JP4524556B2 - Method for producing 2-naphthol derivative - Google Patents
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本発明は2-ナフトール誘導体の製造方法に関する。 The present invention relates to a method for producing a 2-naphthol derivative.
塩素またはフッ素置換2-ナフトール誘導体は、次に示すような種々の液晶化合物 Chlorine or fluorine-substituted 2-naphthol derivatives are various liquid crystal compounds as shown below
本発明が解決しようとする課題は、塩素原子またはフッ素原子を含有する2-ナフトール誘導体の、フッ素化剤を使用しない簡便で安価な製造方法を提供することにある。 The problem to be solved by the present invention is to provide a simple and inexpensive method for producing a 2-naphthol derivative containing a chlorine atom or a fluorine atom without using a fluorinating agent.
本発明者は上記課題を解決するために鋭意検討した結果、フェニル酢酸ハロゲン化物にルイス酸およびアセチレンを作用させることによって2-ナフトール誘導体が得られることを見出し、本発明を完成するに至った。
すなわち本発明は一般式(1)
As a result of intensive studies to solve the above problems, the present inventor has found that a 2-naphthol derivative can be obtained by reacting a phenylacetic acid halide with a Lewis acid and acetylene, and has completed the present invention.
That is, the present invention relates to the general formula (1)
A1は、トランス-1,4-シクロへキシレン基、1,4-フェニレン基、1,4-シクロヘキセニレン基または1,4-ビシクロ[2.2.2]オクチレン基を表し、これらの基はFまたはClで置換されていてもよく、
A 1 represents a trans-1,4-cyclohexylene group, 1,4-phenylene group, 1,4-cyclohexenylene group or 1,4-bicyclo [2.2.2] octylene group, and these groups are Optionally substituted with F or Cl;
Z1は-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF2CF2-、-CF=CF-、-(CH2)4-、-C≡C-または単結合を表し、A1およびZ1が複数存在する場合は、それらは同一でもよく異なっていてもよく、
aは0、1、2または3を表し、
L1 、L2およびL3はそれぞれ独立的にフッ素原子、塩素原子または水素原子を表し、
X1は塩素原子、フッ素原子または臭素原子を表す。)で表されるフェニル酢酸ハロゲン化物誘導体にルイス酸およびアセチレンを作用させることによる一般式(2)
Z 1 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF 2 CF 2 -, - CF = CF -, - (CH 2) 4 -, - C≡C- or a single bond, if a 1 and Z 1 there are a plurality, they may be different may be the same You can,
a represents 0, 1, 2 or 3,
L 1 , L 2 and L 3 each independently represent a fluorine atom, a chlorine atom or a hydrogen atom,
X 1 represents a chlorine atom, a fluorine atom or a bromine atom. General formula (2) by reacting a Lewis acid and acetylene with a phenylacetic acid halide derivative represented by
本発明により、これまで製造工程が複雑で高価なフッ素化剤を使用する必要があった2-ナフトール誘導体を、フッ素化剤を用いることなく簡便で安価に製造できるようになった。 According to the present invention, it has become possible to produce a 2-naphthol derivative, which has heretofore had a complicated production process and required an expensive fluorinating agent, simply and inexpensively without using a fluorinating agent.
本製造法におけるルイス酸としては塩化アルミニウム(III)、フッ化アルミニウム、臭化アルミニウム、塩化亜鉛、塩化すず(IV)、塩化鉄(III)、塩化チタン(IV)等を用いることができるが、収率等から塩化アルミニウム(III)が特に好ましい。 As the Lewis acid in this production method, aluminum chloride (III), aluminum fluoride, aluminum bromide, zinc chloride, tin chloride (IV), iron chloride (III), titanium chloride (IV), etc. can be used. Aluminum chloride (III) is particularly preferable from the viewpoint of yield.
本製造法は溶媒を用いることが好ましく、その溶媒としてはジクロロメタン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、1,1-ジクロロエタン、1,1,1-トリクロロエタン、1,1,2-トリクロロエタン等の塩素化炭化水素、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、オクタン、デカヒドロナフタレン等の飽和炭化水素、ジエチルエーテル、メチル-t-ブチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、1,4-ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、クロロベンゼン等の芳香族化合物などを単独でまたは混合して用いることができるが、なかでも塩素化炭化水素が好ましく、ジクロロメタンまたは1,2-ジクロロエタンが特に好ましい。 This production method preferably uses a solvent, and as the solvent, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane Chlorinated hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, decahydronaphthalene, etc., diethyl ether, methyl-t-butyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, etc. Ether solvents, aromatic compounds such as benzene, toluene, xylene, chlorobenzene and the like can be used alone or in combination. Among them, chlorinated hydrocarbons are preferable, and dichloromethane or 1,2-dichloroethane is particularly preferable.
