JPH03153665A - Preparation of indole and indole derivative - Google Patents
Preparation of indole and indole derivativeInfo
- Publication number
- JPH03153665A JPH03153665A JP1291351A JP29135189A JPH03153665A JP H03153665 A JPH03153665 A JP H03153665A JP 1291351 A JP1291351 A JP 1291351A JP 29135189 A JP29135189 A JP 29135189A JP H03153665 A JPH03153665 A JP H03153665A
- Authority
- JP
- Japan
- Prior art keywords
- indole
- catalyst
- reaction
- oxides
- present
- 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
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000002475 indoles Chemical class 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 5
- 150000001448 anilines Chemical class 0.000 claims description 10
- 229940054051 antipsychotic indole derivative Drugs 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- -1 aniline compound Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229930195212 Fischerindole Natural products 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YPKBCLZFIYBSHK-UHFFFAOYSA-N 5-methylindole Chemical compound CC1=CC=C2NC=CC2=C1 YPKBCLZFIYBSHK-UHFFFAOYSA-N 0.000 description 1
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- Indole Compounds (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、アニリン類と１．２−グリコール類とから液
相反応でインドールまたはインドール誘導体を製造する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing indole or indole derivatives from anilines and 1,2-glycols by liquid phase reaction.
従来の技術
従来、液相反応でインドール誘導体を製造ｔ ル方法と
して、古くはフェニルヒドラジンとアルデヒド基を持っ
た化合物とを反応させるフィッシャーのインドール合成
法がよく知られている。アルデヒド化合物がアセトアル
デヒド以外であれば上述したフィッシャーのインドール
合成法が適用でき、高収率でインドール誘導体が取得で
きるが、アルデヒド化合物がアセトアルデヒドの場合に
は反応が進行せず、インドールは生成しないとされてい
た。BACKGROUND OF THE INVENTION Fischer's indole synthesis method, in which phenylhydrazine and a compound having an aldehyde group are reacted, is well known as a method for producing indole derivatives by liquid phase reaction. If the aldehyde compound is other than acetaldehyde, Fischer's indole synthesis method described above can be applied and an indole derivative can be obtained in high yield. However, if the aldehyde compound is acetaldehyde, the reaction will not proceed and no indole will be produced. was.
別のインドールの製法として、オルト−トルイジンにギ
酸を反応させ、オルト−メチル−Ｎ−、ｈルミルアニリ
ンを製造し、これを水酸化カリウムと溶融して製造する
方法がある。この方法では、出発原料として用いられる
オルト−トルイジンは、通常、オルト体と同量以上のバ
ラ体が併産されている、したがって、副生物として併産
される異性体の処理が、工業的な生産の際に大きな問題
となる。また、アルカリ溶融のような固体の取扱は繁雑
であり、工業的生産には適したものとは言い難い。Another method for producing indole is to react ortho-toluidine with formic acid to produce ortho-methyl-N-,h-lumylaniline, which is then melted with potassium hydroxide. In this method, the ortho-toluidine used as a starting material is usually co-produced with the same amount or more of the bulk as the ortho-isomer. Therefore, the treatment of the isomer co-produced as a by-product is difficult to achieve industrially. This becomes a big problem during production. Furthermore, handling of solids such as alkali melting is complicated, and it is difficult to say that it is suitable for industrial production.
近年に至り、アニリン類とエチレングリコールのような
１．２−グリコール類との液相反応でインドール類を製
造する方法が提案されている。この方法は、安価な原ネ
４を用い、かつ−段の工程でインドールまたはインドー
ル誘導体が製造できるので、工業的製造法として魅力的
である。しかし、現在提案されている液相反応の方法は
、工業的に実施する上でいくつかの問題点があった。In recent years, methods have been proposed for producing indoles through a liquid phase reaction between anilines and 1,2-glycols such as ethylene glycol. This method is attractive as an industrial production method because it uses inexpensive raw material 4 and can produce indole or an indole derivative in a one-step process. However, the currently proposed liquid phase reaction methods have several problems in industrial implementation.
