JPS6015608B2 - 2-,7-dialkoxylphenanthrene compound and method for producing the same - Google Patents
2-,7-dialkoxylphenanthrene compound and method for producing the sameInfo
- Publication number
- JPS6015608B2 JPS6015608B2 JP51044976A JP4497676A JPS6015608B2 JP S6015608 B2 JPS6015608 B2 JP S6015608B2 JP 51044976 A JP51044976 A JP 51044976A JP 4497676 A JP4497676 A JP 4497676A JP S6015608 B2 JPS6015608 B2 JP S6015608B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- dialkoxylphenanthrene
- producing
- same
- carbon atoms
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 phenanthrene compound Chemical class 0.000 description 2
- 150000002987 phenanthrenes Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ORRVRBPWVZVRKU-UHFFFAOYSA-N 1,2-dibromophenanthrene Chemical compound C1=CC=C2C3=CC=C(Br)C(Br)=C3C=CC2=C1 ORRVRBPWVZVRKU-UHFFFAOYSA-N 0.000 description 1
- NGDWMVTZPZDKPM-UHFFFAOYSA-N 2,7-dibromophenanthrene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3C=CC2=C1 NGDWMVTZPZDKPM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical group COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/40—Mixers using gas or liquid agitation, e.g. with air supply tubes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- 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２一・７−ジアルコキシルフェナントレン化合
物およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 2-1,7-dialkoxylphenanthrene compound and a method for producing the same.
本発明の化合物は一般式
（但し、Ｒ，
およびＲ２は炭素数６〜１２のアルキル基を示す）で表
わされる２一・７ージアルコキシルフヱナントレン化合
物である。The compound of the present invention is a 21,7-dialkoxylphenanthrene compound represented by the general formula (wherein R and R2 represent an alkyl group having 6 to 12 carbon atoms).
従来、多くのフェナントレン誘導体が知られているが、
上記フヱナントレン化合物は知られていない。Many phenanthrene derivatives have been known so far, but
The above-mentioned phenanthrene compound is not known.
本発明の化合物は細長い構造であるため公知のフェナン
トレン化合物と異なり液晶又は液晶混合物として有用で
ある。２−・７−ジアルコキシルフェナントレン化合物
は具体的には第１表に示すような化合物がある。The compound of the present invention has an elongated structure, which makes it useful as a liquid crystal or liquid crystal mixture, unlike known phenanthrene compounds. Specific examples of 2-.7-dialkoxylphenanthrene compounds include compounds shown in Table 1.
第１表
この化合物は、内部に−Ｎ−Ｎ−結合や−Ｎ＝Ｃ−結合
など不安定な結合がないので極めて安定な液晶とするこ
とができる。Table 1 This compound has no internal unstable bonds such as -N-N- bonds and -N=C- bonds, so it can be made into an extremely stable liquid crystal.
特にＲ，およびＲ２がＣ５〜７ 付近が液晶として好成
績を示す。また液晶を示さないもの、すなわちＲ，およ
びＲ２がＣ４以下のものは本発明の化合物ではない。本
発明の化合物は２−・７−ジオキシフヱナントレンを有
機溶媒中アルカリの存在下、一般式Ｒ，Ｘ又はＲ２×（
但し、Ｒ，およびＲ２は炭素数５〜２０のアルキル基、
Ｘはハロゲンを示す）で表わされるアルキルハラィドと
反応させることによって合成される。In particular, when R and R2 are around C5-7, good results are obtained as a liquid crystal. Furthermore, compounds that do not exhibit liquid crystallinity, ie, compounds in which R and R2 are C4 or less, are not compounds of the present invention. The compound of the present invention is prepared by preparing 2-,7-dioxyphenanthrene with the general formula R, X or R2×(
However, R and R2 are alkyl groups having 5 to 20 carbon atoms,
It is synthesized by reacting with an alkyl halide represented by (X represents halogen).
有機溶媒はアセトンなど生成物および原料を溶解するも
のが好適であり、またアルカリは水酸化ナトリウム等が
使用できる。Suitable organic solvents are those that dissolve the products and raw materials, such as acetone, and sodium hydroxide and the like can be used as the alkali.
