JPS6254419B2 - - Google Patents
Info
- Publication number
- JPS6254419B2 JPS6254419B2 JP3193581A JP3193581A JPS6254419B2 JP S6254419 B2 JPS6254419 B2 JP S6254419B2 JP 3193581 A JP3193581 A JP 3193581A JP 3193581 A JP3193581 A JP 3193581A JP S6254419 B2 JPS6254419 B2 JP S6254419B2
- Authority
- JP
- Japan
- Prior art keywords
- dihydrophenanthrene
- carboxy
- synthesis example
- water
- crystals
- 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
Links
- -1 4-n-butylcyclohexylcarbonyl group Chemical group 0.000 claims description 8
- KDKMJRJRONOCSH-UHFFFAOYSA-N 9,10-dihydrophenanthrene-2-carboxylic acid Chemical class C1=CC=C2C3=CC=C(C(=O)O)C=C3CCC2=C1 KDKMJRJRONOCSH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004988 Nematic liquid crystal Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XXPBFNVKTVJZKF-UHFFFAOYSA-N 9,10-dihydrophenanthrene Chemical class C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000017105 transposition Effects 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- KMGCTFHTBKBITO-UHFFFAOYSA-N 4-butoxybenzoyl chloride Chemical compound CCCCOC1=CC=C(C(Cl)=O)C=C1 KMGCTFHTBKBITO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OCTICGCHHCNKTA-UHFFFAOYSA-N OC(C1=CC=CC2=C1CCC1=CC=CC=C21)=O Chemical group OC(C1=CC=CC2=C1CCC1=CC=CC=C21)=O OCTICGCHHCNKTA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 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】
本発明は、新規な７−カルボキシ−９，10−ジ
ヒドロフエナントレン誘導体に関するものであ
る。更に詳しくは、本発明を電気光学表示素子材
料として有用なネマチツク液晶の原料となる新規
な７−カルボキシ−９，10−ジヒドロフエナント
レン誘導体に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel 7-carboxy-9,10-dihydrophenanthrene derivatives. More specifically, the present invention relates to a novel 7-carboxy-9,10-dihydrophenanthrene derivative which is a raw material for a nematic liquid crystal useful as an electro-optical display element material.
近年、電気光学表示素子材料では電場印加下に
おいて、該材料の光学的性質たとえば光吸収、光
散乱、複屈折、反射又は色彩の顕著な変化を利用
するものである。このような材料としては液晶、
特にネマチツク液晶が優れている。そしてそれら
の光学的性質は液晶の有する動的散乱現象、液晶
配列の変形に基づくものである。 In recent years, electro-optic display element materials utilize significant changes in optical properties of the material, such as light absorption, light scattering, birefringence, reflection, or color, under the application of an electric field. Such materials include liquid crystal,
Especially the nematic liquid crystal is excellent. Their optical properties are based on the dynamic scattering phenomenon of liquid crystals and the deformation of liquid crystal alignment.
こうしたネマチツク液晶の性質を電気光学表示
素子材料として工業的に適用するには、多くの要
件を満たす必要がある。この意外において特に必
要とされる要件は、湿気、空気、可視部および紫
外部領域の光、および直流または交流電場に対す
る光学的安定性である。さらに又電気光学表示素
子材料は、表示コントラストを高くするために可
視部領域に特性吸収を有してはならない。すなわ
ちそれらは無色でなければならない。そしてこれ
らの要求はネマチツク液晶の中間原料においても
強く望まれることである。 In order to industrially apply these properties of nematic liquid crystal as an electro-optical display element material, many requirements must be met. Particular requirements in this context are optical stability against moisture, air, light in the visible and ultraviolet regions, and direct or alternating electric fields. Furthermore, the electro-optic display element material must not have characteristic absorption in the visible region in order to increase the display contrast. i.e. they must be colorless. These requirements are also strongly desired for intermediate raw materials for nematic liquid crystals.