たとえば、特開昭５６−７３０６０号には第８族金属お
よび／または活性炭を触媒として用いる方法が開示され
ている。しかし、Ｎｉ％ ＣＯもしくはＦｅなどの卑金
属または活性炭の場合、収率は２０％台以下である。第
８族金属としてＰｄまたはＰｔのような貴金属を用いる
と、インドール類の収率は６０％台と高いが、触媒の使
用量が多く工業的に実施する上で問題がある。For example, JP-A-56-73060 discloses a method using a Group 8 metal and/or activated carbon as a catalyst. However, for base metals such as Ni% CO or Fe or activated carbon, the yield is on the order of 20% or less. When a noble metal such as Pd or Pt is used as the Group 8 metal, the yield of indoles is as high as 60%, but the amount of catalyst used is large, which poses a problem in industrial implementation.
また、特開昭５６−１１０６７２号には酸化マグネシウ
ムを触媒として使用する方法が開示されているが、本発
明者らの知見によるとこの触媒は活性の再現性に乏しく
、工業的規模で実施する場合、安定して高収率を得るこ
とが難しいという問題がある。In addition, JP-A-56-110672 discloses a method using magnesium oxide as a catalyst, but according to the findings of the present inventors, this catalyst has poor reproducibility of activity and is difficult to implement on an industrial scale. In this case, there is a problem that it is difficult to obtain a stable high yield.
本発明者らは特願昭６３−６９６７７号の中で種々の金
属酸化物が本願に記載された発明の反応に触媒作用を示
すことを開示しているが、収率の点でまだ満足できるも
のではない。The present inventors have disclosed in Japanese Patent Application No. 63-69677 that various metal oxides exhibit a catalytic effect on the reaction of the invention described in the present application, but the yield is still satisfactory. It's not a thing.
発明が解決しようとする課題
本発明の目的はアニリン類と１．２−グリコール類のよ
うな安価な原料を用い、かつ−段の液相反応でインドー
ルまたはインドール誘導体を工業的に製造する際に、改
良された触媒の存在下に行うインドールまたはインドー
ル誘導体の製造方法を提供することにある。Problems to be Solved by the Invention The purpose of the present invention is to solve the problem in the industrial production of indole or indole derivatives using inexpensive raw materials such as anilines and 1,2-glycols, and in a two-stage liquid phase reaction. An object of the present invention is to provide a method for producing indole or an indole derivative, which is carried out in the presence of an improved catalyst.
！！題を解決するための手段
本発明者らは、アニリン類と１．２−グリコール類とか
らインドールまたはインドール誘導体を製造するに際し
、特定の元素を含存する触媒を使用することによって本
発明の目的が達成されることを見出し、本発明を完成さ
せるに至った。! ! Means for Solving the Problem The present inventors have found that the object of the present invention can be achieved by using a catalyst containing a specific element when producing indole or an indole derivative from anilines and 1,2-glycols. They have found that this can be achieved and have completed the present invention.
すなわち、本発明は、
アニリン類と１，２−グリコール類とを、ＳｉとＣｕの
酸化物を含む触媒の存在下に１００〜５００℃の温度範
囲で液相反応させてインドールおよびインドール誘導体
を製造する際に、ＳｉとＣｕの酸化物の他に、 Ｎｉ、
Ｃｏ 、 Ｃｒ 、、Ｍｎ 、 Ｃａ 、、７
１ｇ。That is, the present invention produces indole and indole derivatives by subjecting anilines and 1,2-glycols to a liquid phase reaction in the temperature range of 100 to 500°C in the presence of a catalyst containing oxides of Si and Cu. In addition to Si and Cu oxides, Ni,
Co, Cr, Mn, Ca, 7
1g.
Ｚｎからなる群より選ばれた一種または二種以上の元素
の酸化物を含む触媒を使用することを特徴とするインド
ールまたはインドール誘導体の製造方法である。This is a method for producing indole or an indole derivative, characterized by using a catalyst containing an oxide of one or more elements selected from the group consisting of Zn.
本発明によれば、例えば、アニリンとエチレングリコー
ルとを反応させることによりインドールを、バラ−トル
イジンとエチレングリコールとを反応させることにより
、５−メチルインドールを得る゛ことができる。According to the present invention, for example, indole can be obtained by reacting aniline with ethylene glycol, and 5-methylindole can be obtained by reacting valatoluidine with ethylene glycol.
すなわち、本発明の利点は以下のとおりである。That is, the advantages of the present invention are as follows.
（１） 原料がアニリン類および１．２−グリコール
類のように非常に安価である。(1) Raw materials are very cheap, such as anilines and 1,2-glycols.
（２）原料からインドールまたはインドール誘導体が一
段で製造される。(2) Indole or an indole derivative is produced in one step from raw materials.
