JPH0434535B2 - - Google Patents
Info
- Publication number
- JPH0434535B2 JPH0434535B2 JP59035671A JP3567184A JPH0434535B2 JP H0434535 B2 JPH0434535 B2 JP H0434535B2 JP 59035671 A JP59035671 A JP 59035671A JP 3567184 A JP3567184 A JP 3567184A JP H0434535 B2 JPH0434535 B2 JP H0434535B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- diphenylethylamine
- asymmetric
- phenols
- 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.)
- Expired - Lifetime
Links
- 150000002989 phenols Chemical class 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 5
- 230000000447 dimerizing effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 14
- DTGGNTMERRTPLR-UHFFFAOYSA-N 1,2-diphenylethanamine Chemical compound C=1C=CC=CC=1C(N)CC1=CC=CC=C1 DTGGNTMERRTPLR-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000011914 asymmetric synthesis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- DZKIUEHLEXLYKM-UHFFFAOYSA-N 9-phenanthrol Chemical compound C1=CC=C2C(O)=CC3=CC=CC=C3C2=C1 DZKIUEHLEXLYKM-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LYXQKPRYDFQZPL-UHFFFAOYSA-N 1-(2-hydroxyphenanthren-1-yl)phenanthren-2-ol Chemical group C1=CC2=CC=CC=C2C2=C1C(C1=C3C(C4=CC=CC=C4C=C3)=CC=C1O)=C(O)C=C2 LYXQKPRYDFQZPL-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KWTSXDURSIMDCE-UHFFFAOYSA-N 1-phenylpropan-2-amine Chemical compound CC(N)CC1=CC=CC=C1 KWTSXDURSIMDCE-UHFFFAOYSA-N 0.000 description 1
- RXMTUVIKZRXSSM-UHFFFAOYSA-N 2,2-diphenylethanamine Chemical compound C=1C=CC=CC=1C(CN)C1=CC=CC=C1 RXMTUVIKZRXSSM-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- DUCXKDDVZDDQIO-UHFFFAOYSA-N 3,3'-Dimethyl-1,1'-binaphthalene-2,2'-diol Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=C(C=3O)C)=C(O)C(C)=CC2=C1 DUCXKDDVZDDQIO-UHFFFAOYSA-N 0.000 description 1
- MYRXDLASSYFCAC-UHFFFAOYSA-N 3-methylnaphthalen-2-ol Chemical compound C1=CC=C2C=C(O)C(C)=CC2=C1 MYRXDLASSYFCAC-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004081 narcotic agent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は光学活性ジオールの製法に係る。更に
詳しくは新規な触媒を用いてフエノール類を二量
化させる光学活性ジオールの製法に係る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing optically active diols. More specifically, the present invention relates to a method for producing optically active diols by dimerizing phenols using a novel catalyst.
（産業上の利用分野）
２，2′−ジヒドロキシ−１，1′−ビナフチル及
びその誘導体の光学活性体は種々の不斉合成反応
や光学分割の不斉源として広く使われている。例
えば不斉還元反応，クラウンエーテルとしての不
斉識別反応，不斉接触水添反応，不斉重合開始剤
などにおいて優れた不斉誘導能力を示すことが知
られている。また２，2′−ジヒドロキシ−１，
1′−ビフエナンスリル及びその誘導体の光学活性
体についてもさらに優れた不斉誘導能力が確めら
れており、これらの簡便な合成法の開発が強く望
まれていた。(Industrial Application Field) Optically active forms of 2,2'-dihydroxy-1,1'-binaphthyl and its derivatives are widely used as chiral sources in various asymmetric synthesis reactions and optical resolutions. For example, it is known to exhibit excellent asymmetric induction ability in asymmetric reduction reactions, asymmetric recognition reactions as crown ethers, asymmetric catalytic hydrogenation reactions, asymmetric polymerization initiators, etc. Also, 2,2'-dihydroxy-1,
Optically active forms of 1'-biphenanthryl and its derivatives have also been confirmed to have superior asymmetric induction ability, and there has been a strong desire to develop a simple synthetic method for these.
