JPH0653708B2 - Phenanthrene carboxylic acid ester compound - Google Patents
Phenanthrene carboxylic acid ester compoundInfo
- Publication number
- JPH0653708B2 JPH0653708B2 JP61080727A JP8072786A JPH0653708B2 JP H0653708 B2 JPH0653708 B2 JP H0653708B2 JP 61080727 A JP61080727 A JP 61080727A JP 8072786 A JP8072786 A JP 8072786A JP H0653708 B2 JPH0653708 B2 JP H0653708B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- liquid crystal
- carboxylic acid
- halide
- acid ester
- 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 - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title description 36
- KFDKNTQGTAEZGC-UHFFFAOYSA-N phenanthrene-1-carboxylic acid Chemical compound C1=CC2=CC=CC=C2C2=C1C(C(=O)O)=CC=C2 KFDKNTQGTAEZGC-UHFFFAOYSA-N 0.000 title 1
- -1 9,10-dihydrophenanthrenecarboxylic acid ester compound Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000004973 liquid crystal related substance Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 230000007704 transition Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000004990 Smectic liquid crystal Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 2
- BIGIDNWEFZRRST-UHFFFAOYSA-N 7-hydroxy-9,10-dihydrophenanthrene-2-carboxylic acid Chemical compound OC1=CC=C2C3=CC=C(C(=O)O)C=C3CCC2=C1 BIGIDNWEFZRRST-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YNPVNLWKVZZBTM-ZETCQYMHSA-N (4s)-4-methylhexan-1-ol Chemical compound CC[C@H](C)CCCO YNPVNLWKVZZBTM-ZETCQYMHSA-N 0.000 description 1
- SEGJDCGIQJESDC-MDZDMXLPSA-N 2-methylbutyl (e)-3-phenylprop-2-enoate Chemical group CCC(C)COC(=O)\C=C\C1=CC=CC=C1 SEGJDCGIQJESDC-MDZDMXLPSA-N 0.000 description 1
- QKZMDPPOZYCJGK-UHFFFAOYSA-N 7-octoxy-9,10-dihydrophenanthrene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(OCCCCCCCC)C=C3CCC2=C1 QKZMDPPOZYCJGK-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QIZJBZATWQIMPK-NRFANRHFSA-N [(2S)-2-methylbutyl] 7-octoxy-9,10-dihydrophenanthrene-2-carboxylate Chemical compound CC[C@H](C)COC(=O)C1=CC=C2C3=CC=C(OCCCCCCCC)C=C3CCC2=C1 QIZJBZATWQIMPK-NRFANRHFSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SYNVQASQYAMPQE-UHFFFAOYSA-N undecyl 4-methylbenzenesulfonate Chemical compound CCCCCCCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 SYNVQASQYAMPQE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene 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】 (産業上の利用分野) 本発明は液晶化合物乃至は、液晶組成物として使用でき
る新規な化合物の提供に係るものであって、それ自体で
又は他の液晶化合物とブレンドして、その性能の改善を
はかるなどして液晶表示素子の作成に利用できる。TECHNICAL FIELD The present invention relates to the provision of a liquid crystal compound or a novel compound that can be used as a liquid crystal composition, and as such or as a blend with another liquid crystal compound. Then, it can be used for producing a liquid crystal display device by improving its performance.
(従来の技術) 液晶による表示素子において使用されている液晶化合物
はネマチック相をとる液晶が大半である。しかし、電気
光学的応答速度の点において発光型表示素子にくらべる
と遥かに及ばず、改善が試みられている。近年、応答速
度が速いことで注目されている液晶化合物に、強誘電性
液晶化合物がある。強誘電性液晶化合物としてはじめて
開発されたのは、ドデシルベンジリデン−p−アミノ−
2−メチルブチルシンナメートであって1975年に合
成された。この化合物はカイラルスメクチックC相をと
るけれども、その転移温度が高いこと、従って室温を含
む広い温度範囲での使用が不可能であること、そのほ
か、シッフ塩基を含んでいるので化学的安定性に欠ける
などの問題点を持っている。その後数多くの化合物が合
成され、性質の究明が行われているけれども、理論づけ
には成功していないし、室温を含む幅広い温度範囲でカ
イラルスメクチックC相をとる液晶化合物はまだ知られ
ていない。(Prior Art) Most liquid crystal compounds used in liquid crystal display devices are liquid crystals having a nematic phase. However, in terms of electro-optical response speed, it is far inferior to that of the light-emitting display element, and improvement is attempted. In recent years, a ferroelectric liquid crystal compound is one of the liquid crystal compounds that has been attracting attention due to its high response speed. The first ferroelectric liquid crystal compound developed was dodecylbenzylidene-p-amino-.
