JPH06145086A - Binaphthol derivative and its production - Google Patents
Binaphthol derivative and its productionInfo
- Publication number
- JPH06145086A JPH06145086A JP4296949A JP29694992A JPH06145086A JP H06145086 A JPH06145086 A JP H06145086A JP 4296949 A JP4296949 A JP 4296949A JP 29694992 A JP29694992 A JP 29694992A JP H06145086 A JPH06145086 A JP H06145086A
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- binaphthol derivative
- methyl
- formula
- binaphthol
- 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
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なビナフトール誘
導体に関するものである。FIELD OF THE INVENTION The present invention relates to a novel binaphthol derivative.
【０００２】[0002]
【従来の技術】従来、不斉合成反応の分野においてビナ
フトールを原料として数多くの工業的にも有用な不斉合
成触媒が開発されている。しかしながら、これらのほと
んどは入手容易な1,1'−ビ−２−ナフトールを原料とし
たものである。2. Description of the Related Art Hitherto, many industrially useful asymmetric synthesis catalysts have been developed using binaphthol as a raw material in the field of asymmetric synthesis reactions. However, most of these are made from readily available 1,1′-bi-2-naphthol.
【０００３】一方、ビナフトールのナフチル環上に置換
基を有するビナフトール誘導体としては、例えば、J. O
rg. Chem., 46, 4988(1981) に記載の6,6',7,7' −テト
ラメチル−1,1'−ビ−２−ナフトール、7,7'−ジアルコ
キシ−1,1'−ビ−２−ナフトール、6,6'−ジブロモ−1,
1'−ビ−２−ナフトール、5,5'−ジブロモ−6,6',7,7'
−テトラメチル−1,1'−ビ−２−ナフトールあるいはJ.
Chem. Soc., Chem. Commun., 1065(1985)に記載の4,4'
−ビ−３−フェナンスロール等が知られている。On the other hand, examples of the binaphthol derivative having a substituent on the naphthyl ring of binaphthol include, for example, J. O.
6,6 ', 7,7'-Tetramethyl-1,1'-bi-2-naphthol, 7,7'-dialkoxy-1,1' described in rg. Chem., 46, 4988 (1981). -Bi-2-naphthol, 6,6'-dibromo-1,
1'-bi-2-naphthol, 5,5'-dibromo-6,6 ', 7,7'
-Tetramethyl-1,1'-bi-2-naphthol or J.
4,4 'described in Chem. Soc., Chem. Commun., 1065 (1985).
-Bi-3-phenanthrol and the like are known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
様に今までに開発されてきたビナフトール誘導体は、ま
だ数も少なく、より有用な不斉合成触媒の開発の観点か
ら、その原料となる新たなビナフトール誘導体の開発が
望まれているのが現状である。However, as described above, the binaphthol derivatives that have been developed up to now are still few in number, and from the viewpoint of the development of more useful asymmetric synthesis catalysts, new raw materials for them are used. At present, the development of binaphthol derivatives is desired.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、式
（Ｉ） で示されるビナフトール誘導体およびその製造法、さら
には式（ＩＩ） または式（ＩＩＩ） で示される光学活性なビナフトール誘導体およびその製
造法を提供するものである。That is, the present invention provides a compound of formula (I) And a method for producing the same, and further the formula (II) Or formula (III) The present invention provides an optically active binaphthol derivative represented by and a method for producing the same.
【０００６】本発明の前記式（Ｉ）で示されるビナフト
ール誘導体は、７−メチル−２−ナフトールを２価銅塩
およびアミン類の存在下に酸化的にカップリングするこ
とにより製造することができる。The binaphthol derivative represented by the above formula (I) of the present invention can be produced by oxidatively coupling 7-methyl-2-naphthol in the presence of a divalent copper salt and amines. .
【０００７】本発明で原料として用いられる７−メチル
−２−ナフトールは、例えば、J. Am. Chem. Soc., 94,
263(1972)に記載の方法に準じて２−メチルナフタレン
より容易に製造することができる。The 7-methyl-2-naphthol used as a raw material in the present invention is, for example, J. Am. Chem. Soc., 94,
It can be easily produced from 2-methylnaphthalene according to the method described in 263 (1972).