（従来技術）
従来これらの光学活性化合物の合成方法は、ラ
セミ体を合成したのち光学分割により光学活性体
を得る方法及び不斉合成反応によりそれぞれの光
学活性体を別々に得る方法に分類される。ラセミ
体の２，2′−ジヒドロキシ−１，1′−ビナフチル
は次の式(1)に示すようにChem.Ber.，59，2159
（1926）に記載されている塩化第２鉄の存在下２
−ナフトールを二量化させることにより得られ
る。(Prior art) Conventionally, methods for synthesizing these optically active compounds are classified into methods of synthesizing a racemate and then obtaining an optically active form by optical resolution, and methods of obtaining each optically active form separately by an asymmetric synthesis reaction. . Racemic 2,2'-dihydroxy-1,1'-binaphthyl is shown in the following formula (1), Chem.Ber., 59 , 2159
(1926) in the presence of ferric chloride.
- Obtained by dimerizing naphthol.
またRec.Trav.Chim.Pays Bas、74，937
（1955）に記載されている如く、銅−アミン錯体
を用いて二量化させる方法により得られる。得ら
れたラセミ体はTetrahedron Lett.，4617（1971）
に記載されているようにリン酸エステルとし、シ
リコニン塩とすることによりジアステレオマ−塩
を分別する方法が知られている。また不斉合成に
より光学活性体を得る方法としては、１−フエニ
ル−２−アミノプロパンの如き光学活性アミンを
用いてフエノール類を酸化的に二量化させる方法
（Bioorg.Chem.，７，397（1978）及び
Tetrahedron Lett.，24，3261（1983））がある。
また光学活性なオキサゾリンを用いてナフチル基
をグリニヤール反応でビナフチル化する方法（J.
Am.Chem.Soc.，104，879（1982））及び光学活性
なナフチルエーテルとナフチルリチウムのカツプ
リング反応による方法（J.Am.Chem.Soc.，104，
881（1982））が知られている。しかし、これらの
反応は不斉収率が低かつたり、用いる光学活性ア
ミンが麻薬取締法上使用が規制されていたり、有
機金属試薬を用いるため無水の反応条件を必要と
するなど工業的に有利な方法とはいえず、これら
の問題を避けうる簡便な方法の開発が強く望まれ
ていた。 Also Rec.Trav.Chim.Pays Bas, 74,937
(1955), it can be obtained by dimerization using a copper-amine complex. The resulting racemate was published in Tetrahedron Lett., 4617 (1971).
As described in , a method is known in which diastereomeric salts are separated by converting them into phosphoric acid esters and siliconine salts. In addition, as a method for obtaining optically active substances by asymmetric synthesis, a method in which phenols are oxidatively dimerized using an optically active amine such as 1-phenyl-2-aminopropane (Bioorg.Chem., 7 , 397) 1978) and
Tetrahedron Lett., 24 , 3261 (1983)).
In addition, a method of binaphthylation of naphthyl groups by Grignard reaction using optically active oxazoline (J.
Am.Chem.Soc., 104 , 879 (1982)) and a coupling reaction method of optically active naphthyl ether and naphthyllithium (J.Am.Chem.Soc., 104 ,
881 (1982)) is known. However, these reactions have low asymmetric yields, the use of the optically active amines used is restricted under the Narcotics Control Law, and the use of organometallic reagents requires anhydrous reaction conditions, making them industrially disadvantageous. However, there has been a strong desire to develop a simple method that can avoid these problems.
（発明の目的）
本発明は従来の方法において先に記した問題を
克服し得るばかりか、不斉収率の低さを著しく改
善することにより精製の必要をなくすことの出来
る優れた合成方法を提供することを目的とする。(Objective of the Invention) The present invention provides an excellent synthetic method that not only overcomes the problems described above in conventional methods, but also eliminates the need for purification by significantly improving the low asymmetric yield. The purpose is to provide.
本発明は次の式(2)に示すように容易に入手可能
な光学活性アミンである１，２−ジフエニルエチ
ルアミンの一方の鏡像体を用いて錯体とし、これ
とフエノール類を反応させることによりその二量
体を光学純度良く高収率で得ることを可能にす
る。 As shown in the following formula (2), the present invention uses one enantiomer of 1,2-diphenylethylamine, which is an optically active amine that is easily available, to form a complex and reacts the complex with phenols. This makes it possible to obtain the dimer with good optical purity and high yield.