It is 2-methylbutyl cinnamate and was synthesized in 1975. Although this compound has a chiral smectic C phase, it has a high transition temperature and therefore cannot be used in a wide temperature range including room temperature. In addition, since it contains a Schiff base, it lacks chemical stability. Have problems such as. After that, many compounds have been synthesized and their properties have been investigated, but theoretics have not been successful, and a liquid crystal compound having a chiral smectic C phase in a wide temperature range including room temperature has not yet been known.
液晶相の転移温度の低下又は、温度範囲の拡大のためネ
マチック液晶の分野で採用されている一般的な方法に、
いくつかの液晶化合物を混合する方法がある。The general method adopted in the field of nematic liquid crystals for lowering the transition temperature of the liquid crystal phase or expanding the temperature range,
There is a method of mixing several liquid crystal compounds.
強誘電性液晶の分野においても同様の方法が検討されて
いて、試行錯誤の現状にある。どのような骨格を選べ
ば、あるいは、どのような置換基を導入すれば他の液晶
化合物との相溶性が高まるか、又は如何なる液晶相をと
って、相転移温度にどのように影響するかといったこと
は化合物一つ一つについてテストしなければ判らず、全
く予想を許さないといっても過言ではない。Similar methods have been studied in the field of ferroelectric liquid crystals and are in the trial and error state. What kind of skeleton should be selected, what kind of substituent should be introduced to improve the compatibility with other liquid crystal compounds, and what kind of liquid crystal phase should be taken to affect the phase transition temperature. It's no exaggeration to say that you can't expect at all unless you test each compound.
本発明に係る化合物と同様の骨格を持つ液晶化合物の研
究がなされているが、例えば、Chemistry and Industr
y, 3 Aug.1974 615ページには、フェナンスレン骨格の
一方に各種炭素鎖長を持ったアシル基を、他方に各種炭
素鎖長を持ったアルキル基を導入した化合物を合成し、
その熱的性質を調べたとの報告があるに過ぎない。A liquid crystal compound having a skeleton similar to that of the compound according to the present invention has been studied, and for example, Chemistry and Industr
y, 3 Aug.1974 p. 615, we synthesized compounds in which an acyl group with various carbon chain lengths was introduced into one of the phenanthrene skeletons and an alkyl group with various carbon chain lengths was introduced into the other,
There are only reports that they have investigated their thermal properties.
(解決しようとする問題点〕 本発明は、フェナンスレン骨格を持った新規な液晶化合
物の探索を行うものである。(Problems to be Solved) The present invention seeks for a novel liquid crystal compound having a phenanthrene skeleton.
(問題解決のための手段) 本発明は、フェナンスレン骨格を持った新規な強誘電性
カイラルスメクチック液晶を提供せんとして、以下に示
す方法に従い、目的化合物を合成した。(Means for Solving the Problem) In the present invention, a target compound was synthesized according to the method described below, without providing a novel ferroelectric chiral smectic liquid crystal having a phenanthrene skeleton.
まず、本発明目的化合物の骨格7−ヒドロキシ−2−カ
ルボキシ−9,10−ジヒドロフェナンスレンは9,1
0−ジヒドロフェナンスレンから公知の方法に従って造
られる(特開昭57−146737)。かくして得られ
る7−ヒドロキシ−2−カルボキシ−9,10−ジヒド
ロフェナンスレンは、RX(Rは炭素原子の数が4〜1
2である直鎖状アルキル基を示す。以下同じ)で示され
るアルキルハライド又はアルキルスルホン酸エステルと
適宜溶媒中で反応に付され、7−アルユキシ−2−カル
ボキシ−9,10−ジヒドロフェナンスレンに変えられ
る。ここにおいてRXで示されるアルキルハライドとし
ては、ブチルハライド、ペンチルハライド、ヘキシルハ
ライド、ヘプチルハライド、オクチルハライド、ノニル
ハライド、デカニルハライド、ウンデカニルハライド、
ドデカニルハライドなどであり、ハライドにはクロリ
ド、ブロミド、ヨージドなどが使われる。また、アルキ
ルスルホン酸エステルの形で使用するときには、上記し
たアルキルのp−トルエンスルホネート、ベンゼンスル
ホネート、メタンスルホネートなどが使われる。First, the skeleton 7-hydroxy-2-carboxy-9,10-dihydrophenanthrene of the object compound of the present invention is 9,1.
