JPH01213254A - Biphenyl derivative and production thereof - Google Patents
Biphenyl derivative and production thereofInfo
- Publication number
- JPH01213254A JPH01213254A JP4162988A JP4162988A JPH01213254A JP H01213254 A JPH01213254 A JP H01213254A JP 4162988 A JP4162988 A JP 4162988A JP 4162988 A JP4162988 A JP 4162988A JP H01213254 A JPH01213254 A JP H01213254A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acetyl
- chloride
- general formula
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- DXXRWDCBHNIVBQ-UHFFFAOYSA-N 1-[4-(4-hydroxyphenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(O)C=C1 DXXRWDCBHNIVBQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 12
- -1 (substituted)phenyl Chemical group 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229940073608 benzyl chloride Drugs 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 abstract description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005574 benzylation reaction Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 2
- UYEIKSZVBNZBKK-UHFFFAOYSA-N 1-[4-(4-phenylmethoxyphenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C(C=C1)=CC=C1OCC1=CC=CC=C1 UYEIKSZVBNZBKK-UHFFFAOYSA-N 0.000 description 2
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BDFZQEDEJPQJNB-UHFFFAOYSA-N 1-(bromomethyl)-4-butoxybenzene Chemical compound CCCCOC1=CC=C(CBr)C=C1 BDFZQEDEJPQJNB-UHFFFAOYSA-N 0.000 description 1
- KQNBRMUBPRGXSL-UHFFFAOYSA-N 1-(bromomethyl)-4-chlorobenzene Chemical compound ClC1=CC=C(CBr)C=C1 KQNBRMUBPRGXSL-UHFFFAOYSA-N 0.000 description 1
- WZRKSPFYXUXINF-UHFFFAOYSA-N 1-(bromomethyl)-4-methylbenzene Chemical compound CC1=CC=C(CBr)C=C1 WZRKSPFYXUXINF-UHFFFAOYSA-N 0.000 description 1
- YBQKGOKXPFDCCT-UHFFFAOYSA-N 1-(bromomethyl)-4-propoxybenzene Chemical compound CCCOC1=CC=C(CBr)C=C1 YBQKGOKXPFDCCT-UHFFFAOYSA-N 0.000 description 1
- DCLMJYZEOSDVCL-UHFFFAOYSA-N 1-(chloromethyl)-4-ethoxybenzene Chemical compound CCOC1=CC=C(CCl)C=C1 DCLMJYZEOSDVCL-UHFFFAOYSA-N 0.000 description 1
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 1
- VDOPPUPAYILRDO-UHFFFAOYSA-N 1-(chloromethyl)-4-propoxybenzene Chemical compound CCCOC1=CC=C(CCl)C=C1 VDOPPUPAYILRDO-UHFFFAOYSA-N 0.000 description 1
- FIXRFLCABDYIGE-UHFFFAOYSA-N 1-(fluoromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CF)C=C1 FIXRFLCABDYIGE-UHFFFAOYSA-N 0.000 description 1
- PARYROBXBUOFAR-UHFFFAOYSA-N 1-[4-[4-[(4-methoxyphenyl)methoxy]phenyl]phenyl]ethanone Chemical group COC1=CC=C(COC2=CC=C(C=C2)C2=CC=C(C=C2)C(C)=O)C=C1 PARYROBXBUOFAR-UHFFFAOYSA-N 0.000 description 1
- FHLGAUMMGWAQOO-UHFFFAOYSA-N 1-[4-[4-[(4-methylphenyl)methoxy]phenyl]phenyl]ethanone Chemical group CC1=CC=C(COC2=CC=C(C=C2)C2=CC=C(C=C2)C(C)=O)C=C1 FHLGAUMMGWAQOO-UHFFFAOYSA-N 0.000 description 1
- DLYHQYZAEIUQLQ-UHFFFAOYSA-N 1-butoxy-4-(chloromethyl)benzene Chemical compound CCCCOC1=CC=C(CCl)C=C1 DLYHQYZAEIUQLQ-UHFFFAOYSA-N 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GBXRJUXIBPGSSH-UHFFFAOYSA-N [bromo(ethoxy)methyl]benzene Chemical compound CCOC(Br)C1=CC=CC=C1 GBXRJUXIBPGSSH-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- ZDKRMIJRCHPKLW-UHFFFAOYSA-N benzyl methanesulfonate Chemical compound CS(=O)(=O)OCC1=CC=CC=C1 ZDKRMIJRCHPKLW-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- VPCOEYXZVJRDCX-UHFFFAOYSA-N imino-methyl-oxidophosphanium Chemical compound C[P+](=N)[O-] VPCOEYXZVJRDCX-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation 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
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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（４）
（式中、Ａは水素原子、ハロゲン原子、炭素数１〜４の
アルキル基または炭素数１〜４のアルコキシル基を示す
）
で示されるビフェニル誘導体およびその製造法に関する
。Detailed Description of the Invention <Industrial Application Field> The present invention is directed to the general formula (4) (wherein A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms). The present invention relates to a biphenyl derivative represented by (representing an alkoxyl group) and a method for producing the same.
