excess zinc was removed with dichloromethane) and concentrated under reduced pressure to obtain 2.373 g of [Val.
反応（ｉ ｉ）で得た［ Ｖ ａｌ２．３７３ｇに過マ
ンガン酸カリウム５．４３７ｇ （３，４６ｘ １０”
”ｍｏｉ）とアセトン２０ｍｆｌを加え、氷−食塩浴で
０℃に冷却し、そのままの温度で１６時間攪拌した。反
応終了後、過剰の過マンガン酸カリウムを除去するため
に、反応液にメタノール４２ ｍａｌ、 １０％Ｆ塩酸
１０ｍＪ１１ ジエチルエーテル１００ｍ ｆｔ、更に
食塩と亜硫酸水素ナトリウムを少し加えた。わずかに結
晶が析出していたので濾過して取り除き、ジエチルエー
テルで抽出 （２００ｍｕ ｘ ５回）、無水硫酸ナ
トリウムて乾燥後、減圧濃縮して結晶物を得た。これを
カラムクロマトグラフィ（シリル化シリカゲル：ヘキサ
ン：ベンゼン＝２＋１）で分１ｉｆｔ精製し、ベンゼン
−ヘキサンにより再結晶を行い、白色の針状結晶３−（
ｐ−（４−トランス−ｎ−プロピルシクロヘキシル）−
フェニル）−テトラフルオロプロピオン酸［ＶＩａｌｏ
、７１２ｇ （２，０５ｘ １０−３ｍｏｊｌ ）を得
た。To 2.373 g of [Val obtained in reaction (ii), 5.437 g of potassium permanganate (3,46 x 10”
``moi'' and 20 mfl of acetone were added, cooled to 0°C in an ice-salt bath, and stirred at that temperature for 16 hours. After the reaction was completed, 42 methanol of methanol was added to the reaction solution to remove excess potassium permanganate. mal, 10% F hydrochloric acid 10 mJ11 diethyl ether 100 m ft, and a small amount of common salt and sodium bisulfite were added.A slight amount of crystals had precipitated, so they were removed by filtration, extracted with diethyl ether (200 mu x 5 times), and anhydrous sulfuric acid. After drying with sodium, it was concentrated under reduced pressure to obtain a crystalline product. This was purified by column chromatography (silylated silica gel: hexane: benzene = 2 + 1) for 1 minute, and recrystallized from benzene-hexane to obtain white needle-like crystals. 3-(
p-(4-trans-n-propylcyclohexyl)-
phenyl)-tetrafluoropropionic acid [VIalo
, 712 g (2,05 x 10-3 mojl) were obtained.
［ＶＩａｌは液晶性を有し相転り点は下記の通りてあっ
た。[VIal had liquid crystallinity and the phase inversion point was as shown below.
結晶−一一−Ｓ ｍ−−→Ｎ ｅ −ｍ−−１ｓ 。Crystal-11-S m--→N e-m--1s.
１４５℃ １６６℃ １６９℃また、ＮＭ
Ｒ，ＩＲ，元素分析の結果は下記に示す通りであった。145℃ 166℃ 169℃Also, NM
The results of R, IR, and elemental analysis were as shown below.
’Ｈ−Ｎ Ｍ Ｒδ＝９．８３ ＜ｓ Ｉｌ＋）
（ＣＤＣｊ２３／ＴＭｓ） ７．４８ （
ｄ ２ＨＪ・６．６１１ｚ）７．１９ （ｄ
２ＨＪ−１６，６１１ｚ）２．５０〜０．７９ （ｍ
１７Ｈ）Ｉ Ｒ（ＫＢ ｒ）ｃｍ−’：
３４００ （ｍ、ｂｒｏａｄ）、２９４５ （Ｓ）、２
８５０（ｚ）１７６０（Ｓ）、 １６１５
（ｍ）、１４４０（ｍ）１３００（ｍ）、
１１４０（Ｓ）、 ９２０（ｍ）８３０（α）
元素分析値（％） Ｃ： ８２．４２ Ｈ： ６．
４０Ｃ＋ａＨ２２Ｆ４０□としての計算値（％）Ｃ：６
２．４６Ｈ二６．３１
無水ベンゼン５ＩｎＡに上記（ｉ ｉ ｉ）で得た［Ｖ
ＩａｌＯ，５２６ｇ （１，５２ｘ ＩＰ３ｍｏＪｌ）
と無水ジメチルホルムアミド３滴、更に塩化チオニル３
．５ｍｌ （４゜８２×１０’−’！ｌ１ｏｆＬ）を
溶解し、２４時間加熱還流した。その後、そのままの温
度でベンゼン、過剰の塩化チオニルを減圧留去した。こ
れを室温に戻し、更に冷却し、無水ジエチルエーテル１
５ｍＡを加え、水冷下とした後、アンモニアガスを２０
分間吹き込んだ。この反応溶液に飽和食塩水５０＋ｎｆ
Ｌとジエチルエーテル３０ｍｕを加え、ジエチルエーテ
ルで抽出（３００１℃× ５回）、無水硫酸マグネシウ
ムで乾燥後、減圧濃縮して結晶物を得た。得られた結晶
をベンゼン−ヘキサンにより再結晶し、３− （ｐ−（
４−ｒ＋−プロピルシクロヘキシル
オロプロピオン酸アミド［■ａ］０．３８９ｇ （１．
１２ｘ１０−’ｍｏＪｌ）を得た（収率７４豹。'H-N M Rδ=9.83 <s Il+)
(CDCj23/TMs) 7.48 (
d 2HJ・6.611z) 7.19 (d
2HJ-16,611z) 2.50~0.79 (m
17H)IR(KBr)cm-': 3400 (m, broad), 2945 (S), 2
850 (z) 1760 (S), 1615
(m), 1440 (m) 1300 (m),
1140 (S), 920 (m) 830 (α) Elemental analysis value (%) C: 82.42 H: 6.
