JPH08208529A - Production of alkylaryl compound - Google Patents
Production of alkylaryl compoundInfo
- Publication number
- JPH08208529A JPH08208529A JP7036023A JP3602395A JPH08208529A JP H08208529 A JPH08208529 A JP H08208529A JP 7036023 A JP7036023 A JP 7036023A JP 3602395 A JP3602395 A JP 3602395A JP H08208529 A JPH08208529 A JP H08208529A
- Authority
- JP
- Japan
- Prior art keywords
- group
- catalyst
- optical purity
- general formula
- phenylene
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 alkylaryl compound Chemical class 0.000 title abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004956 cyclohexylene group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000001721 carbon Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CELOWHKBPDLREM-ZDUSSCGKSA-N C1=CC(C(=O)[C@@H](C)CC)=CC=C1C1=CC=CC=C1 Chemical group C1=CC(C(=O)[C@@H](C)CC)=CC=C1C1=CC=CC=C1 CELOWHKBPDLREM-ZDUSSCGKSA-N 0.000 description 3
- 238000006214 Clemmensen reduction reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- YZVHGHFGYMRTAS-AWEZNQCLSA-N 1-[(2s)-2-methylbutyl]-4-phenylbenzene Chemical group C1=CC(C[C@@H](C)CC)=CC=C1C1=CC=CC=C1 YZVHGHFGYMRTAS-AWEZNQCLSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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、アルキルアリール系化
合物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an alkylaryl compound.
【０００２】[0002]
【従来の技術】アルキルアリール系化合物は、医薬、農
薬、食品、電子材料などの各種の分野で使用されてお
り、こうした全ての分野において高い光学純度が求めら
れている。2. Description of the Related Art Alkylaryl compounds are used in various fields such as pharmaceuticals, agricultural chemicals, foods and electronic materials, and high optical purity is required in all of these fields.
【０００３】一般に、アルキルアリール系化合物は、ア
リールケトン系化合物のメチレン基を還元することによ
り製造されており、たとえば、Ｃｌｅｍｍｅｎｓｅｎ還
元やＷｏｌｆｆ−Ｋｉｓｈｎｅｒ還元が、通常、よく用
いられている。しかし、カルボニル基のα−位に不斉炭
素を有するアリールケトン系化合物のメチレン基の還元
を、Ｃｌｅｍｍｅｎｓｅｎ還元やＷｏｌｆｆ−Ｋｉｓｈ
ｎｅｒ還元により行った場合には、ラセミ化により光学
純度の低下が著しいため、光学活性なアルキルアリール
系化合物の製造にはＣｌｅｍｍｅｎｓｅｎ還元やＷｏｌ
ｆｆ−Ｋｉｓｈｎｅｒ還元は採用されていなかった。Generally, an alkylaryl compound is produced by reducing a methylene group of an arylketone compound, and for example, Clemmensen reduction and Wolff-Kishner reduction are commonly used. However, reduction of a methylene group of an arylketone compound having an asymmetric carbon at the α-position of a carbonyl group can be achieved by Clemmensen reduction or Wolff-Kish
In the case of carrying out the ner reduction, the optical purity is remarkably lowered due to racemization. Therefore, Clemmensen reduction or Wol is used for the production of an optically active alkylaryl compound.
No ff-Kishner reduction was adopted.
【０００４】そのため、従来は、原料の光学純度を保持
したまま、光学活性なアルキルアリール系化合物を製造
するためには、光学純度を低下させない反応を選択した
迂回方法を経由しなければならず、反応工程が増え経済
的に不利であった。Therefore, conventionally, in order to produce an optically active alkylaryl compound while maintaining the optical purity of the raw material, it has been necessary to go through a detouring method in which a reaction that does not lower the optical purity is selected. It was economically disadvantageous because the number of reaction steps increased.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、原料の光学
純度を保持したまま、光学活性なアリールケトン系化合
物を製造する方法を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing an optically active arylketone compound while maintaining the optical purity of the raw material.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討を重ねた結果、還元能を有する触
媒の存在下で、接触水素化を行うことにより、前記目的
を達成できることを見出した。本発明はかかる新たな知
見に基づいて完成されたものである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors achieved the above object by carrying out catalytic hydrogenation in the presence of a catalyst having a reducing ability. I found that I could do it. The present invention has been completed based on this new finding.