〈従来の技術〉
前記一般式（１）で示されるビフェニル誘導体は文献未
記載の新規化合物であり、従来よりその製造法について
は勿論のこと、化合物としての有用性についても全く知
られていない。<Prior Art> The biphenyl derivative represented by the general formula (1) is a new compound that has not been described in any literature, and not only its production method but also its usefulness as a compound has not been known at all.
〈発明が解決すべき課題〉
前記一般式（Ｉ）で示されるビフェニル誘導体は、医薬
、農薬等の中間体としても有用であるが、特に有機電子
材料とりわけ液晶化合物の中間体として非常に有用であ
る。<Problems to be Solved by the Invention> The biphenyl derivative represented by the general formula (I) is useful as an intermediate for medicines, agricultural chemicals, etc., but is particularly useful as an intermediate for organic electronic materials, especially liquid crystal compounds. be.
たとえば、該ビフェニル誘導体は代表的には次式に示さ
れるような方法により新規な液晶化合物へ導くことがで
き、該化合物は強詞電性液晶として非常に優れた性質を
有している。For example, the biphenyl derivative can be typically converted into a novel liquid crystal compound by the method shown in the following formula, and this compound has very excellent properties as a strong electrostatic liquid crystal.
〈課題を解決するための手段〉
本発明は、このような医、農薬中間体としては勿論、有
機電子材料とりわけ液晶化合物の中間体としても有用な
新規化合物である前記一般式（１）で示されるビフェニ
ル誘導体を提供するものである。<Means for Solving the Problems> The present invention provides a novel compound represented by the general formula (1) that is useful not only as such medical and agricultural intermediates but also as an intermediate for organic electronic materials, especially liquid crystal compounds. The present invention provides biphenyl derivatives including:
前記一般式（１）で示されるビフェニル誘導体は４−ア
セチル−４′−ヒドクキシビフエニルシト−般式（■）
（式中、Ａは前記と同じ意味を有し、Ｘはハロゲン原子
または−０８０，Ｒを示す。ここでＲは低級アルキル基
または置換されていてもよいフェニル基を示す）
で示されるベンジル化剤と反応させることによゆ製造す
ることができる。The biphenyl derivative represented by the general formula (1) is 4-acetyl-4'-hydroxybiphenylsite-general formula (■) (wherein A has the same meaning as above, and X is a halogen atom or - 080, R, where R represents a lower alkyl group or an optionally substituted phenyl group).
この反応は、通常塩基性物質の存在下に行われ、該塩基
性物質としては、たとえば水素化ナトリウム、水素化カ
リウムなどのアルカリ金属水累化物、水素化カルシウム
等のアルカリ土類金属水素化物、リチウム、ナトリウム
、カリウム、カルシウム等のアルカリ金属やアルカリ土
類金属、ナトリウムメチラート、ナトリウムエチラート
等のアルカリ金属アルコラード、炭酸ナトリウム、炭酸
カリウム等の炭酸アルカリ金属、水酸化ナトリウム、水
酸カリウム等のアルカリ金属水酸化物、ブチルリチウム
、メチルリチウム等の有機金属が例示される。This reaction is usually carried out in the presence of a basic substance, such as alkali metal water complexes such as sodium hydride and potassium hydride, alkaline earth metal hydrides such as calcium hydride, Alkali metals and alkaline earth metals such as lithium, sodium, potassium, and calcium, alkali metal alcolades such as sodium methylate and sodium ethylate, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydroxide, potassium hydroxide, etc. Examples include organic metals such as alkali metal hydroxides, butyllithium, and methyllithium.