本発明者らはかかる要求に答えるべく種々研究
を重ねた結果、下記一般式（）で示される７−
カルボキシ．９，10−ジヒドロフエナントレン誘
導体にその好適性を見出し本発明を完成するに至
つたものである。 The present inventors have conducted various studies in order to meet such demands, and as a result, we have found that 7-
Carboxy. The present invention was completed by discovering the suitability of 9,10-dihydrophenanthrene derivatives.
一般式
（式中Ｒは水素原子、４−ｎ−ブチルシクロヘ
キシルカルボニル基又は４−ｎ−ブトキシベンゾ
イル基を表わす。）
本発明によれば、一般式（）で表わされる７
−カルボキシ−９，10−ジヒドロフエナントレン
誘導体はＲが４−ｎ−ブチルシクロヘキシルカル
ボニルおよび４−ｎ−ブトキシベンゾイルのと
き、それ自身が無色で液晶性を示すものである。
さらに７位のカルボキシル基をカルボンアミドか
らニトリルに誘導することにより強い正の誘電異
方性を有するネマチツク液晶を得ることができ
る。 general formula (In the formula, R represents a hydrogen atom, a 4-n-butylcyclohexylcarbonyl group, or a 4-n-butoxybenzoyl group.) According to the present invention, 7 represented by the general formula ()
The -carboxy-9,10-dihydrophenanthrene derivative itself is colorless and exhibits liquid crystallinity when R is 4-n-butylcyclohexylcarbonyl or 4-n-butoxybenzoyl.
Further, by deriving the carboxyl group at the 7-position from carbonamide to nitrile, a nematic liquid crystal having strong positive dielectric anisotropy can be obtained.
このように一般式（）で表わされる７−カル
ボキシ−９，10−ジヒドロフエナントレン誘導体
は液晶の中間原料として優れ、それ自身湿気、空
気、光に対して安定であり、しかも無色である。 As described above, the 7-carboxy-9,10-dihydrophenanthrene derivative represented by the general formula () is excellent as an intermediate raw material for liquid crystals, is itself stable against moisture, air, and light, and is colorless.
本発明において一般式で表わされる２−ヒドロ
キシ−７−カルボキシ−９，10−ジヒドロフエナ
ントレンは、９，10−ジヒドロフエナントレンか
ら下記経路を経て合成することができる。 In the present invention, 2-hydroxy-7-carboxy-9,10-dihydrophenanthrene represented by the general formula can be synthesized from 9,10-dihydrophenanthrene via the following route.
ステツプ７を経て得られた２−ヒドロキシ−７
−カルボキシ−９，10−ジヒドロフエナントレン
の２位の水酸基をアシル化又はエーテル化し、７
位のカルボキシル基はそのままかあるいはエステ
ル化、またはカルボンアミドを経てニトリル基に
誘導することにより、下記のような有望なネマチ
ツク液晶を得ることができる。 2-hydroxy-7 obtained through step 7
-Acylation or etherification of the hydroxyl group at the 2-position of carboxy-9,10-dihydrophenanthrene, and
Promising nematic liquid crystals as shown below can be obtained by deriving the carboxyl group at the position as it is or by esterifying it or deriving it into a nitrile group through carbonamide.
転位温度 Ｃ→Ｎ 69℃ ＮＩ 220℃ 転位温度 Ｃ→Ｎ 184℃ ＮＩ 342℃ 転位温度において Ｃは結晶相 Ｎはネマチツク液晶相 Ｉは等方性液体相 矢印は相転位 をそれぞれ意味する。 Transposition temperature C→N 69℃ NI 220℃ Transposition temperature C→N 184℃ NI 342℃ At the transition temperature, C stands for crystalline phase, N stands for nematic liquid crystal phase, I stands for isotropic liquid phase, and the arrows mean phase transition.
ここに例示したネマチツク液晶は強い正の誘電
異方性を有し、湿気、空気、光に対して安定性が
高く、しかも常温で白色の結晶、液晶状態で着色
のない白濁を呈する。 The nematic liquid crystal exemplified here has strong positive dielectric anisotropy, is highly stable against moisture, air, and light, and exhibits white crystals at room temperature and white turbidity without coloration in the liquid crystal state.