【０００８】２価銅塩として具体的には、硝酸銅（Ｉ
Ｉ）、硫酸銅（ＩＩ）、塩化銅（ＩＩ）、臭化銅（Ｉ
Ｉ）等があげられるが、これらの中でも硝酸銅（ＩＩ）
が特に好ましく用いられる。これらの２価銅塩の使用量
は、原料の７−メチル−２−ナフトールに対して１当量
以上、上限については特に制限されないが、通常、１〜
５当量の範囲で使用される。Specifically as the divalent copper salt, copper nitrate (I
I), copper (II) sulfate, copper (II) chloride, copper bromide (I
I) and the like. Among these, copper (II) nitrate
Are particularly preferably used. The amount of these divalent copper salts used is 1 equivalent or more with respect to 7-methyl-2-naphthol as a raw material, and the upper limit is not particularly limited, but usually 1 to
Used in the range of 5 equivalents.
【０００９】アミン類として具体的には、α−フェネチ
ルアミン、１，２−ジフェニルエチルアミン、１−フェ
ニル−２−ｐ−トリルエチルアミン等のフェネチルアミ
ン類があげられる。これらのアミン類の使用量は、原料
の７−メチル−２−ナフトールに対して１当量以上、上
限については特に制限されないが、通常、１〜２０当量
の範囲で使用される。Specific examples of amines include phenethylamines such as α-phenethylamine, 1,2-diphenylethylamine and 1-phenyl-2-p-tolylethylamine. The amount of these amines used is 1 equivalent or more with respect to 7-methyl-2-naphthol as a raw material, and the upper limit is not particularly limited, but it is usually used in the range of 1 to 20 equivalents.
【００１０】反応は、通常、有機溶媒中で行われ、用い
る溶媒としては、反応に影響を与えない溶媒であれば特
に制限されないが、通常、メタノール、エタノール、２
−プロパノール等のアルコール類が好ましく使用され
る。これらの溶媒の使用量は、特に制限されない。The reaction is usually carried out in an organic solvent, and the solvent used is not particularly limited as long as it does not affect the reaction, but usually methanol, ethanol, 2
-Alcohols such as propanol are preferably used. The amount of these solvents used is not particularly limited.
【００１１】反応温度は、低すぎると反応に長時間を要
し、また、高すぎると副反応により目的物の収率が低下
するので、通常、−５０〜１００℃、好ましくは−２０
〜８０℃の範囲である。If the reaction temperature is too low, the reaction will take a long time, and if it is too high, the yield of the desired product will decrease due to side reactions. Therefore, the reaction temperature is usually -50 to 100 ° C., preferably -20.
It is in the range of -80 ° C.
【００１２】反応時間は、反応温度および用いるアミン
類の種類により影響を受けるが、特には制限されず、原
料の７−メチル−２−ナフトールの消失をもって反応終
了とすればよい。The reaction time is affected by the reaction temperature and the type of amines used, but is not particularly limited, and the reaction may be terminated when the starting material, 7-methyl-2-naphthol, disappears.
【００１３】反応終了後、通常の後処理操作、例えば、
抽出、分液、濃縮等の操作を行うことにより、目的の前
記式（Ｉ）で示されるビナフトール誘導体を得ることが
できる。このものは、必要に応じ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, a usual post-treatment operation, for example,
The desired binaphthol derivative represented by the above formula (I) can be obtained by performing operations such as extraction, liquid separation, and concentration. This product can be purified by column chromatography, recrystallization, etc., if necessary.
【００１４】また、前記式（ＩＩ）または式（ＩＩＩ）
で示される光学活性なビナフトール誘導体は、上で得た
前記式（Ｉ）で示されるビナフトール誘導体を光学活性
カラムを用いた高速液体クロマトグラフィーにより、そ
れぞれの光学異性体に分離することにより容易に得るこ
とができる。The above formula (II) or formula (III)
The optically active binaphthol derivative represented by is easily obtained by separating the above-obtained binaphthol derivative represented by the formula (I) into respective optical isomers by high performance liquid chromatography using an optically active column. be able to.
【００１５】[0015]
【発明の効果】本発明により、ナフチル環上に置換基を
有する新規なビナフトール誘導体が容易に得ることがで
きる。また、本発明のビナフトール誘導体および光学活
性なビナフトール誘導体は、新規な不斉合成触媒の原料
として有用である。Industrial Applicability According to the present invention, a novel binaphthol derivative having a substituent on the naphthyl ring can be easily obtained. Further, the binaphthol derivative and the optically active binaphthol derivative of the present invention are useful as a raw material for a novel asymmetric synthesis catalyst.