【０００７】すなわち、本発明は、一般式（１）：Ｒ1
（Ｒ2 ） *ＣＨＣＯ−Φ−Ｘ−Ｙ（式中、Ｒ1 およびＲ
2 は同一でない炭素数１〜６のアルキル基を表し、 *Ｃ
は不斉炭素を表し、Φはフェニレン基を表し、Ｘは単結
合、フェニレン基、シクロヘキシレン基、ピリミジレン
基またはジオキシレン基を表し、Ｙは水素原子、ハロゲ
ン原子、カルボキシル基またはシアノ基を表す）で表さ
れるアリールケトン系化合物を、有機溶媒中、還元能を
有する触媒の存在下で、接触水素化を行うことを特徴と
する一般式（２）：Ｒ1 （Ｒ2 ） *ＣＨＣＨ2 −Φ−Ｘ
−Ｙ（式中、Ｒ1 、Ｒ2 、 *Ｃ、Φ、ＸおよびＹは前記
と同じ）で表されるアルキルアリール系化合物の製造方
法に関する。That is, the present invention relates to the general formula (1): R 1
(R 2 ) * CHCO-Φ-XY (wherein R 1 and R
2 represents an alkyl group having 1 to 6 carbon atoms which are not the same, * C
Represents an asymmetric carbon, Φ represents a phenylene group, X represents a single bond, a phenylene group, a cyclohexylene group, a pyrimidylene group or a dioxylene group, and Y represents a hydrogen atom, a halogen atom, a carboxyl group or a cyano group.) The arylketone compound represented by the formula (2): R 1 (R 2 ) * CHCH 2 —, which is characterized by carrying out catalytic hydrogenation in the presence of a catalyst having reducing ability in an organic solvent. Φ-X
And a method for producing an alkylaryl compound represented by —Y (wherein R 1 , R 2 , * C, Φ, X and Y are the same as above).
【０００８】前記一般式（１）で表されるアリールケト
ン系化合物とは、２種のアルキル基とキラルプロトンを
有する不斉炭素が、カルボニル基のα−位に結合してい
る光学活性なアリールケトン系化合物をいい、絶対配置
がＳ体またはＲ体のいずれも使用できる。また、一般式
（１）で表されるＸが単結合以外の場合に、その結合位
置は特に制限されないが、フェニレン基、シクロヘキシ
レン基としては、通常、１，４−の位置で結合している
ものがあげられる。また、ピリミジレン基は２，５−の
位置で結合しているものがあげられる。また、ジオキシ
レン基は、１，３−ジオキシレン基が、２，５−の位置
で結合しているものがあげられる。また、Ｙのハロゲン
原子としては、フッ素原子、塩素原子、臭素、ヨウ素原
子等があげられる。Ｙとしては水素原子が好ましい。一
般式（１）で表されるアリールケトン系化合物として
は、ベンゼン誘導体、ビフェニル誘導体が好ましい。The arylketone compound represented by the general formula (1) is an optically active aryl having two types of alkyl groups and an asymmetric carbon having a chiral proton bonded to the α-position of a carbonyl group. It refers to a ketone compound, and either the S configuration or the R configuration in absolute configuration can be used. Further, when X represented by the general formula (1) is other than a single bond, the bonding position is not particularly limited, but the phenylene group and the cyclohexylene group are usually bonded at the 1,4-position. I can give you what you have. Further, the pyrimidylene group may be one bonded at the 2,5-position. In addition, the dioxylene group includes one having a 1,3-dioxylene group bonded at the 2,5-position. Further, examples of the halogen atom of Y include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As Y, a hydrogen atom is preferable. The arylketone compound represented by the general formula (1) is preferably a benzene derivative or a biphenyl derivative.
【０００９】本発明では、前記一般式（１）で表される
アリールケトン系化合物を、有機溶媒中、還元能を有す
る触媒の存在下で、接触水素化を行い、前記一般式
（２）で表されるアルキルアリール系化合物を製造す
る。In the present invention, the arylketone compound represented by the general formula (1) is subjected to catalytic hydrogenation in the presence of a catalyst having a reducing ability in an organic solvent to give the compound represented by the general formula (2). The represented alkylaryl compounds are prepared.
