JPH03118351A - Production of 2-aminoindane - Google Patents
Production of 2-aminoindaneInfo
- Publication number
- JPH03118351A JPH03118351A JP1255051A JP25505189A JPH03118351A JP H03118351 A JPH03118351 A JP H03118351A JP 1255051 A JP1255051 A JP 1255051A JP 25505189 A JP25505189 A JP 25505189A JP H03118351 A JPH03118351 A JP H03118351A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- catalyst
- aminoindan
- nickel
- 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.)
- Pending
Links
- LMHHFZAXSANGGM-UHFFFAOYSA-N 2-aminoindane Chemical compound C1=CC=C2CC(N)CC2=C1 LMHHFZAXSANGGM-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- UJLFLOAXKVGYIA-UHFFFAOYSA-N indan-2-one oxime Chemical compound C1=CC=C2CC(=NO)CC2=C1 UJLFLOAXKVGYIA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEHNLVMHWYPNEQ-UHFFFAOYSA-N 2,3-dihydro-1h-inden-2-amine;hydron;chloride Chemical compound Cl.C1=CC=C2CC(N)CC2=C1 XEHNLVMHWYPNEQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 230000002541 vasodepressive effect Effects 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 1so-butanol Chemical compound 0.000 description 1
- XJEVHMGJSYVQBQ-UHFFFAOYSA-N 2,3-dihydro-1h-inden-1-amine Chemical class C1=CC=C2C(N)CCC2=C1 XJEVHMGJSYVQBQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940030600 antihypertensive agent Drugs 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- UMJJFEIKYGFCAT-UHFFFAOYSA-N indan-2-one Chemical compound C1=CC=C2CC(=O)CC2=C1 UMJJFEIKYGFCAT-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ATEGUFMEFAGONB-UHFFFAOYSA-N n-(2,3-dihydroinden-1-ylidene)hydroxylamine Chemical compound C1=CC=C2C(=NO)CCC2=C1 ATEGUFMEFAGONB-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940124597 therapeutic agent Drugs 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
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は薬理学上、特に血圧降下剤、喘息等治療剤の原
料として有用な２−アミノインダンおよび２−アミノイ
ンダン塩酸塩等、２−アミノインダン類の製造方法に関
する。Detailed Description of the Invention <Industrial Application Field> The present invention is useful for pharmacological purposes, particularly for 2-aminoindan and 2-aminoindan hydrochloride, etc., which are useful as raw materials for antihypertensive agents and therapeutic agents for asthma, etc. The present invention relates to a method for producing aminoindans.
〈従来の技術〉
２−アミノインダン類については、従来の研究から数種
類の製造ルートが考案されているが、収率などの点でと
くに注目すべきはインデンまたはその誘導体から合成し
た２−インダノンオキシムを還元する方法である。<Prior art> Regarding 2-aminoindanes, several production routes have been devised based on conventional research, but 2-indanone synthesized from indene or its derivatives is particularly noteworthy in terms of yield etc. This is a method of reducing oxime.
Ｗ、Ｅ、Ｒｏｓｅｎらは、Ｔｈｅ Ｊｏｕｒｎａｌ ｏ
ｆ ＯｒｇａｎｉｃＣｈｅｍｉｓｔｒｙ（１９６３，ｖ
ｏｌ、２８）において、２−インダノンオキシムの還元
反応を検討した結果、２アミノインダンを塩酸塩として
９２〜９５％の高収率で回収したと報告している。W. E. Rosen et al., The Journal o
f Organic Chemistry (1963, v.
ol, 28) reported that as a result of investigating the reduction reaction of 2-indanone oxime, 2-aminoindan was recovered as a hydrochloride with a high yield of 92 to 95%.