（式中、R1，R2，R3，R4は水素，アルキル基，
アルコキシ基，ハロゲン原子又はアルケニル基で
あり、更に隣合つた任意の２つが芳香環をなして
いてもよい。）
（発明の構成）
本発明は、光学活性１，２−ジフエニルエチル
アミンの錯体の存在下、フエノール類を二量化す
ることを特徴とする光学活性ジオールの製法であ
る。適当な錯体としては銅錯体などがある。 (In the formula, R 1 , R 2 , R 3 , R 4 are hydrogen, alkyl groups,
It is an alkoxy group, a halogen atom, or an alkenyl group, and any two adjacent groups may form an aromatic ring. ) (Structure of the Invention) The present invention is a method for producing an optically active diol, which is characterized by dimerizing phenols in the presence of an optically active 1,2-diphenylethylamine complex. Suitable complexes include copper complexes.
本発明に用いる光学活性１，２−ジフエニルエ
チルアミンはその何れの鏡像体も容易に入手する
ことが可能であり、例えば市販のラセミ体１，２
−ジフエニルエチルアミンを光学活性酒石酸との
ジアステレオマー塩として分別する方法により容
易に得られる。 Optically active 1,2-diphenylethylamine used in the present invention can be easily obtained in any of its enantiomers, for example, commercially available racemic 1,2-diphenylethylamine.
- It can be easily obtained by a method of fractionating diphenylethylamine as a diastereomeric salt with optically active tartaric acid.
本発明の方法に用いられるフエノール類として
は９−ヒドロキシフエナンスレン，２−ヒドロキ
シナフタレン及びこれらの誘導体が例示される。
かかる誘導体としてはアルキル基，アルコキシ
基，ハロゲン原子，アルケニル基など本発明の反
応に際し不活性な基が１〜８個ついているものが
あげられる。 Examples of the phenols used in the method of the present invention include 9-hydroxyphenanthrene, 2-hydroxynaphthalene, and derivatives thereof.
Examples of such derivatives include those having 1 to 8 groups that are inactive during the reaction of the present invention, such as alkyl groups, alkoxy groups, halogen atoms, and alkenyl groups.
本発明は、光学活性１，２−ジフエニルエチル
アミンを不斉源とし、その錯体、特に銅錯体を用
いて上記フエノール類を二量化させることを特徴
とする。もちろんラセミ体の１，２−ジフエニル
エチルアミンを用いた場合は高収率でラセミジオ
ールが得られる。 The present invention is characterized in that optically active 1,2-diphenylethylamine is used as an asymmetric source, and the above-mentioned phenols are dimerized using a complex thereof, particularly a copper complex. Of course, when racemic 1,2-diphenylethylamine is used, racemic diol can be obtained in high yield.
（反応方法）
本発明の方法に於ては１，２−ジフエニルエチ
ルアミンの何れかの鏡像体を溶媒に溶解し、窒素
気流下、硝酸銅の溶液を加え室温で１時間撹拌し
た後冷却し、これに反応させるフエノール類を加
える。この反応に用いる溶媒は反応を妨げない範
囲で任意に選ぶことができるが、溶解度等の条件
を考慮するとメタノール，エタノール等のアルコ
ール類が適している。反応温度はアミン−銅錯体
にフエノール類を加える際に一般の不斉合成と同
じように低温に保つほうが光学収率を高める上で
好ましいが、光学収率を低下させない範囲で−80
℃〜100℃の如き広い温度範囲から反応温度を選
んでもよい。アミン−銅錯体とフエノール類の当
量比は、アミン−銅錯体を過剰に用いるほうが収
率を高める上から必要であり、通常1.0〜10倍モ
ル使用することが好ましい。(Reaction method) In the method of the present invention, any enantiomer of 1,2-diphenylethylamine is dissolved in a solvent, a solution of copper nitrate is added under a nitrogen stream, the mixture is stirred at room temperature for 1 hour, and then cooled. , and add the phenols to be reacted. The solvent used in this reaction can be arbitrarily selected as long as it does not interfere with the reaction, but alcohols such as methanol and ethanol are suitable in consideration of conditions such as solubility. When adding phenols to the amine-copper complex, it is preferable to keep the reaction temperature at a low temperature in order to increase the optical yield, as in general asymmetric synthesis.