このような塩基性物質は通常、４−アセチル−４′−ヒ
ドロキシビフェニルに対して１当量倍以上使用され、上
限については特に制限されないが、好ましくは２倍当量
である。Such a basic substance is usually used in an amount of 1 equivalent or more relative to 4-acetyl-4'-hydroxybiphenyl, and is preferably used in an amount of 2 equivalents, although the upper limit is not particularly limited.
この反応で使用されるベンジル化剤とはクロリド、プロ
ミド、ヨード等のハロゲン化物あるいは硫酸エステル類
（メタンスルホン酸エステル、エタンスルホン酸エステ
ル、ベンゼンスルホン酸エステル、トルエンスルホン酸
エステル等）であり、具体的にはメンジルクロライド、
ベンジルブロマイド、ベンジルトシレート、ベンジルメ
シレート、４−メチルベンジルクロライド、４−メチル
ベンジルブロマイド、４−メトキシベンジルフロライド
、２−クロルベンジＪｌ／ クロライド、４−クロルベ
ンジルクロライド、４−クロルベンジルブロマイド、４
−エトキシベンジルクロライド、４−プロポキシベンジ
ルクロライド、４−ブトキシベンジルクロライド、４−
エトキシベンジルブロマイド、４−プロポキシベンジル
ブロマイド、４−ブトキシベンジルブロマイドなどが例
示される。The benzylating agents used in this reaction are halides such as chloride, bromide, and iodine, or sulfuric esters (methanesulfonic acid ester, ethanesulfonic acid ester, benzenesulfonic acid ester, toluenesulfonic acid ester, etc.). Specifically, menzyl chloride,
Benzyl bromide, benzyl tosylate, benzyl mesylate, 4-methylbenzyl chloride, 4-methylbenzyl bromide, 4-methoxybenzyl fluoride, 2-chlorobenzyl Jl/chloride, 4-chlorobenzyl chloride, 4-chlorobenzyl bromide, 4
-Ethoxybenzyl chloride, 4-propoxybenzyl chloride, 4-butoxybenzyl chloride, 4-
Examples include ethoxybenzyl bromide, 4-propoxybenzyl bromide, and 4-butoxybenzyl bromide.
このようなベンジル化剤の使用量は、４−アセチル−４
′−ヒドロキシビフェニルに対して１当量以上任意であ
るが、通常は１〜２当量の範囲である。The amount of such benzylating agent used is 4-acetyl-4
It can be used in an amount of 1 equivalent or more relative to '-hydroxybiphenyl, but is usually in the range of 1 to 2 equivalents.
溶媒としては、たとえばメタノール、エタノール、２−
プロパツール、テトラヒドロフラン、エチルエーテル、
アセトン、メチルエチルケトン、トルエン、ベンゼン、
クロロホルム、クロルベンゼン、ジクロルメタン、ジク
ロルエタン、四塩化炭素、ヘキサン等の脂肪族もしくは
芳香族炭化水素、エーテル、ハロゲン化炭化水素等の反
応に不活性な溶媒の単独または混合物が使ド、ジメチル
スルホキシド、ヘキサメチルホスホリルアミド、Ｎ−メ
チルピロリドン等の極性溶媒を使用することもできる。Examples of solvents include methanol, ethanol, 2-
propatool, tetrahydrofuran, ethyl ether,
Acetone, methyl ethyl ketone, toluene, benzene,
A single or mixture of solvents inert to the reaction such as chloroform, chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, aliphatic or aromatic hydrocarbons such as hexane, ether, halogenated hydrocarbons, etc., dimethyl sulfoxide, hexane, etc. are used. Polar solvents such as methylphosphorylamide and N-methylpyrrolidone can also be used.