【００１６】[0016]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。 実施例１ 撹拌装置、温度計、滴下ロートおよびコンデンサーを装
着した４つ口フラスコに室温で硝酸銅（ＩＩ）三水和物
４８．３ｇ（０．２モル）およびメタノール５００ｍｌ
を仕込み、この混合物に１，２−ジフェニルエチルアミ
ン１１８．４ｇ（０．６モル）を加えた。均一溶液にな
ったことを確認後、１０℃まで冷却し、１０〜１５℃で
７−メチル−２−ナフトール１５．８ｇ（０．１モル）
とメタノール１５０ｍｌの混合物を滴下し、滴下終了
後、同温で１２時間撹拌した。反応終了後、反応混合物
を１Ｍ塩酸水１Ｌ中に注ぎ入れ、トルエン５００ｍｌで
抽出した。得られた有機層を水、飽和食塩水の順で洗浄
した後、減圧濃縮して、粘凋な褐色油状物１５．５ｇを
得た。このものをシリカゲルカラムクロマトグラフィー
（溶出液：トルエン−酢酸エチル）に供し、７，７’−
ジメチル−１，１−ビ−２−ナフトール１３．０ｇを白
色固体として得た。融点： ８４〜８５℃1 Ｈ−ＮＭＲ(CDCl3) ： δ＝7.9-7.5(m, 4H), 7.4-6.
8(m, 6H), 4.99(s, 2H),2.25(s, 6H)The present invention will be described in more detail with reference to the following examples. Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 48.3 g (0.2 mol) of copper (II) nitrate trihydrate and 500 ml of methanol were added at room temperature.
Was charged, and 118.4 g (0.6 mol) of 1,2-diphenylethylamine was added to this mixture. After confirming that a uniform solution was obtained, the mixture was cooled to 10 ° C, and 15.8 g (0.1 mol) of 7-methyl-2-naphthol at 10-15 ° C.
And 150 ml of methanol were added dropwise, and after the addition was completed, the mixture was stirred at the same temperature for 12 hours. After completion of the reaction, the reaction mixture was poured into 1 L of 1M hydrochloric acid water and extracted with 500 ml of toluene. The obtained organic layer was washed with water and saturated brine in this order and then concentrated under reduced pressure to obtain 15.5 g of a viscous brown oily substance. This product was subjected to silica gel column chromatography (eluent: toluene-ethyl acetate) to obtain 7,7'-
13.0 g of dimethyl-1,1-bi-2-naphthol was obtained as a white solid. Melting point: 84-85 ° C. 1 H-NMR (CDCl 3 ): δ = 7.9-7.5 (m, 4H), 7.4-6.
8 (m, 6H), 4.99 (s, 2H), 2.25 (s, 6H)
【００１７】実施例２ 撹拌装置、温度計、滴下ロートおよびコンデンサーを装
着した４つ口フラスコに室温で硝酸銅（ＩＩ）三水和物
４８．３ｇ（０．２モル）およびメタノール５００ｍｌ
を仕込み、さらに１−フェニル−２−ｐ−トリルエチル
アミン１２６．８ｇ（０．６モル）を加えた。この混合
物に室温で７−メチル−２−ナフトール１５．８ｇ
（０．１モル）とメタノール１５０ｍｌの混合物を滴下
し、滴下終了後、同温で８時間撹拌した。反応終了後、
反応混合物を１Ｍ塩酸水１Ｌ中に注ぎ入れ、トルエン５
００ｍｌで抽出した。得られた有機層を水、飽和食塩水
の順で洗浄した後、減圧濃縮して、粘凋な褐色油状物１
５．７ｇを得た。このものをシリカゲルカラムクロマト
グラフィー（溶出液：トルエン−酢酸エチル）に供し、
７，７’−ジメチル−１，１−ビ−２−ナフトール１
１．５ｇを白色固体として得た。Example 2 In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 48.3 g (0.2 mol) of copper (II) nitrate trihydrate and 500 ml of methanol were added at room temperature.
Then, 126.8 g (0.6 mol) of 1-phenyl-2-p-tolylethylamine was added. 15.8 g of 7-methyl-2-naphthol was added to this mixture at room temperature.
A mixture of (0.1 mol) and 150 ml of methanol was added dropwise, and after completion of the addition, the mixture was stirred at the same temperature for 8 hours. After the reaction,
The reaction mixture was poured into 1 L of 1M hydrochloric acid water, and toluene 5 was added.