【００１０】前記有機溶媒としては、エタノール、メタ
ノール、酢酸エチル、ジオキサン等を使用できる。な
お、有機溶媒は、反応速度を向上させるために、塩酸、
硫酸、パラトルエンスルホン酸等を加えて酸性にしたも
のが好ましい。As the organic solvent, ethanol, methanol, ethyl acetate, dioxane or the like can be used. The organic solvent is hydrochloric acid, in order to improve the reaction rate.
It is preferable to add sulfuric acid, p-toluenesulfonic acid or the like to make the mixture acidic.
【００１１】還元能を有する触媒とは、一般に、共役ケ
トンのカルボニル基のみを選択的に接触水素化してメチ
レン基とすることができる触媒をいう。すなわち、本発
明の還元能を有する触媒とは、一般式（１）で表される
アリールケトン系化合物の芳香環を水素化することな
く、カルボニル基のみを選択的に接触水素化することが
できる触媒をいう。かかる還元能を有する触媒として
は、パラジウム、白金等があげられる。これらの中でも
カルボニル基のみを選択性よく接触水素化できることか
らパラジウムが好ましい。なお、かかる水素化触媒は多
孔質で表面積の大きなアルミナ、シリカ（ケイソウ
土）、カーボン、チタニア等の担体に担持して使用して
もよい。本発明では、パラジウム担持カーボンを使用す
るのが好ましい。かかる還元能を有する触媒の使用量
は、特に制限されないが、通常、一般式（１）で表され
るアリールケトン系化合物の０．５〜２．５重量％程
度、好ましくは１〜２．５重量％である。触媒の使用量
が２．５重量％を越える場合にはコスト的に不利であ
り、また０．５重量％に満たない場合には反応時間が長
くなり、いずれの場合も好ましくない。The catalyst having a reducing ability generally means a catalyst capable of selectively catalytically hydrogenating only a carbonyl group of a conjugated ketone to give a methylene group. That is, with the catalyst having reducing ability of the present invention, only the carbonyl group can be selectively catalytically hydrogenated without hydrogenating the aromatic ring of the arylketone compound represented by the general formula (1). Refers to a catalyst. Examples of the catalyst having such reducing ability include palladium and platinum. Among these, palladium is preferable because only the carbonyl group can be catalytically hydrogenated with good selectivity. The hydrogenation catalyst may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon, and titania, which is porous and has a large surface area. In the present invention, it is preferable to use palladium-supporting carbon. The amount of the catalyst having the reducing ability used is not particularly limited, but is usually about 0.5 to 2.5% by weight, preferably 1 to 2.5% by weight of the arylketone compound represented by the general formula (1). % By weight. If the amount of the catalyst used exceeds 2.5% by weight, it is disadvantageous in terms of cost, and if it is less than 0.5% by weight, the reaction time becomes long, which is not preferable.
【００１２】接触水素化反応は、まず、所定量の還元能
を有する触媒を溶媒に懸濁させたものに、所定量の一般
式（１）で表されるアリールケトン系化合物を溶解し反
応容器内を水素置換して反応させる。系内の温度は、通
常、室温（２０〜３０℃）で行う。また、反応時間は通
常５〜３０時間、好ましくは８〜１０時間である。な
お、系内の圧力は、常圧下で行うことができる。反応終
了後は、触媒を除去した後、溶媒で抽出し、目的物であ
る光学活性な一般式（２）で表されるアルキルアリール
系化合物が得られる。In the catalytic hydrogenation reaction, first, a predetermined amount of the arylketone compound represented by the general formula (1) is dissolved in a suspension of a catalyst having a reducing ability in a solvent to prepare a reaction vessel. The inside is replaced with hydrogen to react. The temperature in the system is usually room temperature (20 to 30 ° C.). The reaction time is usually 5 to 30 hours, preferably 8 to 10 hours. The pressure in the system may be normal pressure. After completion of the reaction, the catalyst is removed and the mixture is extracted with a solvent to obtain the objective optically active alkylaryl compound represented by the general formula (2).