The reaction temperature may be selected from a wide temperature range such as from 100°C to 100°C. Regarding the equivalent ratio of the amine-copper complex to the phenols, it is necessary to use an excess of the amine-copper complex in order to increase the yield, and it is usually preferable to use 1.0 to 10 times the mole.
（発明の作用・効果）
本発明において特徴部分をなす不斉源の光学活
性１，２−ジフエニルエチルアミンは容易に入手
しうるものであり、これの銅錯体を合成する方法
も極めて簡単である。またこれを用いるフエノー
ル類の二量化反応も単に撹拌するだけで短時間で
完結し、光学収率，光学収率とも極めて高いた
め、精製工程を省くことができ、工業的にも有利
である。また使用した光学活性１，２−ジフエニ
ルエチルアミンは塩酸塩としてほぼ定量的に回収
することができ、水酸化アンモニウムを作用させ
ることにより再生再使用を繰り返すことが可能で
ある。(Operations and Effects of the Invention) Optically active 1,2-diphenylethylamine, which is an asymmetric source that is a characteristic part of the present invention, is easily available, and the method for synthesizing a copper complex thereof is also extremely simple. . In addition, the dimerization reaction of phenols using this can be completed in a short time simply by stirring, and both the optical yield and the optical yield are extremely high, so a purification step can be omitted and it is industrially advantageous. Further, the optically active 1,2-diphenylethylamine used can be recovered almost quantitatively as a hydrochloride, and can be repeatedly recycled and reused by acting with ammonium hydroxide.
以下具体例により本発明を説明する。 The present invention will be explained below using specific examples.
実施例 １
（−）−１，２−ジフエニルエチルアミンの
（＋）−酒石酸塩｛〔α〕19 D−55゜（H2O）｝15ｇ（2.
75
×10-2モル）に水350mlと濃アンモニア水30mlを
加え十分撹拌した後、エーテル200mlで抽出し水
洗する。水酸化カリウムで乾燥後、エーテルを留
去すると（−）−１，２−ジフエニルエチルアミ
ン｛〔α〕19 D−51゜（エタノール）｝が得られる。こ
れをメタノール30mlにとかし、窒素気流下、硝酸
銅・３水和物2.4ｇのメタノール30ml溶液を一度
に加え、室温で１時間撹拌した後、内温を−５℃
〜−７℃に保ちつつ、９−ヒドロキシフエナンス
レン１ｇ（5.15×10−３モル）のメタノール10ml
溶液を加え、−５℃で１時間撹拌する。次いで2N
塩酸300mlを加え、塩化メチレン200mlで抽出し水
洗後硫酸マグネシウムで乾燥する。乾燥剤を除き
塩化メチレンを留去すると粗（Ｓ）−（−）−２，
2′−ジヒドロキシ−１，1′−ビフエナンスリルを
得る。これを少量のベンゼンに溶解し、30ｇのシ
リカゲルを用いてカラムクロマトをベンゼンを展
開剤として行ない精製すると85％の収率で（Ｓ）
−（−）体が光学純度98％で得られる。このもの
の比旋光度は［α］23 D−69.5゜（クロロホルム）、融
点は165〜166℃である。元素分析値は次の通りで
あつた。Example 1 (+)-tartrate of (-)-1,2-diphenylethylamine {[α] 19 D −55° (H 2 O)} 15 g (2.
75
x 10 -2 mol), add 350 ml of water and 30 ml of concentrated ammonia water, stir thoroughly, then extract with 200 ml of ether and wash with water. After drying with potassium hydroxide, the ether is distilled off to obtain (-)-1,2-diphenylethylamine {[α] 19 D -51° (ethanol)}. Dissolve this in 30 ml of methanol, add a solution of 2.4 g of copper nitrate trihydrate in 30 ml of methanol at once under a nitrogen stream, stir at room temperature for 1 hour, and then lower the internal temperature to -5°C.