Ｗ、Ｅ、Ｒｏｓｅｎらによれば、たとえば、原料２イン
ダノンオキシムに対して、５％パラジウムカーボン５０
重量％、氷酢酸３０重量倍、濃硫酸１〜２重量倍の各比
率で加えるか、ラネーニッケル５０重量％、ＣＨ３０Ｎ
ａ４５重量％、メタノール５重量倍を加えて、２−アミ
ノインダンを得ている。 しかし、この方法を用いて
も、オキシム類の接触還元では副生物の生成率が一般に
高いため、目的とする第アミンを選択的に合成するには
従来と同様、触媒、溶媒、および添加物等が大量に必要
であり、製造コストがかかり過ぎ、工業的に適用は難し
かった。 また、この方法は添加物を分ｌｌｌ１１す
る工程を必要とする点でも、工業的に不利であった。According to W. E. Rosen et al., for example, 5% palladium carbon 50
% by weight, 30 times by weight of glacial acetic acid, 1 to 2 times by weight of concentrated sulfuric acid, or 50% by weight of Raney nickel, CH30N
2-aminoindan was obtained by adding 45% by weight of a and 5 times the weight of methanol. However, even if this method is used, the production rate of by-products is generally high in the catalytic reduction of oximes, so in order to selectively synthesize the desired primary amine, catalysts, solvents, additives, etc. are required as in the past. It was difficult to apply it industrially because a large amount was required and the manufacturing cost was too high. Furthermore, this method was industrially disadvantageous in that it required a step of separating the additives.
〈発明が解決しようとする課題〉
そこで本発明は、従来、工業的に得られにくかった２−
アミノインダン類を少量の触媒、溶媒を用いて安価に製
造することのできる方法を見い出すことを目的とする。<Problems to be solved by the invention> Therefore, the present invention aims to solve two problems that have hitherto been difficult to obtain industrially.
The purpose of this study is to find a method for producing aminoindanes at low cost using a small amount of catalyst and solvent.
く課題を解決するための手段〉
上記課題を解決すべく鋭意検討の結果、本発明に至った
。Means for Solving the Problems> As a result of intensive studies to solve the above problems, the present invention has been arrived at.
すなわち本発明は、下記式［Ｉ］に示ず２アミノインダ
ンを製造するに際し、下記式［Ｉ＋ ］に示す２−イン
ダノンオキシムを極性溶媒中、ニッケル担持触媒を用い
て高圧接触還元することを特徴とする２−アミノインダ
ンの製造方法を提供する。That is, the present invention involves high-pressure catalytic reduction of 2-indanone oxime shown in the following formula [I+] using a nickel-supported catalyst in a polar solvent when producing a 2-aminoindan not shown in the following formula [I]. A method for producing 2-aminoindan characterized by its characteristics is provided.
（上記式中Ｒは、水素、低級アルキル基、低級アルコキ
シ基、またはハロゲンを示す。 ｎは０〜４までの整
数を示す９）
また、前記極性溶媒としてテトラヒドロフランおよび／
または炭素数３〜５の低級アルコールを用いるのが好ま
しい。(In the above formula, R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen. n represents an integer from 0 to 49) In addition, as the polar solvent, tetrahydrofuran and /
Alternatively, it is preferable to use a lower alcohol having 3 to 5 carbon atoms.
さらに本発明は、反応液中に存在する触媒を分Ｈし、塩
化水素で処理することにより、下記式［ＩＩＩ ］に示
す２−アミノインダン塩酸塩を製造することを特徴とす
る２−アミノインダン塩酸塩の製造方法を提供する。Furthermore, the present invention is characterized in that 2-aminoindan hydrochloride represented by the following formula [III] is produced by separating the catalyst present in the reaction solution and treating it with hydrogen chloride. A method for producing hydrochloride is provided.
（上記式中Ｒは、水素、低級アルキル基、低級アルコキ
シ基、またはハロゲンを示す。 ｎは０〜４までの整
数を示す。）
以下、本発明の詳細な説明する。(In the above formula, R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen. n represents an integer from 0 to 4.) Hereinafter, the present invention will be described in detail.