また、溶媒として水単独または水と上記有機溶媒との混
合物を使用することもできるが、混合物を用いる場合、
有機溶媒特に水と混和しない有機溶媒（たとえばトルエ
ン、ベンゼンなど）との２相系においては相関移動触媒
（たとえばテトラブチルアンモニウムクロリド、ベンジ
ルトリメチルアンモニウムクロリド）を共存させること
により、効率よ（ベンジル化することもできる。In addition, water alone or a mixture of water and the above-mentioned organic solvent can be used as a solvent, but when a mixture is used,
In two-phase systems with organic solvents, especially organic solvents that are immiscible with water (e.g., toluene, benzene, etc.), coexistence of phase transfer catalysts (e.g., tetrabutylammonium chloride, benzyltrimethylammonium chloride) improves efficiency (benzylation). You can also do that.
反応温度は、通常−５０℃〜１２０℃、好ましくは一８
０℃〜１００℃の範囲である。The reaction temperature is usually -50°C to 120°C, preferably -80°C.
It is in the range of 0°C to 100°C.
反応終了後、通常の分離手段、たとえば抽出、分液、濃
縮等の操作によりビフェニル誘導体（Ｉ）を収率よく得
ることができ、必要に応じてカラムクロマトグラフィー
、再結晶等により精製することができる。After completion of the reaction, the biphenyl derivative (I) can be obtained in good yield by ordinary separation means such as extraction, separation, concentration, etc., and can be purified by column chromatography, recrystallization, etc. as necessary. can.
〈発明の効果〉
かくして、本発明の方法によれば、新規化合物である一
般式（１）で示されるビフェニル誘導体を工業的有利に
製造することができ、しかも本発明化合物は液晶用材料
として有用であるのみならず、農薬、医薬等の中間体と
しても利用す実施例１
攪拌装置、温度計を備えた４つロフラスコに４−アセチ
ル−４′−ヒドロキシビフェニル２１、２ Ｆ（０，１
モル）およびジメチルホルムアミド２００−を仕込み、
更に無水炭酸カリウム４１．６Ｆ（０，８モル）を加え
て攪拌する。<Effects of the Invention> Thus, according to the method of the present invention, the biphenyl derivative represented by the general formula (1), which is a new compound, can be produced industrially advantageously, and the compound of the present invention is useful as a material for liquid crystals. Example 1 4-acetyl-4'-hydroxybiphenyl 21,2F (0,1
mol) and dimethylformamide 200-,
Further, 41.6 F (0.8 mol) of anhydrous potassium carbonate is added and stirred.
５０°Ｃに昇温後、ベンジルクロリド１５．２Ｐを滴下
し、同温変で７時間反応させる。反応終了後、反応液を
水５００ｄ中にあけて攪拌し、生じた沈澱を炉取し、よ
く水洗したのち乾燥して２８．９Ｆの白色固体を得た。After raising the temperature to 50°C, 15.2P of benzyl chloride was added dropwise, and the mixture was allowed to react at the same temperature for 7 hours. After the reaction was completed, the reaction solution was poured into 500 d of water and stirred, and the resulting precipitate was collected in a furnace, thoroughly washed with water, and then dried to obtain a white solid of 28.9F.
これをエタノールから再結晶して、４−アセチル−４′
−ベンジルオキシビフェニル２６．８ Ｆ （収率８７
％）を得た。This was recrystallized from ethanol and 4-acetyl-4'
-benzyloxybiphenyl 26.8 F (yield 87
%) was obtained.
融点 １７０−１７２℃
実施例２
ベンジルクロリドに代えて、４−クロロベンジルクロリ
ド２０．６Ｐを用いる以外は実施例１と同様に反応、後
処理をおこなって４−７セチルー４’−（４−クロロベ
ンジルオキシ）ビフェニル８０． ＯＦ （収率８９．
６％）を得た。Melting point 170-172°C Example 2 The reaction and post-treatment were carried out in the same manner as in Example 1 except that 4-chlorobenzyl chloride 20.6P was used instead of benzyl chloride. benzyloxy)biphenyl80. OF (yield 89.