次に合成例によつて本発明を具体的に説明する
が、本発明はこれらによつて限定されるものでは
ない。 Next, the present invention will be specifically explained using synthesis examples, but the present invention is not limited thereto.
合成例１ （ステツプ１）
９，10−ジヒドロフエナントレン20.5ｇを酢酸
120mlに溶かし、十分撹拌しながら30℃に保持
し、２時間かけて発煙硝酸30mlを滴下してニトロ
化した。反応液を３の水の中に注ぎ、析出した
結晶を別した。得られた結晶をエチルアルコー
ルで再結晶し融点が80〜81℃の２−ニトロ−９，
10−ジヒドロフエナントレン(A)を得た。収率は55
％であつた。Synthesis Example 1 (Step 1) 20.5g of 9,10-dihydrophenanthrene was dissolved in acetic acid.
The solution was dissolved in 120 ml, kept at 30°C with thorough stirring, and nitrated by adding 30 ml of fuming nitric acid dropwise over 2 hours. The reaction solution was poured into water from Step 3, and the precipitated crystals were separated. The obtained crystals were recrystallized with ethyl alcohol to obtain 2-nitro-9, with a melting point of 80-81℃.
10-dihydrophenanthrene (A) was obtained. Yield is 55
It was %.
合成例２ （ステツプ２）
鉄粉54ｇを濃塩酸2.2mlと水27mlの混液に溶解
した中に、合成例１で得た(A)の28ｇを湯浴上にお
いて、撹拌しながら２時間を要し添加した。添加
後さらに４時間撹拌を続け、この反応液に20％炭
酸ナトリウム水溶液を添加して塩基性となし、析
出した結晶を熱エチルアルコールで洗浄した。続
いて冷却して融点が38〜41℃の２−アミノ−９，
10−ジヒドロフエナントレン(B)を得た。収率は85
％であつた。Synthesis Example 2 (Step 2) In a solution of 54 g of iron powder in a mixture of 2.2 ml of concentrated hydrochloric acid and 27 ml of water, 28 g of (A) obtained in Synthesis Example 1 was placed on a hot water bath and stirred for 2 hours. and added. After the addition, stirring was continued for another 4 hours, a 20% aqueous sodium carbonate solution was added to the reaction solution to make it basic, and the precipitated crystals were washed with hot ethyl alcohol. 2-Amino-9, with a melting point of 38-41°C, is then cooled.
10-dihydrophenanthrene (B) was obtained. Yield is 85
It was %.
合成例３ （ステツプ３）
合成例２で得た(B)20.4ｇを酢酸65mlに溶解し、
無水酢酸20mlを添加した。添加後混合液を80℃に
昇温し30分間撹拌しアセチル化した。冷却後、析
出した結晶をメチルアルコールで再結晶して融点
が173.5〜174.0℃の２−Ｎ−アセチルアミノ−
９，10−ジヒドロフエナントレン(C)を得た。Synthesis Example 3 (Step 3) 20.4g of (B) obtained in Synthesis Example 2 was dissolved in 65ml of acetic acid,
20ml of acetic anhydride was added. After the addition, the mixture was heated to 80°C and stirred for 30 minutes to effect acetylation. After cooling, the precipitated crystals were recrystallized with methyl alcohol to obtain 2-N-acetylamino-
9,10-dihydrophenanthrene (C) was obtained.
合成例４ （ステツプ４）
合成例３で得た(C)16.6ｇと塩化アセチル10.5ｇ
を200mlのニトロベンゼンに溶解し、室温で撹拌
しながら、塩化アルミニウム28ｇをニトロベンゼ
ン100mlに溶解した溶液を除々に加えた。引き続
き一液撹拌後氷水300ml中に注入して得た結晶を
メチルアルコールで再結晶して融点214〜215℃の
２−Ｎ−アセチルアミノ−７−アセチル−９，10
−ジヒドロフエナントレン(D)を得た。Synthesis Example 4 (Step 4) 16.6g of (C) obtained in Synthesis Example 3 and 10.5g of acetyl chloride
was dissolved in 200 ml of nitrobenzene, and while stirring at room temperature, a solution of 28 g of aluminum chloride dissolved in 100 ml of nitrobenzene was gradually added. Subsequently, the solution was stirred and poured into 300 ml of ice water, and the crystals obtained were recrystallized from methyl alcohol to give 2-N-acetylamino-7-acetyl-9,10 with a melting point of 214-215°C.