反応温度は溶媒の凝固点から溶媒還流温度で行うことができるが、-78℃から60℃が好ましく、-30℃から10℃が特に好ましい。 The reaction temperature can be from the freezing point of the solvent to the solvent reflux temperature, preferably -78 ° C to 60 ° C, particularly preferably -30 ° C to 10 ° C.
一般式(1)で表される化合物は多くの化合物を包含するものであるが、次に記載の化合物が好ましい。
一般式(1)においてR1は、aが0の場合はフッ素原子、塩素原子または水素原子を表すことが好ましいが、それ以外の場合は炭素数1〜12のアルキル基、炭素数2〜12のアルケニル基を表すことが好ましく、炭素数1〜7のアルキル基、炭素数2〜7のアルケニル基がより好ましい。
Although the compound represented by General formula (1) includes many compounds, the following compound is preferable.
In the general formula (1), R 1 preferably represents a fluorine atom, a chlorine atom or a hydrogen atom when a is 0, but in other cases, R 1 represents an alkyl group having 1 to 12 carbon atoms and 2 to 12 carbon atoms The alkenyl group is preferably an alkyl group having 1 to 7 carbon atoms, and more preferably an alkenyl group having 2 to 7 carbon atoms.
A1はトランス-1,4-シクロへキシレン基、1,4-フェニレン基、フッ素置換された1,4-フェニレン基または1,4-ビシクロ[2.2.2]オクチレン基が好ましい。
Z1は-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF2CF2-、-CF=CF-、-C≡C-または単結合を表すことが好ましく、-CH2CH2-、-CH=CH-または単結合がより好ましい。
X1は塩素原子、フッ素原子を表すことが好ましく、塩素原子がより好ましい。
aは0、1または2を表すことが好ましく、0がより好ましい。
A 1 is preferably a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a fluorine-substituted 1,4-phenylene group or a 1,4-bicyclo [2.2.2] octylene group.
Z 1 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- It preferably represents CF 2 CF 2 —, —CF═CF—, —C≡C— or a single bond, more preferably —CH 2 CH 2 —, —CH═CH— or a single bond.
X 1 preferably represents a chlorine atom or a fluorine atom, and more preferably a chlorine atom.
a preferably represents 0, 1 or 2, and more preferably 0.
L1、L2およびL3は、少なくとも一つがフッ素原子を表すことが好ましく、L1またはL2の少なくとも一つがフッ素原子を表すことがさらに好ましく、L1、L2およびL3の二つがフッ素原子を表すことが好ましい。 L 1 , L 2 and L 3 preferably represent at least one fluorine atom, more preferably at least one of L 1 or L 2 represents a fluorine atom, and two of L 1 , L 2 and L 3 represent It preferably represents a fluorine atom.
さらに詳述すると、一般式(1)の化合物の中で、特に好ましい化合物として次に示す化合物を挙げることができる。 More specifically, among the compounds of the general formula (1), the following compounds can be given as particularly preferred compounds.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。化合物の構造は、核磁気共鳴スペクトル(NMR)、質量スペクトル(MS)等により確認した。
(実施例1)5,6,7-トリフルオロ-2-ナフトールの合成
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like.
Example 1 Synthesis of 5,6,7-trifluoro-2-naphthol
MS m/z
198 (M+, 100)
1H-NMR (400 MHz, CDCl3)δ
1.0 5.0 (br, 1 H), 7.07 (s, 1 H), 7.1 7.3 (m, 2 H), 7.94(d, J = 9.0 Hz, 1 H)
(比較例1)5,6,7-トリフルオロ-2-ナフトールの合成
MS m / z
198 (M + , 100)
1 H-NMR (400 MHz, CDCl 3 ) δ
1.0 5.0 (br, 1 H), 7.07 (s, 1 H), 7.1 7.3 (m, 2 H), 7.94 (d, J = 9.0 Hz, 1 H)
Comparative Example 1 Synthesis of 5,6,7-trifluoro-2-naphthol