It is prepared from 0-dihydrophenanthrene according to a known method (JP-A-57-146737). The thus-obtained 7-hydroxy-2-carboxy-9,10-dihydrophenanthrene is RX (R has 4 to 1 carbon atoms).
2 shows a straight chain alkyl group. The same applies hereinafter to an alkyl halide or alkyl sulfonic acid ester represented by the formula (1) in a solvent, and converted to 7-aruxy-2-carboxy-9,10-dihydrophenanthrene. Here, as the alkyl halide represented by RX, butyl halide, pentyl halide, hexyl halide, heptyl halide, octyl halide, nonyl halide, decanyl halide, undecanyl halide,
Such as dodecanyl halide, chloride, bromide, iodide is used for the halide. When used in the form of an alkyl sulfonate, the above-mentioned alkyl p-toluene sulfonate, benzene sulfonate, methane sulfonate, etc. are used.
反応は、イ)水、アルコール−水を溶媒として用い、水
酸化カリウム、水酸化ナトリウムなどのアルカリ水酸化
物を使用して行うか、ロ)ジメチルホルムアミド、アル
コール、ジメチルスルホキシド、ジグリム、テトラヒド
ロフラン、トルエン、キシレン、アセトンなどを溶媒と
して用い、ナトリウム、カリウムなどのアルカリ金属、
又は炭酸カリウム、炭酸ナトリウムなどの塩を使用して
7位の水酸基をアルキル化すると同時に、2位のカルボ
キシル基をアルキルエステル化したあと、2位のカルボ
キシル基アルキルエステルを加水分解して行われる。か
くて、7−アルコキシ−2−カルボキシ−9,10−ジ
ヒドロフェナンスレンが得られる。The reaction is carried out a) using water or alcohol-water as a solvent and using an alkali hydroxide such as potassium hydroxide or sodium hydroxide, or b) dimethylformamide, alcohol, dimethylsulfoxide, diglyme, tetrahydrofuran, toluene. Alkali metals such as sodium and potassium, using xylene, acetone, etc. as solvents,
Alternatively, a salt of potassium carbonate, sodium carbonate or the like is used to alkylate the hydroxyl group at the 7-position, at the same time alkylate the carboxyl group at the 2-position, and then hydrolyze the alkyl ester at the 2-position. Thus, 7-alkoxy-2-carboxy-9,10-dihydrophenanthrene is obtained.
次いで、7−アルコキシ−2−カルボキシ−9,10−
ジヒドロフェナンスレンは、そのまゝであるいは酸ハラ
イド(チオニルクロリド、三臭化燐等から造られる)、
その他活性エステルなどの反応性誘導体にして、分子鎖
中に不斉炭素原子を持つ光学活性なアルコール(R*OH
〔R*は で示される不斉炭素原子 を有するアルキル基(nは0〜6の整数である)を示
す。以下同じ〕)と反応させて、エステル化される。こ
こにおいて、分子鎖中に不斉炭素原子を持つ光学活性な
アルコールとしては、1−メチルプロピルアルコール、
2−メチルブチルアルコール、3−メチルペンチルアル
コール、4−メチルヘキシルアルコール、5−メチルヘ
プチルアルコール、6−メチルオクチルアルコール、7
−メチルノニルアルコールなどの光学活性体があげられ
る。Then, 7-alkoxy-2-carboxy-9,10-
Dihydrophenanthrene is as it is or an acid halide (made from thionyl chloride, phosphorus tribromide, etc.),
Optically active alcohols (R * OH) that have asymmetric carbon atoms in their molecular chains are made into reactive derivatives such as active esters.