-Dihydrophenanthrene (D) was obtained.
合成例５ （ステツプ５）
合成例４で得た(D)17.7ｇとヨウ素16.5ｇ、ピリ
ジン60mlの混合液を100℃で２時間反応させた。
冷却後、茶褐色の固体を水、希塩酸、水の順で洗
浄し、式(E)で表わされるピリジニウム塩を得た。Synthesis Example 5 (Step 5) A mixture of 17.7 g of (D) obtained in Synthesis Example 4, 16.5 g of iodine, and 60 ml of pyridine was reacted at 100° C. for 2 hours.
After cooling, the brown solid was washed with water, diluted hydrochloric acid, and water in this order to obtain a pyridinium salt represented by formula (E).
合成例６ （ステツプ６）
合成例５で得た(E)を10％水酸化カリウム水溶液
400mlに入れ５時間還流後、冷却し塩酸で酸性と
し、結晶を析出させた。得られた結晶をメチルア
ルコールで再結晶し、融点が239〜240℃の２−ア
ミノ−７−カルボキシ−９，10−ジヒドロフエナ
ントレン(E)を得た。Synthesis Example 6 (Step 6) Add (E) obtained in Synthesis Example 5 to 10% potassium hydroxide aqueous solution.
The mixture was poured into 400 ml and refluxed for 5 hours, then cooled and acidified with hydrochloric acid to precipitate crystals. The obtained crystals were recrystallized from methyl alcohol to obtain 2-amino-7-carboxy-9,10-dihydrophenanthrene (E) having a melting point of 239-240°C.
合成例７ （ステツプ７）
合成例６で得た(F)8.8ｇに酢酸130ml、水20mlを
加え80℃に昇温撹拌する。この中に濃硫酸４mlお
よび水130mlからなる希硫酸を加え、硫酸塩とな
し０℃まで冷却する。次にこの液に亜硝酸ナトリ
ウム３ｇを水150mlに溶かした液を徐徐に滴下し
ジアゾ化反応を行なつた。過剰の亜硝酸ナトリウ
ムは尿素を加えて分解した。濃硫酸22ml、水60ml
からなる溶液を沸騰させておいて、この中に上記
ジアゾ化反応液を徐々に加え、添加後20分間還流
後、水で２倍量に希釈して白色の結晶を得た。こ
れをエチルアルコールと水の混合溶媒で再結晶
し、融点248〜250℃の結晶を得た。また元素分
析、IRおよびNMRの下記の結果から２−ヒドロ
キシ−７−カルボキシ−９，10−ジヒドロフエナ
ントレン(G)であることを確認した。Synthesis Example 7 (Step 7) 130 ml of acetic acid and 20 ml of water were added to 8.8 g of (F) obtained in Synthesis Example 6, and the mixture was heated to 80°C and stirred. Dilute sulfuric acid consisting of 4 ml of concentrated sulfuric acid and 130 ml of water is added to this to form a sulfate, and the mixture is cooled to 0°C. Next, a solution prepared by dissolving 3 g of sodium nitrite in 150 ml of water was gradually added dropwise to this solution to effect a diazotization reaction. Excess sodium nitrite was destroyed by adding urea. 22ml concentrated sulfuric acid, 60ml water
The above diazotization reaction solution was gradually added to the boiling solution, and after the addition, the solution was refluxed for 20 minutes, and then diluted to twice the volume with water to obtain white crystals. This was recrystallized with a mixed solvent of ethyl alcohol and water to obtain crystals with a melting point of 248-250°C. Furthermore, it was confirmed that it was 2-hydroxy-7-carboxy-9,10-dihydrophenanthrene (G) from the following results of elemental analysis, IR, and NMR.