【００１３】[0013]
【発明の効果】本発明の製造方法によれば、原料である
アリールケトン系化合物の光学純度を保持したまま、光
学活性なアルキルアリール系化合物を一段階で製造する
方法を提供することができる。According to the production method of the present invention, it is possible to provide a method for producing an optically active alkylaryl compound in a single step while maintaining the optical purity of the starting material arylketone compound.
【００１４】[0014]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
【００１５】実施例１ 濃塩酸６ｍｌを加えたエタノール２６００ｍｌに、５重
量％パラジウム担持カーボン１３０ｇを懸濁させたもの
に、（Ｓ）−４−（２−メチルブタノイル）ビフェニル
２７２．６ｇ（１．１モル、比施光度：［α］20 D ＝＋
２９．７度（ｃ＝５，ＣＨＣｌ3 ），光学純度９６％ｅ
ｅ）を溶解したのち、反応容器内を水素置換し、室温で
１０時間反応させた。触媒を濾別後、溶媒を濃縮した
後、酢酸エチル１０００ｍｌを加えた。有機層を、飽和
炭酸水素カリウムと飽和食塩水でそれそれ洗った後、硫
酸マグネシウムで乾燥した。溶媒を濃縮後、減圧蒸留に
より精製を行い、（Ｓ）−４−（２−メチルブチル）ビ
フェニル２２５．５ｇ（収率９０モル％，比施光度：
［α］20 D ＝＋１１．７度（ｃ＝５，ＣＨＣｌ3 ），光
学純度９６％ｅｅ）を得た。なお、光学純度の測定は、
キラルセルＯＤＨ（ダイセル化学工業（株）製）を用い
た。EXAMPLE 1 130 g of 5% by weight palladium-supporting carbon was suspended in 2600 ml of ethanol containing 6 ml of concentrated hydrochloric acid, and 272.6 g (1) of (S) -4- (2-methylbutanoyl) biphenyl was added. .1 mol, specific illuminance: [α] 20 D = +
29.7 degrees (c = 5, CHCl 3 ), optical purity 96% e
After e) was dissolved, the inside of the reaction vessel was replaced with hydrogen, and the reaction was carried out at room temperature for 10 hours. After the catalyst was filtered off, the solvent was concentrated and 1000 ml of ethyl acetate was added. The organic layer was washed with saturated potassium hydrogen carbonate and saturated brine, and then dried over magnesium sulfate. After the solvent was concentrated, purification was carried out by distillation under reduced pressure, and 225.5 g of (S) -4- (2-methylbutyl) biphenyl (yield 90 mol%, relative luminous efficiency:
[Α] 20 D = + 11.7 degrees (c = 5, CHCl 3 ) and an optical purity of 96% ee) were obtained. The measurement of optical purity is
Chiral cell ODH (manufactured by Daicel Chemical Industries, Ltd.) was used.
【００１６】1Ｈ−ＮＭＲ：δ＝７．５８（ｄ，２
Ｈ）、７．５０（ｍ，２Ｈ）、７．４０（ｔ，２Ｈ）、
７．３０（ｔ，１Ｈ）、７．２０（ｄ，２Ｈ）、２．４
０，２．６６（ｍ，２Ｈ）、１．６８（ｍ，１Ｈ）、
１．２１，１．４２（ｍ，２Ｈ）、０．９５（ｄ，３
Ｈ）、０．９５（ｔ，３Ｈ）。 1 H-NMR: δ = 7.58 (d, 2
H), 7.50 (m, 2H), 7.40 (t, 2H),
7.30 (t, 1H), 7.20 (d, 2H), 2.4
0, 2.66 (m, 2H), 1.68 (m, 1H),
1.21, 1.42 (m, 2H), 0.95 (d, 3
H), 0.95 (t, 3H).