[R * is Asymmetric carbon atom Represents an alkyl group having n (n is an integer of 0 to 6). The same shall apply hereinafter)) to esterify. Here, as the optically active alcohol having an asymmetric carbon atom in the molecular chain, 1-methylpropyl alcohol,
2-methylbutyl alcohol, 3-methylpentyl alcohol, 4-methylhexyl alcohol, 5-methylheptyl alcohol, 6-methyloctyl alcohol, 7
Examples include optically active forms such as methylnonyl alcohol.
7−アルコキシ−2−カルボキシ−9,10−ジヒドロ
フェナンスレンの2位カルボキシル基遊離のまゝで反応
させるときは、ジメチルホルムアミド、酢酸エチル、n
−ヘキサン、ベンゼン、トルエン、ジメチルスルホキシ
ド、ピリジンなどの溶媒中加熱するか、又はジシクロヘ
キシルカルボジイミド、オキシ塩化燐、塩化チオニルな
どの縮合剤を共存させるかして、反応させるとよい。ま
た、酸ハライドを使用するときは、トリエチルアミン、
ピリジン、ジメチルアニリンなどの三級アミンを共存さ
せるとよい。When the 2-position carboxyl group of 7-alkoxy-2-carboxy-9,10-dihydrophenanthrene is allowed to react, dimethylformamide, ethyl acetate, n
The reaction may be carried out by heating in a solvent such as hexane, benzene, toluene, dimethylsulfoxide, pyridine, or in the presence of a condensing agent such as dicyclohexylcarbodiimide, phosphorus oxychloride, thionyl chloride. When using an acid halide, triethylamine,
It is advisable to coexist with a tertiary amine such as pyridine or dimethylaniline.
かくて、式(I) (式中、R、R*は前記と同じ) で示される本発明化合物が得られる。式(I)で示され
る化合物においてRとR*とが入れ換った化合物も容易に
造ることができ、かゝる場合該化合物は7−ヒドロキシ
−2−カルボキシ−9,10−ジヒドロフェナンスレン
に、まず先に例示したところの分子鎖中に不斉炭素原子
を持つ光学活性なアルコールをハライド若しくはスルホ
ン酸エステルに誘導して反応させ、次いで先にアルキル
ハライドとして例した直鎖アルキルのアルコールを反応
させることによって造られる。Thus, the formula (I) (Wherein R and R * are the same as above), the compound of the present invention can be obtained. A compound of the formula (I) in which R and R * are interchanged can be easily prepared, and in such a case, the compound is 7-hydroxy-2-carboxy-9,10-dihydrophenanthene. First, an optically active alcohol having an asymmetric carbon atom in the molecular chain, as exemplified above, is introduced into a halide or sulfonic acid ester to react with len, and then reacted, and then a linear alkyl alcohol exemplified above as an alkyl halide. It is made by reacting.
(本発明の効果) 本発明化合物はカルボキシル基における光学活性なアル
キルエステルであるので、中間相としてカイラルスメク
チックC相をとることが期待されたところ、案に相違し
て、カイラルスメクチックC相はとらなかったけれども
常温を含め相当低い温度まで中間相(SA相とみうけられ
る)をとるもの、他の液晶の転移温度の範囲を低温側に
拡げる効果を持っているものなどが得られた。(Effect of the present invention) Since the compound of the present invention is an optically active alkyl ester in a carboxyl group, it was expected to take a chiral smectic C phase as an intermediate phase. It shall take mesophase to a temperature considerably lower, including room temperature but was not (seen as S a phase), such as those that have the effect of widening the range of transition temperatures of the other liquid crystal temperature side was obtained.
以下実施例を記述して本発明を更に詳述する。The present invention will be described in more detail with reference to the following examples.
