WO1982000032A1 - Procede de preparation d'indoles - Google Patents

Procede de preparation d'indoles Download PDF

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Publication number
WO1982000032A1
WO1982000032A1 PCT/JP1980/000146 JP8000146W WO8200032A1 WO 1982000032 A1 WO1982000032 A1 WO 1982000032A1 JP 8000146 W JP8000146 W JP 8000146W WO 8200032 A1 WO8200032 A1 WO 8200032A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
oxide
group
solid acid
silica
Prior art date
Application number
PCT/JP1980/000146
Other languages
English (en)
Japanese (ja)
Inventor
Seiyaku Co Ltd Tanabe
Original Assignee
Tsuchiya M
Matsuoka M
Tokuda Y
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tsuchiya M, Matsuoka M, Tokuda Y filed Critical Tsuchiya M
Priority to PCT/JP1980/000146 priority Critical patent/WO1982000032A1/fr
Publication of WO1982000032A1 publication Critical patent/WO1982000032A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring

Definitions

  • the present invention is fin dollars such and H 'to the preparation s further more and rather is ⁇ two Li down such a grayed Li co Lumpur acids also rather is O key Size Lee earths and dehydration dehydrogenation activity
  • the present invention relates to a method for producing indole by performing a gas phase reaction in the presence of a solid catalyst. Background art
  • Indole is a compound useful as a raw material such as triple phan, fragrance, medicine, pesticide, and polymer stabilizer.
  • various methods are known for producing indoles by a gas phase reaction.
  • Japanese Patent No. 487-178163 contains 2-alkylanilines at 500-750 ° C and contains iron oxide catalysts containing iron metal compounds. It is disclosed that by contacting with, it is possible to obtain reindoles.
  • Japanese Patent Application Laid-Open No. 48-579766 discloses that 0-nitrosolic benzene is used in the temperature range of 300 to 550 ° G. Alternatively, by contacting with a catalyst containing platinum, it is possible to obtain a reinforce-like force; the power to be obtained is disclosed.
  • aniline and glycols or oxides can be dehydrated in the presence of a solid acid catalyst having dehydrating hydrogen activity. It has been found that if they are subjected to a gas phase reaction, they can easily produce indoles. That is, according to the present invention,
  • R 1 represents a hydrogen atom, an alkyl group, an aryl 'group or an alkyl group
  • R 2 represents an alkylene group or an alkoxy group.
  • Table Wa and s 11 is an integer of ⁇ ⁇ 4)
  • R 3 ⁇ are the same or horn such One to Table Wa hydrogen or ⁇ Le key Le group, R 5 and R 6 ⁇ - or different - represents a hydrogen atom or an aralkyl key Le group Do Tsu )
  • R 1 to R 4 and ⁇ have the same meanings as described above).
  • the aniline used in the method of the present invention is produced by the following method.
  • R 1 is a hydrogen atom; a methyl group; an ethyl group, an ⁇ -propyl group, an isopyl pill group, and a butyl group.
  • Chi Honoré group (3 Bok 4 ⁇ Honoré key Le group 5 off e alkylsulfonyl group ⁇ conversion full - two Le group (e.g.
  • main Chi le full We two Le group 9 main preparative key sheet full - two Le group Aryl groups such as Ci-4 alkyl group to Ci-4 alkyl group-substituted phenyl group); or benzyl group, K-substituted benzyl group ( For example, a methyl benzyl group, a methyl benzyl group, a Ci- 4 alkyl group to a quaternary 4 alkoxy group-substituted benzyl group, etc.
  • N-tono resin 1 — phenol-tono resin
  • N-F-2-P-Tonage N-benzolene-no-rezin
  • Ieba ' -benzhenol-o-tohrenzin
  • Anilgin for example; p-tolidine
  • o-anisigine m-anisigine P—anisigine
  • N-alkylanisigine 'eg N-meta-P-anisegine
  • di emissions N - Echiru - P - Anishi down
  • N - full et d Le ⁇ two Shi di emissions eg; 3ST - full et two Le - p - ⁇ two sheets di emissions
  • N - pen di Honoré A Power eg, N ⁇ - ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ .
  • glycols include a hydrogen atom in which R 3 and R are the same or different in the formula (H); or a methyl group, an ethyl group, an n-propyl group.