6%).
融点 １７８−１７９．６℃
実施例８
無水炭酸カリウムに代えて水素化ナトリウム（６０％）
４．４ｔ？（０，１１モル）を用いる以外は実施例１と
同様に反応（但し、反応時間８時間）、後処理をおこな
って、４−アセチル−４′−ベンジルオキシビフェニル
２７．０１を得た。Melting point 178-179.6°C Example 8 Sodium hydride (60%) in place of anhydrous potassium carbonate
4.4t? The reaction and post-treatment were carried out in the same manner as in Example 1 except that (0.11 mol) was used (however, the reaction time was 8 hours) to obtain 27.01 of 4-acetyl-4'-benzyloxybiphenyl.
実施例４
無水炭酸カリウムに代えて水素化ナトリウム（６０％）
７４．４Ｆ（０，１１モル）をベンジルクロリドに代え
てｐ−メトキシベンジルクロリド１７．２ Ｆを用いる
以外は、実施例１と面様に反応（但し、反応時間は８時
間）後処理をお仁ない、得られた薄黄色固体をエタノー
ルから再結晶して、４−アセチル−４′−（ｐ−メトキ
シベンジル）オキシビフェニル２６、０ Ｐ （収率７
９％’）を得た。Example 4 Sodium hydride (60%) in place of anhydrous potassium carbonate
The reaction was carried out in the same manner as in Example 1, except that p-methoxybenzyl chloride 17.2F was used in place of benzyl chloride in place of 74.4F (0.11 mol) (however, the reaction time was 8 hours). The pale yellow solid obtained was recrystallized from ethanol to give 4-acetyl-4'-(p-methoxybenzyl)oxybiphenyl 26,0P (yield 7).
9%') was obtained.
融点 １９５−１９７℃
実施例５
ベンジルクロリドに代えてｐ−メチルベンジルクロリド
１６．８Ｆを用いる以外は実施例１と同様に反応、後処
理をおこない、得られた薄黄色固体をエタノールから再
結晶して、４−アセチル−４’−（ｐ−メチルベンジル
）オキシビフェニル２５．６Ｐ（収率８１％）を得た。Melting point: 195-197°C Example 5 The reaction and post-treatment were carried out in the same manner as in Example 1, except that p-methylbenzyl chloride 16.8F was used instead of benzyl chloride, and the obtained pale yellow solid was recrystallized from ethanol. Thus, 4-acetyl-4'-(p-methylbenzyl)oxybiphenyl 25.6P (yield 81%) was obtained.
融点 １７９−１８１．５°Ｃ （以下余白）Melting point: 179-181.5°C (Margin below)
Claims (2)
般式 ▲数式、化学式、表等があります▼ （式中、Ａは水素原子、ハロゲン原子、炭 素数１〜４のアルキル基または炭素数１〜 ４のアルコキシル基を示し、Ｘはハロゲン 原子または−ＯＳＯ＿２Ｒを示す。ここでＲは低級アル
キル基または置換されていてもよいフェニル基を示す） で示されるベンジル化剤を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▼ （式中、Ａは前記と同じ意味を有する） で示されるビフェニル誘導体の製造法。(2) 4-acetyl-4'-hydroxybiphenyl and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a 4 represents an alkoxyl group, X represents a halogen atom or -OSO_2R, where R represents a lower alkyl group or an optionally substituted phenyl group). A method for producing biphenyl derivatives represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, A has the same meaning as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63041629A JP2531228B2 (en) | 1988-02-23 | 1988-02-23 | Biphenyl derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63041629A JP2531228B2 (en) | 1988-02-23 | 1988-02-23 | Biphenyl derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01213254A true JPH01213254A (en) | 1989-08-28 |
| JP2531228B2 JP2531228B2 (en) | 1996-09-04 |
Family
ID=12613620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63041629A Expired - Lifetime JP2531228B2 (en) | 1988-02-23 | 1988-02-23 | Biphenyl derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2531228B2 (en) |
-
1988
- 1988-02-23 JP JP63041629A patent/JP2531228B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2531228B2 (en) | 1996-09-04 |
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