Calculated value (%) as 40C+aH22F40□C:6
2.46H26.31 [V obtained in (ii) above to anhydrous benzene 5InA
IalO, 526g (1,52x IP3moJl)
and 3 drops of anhydrous dimethylformamide, and 3 drops of thionyl chloride.
．． 5ml (4°82x10'-'!11ofL) was dissolved and heated under reflux for 24 hours. Thereafter, benzene and excess thionyl chloride were distilled off under reduced pressure at the same temperature. This was returned to room temperature, further cooled, and anhydrous diethyl ether 1
After adding 5 mA and cooling with water, ammonia gas was
It blew for a minute. Add 50+nf of saturated saline to this reaction solution.
L and 30 mu of diethyl ether were added, extracted with diethyl ether (3001°C x 5 times), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crystalline product. The obtained crystals were recrystallized from benzene-hexane to give 3-(p-(
4-r+-propylcyclohexylolopropionic acid amide [■a] 0.389 g (1.
12 x 10-'moJl) were obtained (yield 74 leopards).
本化合物は、結晶からネマチック液晶への転穆温度が１
７８℃で、ネマチック液晶から等方性液体への転８温度
が１９０℃であった。This compound has a transition temperature from crystal to nematic liquid crystal of 1
At 78°C, the transition temperature from nematic liquid crystal to isotropic liquid was 190°C.
フラスコに五酸化ニリン１．６００ｇ （１．３９ｘ
１０””ｍａｉｌ ）を入れ、その上に（ｉｖ）で得た
３− （ｐ− （４−ｎ−プロピルシクロヘキシル）−
フェニル）−テトラフルオロプロピオン酸アミド［■ａ
ｌＯ．２７８ｇ（８．Ｏｘ ｔｏ−’ｍｏλ）を入れた
。これに、窒素を吹き込み反応系内を無水とした後、減
圧しながらシリコーンオイル浴中２００℃で１時間加熱
した。反応終了後、フラスコ内にジエチルエーテル３０
ｍｆｔと水５０ｍＪ！をゆっくり注ぎ込んだ。ジエチル
エーテルで抽出（３０ｍｌ ｘ ３回）、無水硫酸マ
グネシウムで乾燥後、減圧濃縮して油状物を得た。この
油状物をカラムクロマトグラフィ（シリカゲル；ヘキサ
ン）て分離精製し、無色透明の油状物３− （ｐ− （
４−ｎ−プロピルシクロヘキシル）−フェニル）−テト
ラフルオロプロパンニトリル［ Ｉ ａｌｏ．１７９ｇ
（５．４７Ｘ １０−’ｍｏｕ）を得た（収率６８駒
。1.600 g of niline pentoxide (1.39x
3-(p-(4-n-propylcyclohexyl)- obtained in (iv))
phenyl)-tetrafluoropropionic acid amide [■a
lO. 278g (8.Ox to'moλ) was added. After nitrogen was blown into the reaction system to make the reaction system anhydrous, the reaction system was heated at 200° C. for 1 hour in a silicone oil bath under reduced pressure. After the reaction is complete, add 30 ml of diethyl ether to the flask.
mft and water 50mJ! I poured it slowly. The extract was extracted with diethyl ether (30 ml x 3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain an oil. This oily substance was separated and purified by column chromatography (silica gel; hexane), and a colorless and transparent oily substance 3- (p- (
4-n-propylcyclohexyl)-phenyl)-tetrafluoropropane nitrile [I alo. 179g
(5.47X 10-'mou) was obtained (yield: 68 pieces).
得られた化合物［ １ ａ］の諸物性は下記の通りであ
った。The physical properties of the obtained compound [1a] were as follows.
