JPS63218648A - Production of liquid crystal intermediate - Google Patents
Production of liquid crystal intermediateInfo
- Publication number
- JPS63218648A JPS63218648A JP62053669A JP5366987A JPS63218648A JP S63218648 A JPS63218648 A JP S63218648A JP 62053669 A JP62053669 A JP 62053669A JP 5366987 A JP5366987 A JP 5366987A JP S63218648 A JPS63218648 A JP S63218648A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- water
- group
- liquid crystal
- optically active
- 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.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 5
- 239000005711 Benzoic acid Substances 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 4
- 235000019256 formaldehyde Nutrition 0.000 abstract description 4
- 239000004990 Smectic liquid crystal Substances 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- -1 propionate ester Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000006340 racemization Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 235000007575 Calluna vulgaris Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、一般式（２）で示される液晶中間体の合成法
に関する物である。一般式（３）で示される分子内に光
学活性基を有する液晶は、カイラルスメチック相を示す
強誘電性液晶として注目されており、本発明により得ら
れる（２）は強誘電性液晶の有用な中間体を成りうる。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for synthesizing a liquid crystal intermediate represented by general formula (2). The liquid crystal having an optically active group in the molecule represented by the general formula (3) has attracted attention as a ferroelectric liquid crystal exhibiting a chiral smectic phase, and (2) obtained by the present invention is useful as a ferroelectric liquid crystal. It can be an intermediate.
（従来技術）
一般式（３）で示される強誘電性液晶の従来合成法を次
に示す。以下反応式で例示するが式中Ａ、Ｂ、ｍ、ｎは
式（１）で規定したものである。(Prior Art) A conventional method for synthesizing the ferroelectric liquid crystal represented by the general formula (3) is shown below. The reaction formula will be illustrated below, in which A, B, m, and n are defined in formula (1).
Ｉ）（Ｉ−ａ）Ｂが０ＣＨ２の場合 （但し、式中Ｒ１本は光学活性アルキル基を示す。） （Ｉ −ｂ） ＢがＣＨ２Ｏの場合 （但し、式中Ｒ１＊！よ光学活性アルキル基を示す。） Ｊ杢匹ｊ旦→（３） （但し、式中Ｒ１’ｌよ光学活性アルキル基を示す。） （ＩＩ−ｂ）ＢがＣＨ２Ｏの場合 （但し、式中ぶ＊は一級光学活性アルキル基を示す。） （但し、式中Ｒ１町よ二級光学活性アルキル基を示す。I) (I-a) When B is 0CH2 (However, in the formula, R1 represents an optically active alkyl group.) (I-b) When B is CH2O (However, in the formula, R1*! represents an optically active alkyl group.) J heather jdan → (3) (However, in the formula, R1'l represents an optically active alkyl group.) (II-b) When B is CH2O (However, * in the formula represents a primary optically active alkyl group.) (However, in the formula, R1 represents a secondary optically active alkyl group.
）
（Ｉ −ａ）、（Ｉ −ｂ）、（Ｉ−ｃ）、および（Ｉ
−ｄ）の方法はいずれも特開昭６０−１４９５４７に記
載された方法である。) (I-a), (I-b), (I-c), and (I
Methods -d) are all described in JP-A No. 60-149547.