(1) 1,1-ジフルオロ-6-メトキシ-1H-ナフタレン-2-オンの合成
6-メトキシ-2-ナフトールのアセトニトリル溶液に室温でF-TEDA-BF4(1-クロロメチル-4-フルオロ-1,4-ジアゾニウムビシクロ[2,2,2]オクタンビス(テトラフルオロボレート)、AIR PRODUCTS製)を3回に分けて15分おきに加えた。室温で5時間撹拌した後、反応混合物を氷水に加え、10%水酸化ナトリウム水溶液で中和しトルエンで抽出した。有機層を水洗した後、溶媒を減圧留去して得られた粗生成物をカラムクロマトグラフィーにて精製し、1,1-ジフルオロ-6-メトキシ-1H-ナフタレン-2-オンを得た。
(2) 6-メトキシ-1,1,2,2-テトラフルオロ-1,2-ジヒドロナフタレンの合成
1,1-ジフルオロ-6-メトキシ-1H-ナフタレン-2-オンのTHF(テトラヒドロフラン)溶液にDAST(ジエチルアミノ三フッ化ほう素)を加え、50℃で2時間撹拌した。反応混合物を氷水に加え、10%炭酸水素ナトリウム水溶液で中和しヘキサンで抽出した。有機層を水洗した後、溶媒を減圧留去して得られた粗生成物をカラムクロマトグラフィーにて精製し、6-メトキシ-1,1,2,2-テトラフルオロ-1,2-ジヒドロナフタレンを得た。
(3) 6-メトキシ-1,1,2,2-テトラフルオロ-1,2,3,4-テトラヒドロナフタレンの合成
6-メトキシ-1,1,2,2-テトラフルオロ-1,2-ジヒドロナフタレンの酢酸エチル溶液をオートクレーブに加え、5%パラジウム炭素(50%含水品)、トリエチルアミン、シリカゲルを加え水素圧0.4 MPaで3時間撹拌した。反応混合物をセライトろ過し、ろ液から溶媒を減圧留去して得られた粗生成物をカラムクロマトグラフィーにて精製し、6-メトキシ-1,1,2,2-テトラフルオロ-1,2,3,4-テトラヒドロナフタレンを得た。
(4) 1,2-ジフルオロ-6-メトキシナフタレンの合成
6-メトキシ-1,1,2,2-テトラフルオロ-1,2,3,4-テトラヒドロナフタレンのTHF溶液に氷冷下、カリウム-t-ブトキシドを加えた後昇温し、室温で2時間撹拌した。反応混合物を氷水に加え、10%炭酸水素ナトリウム水溶液で中和しヘキサンで抽出した。有機層を水洗した後、溶媒を留去して得られた粗生成物をカラムクロマトグラフィーにて精製し、1,2-ジフルオロ-6-メトキシナフタレンを得た。
(5) 6-メトキシ-1,2,3-トリフルオロナフタレンの合成
1,2-ジフルオロ-6-メトキシナフタレンをTHF/トルエン混合溶媒に溶解し、-40℃に冷却してブチルリチウム(1.5 Mヘキサン溶液)をゆっくり滴下した。-40度で1時間撹拌後ACCUFLOR NFSi(N-フルオロベンゼンスルフィンイミド、AlliedSignal製)を加えた後、室温まで徐々に昇温し室温で8時間撹拌した。反応混合物を氷水に加え、ヘキサン抽出した。有機層を水洗した後、溶媒を留去して得られた粗生成物をカラムクロマトグラフィーにて精製し、6-メトキシ-1,2,3-トリフルオロナフタレンを得た。
(6) 5,6,7-トリフルオロ-2-ナフトールの合成
6-メトキシ-1,2,3-トリフルオロナフタレンのジクロロメタン溶液を-70℃に冷却し、三臭化ほう素のジクロロメタン溶液をゆっくり加えた。室温まで昇温後10時間撹拌し、反応混合物を水に加えた。有機層を分取し、水、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥後溶媒を減圧留去した。得られた固体をカラムクロマトグラフィーで精製し、5,6,7-トリフルオロ-2-ナフトールを得た。
(1) Synthesis of 1,1-difluoro-6-methoxy-1H-naphthalen-2-one
F-TEDA-BF 4 (1-chloromethyl-4-fluoro-1,4-diazonium bicyclo [2,2,2] octanebis (tetrafluoroborate), AIR at room temperature in 6-methoxy-2-naphthol in acetonitrile PRODUCTS) was added in 3 portions every 15 minutes. After stirring at room temperature for 5 hours, the reaction mixture was added to ice water, neutralized with 10% aqueous sodium hydroxide solution, and extracted with toluene. After washing the organic layer with water, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography to obtain 1,1-difluoro-6-methoxy-1H-naphthalen-2-one.
(2) Synthesis of 6-methoxy-1,1,2,2-tetrafluoro-1,2-dihydronaphthalene
DAST (diethylamino boron trifluoride) was added to a THF (tetrahydrofuran) solution of 1,1-difluoro-6-methoxy-1H-naphthalen-2-one and stirred at 50 ° C. for 2 hours. The reaction mixture was added to ice water, neutralized with 10% aqueous sodium hydrogen carbonate solution, and extracted with hexane. After washing the organic layer with water, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography to obtain 6-methoxy-1,1,2,2-tetrafluoro-1,2-dihydronaphthalene. Got.