1 g (5.15 x 10-3 mol) of 9-hydroxyphenanthrene in 10 ml of methanol while keeping the temperature at ~-7°C.
Add the solution and stir at -5°C for 1 hour. Then 2N
Add 300 ml of hydrochloric acid, extract with 200 ml of methylene chloride, wash with water, and dry over magnesium sulfate. When the drying agent is removed and methylene chloride is distilled off, crude (S)-(-)-2,
2'-dihydroxy-1,1'-biphenanthryl is obtained. When this was dissolved in a small amount of benzene and purified by column chromatography using 30 g of silica gel with benzene as the developing agent, the yield of (S) was 85%.
-(-) form is obtained with optical purity of 98%. The specific optical rotation of this product is [α] 23 D −69.5° (chloroform), and the melting point is 165-166°C. The elemental analysis values were as follows.
C8H18O2
理論値 Ｃ 87.25％ Ｈ 4.93％
分析値 Ｃ 87.02％ Ｈ 4.89％
実施例 ２
実施例１と同様にして（＋）−１，２−ジフエ
ニルエチルアミンを用いて合成を行なつたとこ
ろ、（Ｒ）−（＋）−２，2′−ジヒドロキシ−１，
1′−ビフエナンスリルが光学純度98％で得られ
た。C 8 H 18 O 2 Theoretical value C 87.25% H 4.93% Analytical value C 87.02% H 4.89% Example 2 Synthesis was carried out in the same manner as in Example 1 using (+)-1,2-diphenylethylamine. However, (R)-(+)-2,2'-dihydroxy-1,
1'-Biphenanthryl was obtained with an optical purity of 98%.
比較例 １
代表的な光学活性アミンである光学活性フエニ
ルエチルアミンを用いて実施例１と同様の反応を
行なつたところ、収率よく２，2′−ジヒドロキシ
−１，1′−ビフエナンスリルが得られたが、光学
収率は極めて低かつた。Comparative Example 1 When the same reaction as in Example 1 was carried out using optically active phenylethylamine, which is a typical optically active amine, 2,2'-dihydroxy-1,1'-biphenanthryl was obtained in good yield. However, the optical yield was extremely low.
実施例 ３
実施例１と同様にして３−メチル−２−ナフト
ールを反応させたところ、次式に従つて（−）−
３，3′−ジメチル−２，2′−ジヒドロキシ−ビナ
フチルが収率85％，光学収率70％で得られた。Example 3 When 3-methyl-2-naphthol was reacted in the same manner as in Example 1, (-)-
3,3'-dimethyl-2,2'-dihydroxy-binaphthyl was obtained in a yield of 85% and an optical yield of 70%.
Claims (1)
エチルアミン錯体を用いて二量化させることを特
徴とする光学活性ジオールの製法。1. A method for producing optically active diols, which comprises dimerizing phenols using an optically active 1,2'-diphenylethylamine complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59035671A JPS60181044A (en) | 1984-02-27 | 1984-02-27 | Preparation of optically active diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59035671A JPS60181044A (en) | 1984-02-27 | 1984-02-27 | Preparation of optically active diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60181044A JPS60181044A (en) | 1985-09-14 |
| JPH0434535B2 true JPH0434535B2 (en) | 1992-06-08 |
Family
ID=12448336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59035671A Granted JPS60181044A (en) | 1984-02-27 | 1984-02-27 | Preparation of optically active diol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60181044A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029227C (en) * | 1989-02-08 | 1995-07-05 | 大制药株式会社 | Composition for denatured denaturation or protection agent for nerve cell and process for preparing benzene derivatives used for composition |
| JP2872800B2 (en) * | 1990-10-29 | 1999-03-24 | ダイセル化学工業株式会社 | Optically active biphenyl derivative and optical resolution method |
-
1984
- 1984-02-27 JP JP59035671A patent/JPS60181044A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60181044A (en) | 1985-09-14 |
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