（Ｉ−ａ）および（Ｉ−ｂ）法は、水素化ナトリウムの
ような強アルカリを用いるため、Ｒ１＊ＯＨに対応する
アルコールがラセミ化しやすいアルコール、例えば乳酸
エステル、３−ヒドロキシ、２−メチルプロピオン酸エ
ステルの様に光学活性点に酸性度の大きい水素原子を有
するアルコールを用いた場合、縮合反応時にラセミ化が
進行するため、使用できる光学活性アルコールは限られ
たものになる。また（ＩＬａ）の方法は、光学活性基の
ラセミ化は抑制されるが（１０）から（１１）の段階で
、シアン化第−銅の様な毒物を用いることから、安全上
取扱いが困難である。更に（ＩＩ−ｂ）の方法は（Ｉ−
ｂ）の方法で得られた光学活性エステル（１５）を出発
原料に用い、加水分解ののち、酸クロライド（１７）と
し、最後に二級の光学活性アルコールとの反応により（
３）を合成するものである。この方法によれば化合物（
１８）においてラセミ化しやすい光学活性アルコールを
用いた場合でも、高い光学純度で（３）が合成できる。In methods (I-a) and (I-b), since a strong alkali such as sodium hydride is used, the alcohol corresponding to R1*OH is easily racemized, such as lactic acid ester, 3-hydroxy, 2-methyl When an alcohol having a highly acidic hydrogen atom at an optically active site, such as a propionate ester, is used, racemization progresses during the condensation reaction, so the number of optically active alcohols that can be used is limited. In addition, although the method (ILa) suppresses racemization of optically active groups, it is difficult to handle safely because it uses a poisonous substance such as cupric cyanide in steps (10) to (11). be. Furthermore, the method (II-b) is (I-
The optically active ester (15) obtained by the method b) was used as a starting material, and after hydrolysis, it was converted into acid chloride (17), and finally by reaction with a secondary optically active alcohol (
3). According to this method, the compound (
Even when an optically active alcohol that is easily racemized is used in 18), (3) can be synthesized with high optical purity.
しかしながら、（ＩＩ−ｂ）の方法は光学活性液晶（１
５）から光学活性アルコール部分を変換し、種々の光学
活性液晶（３）が合成できることを特徴とするものであ
り、高価な光学活性アルコール（Ｒ２”ＯＨ）を消費す
ることから、経済的でないと考えられる。However, method (II-b) uses optically active liquid crystal (1
It is characterized by the fact that various optically active liquid crystals (3) can be synthesized by converting the optically active alcohol moiety from 5), and it is not economical because it consumes expensive optically active alcohol (R2''OH). Conceivable.
従来法は以上のような個々の問題点を有するが更に大き
な問題点として、一般式（３）で表される液晶化合物の
置換基Ｂの違いによりそれぞれ異なった合成法を用いな
ければならないことが挙げられる。Conventional methods have individual problems as mentioned above, but an even bigger problem is that different synthesis methods must be used depending on the substituent B of the liquid crystal compound represented by general formula (3). Can be mentioned.
強誘電性液晶のスクリーニングにあたっては特定の中間
体から、短い行程で且つ光学活性基のラセミ化を抑制し
ながら、多くの液晶分子を合成できる方法が望まれてお
り、このことから一般式（１）及び（２）で示される化
合物は強誘電性液晶の優れた中間体と考えられる。一般
式（１）で示される化合物から一般式（２）で示される
化合物を合成する方法は（ＩＩ−ｂ）の方法に一部記載
されているが、実験条件等の詳しい記述がなされてく、
又比較例１に示すような一般的な方法では目的とする液
晶中間体（２）はほとんど得られなかった。When screening ferroelectric liquid crystals, there is a need for a method that can synthesize many liquid crystal molecules from specific intermediates in short steps and while suppressing racemization of optically active groups. ) and (2) are considered to be excellent intermediates for ferroelectric liquid crystals. The method for synthesizing the compound represented by general formula (2) from the compound represented by general formula (1) is partially described in the method (II-b), but detailed descriptions of experimental conditions etc. are not provided.
Moreover, by the general method shown in Comparative Example 1, the desired liquid crystal intermediate (2) could hardly be obtained.
（問題を解決するための手段）
本発明者らは前述の問題解決すべく鋭意研究した結果
一般式
（但し、上式に於て、Ａは炭素数１〜１８のアルキル基
又はアルキルオキシ基であり、ＢはＣＨ２Ｏ，或いは０
ＣＲ２である。ｍは１又は２であり、ｎは１又は２であ
り、Ｒはアルキル基である。）で表される化合物に水及
び水溶性非プロトン溶媒混合溶液中でアルカリ金属水酸
化物を作用させることを特徴とする。(Means for Solving the Problem) The present inventors have conducted intensive research to solve the above-mentioned problem, and as a result, the general formula (however, in the above formula, A is an alkyl group or an alkyloxy group having 1 to 18 carbon atoms) Yes, B is CH2O, or 0
It is CR2. m is 1 or 2, n is 1 or 2, and R is an alkyl group. ) is treated with an alkali metal hydroxide in a mixed solution of water and a water-soluble aprotic solvent.