(3) Synthesis of 6-methoxy-1,1,2,2-tetrafluoro-1,2,3,4-tetrahydronaphthalene
Add 6-methoxy-1,1,2,2-tetrafluoro-1,2-dihydronaphthalene in ethyl acetate to the autoclave, add 5% palladium on carbon (50% water), triethylamine, and silica gel, and add hydrogen pressure 0.4 MPa. For 3 hours. The reaction mixture was filtered through Celite, and the crude product obtained by distilling off the solvent from the filtrate under reduced pressure was purified by column chromatography to give 6-methoxy-1,1,2,2-tetrafluoro-1,2 1,3,4-tetrahydronaphthalene was obtained.
(4) Synthesis of 1,2-difluoro-6-methoxynaphthalene
To the THF solution of 6-methoxy-1,1,2,2-tetrafluoro-1,2,3,4-tetrahydronaphthalene was added ice-cooled potassium-t-butoxide, and the temperature was raised. Stir. The reaction mixture was added to ice water, neutralized with 10% aqueous sodium hydrogen carbonate solution, and extracted with hexane. After the organic layer was washed with water, the crude product obtained by distilling off the solvent was purified by column chromatography to obtain 1,2-difluoro-6-methoxynaphthalene.
(5) Synthesis of 6-methoxy-1,2,3-trifluoronaphthalene
1,2-Difluoro-6-methoxynaphthalene was dissolved in a THF / toluene mixed solvent, cooled to −40 ° C., and butyl lithium (1.5 M hexane solution) was slowly added dropwise. After stirring at −40 ° C. for 1 hour, ACCUFLOR NFSi (N-fluorobenzenesulfinimide, manufactured by AlliedSignal) was added, and the mixture was gradually warmed to room temperature and stirred at room temperature for 8 hours. The reaction mixture was added to ice water and extracted with hexane. After washing the organic layer with water, the solvent was distilled off and the resulting crude product was purified by column chromatography to obtain 6-methoxy-1,2,3-trifluoronaphthalene.
(6) Synthesis of 5,6,7-trifluoro-2-naphthol
The dichloromethane solution of 6-methoxy-1,2,3-trifluoronaphthalene was cooled to -70 ° C, and boron tribromide in dichloromethane was slowly added. After warming to room temperature, the mixture was stirred for 10 hours, and the reaction mixture was added to water. The organic layer was separated, washed with water and saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained solid was purified by column chromatography to obtain 5,6,7-trifluoro-2-naphthol.
この製造方法では、5,6,7-トリフルオロ-2-ナフトールの収率は全6工程で、出発物質の6-メトキシ-2-ナフトールから9%であった。 In this production method, the yield of 5,6,7-trifluoro-2-naphthol was 9% from the starting 6-methoxy-2-naphthol in all 6 steps.
比較例1記載の製造方法は工程数が6工程と長く、その全収率は9%と低い。その上F-TEDA-BF4やACCUFLOR NFSiといった高価格のフッ素化剤を使用しなければならない問題を有している。それに対し実施例1記載の製造方法は、1工程で2-ナフトール誘導体を合成でき、また使用する反応剤も安価である。 In the production method described in Comparative Example 1, the number of steps is as long as 6, and the overall yield is as low as 9%. In addition, there is a problem that expensive fluorinating agents such as F-TEDA-BF 4 and ACCUFLOR NFSi must be used. In contrast, the production method described in Example 1 can synthesize a 2-naphthol derivative in one step, and the reactants used are inexpensive.
(実施例2)7,8-ジフルオロ-2-ナフトールの合成
3,4,5-トリフルオロフェニル酢酸塩化物に替えて2,3-ジフルオロフェニル酢酸塩化物を用いている以外は、実施例1と同様な条件下、7,8-ジフルオロ-2-ナフトールを得た。
Example 2 Synthesis of 7,8-difluoro-2-naphthol
Under the same conditions as in Example 1, except that 2,3-difluorophenylacetic acid chloride was used instead of 3,4,5-trifluorophenylacetic acid chloride, 7,8-difluoro-2-naphthol was used. Obtained.
本発明は、液晶化合物の中間体製造法として非常に有用である。
The present invention is very useful as a method for producing an intermediate of a liquid crystal compound.
Claims (4)
aは0を表し、
L1 、L2およびL3はそれぞれ独立的にフッ素原子、塩素原子または水素原子を表すが、L1、L2およびL3は少なくとも一つがフッ素原子を表し、
X1は塩素原子、フッ素原子または臭素原子を表す。)で表されるフェニル酢酸ハロゲン化物誘導体にルイス酸およびアセチレンを作用させることによる一般式(2)
a represents 0,
L 1 , L 2 and L 3 each independently represent a fluorine atom, a chlorine atom or a hydrogen atom, but L 1 , L 2 and L 3 each represents at least one fluorine atom,
X 1 represents a chlorine atom, a fluorine atom or a bromine atom. General formula (2) by reacting a Lewis acid and acetylene with a phenylacetic acid halide derivative represented by
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