アルキルハライドは臭素化物が好適であり、アルキル基
の炭素数は目的物のァルコキシル基の炭素数に対応する
。反応は還流条件下で数時間縄拝することにより行われ
る。アルキル基の炭素数によっても異なるが収率は７０
％前後に達する。原料２一・７−ジオキシフェナントレ
ンは、２一・７−ジブロムフェナントレンから合成する
ことが有利である。The alkyl halide is preferably a brominated compound, and the number of carbon atoms in the alkyl group corresponds to the number of carbon atoms in the alkoxyl group of the target product. The reaction is carried out under reflux conditions for several hours. The yield varies depending on the number of carbon atoms in the alkyl group, but the yield is 70
It reaches around %. The raw material 21,7-dioxyphenanthrene is advantageously synthesized from 21,7-dibromophenanthrene.
すなわち、２一・７ージプロムフェナントレンを銅およ
び硫酸鋼の存在下、アルカリで加水分解して２−・７−
ジオキシフェナントレンを得る方法である。反応はアル
カリ水溶液中で、５０〜１００℃に加熱することにより
進行し、４０％前後の収率が得られる。更に、２−・７
−ジプロムフェナントレンも直接フェナントレンから合
成することは極めて困難であるので、最初の出発原料と
してフルオレンを用い、置換フルオレンを合成しこれを
増環反応により２−・７−ジブロムフエナントレンとす
ることが有利である。That is, 2-,7-dipromophenanthrene is hydrolyzed with an alkali in the presence of copper and steel sulfate to produce 2-,7-
This is a method for obtaining dioxyphenanthrene. The reaction proceeds in an alkaline aqueous solution by heating to 50 to 100°C, and a yield of about 40% is obtained. Furthermore, 2-7
- Since it is extremely difficult to synthesize dibromophenanthrene directly from phenanthrene, fluorene is used as the first starting material to synthesize substituted fluorene, which is then subjected to a ring addition reaction to produce 2-/7-dibromophenanthrene. That is advantageous.
すなわち、２一・７ージブロムフェナントレンは次のよ
うにして合成される。まず、フルオレンを二硫化炭素溶
媒中臭素で臭素化して、バラジブロムフルオレンを得、
次いでこれをヱーテル溶媒中カリウムェチラート、ギ酸
エチルによりホルミル化し、次にこれをｉープロパノー
ル中アルミニウムｉ−プロパラートによりホルミル基を
メチラール基に還元し、そしてこれをキシレン溶媒中五
酸化リンにより増環させて２−・７ージブロムフェナン
トレンとする。このようにして、２一・７−ジブロムフ
ェナントレンを合成することにより、フェナントレンを
直接臭素化した場合は２−・７−体を得ることは困難で
あるにもかかわらず、収率よく２−・７一体を得ること
ができる。実施例 １
フルオレンを最初の出発原料として合成して得た２・７
ージブロムフェナントレン４夕、銅粉３．２夕、硫酸鋼
３３．２夕の３５％水酸化ナトリウム水溶液を２６０ｏ
ｏに加圧下加熱し、１時間反応を行い、２一・７−ジオ
キシフエナントレン２．２夕を得た。That is, 2-1,7-dibromophenanthrene is synthesized as follows. First, fluorene was brominated with bromine in a carbon disulfide solvent to obtain balajibromofluorene,
This was then formylated with potassium ethylate and ethyl formate in ether solvent, the formyl group was reduced to a methylal group with aluminum i-propanol in i-propanol, and this was ring-enlarged with phosphorus pentoxide in xylene solvent. to obtain 2-.7-dibromophenanthrene. In this way, by synthesizing 2-,7-dibromophenanthrene, the 2-2-・You can get 7 pieces. Example 1 2.7 obtained by synthesizing fluorene as the first starting material
A 35% aqueous solution of sodium hydroxide containing 4 hours of -dibromophenanthrene, 3.2 hours of copper powder, and 33.2 hours of sulfuric acid steel was heated at 260oC.
The reaction mixture was heated under pressure at a temperature of 100.degree. C. and reacted for 1 hour to obtain 2.2 hours of 2-1,7-dioxyphenanthrene.