一般式
（但し、上式に於て、Ａ、Ｂ、ｍ、ｎ、は一般式（１）
で規定した通りである。）で表される化合物の合成法を
見出した。General formula (However, in the above formula, A, B, m, n are general formula (1)
As stipulated in. ) has been discovered.
本発明は二股式（１）で表される化合物の加水分解反応
において、ジメチルスルホキシド等水溶性非プロトン溶
媒を用いることを特徴とするものである。水溶性非プロ
トン溶媒としてはジメチルスルホキシド、ジメチルホル
ムアミド、アセトニトリル、アセトン等が挙げられる。The present invention is characterized in that a water-soluble aprotic solvent such as dimethyl sulfoxide is used in the hydrolysis reaction of the compound represented by the bifurcated formula (1). Examples of water-soluble aprotic solvents include dimethyl sulfoxide, dimethyl formamide, acetonitrile, and acetone.
式（１）及び式（２）において、Ａは炭素数１から１８
の飽和直鎖状アルキル基、及び飽和直鎖状アルキルオキ
シ基であり、メチル基、エチル基、ペンチル基、オクチ
ル基、ノニル基、ドデシル基、ペンタデシル基、オクタ
デシル基、或いはメチルオキシ基、エチルオキシ基、ペ
ンチルオキシ基、オクチルオキシ基、ノニルオキシ基、
ドデシルオキシ基、ペンタデシルオキシ基、オクタデシ
ルオキシ基等が例示出来るが、更にアルケニル基、アル
キニル基などの不飽和炭化水素、及びヒドロキシ基、ア
ルコキシ基を置換基として持つアルキル基及びアルキル
オキシ基も含まれる。ｍ及びｎは１又は２の整数からそ
れぞれ独立して選ばれる。Ｒは直鎖状或いは分岐状アル
キル基であり、特にアルキル基の炭素数は限定するもの
でない。しかしながら経済性から見て炭素数１から４が
好ましく例えばｎ−メチル基、ｎ−エチル基、ｎ−プロ
ピル基、ｎ−ブチル基、１ｓｏ−プロピル基、５ｅｃ−
ブチル基、及びｔ−ブチル基が例示できる。アルカリ金
属水酸化物としては、水酸化ナトリウム、水酸化カリウ
ム、水酸化リチウムが挙げられる。アルカリ金属水酸化
物の量は（１）に対して１〜１０倍当量であり好ましく
は３〜５当量である。反応溶媒として用いる水及び水溶
性非プロトン溶媒は任意の割合で用いられ、更にメタノ
ール、エタノールなど水溶性の溶媒を第三成分として添
加してもよいが第三成分の有無及びその割合は特に限定
する物ではない。又反応温度及び反応時間はアルカリ金
属水酸化物の量及び種類により変化し、特に限定するも
のでない。In formula (1) and formula (2), A has a carbon number of 1 to 18
A saturated linear alkyl group and a saturated linear alkyloxy group, such as a methyl group, ethyl group, pentyl group, octyl group, nonyl group, dodecyl group, pentadecyl group, octadecyl group, or methyloxy group, ethyloxy group , pentyloxy group, octyloxy group, nonyloxy group,
Examples include dodecyloxy groups, pentadecyloxy groups, octadecyloxy groups, etc., but also include unsaturated hydrocarbons such as alkenyl groups and alkynyl groups, and alkyl groups and alkyloxy groups having hydroxy groups and alkoxy groups as substituents. It will be done. m and n are each independently selected from an integer of 1 or 2. R is a linear or branched alkyl group, and the number of carbon atoms in the alkyl group is not particularly limited. However, from an economic point of view, it is preferable to have 1 to 4 carbon atoms, such as n-methyl group, n-ethyl group, n-propyl group, n-butyl group, 1so-propyl group, 5ec-
Examples include butyl group and t-butyl group. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of alkali metal hydroxide is 1 to 10 times equivalent to (1), preferably 3 to 5 equivalents. Water and a water-soluble aprotic solvent used as a reaction solvent may be used in any ratio, and a water-soluble solvent such as methanol or ethanol may be added as a third component, but the presence or absence of the third component and its ratio are particularly limited. It's not something you do. Furthermore, the reaction temperature and reaction time vary depending on the amount and type of alkali metal hydroxide, and are not particularly limited.