元素分析
C15H12O3としての計算値
Ｃ：75.00％，Ｈ：5.00％
分析値
Ｃ：74.92％，Ｈ：5.11％
IR
添付図面第１図参照
NMR
添付図面第２図参照
合成例 ８
２−ヒドロキシ−７−カルボキシ−９，10−ジ
ヒドロフエナントレン(G)8.0ｇ、ピリジン30mlと
ベンゼン150mlの混合液を40℃に加算し撹拌しな
がら、この中に４−ｎ−ブチル−トランス−シク
ロヘキシルカルボニルクロリド７ｇをベンゼン30
mlに溶かした液を滴下した。滴下終了後３時間還
流後、反応液を水、希塩酸、水の順で洗浄し、続
いてベンゼンを留去した。残渣はベンゼンで再結
晶して白色結晶を得た。この結晶を昇温したとこ
ろ184℃でネマチツク液晶相となり、さらに342℃
では等方性液体相となつた。元素分析、IR，
NMRの下記の結果から得られた結晶は２−（４−
ｎ−ブチルシクロヘキシルカルボニルオキシ）−
７−カルボキシ−９，10−ジヒドロフエナントレ
ンであることを確認した。 Elemental analysis Calculated value as C 15 H 12 O 3 C: 75.00%, H: 5.00% Analysis value C: 74.92%, H: 5.11% IR See attached drawing Figure 1 NMR See attached drawing Figure 2 Synthesis example 8 2 A mixture of 8.0 g of -hydroxy-7-carboxy-9,10-dihydrophenanthrene (G), 30 ml of pyridine and 150 ml of benzene was added to 40°C, and while stirring, 4-n-butyl-trans- 7g of cyclohexylcarbonyl chloride and 30g of benzene
ml of solution was added dropwise. After refluxing for 3 hours after the completion of the dropwise addition, the reaction solution was washed with water, diluted hydrochloric acid, and water in this order, and then benzene was distilled off. The residue was recrystallized with benzene to obtain white crystals. When this crystal was heated, it became a nematic liquid crystal phase at 184℃, and then further heated to 342℃.
Now it becomes an isotropic liquid phase. Elemental analysis, IR,
The crystal obtained from the NMR results below is 2-(4-
n-butylcyclohexylcarbonyloxy)-
It was confirmed that it was 7-carboxy-9,10-dihydrophenanthrene.
元素分析
C26H30O4としての計算値
Ｃ：76.85％，Ｈ：7.39％
分析値
Ｃ：76.56％，Ｈ：7.40％
IR
添付図面第３図参照
NMR
添付図面第４図参照
合成例 ９
２−ヒドロキシ−７−カルボキシ−９，10−ジ
ヒドロフエナントレン(G)8.0ｇをピリジン30mlと
ベンゼン150ml中に溶解し、これに４−ｎ−ブト
キシベンゾイルクロリド7.2ｇをベンゼン30mlに
溶解した液を加えた。合成例８と同様に反応さ
せ、２−（４−ｎ−ブトキシベンゾイルオキシ）−
７−カルボキシ−９，10−ジヒドロフエナントレ
ンを得た。 Elemental analysis Calculated values as C 26 H 30 O 4 C: 76.85%, H: 7.39% Analytical values C: 76.56%, H: 7.40% IR See Figure 3 of the attached drawings NMR See Figure 4 of the attached drawings Synthesis example 9 2 -Hydroxy-7-carboxy-9,10-dihydrophenanthrene (G) 8.0g was dissolved in pyridine 30ml and benzene 150ml, and a solution of 4-n-butoxybenzoyl chloride 7.2g dissolved in benzene 30ml was added to this. added. The reaction was carried out in the same manner as in Synthesis Example 8, and 2-(4-n-butoxybenzoyloxy)-
7-carboxy-9,10-dihydrophenanthrene was obtained.
この化合物は156℃でネマチツク液晶相を、350
℃で等方性液体相を示した。 This compound exhibits a nematic liquid crystal phase at 156°C and a nematic liquid crystal phase at 350°C.