本発明の製造方法によれば、下記式［Ｉ＋ ］で示す２
−インダノンオキシムを極性溶媒中、ニッケル担持触媒
を用いて高圧接触還元することで、下記式［ｒｌで示す
２−アミノインダンを得ることができる。According to the production method of the present invention, 2 represented by the following formula [I+]
- By subjecting indanone oxime to high-pressure catalytic reduction using a nickel-supported catalyst in a polar solvent, 2-aminoindan represented by the following formula [rl] can be obtained.
（上記式中Ｒは、水素、低級アルキル基、低級アルコキ
シ基、またはハロゲンを示す。(R in the above formula represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen.
θ〜４までの整数を示す。）
ｎは
本発明の出発原料である２−インダノンオキシムは、下
記式［Ｉ＋ ］で示される。Indicates an integer from θ to 4. ) 2-indanone oxime, where n is the starting material of the present invention, is represented by the following formula [I+].
置換基Ｒは、水素、低級アルキル基、低級アルコキシ基
またはハロゲンを表す。The substituent R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen.
低級アルキル基としては、メチル基、エチル基、プロピ
ル基、ブチル基等が挙げられる。Examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like.
低級アルコキシ基としては、メトキシ基、エトキシ基、
プロポキシ基、ブトキシ基等が挙げられる。Examples of lower alkoxy groups include methoxy group, ethoxy group,
Examples include propoxy group and butoxy group.
また、置換基Ｒは、特に存在していなくてもよく置換基
の数ｎは０〜４までの整数を表す。Further, the substituent R may not be particularly present, and the number n of substituents represents an integer from 0 to 4.
本発明の２−インダノンオキシム［ＴＩ ］を還元する
ために用いる触媒としてはニッケルを適当な担体、たと
えば珪藻土、シリカ・アルミナ、シリカ、アルミナなど
に担持したものが挙げられる。 このニッケル担持触媒
は取り扱いが容易で、かつ、安価である。 このニッケ
ル担持触媒は、特には、触媒表面を一部酸化し、安定化
させたものを用いるのがよい。The catalyst used for reducing 2-indanone oxime [TI2] of the present invention includes those in which nickel is supported on a suitable carrier such as diatomaceous earth, silica-alumina, silica, alumina, etc. This nickel-supported catalyst is easy to handle and inexpensive. It is particularly preferable to use a nickel-supported catalyst whose surface is partially oxidized and stabilized.
触媒の添加量は、２−インダノンオキシム［Ｉ＋ ］に
対して１重量％以上、より好ましくは５重量％以上用い
るのがよい。 ２０重量％を超えて加えてもよいが、特
に実質的な効果は向上せず、５〜２０重量％が適当な範
囲である。The amount of the catalyst added is preferably 1% by weight or more, more preferably 5% by weight or more, based on 2-indanone oxime [I+]. Although it may be added in an amount exceeding 20% by weight, the substantial effect is not particularly improved, and the appropriate range is 5 to 20% by weight.
また、本発明の合成方法は、液相接触還元であり、極性
溶媒中にて行なう。Furthermore, the synthesis method of the present invention is a liquid phase catalytic reduction, which is carried out in a polar solvent.
極性溶媒としてはエーテル、アルコール系のものが一般
にオキシムに対して高い溶解性を示し、好都合である。Ether and alcohol-based polar solvents generally exhibit high solubility for oximes and are convenient.
たとえば、ジエチルエーテル、テトラヒドロフラン、
メタノール、エタノール、プロパツール、ｆｓｏ−プロ
パツール、ブタノール、１ｓｏ−ブタノール、ｔｅｒｔ
−ブタノール、アミルアルコール、１ｓｏ−アミルアル
コール、ｔａｒｔ−アミルアルコールなどが挙げられる
。 特に収率の点でテトラヒドロフランおよび炭素数３
〜５の低級アルコールがより効果的である。For example, diethyl ether, tetrahydrofuran,
methanol, ethanol, propatool, fso-propatool, butanol, 1so-butanol, tert
-butanol, amyl alcohol, 1so-amyl alcohol, tart-amyl alcohol, and the like. Especially in terms of yield, tetrahydrofuran and carbon number 3
-5 lower alcohols are more effective.