（発明の効果）
本発明により得られる化合物（２）から種々の光学活性
液晶が光学純度よく合成できる。化合物（２）はカイラ
ルスメチツク相を示す液晶化合物（３）の重要な中間体
と成り得る。(Effects of the Invention) Various optically active liquid crystals can be synthesized with high optical purity from the compound (2) obtained by the present invention. Compound (2) can be an important intermediate for liquid crystal compound (3) exhibiting a chiral smectic phase.
実施例１
［ｐ−（４−オクチルオキシ−４−ビフェニルカルビニ
ルオキシ
キシ基、Ｂ＝ＣＨ２０，ｍ＝２，ｎ＝１）（２ａ）の製
造］ｐ−（４−オクチルオキシ４−ビフェニルカルビニ
ルオキシ（６０ミリリツトル）とジメチルスルホキシド
（６０ミリリツトル）及び１規定水酸化ナトリウム（６
０ミリリツトル）を加え、加熱還流下で４時間作用させ
た。反応液を酸性化した後析出した結晶をろ別した。結
晶は水及びエタノールで洗浄した後減圧下乾燥すること
によりｐ−（４−オクチルオキシ−４−ビフェニルカル
ビニルオキシ）−安息香酸が４．６グラム（８０．５％
）得られた。Example 1 [Production of p-(4-octyloxy-4-biphenylcarbinyloxy group, B=CH20, m=2, n=1) (2a)] p-(4-octyloxy-4-biphenylcarbinyloxy group, B=CH20, m=2, n=1) (2a) Vinyloxy (60ml), dimethyl sulfoxide (60ml) and 1N sodium hydroxide (60ml)
0 ml) was added and allowed to react under heating and reflux for 4 hours. After the reaction solution was acidified, the precipitated crystals were filtered off. The crystals were washed with water and ethanol and dried under reduced pressure to yield 4.6 g (80.5%) of p-(4-octyloxy-4-biphenylcarbinyloxy)-benzoic acid.
) obtained.
ＩＲスペクトル（ＫＢｒディスク、ａｍ−１） ； １
６９０， １６１０。IR spectrum (KBr disk, am-1); 1
690, 1610.
１５００、 １２５０
実施例２
［ｐ−（４−才クチルオキシ−４−ビフェニルカルビニ
ルオキシ
キシ基、Ｂ＝ＣＨ２０，ｍ＝２，ｎ＝１（２ａ））の製
造］実施例１に於てエタノールを使用しない他は実施例
１と同様の方法により、ｐ−（４’−才クチルオキシ−
４゜ビフェニルカルビニルオキシ）−安息香酸が３．６
５グラム（６３，０％）で得られた。1500, 1250 Example 2 [Production of p-(4-year-old ctyloxy-4-biphenylcarbinyloxy group, B=CH20, m=2, n=1 (2a))] In Example 1, ethanol was p-(4'-cutyloxy-
4゜Biphenylcarbinyloxy)-benzoic acid is 3.6
5 grams (63,0%) were obtained.
実施例３
［ｐ−（４−オクチルオキシ−４−ビフェニルオキシカ
ルビニル
基、Ｂ ＝ＯＣＨ２，ｍ ＝２，ｎ＝１（２ｂ））の製
法】ｐ−（４−オクチルオキシ−４−ビフェニルオキシ
カルビニルの方法で処理し、得られた粗精製物を酢酸か
ら再結することによりｐ−（４−オクチル−４−ビフェ
ニルオキシカルビニル）−安息香酸が６．１８グラム（
７５パーセント）得られた。Example 3 [Production of p-(4-octyloxy-4-biphenyloxycarbinyl group, B = OCH2, m = 2, n = 1 (2b))] p-(4-octyloxy-4-biphenyloxy 6.18 g of p-(4-octyl-4-biphenyloxycarbinyl)-benzoic acid was obtained by treating the crude product by the carbinyl method and recrystallizing the obtained crude product from acetic acid.
75%) was obtained.