この２−・７ージオキシフヱナントレン１．０夕、ｎ−
へキシルブロミド２．５夕、水酸化ナトリウム５夕のア
セトン溶液を１畑時間還流させて反応を行ったところ、
２−・７−ジヘキサアルコキシルフェナントレン３．５
夕を得た。This 2-,7-dioxyphenanthrene 1.0, n-
When a reaction was carried out by refluxing an acetone solution of 2.5 hours of hexyl bromide and 5 hours of sodium hydroxide,
2-,7-dihexaalkoxylphenanthrene 3.5
I got the evening.
これをアセトンで再結晶精製して物性を測定した所、色
は無色で、融点は７２〜１１８００であり、また、特性
赤外線吸収により２一・７ージヘキサアルコキシルフェ
ナントレンであることが確認された。When this was purified by recrystallization with acetone and its physical properties were measured, it was found to be colorless and had a melting point of 72 to 11,800, and was confirmed to be 2-1,7-dihexaalkoxylphenanthrene by characteristic infrared absorption. .
更に液晶としての物性を測定した所次の結果カギ得られ
た。液晶形；ネマティック形、液晶相と液相との転移点
１１８００精製された上記化合物を液晶セル内に封入実
装し動作させた結果、８０ｑｏから１１０００の間で良
好な表示効果が得られた。Furthermore, the physical properties of the liquid crystal were measured and the following key results were obtained. Liquid crystal type: Nematic type, transition point between liquid crystal phase and liquid crystal phase: 11,800 When the purified compound was sealed and mounted in a liquid crystal cell and operated, a good display effect was obtained between 80 qo and 11,000 qo.
また、上記例と同様にして、ｎーヘキシルブロミドの代
りにＣ，からＣ２。Also, in the same manner as in the above example, C, to C2 were used instead of n-hexyl bromide.
Claims (1)
わされる２−・７−ジアルコキシルフエナントレン化合
物。 ２ ２−・７−ジオキシフエナントレンを有機溶媒中ア
ルカリの存在下、一般式Ｒ＿１Ｘ又はＲ＿２Ｘ（但し、
Ｒ＿１およびＲ＿２は炭素数６〜１２のアルキル基、Ｘ
はハロゲンを示す）で表されるアルキルハライドと反応
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▼ （但し、Ｒ＿１ およびＲ＿２は前記と同じものを示す）で表される２−
・７−ジアルコキシルフエナントレン化合物の製造方法
。[Claims] 1 2-/7-dialkoxylphenanthrene represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein R_1 and R_2 represent an alkyl group having 6 to 12 carbon atoms) Compound. 2 2-/7-dioxyphenanthrene in the presence of an alkali in an organic solvent with the general formula R_1X or R_2X (however,
R_1 and R_2 are alkyl groups having 6 to 12 carbon atoms, X
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R_2 are the same as above) −
- A method for producing a 7-dialkoxylphenanthrene compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51044976A JPS6015608B2 (en) | 1976-04-22 | 1976-04-22 | 2-,7-dialkoxylphenanthrene compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51044976A JPS6015608B2 (en) | 1976-04-22 | 1976-04-22 | 2-,7-dialkoxylphenanthrene compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52131565A JPS52131565A (en) | 1977-11-04 |
| JPS6015608B2 true JPS6015608B2 (en) | 1985-04-20 |
Family
ID=12706490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51044976A Expired JPS6015608B2 (en) | 1976-04-22 | 1976-04-22 | 2-,7-dialkoxylphenanthrene compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015608B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648021A (en) * | 1994-01-17 | 1997-07-15 | Hoechst Aktiengesellschaft | Phenanthrene derivatives and their use in liquid-crystalline mixtures |
| JP4605412B2 (en) * | 1999-08-27 | 2011-01-05 | Ｄｉｃ株式会社 | Phenanthrene and fluorene derivatives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4986536A (en) * | 1972-12-26 | 1974-08-19 |
-
1976
- 1976-04-22 JP JP51044976A patent/JPS6015608B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4986536A (en) * | 1972-12-26 | 1974-08-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52131565A (en) | 1977-11-04 |
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