さらに本発明は、上述の極性溶媒、ニッケル担持触媒中
、高圧条件下で還元を行なう。 高圧条件下で反応を行
なうためには、高圧設備を必要とするが、その反面、他
に添加物を用いなく−Ｃも２−アミノインダン［Ｉ］を
高収率で得ることができる。Furthermore, in the present invention, the reduction is carried out under high pressure conditions in the above-mentioned polar solvent and nickel-supported catalyst. Although high-pressure equipment is required to carry out the reaction under high-pressure conditions, -C-2-aminoindan [I] can also be obtained in high yield without using any other additives.
反応時におりる、水素圧力および反応温度は反応速度、
選択率、収率に影響を及ぼす。 たとえば、水素圧力が
低すぎると主反応の水素化が進行しにくくなる。 検討
の結果、３０〜２００ ｊｔｇｆ／ｃｍ’ 、より好ま
しくは５０〜１５０にｇｆ／ｃｍ’の水素圧力が適当で
ある。The hydrogen pressure and reaction temperature during the reaction are the reaction rate,
Affects selectivity and yield. For example, if the hydrogen pressure is too low, the hydrogenation of the main reaction will be difficult to proceed. As a result of studies, a hydrogen pressure of 30 to 200 gf/cm', more preferably 50 to 150 gf/cm', is appropriate.
また反応温度に関して、本反応系に好ましい温度条件は
１１０〜１８０℃であり、より好ましくは１２０〜１４
０℃である。 しかし、１８０℃超とすると、ベンゼン
核に対する水素化活性を示すようになるので好ましくな
い。Regarding the reaction temperature, the preferred temperature conditions for this reaction system are 110 to 180°C, more preferably 120 to 140°C.
It is 0°C. However, if the temperature exceeds 180°C, hydrogenation activity for benzene nuclei will be exhibited, which is not preferable.
以上の条件で１０分〜３時間、より好ましくは２０分〜
１時間撹拌を行なうと水素消費が停止し、その時点で反
応工程を終了する。Under the above conditions, 10 minutes to 3 hours, more preferably 20 minutes to
After stirring for 1 hour, hydrogen consumption stops and the reaction process is terminated at that point.
この反応によって生成される２−アミノインダンは、下
記式［■］で示される。The 2-aminoindan produced by this reaction is represented by the following formula [■].
置換基Ｒは、水素、低級アルキル基、低級アルコキシ基
またはハロゲンを表し、これら置換基の詳細については
２−インダノンオキシム式［０］と同様である。The substituent R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen, and the details of these substituents are the same as in the 2-indanone oxime formula [0].
また、これら置換基の数ｎは０〜４までの整数であれば
よい。Further, the number n of these substituents may be an integer from 0 to 4.
さらに本発明は、２−インダノンオキシム式［Ｉ＋ ］
から］２−アミノインダン式Ｉ］を合成した後、反応液
中に存在する触媒を分離し、塩化水素と反応させること
で、下記式［Ｉｌ＋ ］に示す２−アミノインダン塩酸
塩を製造することができる。Furthermore, the present invention provides 2-indanone oxime formula [I+]
After synthesizing 2-aminoindan formula I], the catalyst present in the reaction solution is separated and reacted with hydrogen chloride to produce 2-aminoindan hydrochloride shown in the following formula [Il+]. I can do it.
置換基Ｒは、水素、低級アルキル基、低級アルコキシ基
またはハロゲンを示し、これら置換基の詳細については
、２−インダノンオキシム式［ＴＩ ］と同様である。The substituent R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen, and details of these substituents are the same as in the 2-indanone oxime formula [TI].
また、これら置換基の数ｎは、０〜４までの整数を表
す。Moreover, the number n of these substituents represents an integer from 0 to 4.