実施例1 (1)9,10−ジヒドロ−7−n−オクチルオキシフ
ェナンスレン−2−カルボン酸の合成: 50%水酸化ナトリウム0.66g、乾燥ジメチルホル
ムアミド30ml、9,10−ジヒドロ−7−ヒドロキ
シフェナンスレン−2−カルボン酸3gを80℃で40
分間混合撹拌した。次いで、オクチルトシレート7.8
gをジメチルホルムアミド15mlに溶かして加え、8
0℃で8時間撹拌した。反応混合物を氷水に注ぎ、塩酸
酸性としたのち、酢酸エチルで抽出した。水洗乾燥後濃
縮し7gの油状物を得た。これを49g水酸化ナトリウ
ム水溶液8ml、メタノール250mlと混ぜ4時間還
流した。反応終了後溶媒を留去し、塩酸酸性にして、ク
ロロホルム抽出し、クロロホルム層から題記化合物を得
た。得量 0.88g IRνmaxcm-1:3600〜3200(−OH)169
0(C=0) (2)(S)−2−メチルブチル−9,10−ジヒドロ
−7−オクチルオキシフェナンスレン−2−カルボキシ
レートの合成: (1)で得た油状物0.88g、2−(S)−メチルブ
チルアルコール0.22g、ジシクロヘキシルカルボジ
イミド0.57g、4−ジメチルアミノピリジン15m
g、酢酸エチル25mlを室温で9時間混合撹拌した。
反応混合物を氷水に注ぎ、塩酸酸性とし、エチルで抽出
した。酢酸エチル層を水洗乾燥後、溶媒を留去した。残
渣をシリカゲルカラムクロマトグラフィー(3cmφ×4
0cm、展開溶媒:クロロホルム)で精製し題記化合物を
得た。得量0.4g IRνmaxcm-1:1720,1610,1280,12
40,1115,7751 H−NMR(CDCl3)δ(ppm): 0.6〜2.10(m,24H) 2.85(s,4H) 3.95(t,2H) 4.10(d,2H) 6.0〜8.0(m,6H) このものは次の相転移温度を示した。Example 1 (1) Synthesis of 9,10-dihydro-7-n-octyloxyphenanthrene-2-carboxylic acid: 0.66 g of 50% sodium hydroxide, 30 ml of dry dimethylformamide, 9,10-dihydro-7. -Hydroxyphenanthrene-2-carboxylic acid 3 g at 80 ° C
Mix and stir for minutes. Then, octyl silate 7.8
g dissolved in 15 ml of dimethylformamide and added,
The mixture was stirred at 0 ° C for 8 hours. The reaction mixture was poured into ice water, acidified with hydrochloric acid and then extracted with ethyl acetate. The extract was washed with water, dried and concentrated to give 7 g of an oily substance. This was mixed with 49 g of an aqueous sodium hydroxide solution (8 ml) and methanol (250 ml) and refluxed for 4 hours. After completion of the reaction, the solvent was distilled off, the mixture was acidified with hydrochloric acid and extracted with chloroform to obtain the title compound from the chloroform layer. Obtained amount 0.88 g IRν max cm −1 : 3600 to 3200 (—OH) 169
0 (C = 0) (2) (S) -2-Methylbutyl-9,10-dihydro-7-octyloxyphenanthrene-2-carboxylate synthesis: 0.88 g of the oil obtained in (1), 0.22 g of 2- (S) -methylbutyl alcohol, 0.57 g of dicyclohexylcarbodiimide, 15 m of 4-dimethylaminopyridine
g and 25 ml of ethyl acetate were mixed and stirred at room temperature for 9 hours.
The reaction mixture was poured into ice water, acidified with hydrochloric acid, and extracted with ethyl. The ethyl acetate layer was washed with water and dried, and then the solvent was distilled off. Silica gel column chromatography (3 cmφ x 4)
Purification with 0 cm, developing solvent: chloroform) gave the title compound. Yield 0.4 g IRv max cm -1 : 1720, 1610, 1280, 12
40,1115,775 1 H-NMR (CDCl 3 ) δ (ppm): 0.6~2.10 (m, 24H) 2.85 (s, 4H) 3.95 (t, 2H) 4.10 ( d, 2H) 6.0-8.0 (m, 6H) This showed the following phase transition temperatures.
−20℃でSA相を維持し、−70℃でも結晶化しなかっ
た。 Maintaining the S A phase at -20 ° C., it was not -70 ° C. even crystallization.