ＩＲスペクトル（ＫＢｒディスク、ｅｍ−１；１６９０
、１６０５，１５００，１２５０実施例４
［４’−（ｐ−オクチルオキシベンジルオキシ）−４−
ビフェニルカルボン酸（式（２）に於て、Ａ＝ｎ−オク
チルオキシ基，ｎ＝ＣＨ２０，ｍ＝１，ｎ＝２）（２ｃ
）の製造１４’−（ｐ−オクチルオキシベンジルオキシ
ル４−ビフェニルカルボン酸エチル６、３グラムを実施
例１と同様の方法で処理が得られる粗精製物を酢酸がら
再結することにより４’−（ｐ−オクチルオキシベンジ
ルオキシ）−４−ヒフェニルカルボン酸１．８１グラム
（９０パーセント）を得た。IR spectrum (KBr disk, em-1; 1690
, 1605, 1500, 1250 Example 4 [4'-(p-octyloxybenzyloxy)-4-
Biphenylcarboxylic acid (in formula (2), A=n-octyloxy group, n=CH20, m=1, n=2) (2c
) Production 14'-(p-Octyloxybenzyloxyl 4-biphenylcarboxylic acid ethyl 6.3 grams was treated in the same manner as in Example 1.) The crude product obtained was reconsolidated with acetic acid to produce 4'- 1.81 grams (90 percent) of (p-octyloxybenzyloxy)-4-hyphenylcarboxylic acid was obtained.
ＩＲスペクトル（ＫＢｒディスク、ｃｍ−ｉ・１６９０
、１６０５，１５１０．１２５３比較例１
［ｐ−（４−オクチルオキシ−４−ビフェニルカルビニ
ルオキシ
基、ｎ＝ＣＨ２０，ｍ＝２，ｎ＝１，（２ａ））の製造
Ｊ実施例１に於てジメチルスルホキシドを用いない他は
、実施例１と同様の操作を行ったが、この場合目的の（
２ａ）の収率は５％であり原料（１ａ）を９３％回収し
た。IR spectrum (KBr disk, cm-i 1690
, 1605, 1510.1253 Comparative Example 1 [Production of p-(4-octyloxy-4-biphenylcarbinyloxy group, n=CH20, m=2, n=1, (2a)) J In Example 1 The same operation as in Example 1 was carried out except that dimethyl sulfoxide was not used.
The yield of 2a) was 5%, and 93% of the raw material (1a) was recovered.
Claims (1)
又はアルキルオキシ基であり、ＢはＣＨ＿２Ｏ、或いは
ＯＣＨ＿２である。ｍは１又は２であり、ｎは１又は２
であり、Ｒはアルキル基である。）で表される化合物に
水及び水溶性非プロトン溶媒混合溶液中でアルカリ金属
水酸化物を作用させることを特徴とする。 一般式 ▲数式、化学式、表等があります▼（２） （但し、上式に於て、Ａ、Ｂ、ｍ、ｎ、は一般式（１）
で規定した通りである。）で表される化合物の合成法。 ２）上記水溶性非プロトン溶媒がジメチルスルホキシド
であることを特徴とする特許請求範囲第一項記載の方法
。[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (However, in the above formula, A is an alkyl group or an alkyloxy group having 1 to 18 carbon atoms, and B is CH_2O or OCH_2. m is 1 or 2, n is 1 or 2
and R is an alkyl group. ) is treated with an alkali metal hydroxide in a mixed solution of water and a water-soluble aprotic solvent. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (However, in the above formula, A, B, m, n are general formula (1)
As stipulated in. ) Synthesis method of the compound represented by. 2) The method according to claim 1, wherein the water-soluble aprotic solvent is dimethyl sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053669A JPS63218648A (en) | 1987-03-09 | 1987-03-09 | Production of liquid crystal intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053669A JPS63218648A (en) | 1987-03-09 | 1987-03-09 | Production of liquid crystal intermediate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63218648A true JPS63218648A (en) | 1988-09-12 |
Family
ID=12949248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62053669A Pending JPS63218648A (en) | 1987-03-09 | 1987-03-09 | Production of liquid crystal intermediate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218648A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60149547A (en) * | 1983-11-22 | 1985-08-07 | Chisso Corp | Liquid crystal substance and liquid crystal composition |
-
1987
- 1987-03-09 JP JP62053669A patent/JPS63218648A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60149547A (en) * | 1983-11-22 | 1985-08-07 | Chisso Corp | Liquid crystal substance and liquid crystal composition |
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