まず、２−アミノインダンを合成反応終了後、反応生成
液をｆ通して触媒を分離する。 生成液中の成分は２−
アミノインダン式［■］、溶媒および反応副生物である
。 この中に塩化水素ガスを導入すれば、２−アミノイ
ンダン式［！］のみを２−アミノインダン塩酸塩式［Ｉ
ＩＩ ］の結晶として析出させることができる。 結晶
はｆ過で分離し、反応溶媒またはその他の揮発性有機溶
媒で洗浄したのち乾燥を行なう。 以上の操作により、
高純度な２−アミノインダン塩酸塩式［Ｉ１１コの白色
結晶が得られる。First, after the synthesis reaction of 2-aminoindan is completed, the reaction product liquid is passed through f to separate the catalyst. The components in the product liquid are 2-
Aminoindan formula [■], solvent and reaction by-product. If hydrogen chloride gas is introduced into this, the 2-aminoindan formula [! ] only 2-aminoindan hydrochloride formula [I
II] can be precipitated as crystals. The crystals are separated by filtration, washed with a reaction solvent or other volatile organic solvent, and then dried. By the above operations,
Highly pure white crystals of 2-aminoindan hydrochloride formula [I11] are obtained.
〈実施例〉
以下に、本発明を実施例に基づいて、さらに具体的に説
明する。<Examples> The present invention will be described in more detail below based on Examples.
（実施例１）
ステンレス製オートクレーブに２−インダノンオキシム
１５．０ｇ （０，１０２ｍｏｌ）、ニッケル珪藻±０
．１５ｇ、テトラヒドロフラン５０．０ｇを仕込んだ。(Example 1) 15.0 g (0,102 mol) of 2-indanone oxime and nickel diatom ±0 in a stainless steel autoclave
．． 15 g and 50.0 g of tetrahydrofuran were charged.
オートクレーブ内を窒素ガスで置換した後、水素を９
０ Ｋｇｆ／ｃｍ’の圧力で充填した。 電気炉により
１３０℃に昇温後、３０分間撹拌を行なった。 オート
クレーブを冷却して水素の残ガスを放出した後、反応生
成液を抜き出し触媒をｆ過分前した。 この液中に存在
する２−アミノインダンは、ガスクロマトグラフィーに
よる定量から０．０７８ｍｏ＋であり、反応収率は７６
％であった。After replacing the inside of the autoclave with nitrogen gas, hydrogen was replaced with 9
It was filled with a pressure of 0 Kgf/cm'. After raising the temperature to 130° C. using an electric furnace, stirring was performed for 30 minutes. After the autoclave was cooled and residual hydrogen gas was discharged, the reaction product liquid was extracted and the catalyst was thoroughly removed. The amount of 2-aminoindan present in this liquid was determined to be 0.078 mo+ by gas chromatography, and the reaction yield was 76
%Met.
次に、塩化水素ガスを常圧下で反応生成液中に導入して
、１時間撹拌を行なった。 析出した白色結晶はか過分
前により回収し、ナトラヒ１
ドロフランで洗浄した後、乾燥した。 回収した２−ア
ミノインダン塩酸塩は１２．０ｇで純度９９％以上、収
率は原料２−インダノンオキシム基準で７０％であフた
。Next, hydrogen chloride gas was introduced into the reaction product solution under normal pressure, and stirring was performed for 1 hour. The precipitated white crystals were collected before fractionation, washed with Natrahydrofuran, and then dried. The recovered 2-aminoindan hydrochloride weighed 12.0 g and had a purity of 99% or more, and the yield was 70% based on the raw material 2-indanone oxime.
（実施例２）
触媒としてシリカ・アルミナ担体に酸化ニッケルを担持
した触媒を０．１５ｇ用いた以外は実施例１と同様の操
作を行なった。(Example 2) The same operation as in Example 1 was performed except that 0.15 g of a catalyst in which nickel oxide was supported on a silica-alumina carrier was used as the catalyst.
接触還元による、２−アミノインダンの収率は７４％、
塩化水素ガス導入後の２−アミノインダン塩酸塩の収率
は６８％であった。The yield of 2-aminoindan by catalytic reduction was 74%.
The yield of 2-aminoindan hydrochloride after introducing hydrogen chloride gas was 68%.