（３）安価な触媒を用いているにもかかわらず収率が高
いので、工業的にを利にインドールまたはインドール誘
導体が得られる。(3) Since the yield is high despite using an inexpensive catalyst, indole or indole derivatives can be obtained industrially.
本発明で使用されるアニリン類は、−ｍ式（１）（式中
、Ｒは、水素原子、ハロゲン原子、水酸基、アルキル基
またはアルコキシ基を示す）で表わされる化合物である
０例えば、アニリン、オルト−トルイジン、メタ−トル
イジン、バラ−トルイジン、オルト−ハロアニリン、メ
タ−ハロアニリン、バラ−ハロアニリン、オルト−アミ
ノフェノール、メタ−アミノフェノール、バラ−アミノ
フェノール、牙ルトーアニシジン、メタ−アニシジンお
よびバラ−アニシジンなどがあげられる。The anilines used in the present invention are compounds represented by formula (1) (wherein R represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group). For example, aniline, Ortho-toluidine, meta-toluidine, para-toluidine, ortho-haloaniline, meta-haloaniline, para-haloaniline, ortho-aminophenol, meta-aminophenol, para-aminophenol, lutho-anisidine, meta-anisidine and para-anisidine, etc. can be given.
本発明で使用される１、２−グリコール類は、エチレン
グリコール、プロピレングリコール、■。The 1,2-glycols used in the present invention include ethylene glycol, propylene glycol, and ■.
２−ブタンジオール、１．２．４−ブタントリオール、
２．３−ブタンジオールおよびジエチレングリコールな
どである。2-butanediol, 1.2.4-butanetriol,
These include 2,3-butanediol and diethylene glycol.
本発明は触媒の存在下で行われる。The invention is carried out in the presence of a catalyst.
本発明で使用される触媒は、ＳｉとＣｕの酸化物の他に
Ｎｉ、 Ｃｏ 、、Ｃｒ 、 門口、Ｃａ 、 Ｍ
ｇ、 Ｚｎからなる群より選ばれた一種または二種以
上の元素の酸化物を含む触媒である。The catalyst used in the present invention includes oxides of Si and Cu as well as Ni, Co, Cr, gate, Ca, M
It is a catalyst containing an oxide of one or more elements selected from the group consisting of g, Zn.
このような触媒の中でも、Ｃｕ／Ｓｉの原子比が１／９
〜６／４の範囲にある触媒が好ましい。Among such catalysts, the Cu/Si atomic ratio is 1/9.
Catalysts in the range of ~6/4 are preferred.
Ｎｉ、 Ｃｏ、 Ｃｒ、、Ｍｎ、 Ｃａ、？！ｇ
、、Ｚｎの合計とＳｉ、 Ｃｕの合計との原子比が０
．５／９．５〜５／Ｓの範囲にある触媒がさらに好まし
い。Ni, Co, Cr,, Mn, Ca,? ! g
,, the atomic ratio of the sum of Zn and the sum of Si and Cu is 0
．． More preferred are catalysts in the range of 5/9.5 to 5/S.
本発明で使用される触媒は、本技術分野で知られている
任意の方法により製造することができる。The catalyst used in the present invention can be made by any method known in the art.
すなわち、触媒構成元素の水可溶性塩を加水分解して水
酸化物とし、得られたゲルを乾燥、焼成する方法、また
は易分解性塩を空気中で熱分解する方法等により製造す
ることができる。That is, it can be produced by hydrolyzing a water-soluble salt of a catalyst constituent element to form a hydroxide, drying and calcining the resulting gel, or by thermally decomposing an easily decomposable salt in the air. .
これら触媒の本来持っている活性を有効に利用するため
に本技術分野で通常用いられる手段であるが、これら触
媒を担体に担持する方法も好ましく用いられる。Although these methods are commonly used in this technical field to effectively utilize the inherent activity of these catalysts, a method of supporting these catalysts on a carrier is also preferably used.
担体としては、−Ｃに使用されているものがいずれも使
用できる０通常、ケイソウ土、軽石、チタニア、シリカ
−アルミナ、アルミナ、マグネシア、シリカゲル、活性
炭、活性白土、石綿等が用いられる。これらの担体に前
記触媒を常法により担持させて担持触媒を調製する。前
記触媒の担体に対する担持量には待に制限はなく、通常
、担体に応じて適当量、たとえば１〜５Ｑｗｔ％の前記
触媒を担持させてよい。As the carrier, any of those used for -C can be used; diatomaceous earth, pumice, titania, silica-alumina, alumina, magnesia, silica gel, activated carbon, activated clay, asbestos, etc. are usually used. A supported catalyst is prepared by supporting the catalyst on these carriers by a conventional method. There is no particular limit to the amount of the catalyst supported on the carrier, and usually an appropriate amount, for example 1 to 5 Qwt%, of the catalyst may be supported depending on the carrier.