It showed an isotropic liquid phase at ℃.
第１図および第２図は２−ヒドロキシ−７−カ
ルボキシ−９，10−ジヒドロフエナントレンのそ
れぞれIR，NMRスペクトル図であり、第３図お
よび第４図は２−（４−ｎ−ブチルシクロヘキシ
ルカルボニルオキシ）−７−カルボキシ−９，10
−ジヒドロフエナントレンのそれぞれIR，NMR
スペクトル図である。
Figures 1 and 2 are IR and NMR spectra of 2-hydroxy-7-carboxy-9,10-dihydrophenanthrene, respectively, and Figures 3 and 4 are 2-(4-n-butyl cyclohexylcarbonyloxy)-7-carboxy-9,10
-IR and NMR of dihydrophenanthrene, respectively
It is a spectrum diagram.
Claims (1)
キシルカルボニル基又は４−ｎ−ブトキシベンゾ
イル基を表す。） で表わされる７−カルボキシ−９，10−ジヒドロ
フエナントレン誘導体。[Claims] 1. General formula (In the formula, R represents a hydrogen atom, a 4-n-butylcyclohexylcarbonyl group, or a 4-n-butoxybenzoyl group.) A 7-carboxy-9,10-dihydrophenanthrene derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193581A JPS57146737A (en) | 1981-03-07 | 1981-03-07 | 7-carboxy-9,10-dihydrophenanthrene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193581A JPS57146737A (en) | 1981-03-07 | 1981-03-07 | 7-carboxy-9,10-dihydrophenanthrene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57146737A JPS57146737A (en) | 1982-09-10 |
| JPS6254419B2 true JPS6254419B2 (en) | 1987-11-14 |
Family
ID=12344822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3193581A Granted JPS57146737A (en) | 1981-03-07 | 1981-03-07 | 7-carboxy-9,10-dihydrophenanthrene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57146737A (en) |
-
1981
- 1981-03-07 JP JP3193581A patent/JPS57146737A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57146737A (en) | 1982-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6136247A (en) | Organic compound having chiral structure, use for liquid crystal mixture and manufacture | |
| FR2486955A1 (en) | TYPE A SMOTIC LIQUID CRYSTAL HAVING POSITIVE DIELECTRIC ANISOTROPY | |
| WO2020082605A1 (en) | Pyrazolyl azophenol compound and synthesis and derivation thereof | |
| JPS6254419B2 (en) | ||
| JPS6045872B2 (en) | liquid crystal compound | |
| JPH0455476B2 (en) | ||
| JPH04338360A (en) | New cyclobutanecarboxylic acid derivative and liquid crystal composition containing the same | |
| JP3516698B2 (en) | Benzoate compound | |
| JPH0430938B2 (en) | ||
| JPS6125702B2 (en) | ||
| JP2796722B2 (en) | Liquid crystal for optical elements | |
| JPS6059223B2 (en) | liquid crystal compound | |
| JPS58140086A (en) | 4-(trans-5-alkyl-1, 3-dioxa-2-yl)benzoic acid derivative | |
| JP2811825B2 (en) | Pyrimidine derivatives | |
| JPH04234837A (en) | lactic acid derivative | |
| JPH04227681A (en) | Liquid crystal composition | |
| JPS6013032B2 (en) | 4↓-alkyl↓-4′↓-(4″↓-cyanobenzoyloxy)↓-3′↓-cyanobiphenyl | |
| JPS6216238B2 (en) | ||
| JPS6058218B2 (en) | liquid crystalline ester compound | |
| JPS6154781B2 (en) | ||
| JPH1160538A (en) | Ester compound and liquid crystal composition containing the same | |
| JPH0133091B2 (en) | ||
| JPS59110651A (en) | Novel nematic liquid crystal compound | |
| JPS6058902B2 (en) | liquid crystalline ester compound | |
| JPS61215356A (en) | 2-(4-substituted cyclohexanoyloxy)-9,10-dihydrophenanthrene derivative |