（実施例３）
溶媒として１ｓｏ−アミルアルコールを５０．０ｇ用い
た以外は、実施例１と同様の操作を行なった。(Example 3) The same operation as in Example 1 was performed except that 50.0 g of 1so-amyl alcohol was used as the solvent.
２−アミノインダンの収率は６７％、２−アミノインダ
ン塩酸塩の収率は６０％であった。The yield of 2-aminoindan was 67%, and the yield of 2-aminoindan hydrochloride was 60%.
（比較例１）
溶媒としてベンゼンを用いた以外は、実施例 ２
１と同様の操作を行なった。 ２−アミノインダンの
収率は１２％であった。(Comparative Example 1) The same operation as in Example 21 was performed except that benzene was used as the solvent. The yield of 2-aminoindan was 12%.
（比較例２）
触媒として、５％パラジウムカーボンを用いた以外は、
実施例１と同様の操作を行なった。(Comparative Example 2) Except for using 5% palladium carbon as a catalyst,
The same operation as in Example 1 was performed.
２−アミノインダンの収率は２５％であった。The yield of 2-aminoindan was 25%.
〈発明の効果〉
本発明の方法によれば、還元時に特に添加物を必要とし
ないため、反応後の分離・精製工程を短縮することがで
きる。 そのため、工業的規模においても、経済的にし
かも従来の方法と比べても容易に、高い収率で２−アミ
ノインダン類を製造することができる。<Effects of the Invention> According to the method of the present invention, no additives are particularly required during reduction, so that the separation and purification steps after the reaction can be shortened. Therefore, even on an industrial scale, 2-aminoindanes can be produced economically and easily in high yields compared to conventional methods.
Claims (3)
するに際し、下記式［II］に示す２−インダノンオキシ
ムを極性溶媒中、ニッケル担持触媒を用いて高圧接触還
元することを特徴とする２−アミノインダンの製造方法
。 式［ I ］▲数式、化学式、表等があります▼ 式［II］▲数式、化学式、表等があります▼ （上記式中Ｒは、水素、低級アルキル基、低級アルコキ
シ基、またはハロゲンを示す。ｎは０〜４までの整数を
示す。）(1) When producing the 2-aminoindan shown in the following formula [I], the 2-indanone oxime shown in the following formula [II] is subjected to high-pressure catalytic reduction using a nickel-supported catalyst in a polar solvent. A method for producing 2-aminoindan. Formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen. n indicates an integer from 0 to 4.)
または炭素数３〜５の低級アルコールを用いる請求項１
に記載の２−アミノインダン類の製造方法。(2) Tetrahydrofuran and/or as the polar solvent
or Claim 1 using a lower alcohol having 3 to 5 carbon atoms.
The method for producing 2-aminoindanes as described in .
る触媒を分離し、塩化水素で処理することにより、下記
式［III］に示す２−アミノインダン塩酸塩を製造する
ことを特徴とする２−アミノインダン塩酸塩の製造方法
。 式［III］▲数式、化学式、表等があります▼ （上記式中Ｒは、水素、低級アルキル基、低級アルコキ
シ基、またはハロゲンを示す。ｎは０〜４までの整数を
示す。）(3) The catalyst present in the reaction solution obtained in claim 1 or 2 is separated and treated with hydrogen chloride to produce 2-aminoindan hydrochloride represented by the following formula [III]. Characteristic method for producing 2-aminoindan hydrochloride. Formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R represents hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen. n represents an integer from 0 to 4.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1255051A JPH03118351A (en) | 1989-09-29 | 1989-09-29 | Production of 2-aminoindane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1255051A JPH03118351A (en) | 1989-09-29 | 1989-09-29 | Production of 2-aminoindane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03118351A true JPH03118351A (en) | 1991-05-20 |
Family
ID=17273475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1255051A Pending JPH03118351A (en) | 1989-09-29 | 1989-09-29 | Production of 2-aminoindane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03118351A (en) |
-
1989
- 1989-09-29 JP JP1255051A patent/JPH03118351A/en active Pending
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