本発明は液相で実施する。The invention is practiced in the liquid phase.
反応はアニリン類および１，２−グリコール類との混合
物を前記触媒のなかから選ばれた一種以上の触媒の存在
下に加熱することにより実施される。ごの際、原料の稀
釈剤として、種々の溶剤を共存させることができる。こ
のような溶剤としては、例えば、ベンゼン、トルエン、
キシレン、ヘキサン、オクタン、流動パラフィン、メタ
ノール、エタノール、イソプロパツール、ジオキサン、
ジメチルホルムアミド、ジメチルスルホキシド、ピリジ
ン、Ｎ−メチルピロリドン、トリメチルアミン、ジエチ
ルアミン、トリエチルアミン、トリプロピルアミン、ト
リブチルアミン、ジフェニルアミンおよびトリフェニル
アミン等の有機溶剤があげられる。The reaction is carried out by heating a mixture of anilines and 1,2-glycols in the presence of one or more catalysts selected from the above catalysts. During this process, various solvents can be used as diluents for the raw materials. Examples of such solvents include benzene, toluene,
xylene, hexane, octane, liquid paraffin, methanol, ethanol, isopropanol, dioxane,
Examples include organic solvents such as dimethylformamide, dimethylsulfoxide, pyridine, N-methylpyrrolidone, trimethylamine, diethylamine, triethylamine, tripropylamine, tributylamine, diphenylamine, and triphenylamine.
この液相反応は固定層、流動層または移動層反応器、回
分式または連続式の液相反応装置で実施されるが、特に
限定はない。This liquid phase reaction is carried out in a fixed bed, fluidized bed or moving bed reactor, batch type or continuous liquid phase reactor, but is not particularly limited.
この反応において、使用する原料のアニリン類と１．２
−グリコール類の使用量は、アニリン類１モルに対して
１．２−グリコール類０．０５〜５モルの範囲、好まし
くは００１〜２モルの範囲である。In this reaction, the anilines used as raw materials and 1.2
- The amount of glycols to be used is in the range of 0.05 to 5 moles, preferably in the range of 0.01 to 2 moles, of 1,2-glycols per mole of aniline.
反応に用いられる触媒の使用量は、特に制限はないが、
一般に原料アニリン９１モルに対して、触媒成分として
０．０１〜２０ｇ、好ましくは０．１〜１０ｇの範囲で
ある。There is no particular restriction on the amount of catalyst used in the reaction, but
Generally, the amount of the catalyst component is in the range of 0.01 to 20 g, preferably 0.1 to 10 g, per 91 moles of raw aniline.
反応温度はｌＯＯ〜５００ ’Ｃの範囲、好ましくは１
５０〜４００ ’Ｃの範囲である。１００’Ｃ未満では
反応がほとんど進行せず、５００℃を越えると副生物の
生成が多くなり好ましくない０反応圧力は加圧または常
圧のいずれでもよい。The reaction temperature ranges from 100 to 500'C, preferably 1
It ranges from 50 to 400'C. At temperatures below 100'C, the reaction hardly proceeds, and at temperatures above 500'C, a large amount of by-products are produced, which is undesirable.The zero reaction pressure may be either elevated pressure or normal pressure.
本発明において、インドールまたはインドール誘導体は
、反応生成物から適当な方法、例えば蒸留のような常法
によって容易に分離精製できる。In the present invention, indole or an indole derivative can be easily separated and purified from the reaction product by an appropriate method, for example, a conventional method such as distillation.
実施例 以下に実施例を示して本発明をさらに説明する。Example The present invention will be further explained by showing examples below.