実施例2 (1)9,10−ジヒドロロ−7−n−ウンデシルオキ
シフェナンスレン−2−カルボン酸の合成: 50%水素化ナトリウム0.06g、乾燥ジメチルルホ
ルムアミド3ml、9,10−ジヒドロ−7−ヒドロキ
シフェナンスレン−2−カルボン酸0.28gを80℃
で1時間混合撹拌した。次いで、n−ウンデシルトシレ
ート0.84をジメチルホルムアミド2mlに溶かして
加え、80℃で8時間撹拌した。反応混合物を氷水に注
ぎ、酢酸エチルで抽出した。水洗乾燥後、濃縮し、油状
物0.7gを得た。これを49g水酸化ナトリウム水溶
液0.8ml、メタノール25mlと共に3時間還流し
た。冷却後、塩酸酸性とし、クロロホルムで抽出した。
クロロホルム層を水洗乾燥濃縮し、題記化合物を得た。
得量 0.73g IRνmaxcm-1:3450〜2350、1680、16
10、1470、1430、1300、1280、12
401 H−NMR(D6−DMSO)δ(ppm): 0.6〜2.10(m,21H) 2.88(s,4H) 4.00(t,2H) 6.6〜8.35(m,6H) (2)(S)−4−メチルヘキシル−9,10−7−ウ
ンデシニルオキシフェナンスレン−2−カルボキシレー
トの合成: 酢酸エチル20ml、(1)で得た化合物1.88g、
4−(S)−メチルヘキサノール0.6g、ジシクロヘ
キシルカルボジイミド1.08g、4−ジメチルアミノ
ピリジン60mgを15時間室温で混合撹拌した。実施例
1(2)と同様に処理して題記化合物を得た。得量1.
3g IRνmaxcm-1:1720、1470、1285、11
90、1115、7751 H−NMR(CDCl3)δ(ppm): 0.6〜2.10(m,34H) 2.85(s,4H) 3.95(t,2H) 4.28(t,2H) 6.60〜8.10(m,6H) 得られた化合物は次の相転移温度を示した。Example 2 (1) Synthesis of 9,10-dihydrolo-7-n-undecyloxyphenanthrene-2-carboxylic acid: 50% sodium hydride 0.06 g, dry dimethylformamide 3 ml, 9,10-dihydro. 0.28 g of -7-hydroxyphenanthrene-2-carboxylic acid was added at 80 ° C.
The mixture was stirred for 1 hour. Then, 0.84 of n-undecyl tosylate was dissolved in 2 ml of dimethylformamide and added, and the mixture was stirred at 80 ° C. for 8 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. After washing with water, drying, and concentration, 0.7 g of an oily substance was obtained. This was refluxed with 49 g of sodium hydroxide aqueous solution 0.8 ml and methanol 25 ml for 3 hours. After cooling, the mixture was acidified with hydrochloric acid and extracted with chloroform.
The chloroform layer was washed with water, dried and concentrated to give the title compound.
Yield 0.73 g IRv max cm -1 : 3450 to 2350, 1680, 16
10, 1470, 1430, 1300, 1280, 12
40 1 H-NMR (D 6 -DMSO) δ (ppm): 0.6 to 2.10 (m, 21H) 2.88 (s, 4H) 4.00 (t, 2H) 6.6 to 8. 35 (m, 6H) (2) (S) -4-Methylhexyl-9,10-7-undecynyloxyphenanthrene-2-carboxylate synthesis: 20 ml of ethyl acetate, compound 1 obtained in (1) .88g,
0.6 g of 4- (S) -methylhexanol, 1.08 g of dicyclohexylcarbodiimide and 60 mg of 4-dimethylaminopyridine were mixed and stirred at room temperature for 15 hours. The title compound was obtained by the same procedure as in Example 1 (2). Gain 1.
3g IRν max cm -1 : 1720, 1470, 1285, 11
90, 1115, 775 1 H-NMR (CDCl 3 ) δ (ppm): 0.6 to 2.10 (m, 34H) 2.85 (s, 4H) 3.95 (t, 2H) 4.28 ( t, 2H) 6.60 to 8.10 (m, 6H) The obtained compound showed the following phase transition temperatures.
この化合物は過冷却でSA相が安定であり、他の液晶化合
物とブレンドしたとき、相転移温度を低温側へ拡げる効
果を有している。 This compound has a stable SA phase under supercooling, and when blended with other liquid crystal compounds, it has the effect of expanding the phase transition temperature to the low temperature side.