融 点 ６〜７ ℃
’Ｈ − Ｎ Ｍ Ｒ δ＝ ７．５３ （ｄ
２Ｈ Ｊ−９．ＯＨｚ）（ＣＤＣｊｌ ３／ＴＭＳ
） ７．３２ （ｄ ２Ｈ Ｊ・９．０Ｈ
ｚ）２、６９〜０．８２ 輸 １ ７ ＩＩ ）Ｉ Ｒ
（Ｉｌｆ）ｃｍ−’：
２９５０（Ｓ）、 ２８８０（ｍ）、 ２２７０（ｍ）
１８２０（ｍ）、 １４５０（ｍ）、 １１６０（Ｓ）
８３０（ｍ）
元素分析値（％） ｌ；：６１ｉ．ＩＳ ）Ｉ：８．
４９ Ｎ：４．１９ＣＩＪ２１Ｆ４Ｎとしての計算値
（％）Ｃ：６６．０４ Ｈ：６．４７ Ｎ：４．２
８実施例２
実施例１で得られた含フッ素化合物をＥ． Ｍｅｒｃｋ
社からＺＬＩ−１１３２ （結晶からネマチック液晶へ
の転ｆＪ温度；−６℃、ネマチック液晶から等方性液晶
への転穆温度．７０℃）として市販されている混合液晶
に１０重量％混合したところ、ネマチック液晶から等方
性液体への転穆温度は６０．８℃であった。なお、結晶
からネマチック相に相転移する温度は、過冷却現象によ
り、試料が結晶化しにくいため、測定困難であった。Melting point 6-7℃'H-NMR δ=7.53 (d
2H J-9. OHz) (CDCjl 3/TMS
) 7.32 (d 2H J・9.0H
z) 2,69~0.82 Import 1 7 II) I R
(Ilf) cm-': 2950 (S), 2880 (m), 2270 (m)
1820(m), 1450(m), 1160(S)
830 (m) Elemental analysis value (%) l;:61i. IS)I:8.
49 N: 4.19 Calculated value (%) as CIJ21F4N C: 66.04 H: 6.47 N: 4.2
8 Example 2 The fluorine-containing compound obtained in Example 1 was treated with E. Merck
10% by weight was mixed into a mixed liquid crystal commercially available as ZLI-1132 (transition fJ temperature from crystal to nematic liquid crystal: -6℃, transition temperature from nematic liquid crystal to isotropic liquid crystal: 70℃) from the company. , the transition temperature from nematic liquid crystal to isotropic liquid was 60.8°C. Note that it was difficult to measure the temperature at which the phase transition from crystal to nematic phase occurred because the sample was difficult to crystallize due to the supercooling phenomenon.
［発明の効果］
以上詳述した通り、本発明の含フッ素プロパンニトリル
系化合物は、液晶組成物の成分として使用することがで
きる新規な化合物であって、公知の液晶化合物と組み合
せて使用することができ、■ 水分、空気、光、熱等に
対して安定である。[Effects of the Invention] As detailed above, the fluorine-containing propanenitrile compound of the present invention is a novel compound that can be used as a component of a liquid crystal composition, and can be used in combination with a known liquid crystal compound. ■ Stable against moisture, air, light, heat, etc.
■ 広い温度範囲で液晶状態を示す。■ Exhibits liquid crystal state over a wide temperature range.
■ 低粘性で応答速度が高い。■Low viscosity and high response speed.
等の効果を奏し、工業的に極めて有用で、ある。It has the following effects and is extremely useful industrially.
Claims (1)
ルキル基であることを特徴とする特許請求の範囲第１項
に記載の含フッ素プロパンニトリル系化合物。[Claims] A fluorine-containing propanenitrile compound represented by the general formula [I] ▲Mathematical formula, chemical formula, table, etc.▼...[I] (In the formula, R represents an alkyl group.) (2) The fluorine-containing propanenitrile compound according to claim 1, wherein in the general formula [I], R is an alkyl group having 1 to 8 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22156386A JP2503440B2 (en) | 1986-09-19 | 1986-09-19 | Fluorine-containing propane nitrile compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22156386A JP2503440B2 (en) | 1986-09-19 | 1986-09-19 | Fluorine-containing propane nitrile compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6377850A true JPS6377850A (en) | 1988-04-08 |
| JP2503440B2 JP2503440B2 (en) | 1996-06-05 |
Family
ID=16768688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22156386A Expired - Lifetime JP2503440B2 (en) | 1986-09-19 | 1986-09-19 | Fluorine-containing propane nitrile compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2503440B2 (en) |
-
1986
- 1986-09-19 JP JP22156386A patent/JP2503440B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2503440B2 (en) | 1996-06-05 |
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