実施例１
内容積２００ｍ１の撹拌機付きＳＵＳ製オートクレーブ
中にアニリン９３．ｔｇ （１モル）、エチレングリコ
ール６．２ｇ （０，１モル）と共沈法で調製したＳｉ
ｆｔ−ＣｕＯ−Ｍｎ０ｚ（Ｓｉ／Ｃｕ／Ｍｎ原子比４／
３／３）触媒０．６５ｇを入れ、オートクレーブ中の空
気を窒素ガスで置換し、次いで水素ガスを圧力５ｋｇ／
ｃｍ”まで圧入した後、反応温度３５０℃，２時間オー
トクレーブを撹拌しながら反応させた０反応後、反応液
から触媒をろ別し、反応生成物をガスクロマトグラフで
分析したところ、エチレングリコール基準の収率７４％
でインドール（ＮＬと略称）が生成していることを認め
た。Example 1 93% of aniline was placed in an SUS autoclave with an internal volume of 200 m1 and equipped with a stirrer. Si prepared by coprecipitation method with tg (1 mol) and 6.2 g (0.1 mol) of ethylene glycol.
ft-CuO-Mn0z (Si/Cu/Mn atomic ratio 4/
3/3) Add 0.65g of catalyst, replace the air in the autoclave with nitrogen gas, and then replace hydrogen gas at a pressure of 5kg/
After the reaction was carried out at a reaction temperature of 350°C for 2 hours with stirring in an autoclave, the catalyst was filtered from the reaction solution and the reaction product was analyzed by gas chromatography. Yield 74%
It was recognized that indole (abbreviated as NL) was produced.
実施例２
実施例１と同様の反応を、触媒を第１表に示したものに
変えて行った０反応生成物をガスクロマトグラフで分析
した。第１表に結果を示す。Example 2 The same reaction as in Example 1 was carried out using the catalyst shown in Table 1, and the reaction product was analyzed by gas chromatography. Table 1 shows the results.
第１表
比較例」
実施例１と同様の反応を、触媒を第２表に示したものに
変えて行った０反応生成物をガスクロマトグラフで分析
した。第２表に結果を示す。Comparative Example in Table 1 The same reaction as in Example 1 was carried out using the catalyst shown in Table 2, and the reaction product was analyzed by gas chromatography. Table 2 shows the results.
第２表
発明の効果
本発明によれば、実施例と比較例との比較からあきらか
なように、インドールまたはインドール誘導体を高収率
で得ることができる。Table 2 Effects of the Invention According to the present invention, indole or indole derivatives can be obtained in high yield, as is clear from the comparison between Examples and Comparative Examples.
Claims (3)
Ｃｕの酸化物を含む触媒の存在下に１００〜５００℃の
温度範囲で液相反応させてインドールおよびインドール
誘導体を製造する際に、ＳｉとＣｕの酸化物の他に、Ｎ
ｉ、Ｃｏ、Ｃｒ、Ｍｎ、Ｃａ、Ｍｇ、Ｚｎからなる群よ
り選ばれた一種または二種以上の元素の酸化物を含む触
媒を使用することを特徴とするインドールまたはインド
ール誘導体の製造方法。(1) When producing indole and indole derivatives by subjecting anilines and 1,2-glycols to a liquid phase reaction in the temperature range of 100 to 500°C in the presence of a catalyst containing oxides of Si and Cu. , in addition to oxides of Si and Cu, N
A method for producing indole or an indole derivative, which comprises using a catalyst containing an oxide of one or more elements selected from the group consisting of i, Co, Cr, Mn, Ca, Mg, and Zn.
る請求項１に記載の方法。(2) The method according to claim 1, wherein the atomic ratio of Cu/Si is in the range of 1/9 to 6/4.
計とＳｉ、Ｃｕの合計との原子比が０．５／９．５〜５
／５の範囲である請求項１に記載の方法。(3) The atomic ratio of the total of Ni, Co, Cr, Mn, Ca, Mg, and Zn to the total of Si and Cu is 0.5/9.5 to 5
2. The method according to claim 1, wherein the range is /5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1291351A JP2795492B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing indole or indole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1291351A JP2795492B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing indole or indole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03153665A true JPH03153665A (en) | 1991-07-01 |
| JP2795492B2 JP2795492B2 (en) | 1998-09-10 |
Family
ID=17767805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1291351A Expired - Lifetime JP2795492B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing indole or indole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2795492B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256323A (en) * | 2019-04-26 | 2019-09-20 | 太原理工大学 | A kind of method of coal-ethylene glycol and aniline synthesis of indole |
-
1989
- 1989-11-10 JP JP1291351A patent/JP2795492B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256323A (en) * | 2019-04-26 | 2019-09-20 | 太原理工大学 | A kind of method of coal-ethylene glycol and aniline synthesis of indole |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2795492B2 (en) | 1998-09-10 |
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