実施例3 (2)−2−メチルブチル−9,10−ジヒドロ−7−
n−ウンデシルオキシフェナンスレン−2−カルボキシ
レートの合成: 実施例2(1)で得た9,10−ジヒドロ−7−n−ウ
ンデシルオキシフェナンスレン−2−カルボン酸1g、
2−(S)−メチルブチルアルコール0.25g、酢酸
エチル10ml、ジシクロヘキシルカルボジイミド0.
58g、4−ジメチルアミノピリジン34mgを室温で1
5時間混合撹拌した。反応混合物を実施例2(2)と同
様に処理し、題記化合物を得た。 得量 0.45g IRνmaxcm-1:1710、1603、1280、 1240、1190、1110、 7751 H−NMR(CDCl3)δ(ppm): 0.6〜2.10(m,30H) 2.87(s,4H) 3.98(t,2H) 4.17(d,2H) 6.6〜8.10(m,6H) 得られた化合物は次の相転移温度を示した。Example 3 (2) -2-Methylbutyl-9,10-dihydro-7-
Synthesis of n-undecyloxyphenanthrene-2-carboxylate: 9,10-dihydro-7-n-undecyloxyphenanthrene-2-carboxylic acid 1 g obtained in Example 2 (1),
0.25 g of 2- (S) -methylbutyl alcohol, 10 ml of ethyl acetate, dicyclohexylcarbodiimide.
58 g, 4-dimethylaminopyridine 34 mg at room temperature 1
The mixture was stirred for 5 hours. The reaction mixture was treated similarly to that in Example 2 (2) to give the title compound. Yield of 0.45g IRν max cm -1: 1710,1603,1280, 1240,1190,1110, 775 1 H-NMR (CDCl 3) δ (ppm): 0.6~2.10 (m, 30H) 2 .87 (s, 4H) 3.98 (t, 2H) 4.17 (d, 2H) 6.6 to 8.10 (m, 6H) The obtained compound showed the following phase transition temperatures.
この化合物は、低温までSA相が安定であった。 This compound had a stable S A phase even at low temperatures.
実施例4 実施例1〜3の化合物を、下に示したフェニルピリミジ
ン系液晶組成物Aに、重量比5:1でブレンドし、その
転移温度を測定した。Example 4 The compounds of Examples 1 to 3 were blended with the phenylpyrimidine liquid crystal composition A shown below in a weight ratio of 5: 1, and the transition temperature thereof was measured.
ここで、組成物Aは、以下の組成である。 Here, the composition A has the following composition.
以上見たように、フェニルピリミジン系液晶組成物に、
本発明の化合物をブレンドすることにより、SC *の下限
を大きく広げる事ができる。 As described above, in the phenylpyrimidine-based liquid crystal composition,
By blending the compound of the present invention, the lower limit of S C * can be greatly widened.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田口 雅明 東京都江東区亀戸6丁目31番1号 セイコ ー電子工業株式会社内 (72)発明者 原田 隆正 東京都江東区亀戸6丁目31番1号 セイコ ー電子工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masaaki Taguchi 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Co., Ltd. (72) Takamasa Harada 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Industry Co., Ltd.
Claims (1)
キル基を、R*は で示される不斉炭素原子 を有するアルキル基(nは0〜6の整数である)を示
す〕で示される光学的に活性な9、10−ジヒドロフェ
ナンスレンカルボン酸エステル化合物。1. A formula [Wherein R represents a linear alkyl group having 4 to 12 carbon atoms, and R * represents Asymmetric carbon atom Represents an alkyl group having n (n is an integer of 0 to 6)], which is an optically active 9,10-dihydrophenanthrenecarboxylic acid ester compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61080727A JPH0653708B2 (en) | 1986-04-08 | 1986-04-08 | Phenanthrene carboxylic acid ester compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61080727A JPH0653708B2 (en) | 1986-04-08 | 1986-04-08 | Phenanthrene carboxylic acid ester compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62238245A JPS62238245A (en) | 1987-10-19 |
JPH0653708B2 true JPH0653708B2 (en) | 1994-07-20 |
Family
ID=13726400
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61080727A Expired - Fee Related JPH0653708B2 (en) | 1986-04-08 | 1986-04-08 | Phenanthrene carboxylic acid ester compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0653708B2 (en) |
-
1986
- 1986-04-08 JP JP61080727A patent/JPH0653708B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPS62238245A (en) | 1987-10-19 |
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