【００１７】実施例２ 実施例１において、（Ｓ）−４−（２−メチルブタノイ
ル）ビフェニルの代わりに、（Ｓ）−４−（２−メチル
ブタノイル）フェニル１７８．５ｇ（１．１モル、比施
光度：［α］20 D ＝＋３４．６度（ｃ＝５，ＣＨＣｌ
3 ），光学純度９６％ｅｅ）を使用した以外は、実施例
１と同様に反応を行った。そして、実施例１と同様に濃
縮、乾燥して、精製を行い、（Ｓ）−４−（２−メチル
ブチル）フェニル１４５．２ｇ（収率８９モル％，比施
光度：［α］20 D ＝＋１５．２度（ｃ＝５，ＣＨＣｌ
3 ），光学純度９６％ｅｅ）を得た。なお、光学純度の
測定は、キラルセルＯＤＨ（ダイセル化学工業（株）
製）を用いた。Example 2 In Example 1, instead of (S) -4- (2-methylbutanoyl) biphenyl, 178.5 g (1.1) of (S) -4- (2-methylbutanoyl) phenyl. Molarity, specific optical rotation: [α] 20 D = + 34.6 degrees (c = 5, CHCl
3 ) The reaction was performed in the same manner as in Example 1 except that the optical purity was 96% ee). Then, concentration, drying and purification were carried out in the same manner as in Example 1, and 145.2 g of (S) -4- (2-methylbutyl) phenyl (yield 89 mol%, specific light rotation: [α] 20 D = +15.2 degrees (c = 5, CHCl
3 ) and an optical purity of 96% ee) were obtained. The optical purity was measured by Chiralcel ODH (Daicel Chemical Industries Ltd.).
Manufactured) was used.
【００１８】1Ｈ−ＮＭＲ：δ＝７．１２（ｍ，５
Ｈ）、２．６２（ｑ，１Ｈ）、２．３５（ｑ，１Ｈ）、
１．６５（ｍ，１Ｈ）、１．３８（ｍ，１Ｈ）、１．１
５（ｍ，１Ｈ）、０．８８（ｄ，３Ｈ）、０．８４
（ｔ，３Ｈ）。 1 H-NMR: δ = 7.12 (m, 5
H), 2.62 (q, 1H), 2.35 (q, 1H),
1.65 (m, 1H), 1.38 (m, 1H), 1.1
5 (m, 1H), 0.88 (d, 3H), 0.84
(T, 3H).
【００１９】比較例１ （Ｓ）−４−（２−メチルブタノイル）ビフェニル１
０．８ｇ（４．５ミリモル、比施光度：［α］20 D ＝＋
２９．７度（ｃ＝５，ＣＨＣｌ3 ），光学純度９６％ｅ
ｅ）を、１水和ヒドラジン９．１ｇ（１８０ミリモ
ル），水酸化ナトリウム９．７ｇ（２４０ミリモル）お
よびジエチレングリコール１１５ｍｌからなる溶液に溶
解し、１２０℃で２．５時間加熱した後、さらに２００
℃で２時間加熱した。その後、水３００ｍｌを加え、ト
ルエンで抽出して有機層を硫酸マグネシウムで乾燥し、
蒸留により精製を行い、（Ｓ）−４−（２−メチルブチ
ル）ビフェニル８．１ｇ（収率８９モル％，比施光度：
［α］20 D ＝０．０度（ｃ＝５，ＣＨＣｌ3 ））を得
た。なお、光学純度の測定は、キラルセルＯＤＨ（ダイ
セル化学工業（株）製）を用いた。Comparative Example 1 (S) -4- (2-methylbutanoyl) biphenyl 1
0.8 g (4.5 mmol, specific illuminance: [α] 20 D = +
29.7 degrees (c = 5, CHCl 3 ), optical purity 96% e
e) was dissolved in a solution consisting of 9.1 g (180 mmol) of hydrazine monohydrate, 9.7 g (240 mmol) of sodium hydroxide and 115 ml of diethylene glycol and heated at 120 ° C. for 2.5 hours, and then 200
Heated at ° C for 2 hours. Then, add 300 ml of water, extract with toluene, dry the organic layer with magnesium sulfate,
Purification was carried out by distillation, and 8.1 g of (S) -4- (2-methylbutyl) biphenyl (yield 89 mol%, specific illuminance:
[Α] 20 D = 0.0 degree (c = 5, CHCl 3 )) was obtained. The optical purity was measured using Chiralcel ODH (manufactured by Daicel Chemical Industries, Ltd.).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 15/14 17/35 23/18 25/18 61/39 9450−4Ｈ 63/04 9450−4Ｈ 63/33 9450−4Ｈ 255/46 255/50 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｍ 7:00 (72)発明者 曽根 孝明 大阪市鶴見区鶴見１丁目１番９号荒川化学 工業株式会社研究所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07C 15/14 17/35 23/18 25/18 61/39 9450-4H 63/04 9450-4H 63/33 9450-4H 255/46 255/50 // C07B 61/00 300 C07M 7:00 (72) Inventor Takaaki Sone 1-1-9 Tsurumi, Tsurumi-ku, Osaka Arakawa Chemical Industry Co., Ltd.