It was extracted with 00 ml. The obtained organic layer was washed with water and saturated brine in this order and then concentrated under reduced pressure to give a viscous brown oily substance 1.
5.7 g was obtained. This product was subjected to silica gel column chromatography (eluent: toluene-ethyl acetate),
7,7'-Dimethyl-1,1-bi-2-naphthol 1
1.5 g was obtained as a white solid.
【００１８】実施例３ 実施例１で得た７，７’−ジメチル−１，１−ビ−２−
ナフトール１．０ｇを光学活性カラム（SUMICHIRAL OA
、移動相：ｎ−ヘキサン／２−プロパノール）により
光学異性体を分離し、（＋）−７，７’−ジメチル−
１，１−ビ−２−ナフトール０．４９ｇおよび（−）−
７，７’−ジメチル−１，１−ビ−２−ナフトール０．
４９ｇを得た。Example 3 7,7'-Dimethyl-1,1-bi-2-obtained in Example 1
1.0 g of naphthol was added to an optically active column (SUMICHIRAL OA
, Mobile phase: n-hexane / 2-propanol) to separate optical isomers, and (+)-7,7'-dimethyl-
0.49 g of 1,1-bi-2-naphthol and (-)-
7,7'-Dimethyl-1,1-bi-2-naphthol 0.
49 g were obtained.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 37/11 8930−4Ｈ 37/82 8930−4Ｈ // Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C07C 37/11 8930-4H 37/82 8930-4H // C07B 61/00 300
Claims (4)
よびアミン類の存在下に酸化的にカップリングすること
を特徴とする前記式（Ｉ）で示されるビナフトール誘導
体の製造法。3. A process for producing a binaphthol derivative represented by the above formula (I), which comprises oxidatively coupling 7-methyl-2-naphthol in the presence of a divalent copper salt and amines.
体を光学活性カラムを用いた高速液体クロマトグラフィ
ーにより光学分割することを特徴とする前記式（ＩＩ）
または前記式（ＩＩＩ）で示される光学活性なビナフト
ール誘導体の製造法。4. The above formula (II), which is characterized in that the binaphthol derivative represented by the above formula (I) is optically resolved by high performance liquid chromatography using an optically active column.
Alternatively, a method for producing an optically active binaphthol derivative represented by the above formula (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29694992A JP3252491B2 (en) | 1992-11-06 | 1992-11-06 | Binaphthol derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29694992A JP3252491B2 (en) | 1992-11-06 | 1992-11-06 | Binaphthol derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06145086A true JPH06145086A (en) | 1994-05-24 |
| JP3252491B2 JP3252491B2 (en) | 2002-02-04 |
Family
ID=17840273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29694992A Expired - Fee Related JP3252491B2 (en) | 1992-11-06 | 1992-11-06 | Binaphthol derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3252491B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002085829A1 (en) * | 2001-04-19 | 2002-10-31 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for production of dimers of aromatic monohydroxyl compounds |
| US6849742B2 (en) | 2001-04-19 | 2005-02-01 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Binaphthol derivative and process for producing the same |
| CN113149871A (en) * | 2021-03-01 | 2021-07-23 | 辽宁石油化工大学 | One-step in-situ catalytic reaction green synthesis method for generating symmetrical sulfonic 1, 1' -binaphthol |
-
1992
- 1992-11-06 JP JP29694992A patent/JP3252491B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002085829A1 (en) * | 2001-04-19 | 2002-10-31 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for production of dimers of aromatic monohydroxyl compounds |
| JP2002316961A (en) * | 2001-04-19 | 2002-10-31 | Ueno Seiyaku Oyo Kenkyusho:Kk | Method for producing aromatic compound dimer |
| US6849742B2 (en) | 2001-04-19 | 2005-02-01 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Binaphthol derivative and process for producing the same |
| US6891072B2 (en) | 2001-04-19 | 2005-05-10 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for production of dimers or aromatic monohydroxyl compounds |
| EP1380564A4 (en) * | 2001-04-19 | 2006-02-22 | Ueno Seiyaku Oyo Kenkyujo Kk | Binaphtol derivative and process for producing the same |
| CN113149871A (en) * | 2021-03-01 | 2021-07-23 | 辽宁石油化工大学 | One-step in-situ catalytic reaction green synthesis method for generating symmetrical sulfonic 1, 1' -binaphthol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3252491B2 (en) | 2002-02-04 |
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| LAPS | Cancellation because of no payment of annual fees |