Claims (2)
−Φ−Ｘ−Ｙ（式中、Ｒ1 およびＲ2 は同一でない炭素
数１〜６のアルキル基を表し、 *Ｃは不斉炭素を表し、
Φはフェニレン基を表し、Ｘは単結合、フェニレン基、
シクロヘキシレン基、ピリミジレン基またはジオキシレ
ン基を表し、Ｙは水素原子、ハロゲン原子、カルボキシ
ル基またはシアノ基を表す）で表されるアリールケトン
系化合物を、有機溶媒中、還元能を有する触媒の存在下
で、接触水素化を行うことを特徴とする一般式（２）：
Ｒ1 （Ｒ2 ） *ＣＨＣＨ2 −Φ−Ｘ−Ｙ（式中、Ｒ1 、
Ｒ2 、 *Ｃ、Φ、ＸおよびＹは前記と同じ）で表される
アルキルアリール系化合物の製造方法。1. General formula (1): R 1 (R 2 ) * CHCO
-Φ-XY (in the formula, R 1 and R 2 represent an alkyl group having 1 to 6 carbon atoms which are not the same, * C represents an asymmetric carbon,
Φ represents a phenylene group, X is a single bond, a phenylene group,
A cyclohexylene group, a pyrimidylene group or a dioxylene group, and Y represents a hydrogen atom, a halogen atom, a carboxyl group or a cyano group) in an organic solvent in the presence of a catalyst having reducing ability. In the general formula (2), which is characterized by carrying out catalytic hydrogenation:
R 1 (R 2 ) * CHCH 2 —Φ-X—Y (wherein R 1 ,
Method of manufacturing R 2, * C, Φ, alkylaryl compounds X and Y is represented by the same) and the.
る請求項１記載の製造方法。2. The production method according to claim 1, wherein the catalyst having a reducing ability is palladium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7036023A JPH08208529A (en) | 1995-01-31 | 1995-01-31 | Production of alkylaryl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7036023A JPH08208529A (en) | 1995-01-31 | 1995-01-31 | Production of alkylaryl compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08208529A true JPH08208529A (en) | 1996-08-13 |
Family
ID=12458134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7036023A Pending JPH08208529A (en) | 1995-01-31 | 1995-01-31 | Production of alkylaryl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08208529A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349087A (en) * | 2015-09-02 | 2017-01-25 | 四川瑞希康生物医药有限公司 | Synthesis of (R)-2-amino-3-(xenyl-4-yl)-1-propyl alcohol |
| CN116023200A (en) * | 2022-01-27 | 2023-04-28 | 浙江扬帆新材料股份有限公司 | A method for preparing methylene compounds by reduction of aromatic aldehyde (ketone) compounds |
-
1995
- 1995-01-31 JP JP7036023A patent/JPH08208529A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349087A (en) * | 2015-09-02 | 2017-01-25 | 四川瑞希康生物医药有限公司 | Synthesis of (R)-2-amino-3-(xenyl-4-yl)-1-propyl alcohol |
| CN116023200A (en) * | 2022-01-27 | 2023-04-28 | 浙江扬帆新材料股份有限公司 | A method for preparing methylene compounds by reduction of aromatic aldehyde (ketone) compounds |
| CN116023200B (en) * | 2022-01-27 | 2023-07-25 | 江西扬帆新材料有限公司 | Method for preparing methylene compound by reduction of aromatic aldehyde (ketone) compound |
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