  • An alkyl group such as a propyl group or an n-butyl group, wherein R5 and R5 are the same or different and are each a hydrogen atom, a methionole group, an ethyl group, or a propyl group;
  • Compounds that are phenolic groups such as a pill group and an n-butyl group are exemplified.
  • glycols include ethylene glycol, propylene glycol, 1,2-butylene glycol, 2 , 3-butyrene glycol, etc.
  • Ethylene lithium 'monomethynoethylene, ethylen', alcohol mono-n-butyl ether, and the like;
  • R 3 and R 3 are the same or different and a hydrogen atom: or a methyl group-ethyl group, an n-propynole group 9
  • Examples include compounds that are alkyl groups of Gi- 4 such as n-butyl groups, and a typical example of such oxides is ethylene oxide. , Propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, etc.
  • the catalyst used in the method of the present invention may be any solid acid catalyst having dehydration / dehydrogenation activity.
  • examples of such catalysts include aluminum oxide and kerosene oxide.
  • a solid acid catalyst having at least one selected from activated carbon as a constituent component is to re mosquito catalyst s A Le Mi Na catalyst, shea Li Ca - A Le Mi Na catalyst, Ru include pumice catalyst or activated carbon catalyst. These catalysts may optionally carry a metal oxide.
  • metal oxides are aluminum metal oxides (eg, sodium oxide and potassium oxide); alkaline metal oxides (eg, magnesium oxide) , Calcium oxide); zinc oxide, silicon oxide antioxidant; bismuth oxide
  • silica catalysts aluminum catalysts, silica-alumina catalysts 5 or sodium oxides for these catalysts.
  • Um potassium oxide; oxidation Examples of such catalysts include metal oxides such as lead, chromium oxide, iron oxide, and nickel oxide.
  • the aniline (I) and the glycol (II) or the oxide () are reacted in the gas phase with the above-mentioned large catalyst in the gas phase. 4 0 0. This can be achieved by contacting with C.
  • anilines (I) and glycols (E) or oxides') are vaporized in a vaporizer and reacted in a vapor state. It is preferable to introduce it in the vessel.
  • the molar ratio of glycols ( ⁇ ) or glyoxides ( ⁇ ') to anilines (I) is 0.5 to I 0. : 1 is preferred. Below a molar specific force of 0.5: 1, the decomposition of aniline increases, and above 10: 1, side reactions increase. It is also preferable to introduce these starting compounds into the reactor together with the inert diluent.
  • Such diluents include, for example, steam 3 nitrogen gas, gas carbonate, benzene vapor, toluene vapor, or a mixture thereof.
  • the initial partial pressure of the aniline (I) is preferably in the range of 0.01 to 0.1 atm.
  • the reaction temperature is preferably 250 to 400 ° C.
  • a particularly preferred reaction temperature is 275-350 C C.
  • the reaction can be carried out under reduced pressure, atmospheric pressure or reduced pressure, but it is generally preferred to carry out the reaction at atmospheric pressure.
  • the contact time () defined by the following equation is 10 to 100 ⁇ ⁇ cat iir / mole, preferably 20 to 200 ⁇ ⁇ cat-r / mole. Is preferred. (Contact time)
  • reaction mixture is cooled and collected as condensate at a total flow rate (Pmols / hr) per hour.
  • This condensate contains indole and unreacted starting compound, which can be extracted by distillation 9 or by a method such as derivation to an acid addition salt (for example, salt salt). It can be separated more. Unreacted starting compounds can be reused in the reaction of the present invention.
  • Examples of the indole obtained by the above method of the present invention include an indole, a 1-methyl indole, a 1-ethylindole, 1 1 Feninoreindoru, 1 1 Benjinoreindoru, 3-Methylinoredo-Nore, 4-Methylinoledole, 5-Methylinole WINDOWS-NODE-6-METINOLEINDOLE, 7-METHONOINDLE, 1,2-DIMENSION NODE INDEX, 1, 3-DIMENSION 1,4-dimethyl indole, 1,5-dimethyl indole, 1,6-dimethyl indole, 1, 7 — dimethyl indole ; 3, 4 dimethyl indole, 3, 5 — dimethyl indole, 3, 6-dimethyl ind Dor, 3 7 - di main Chi le Lee down de one Nore, 1-ethylnole-2-methylindole-Nore, 1-ethylnole
  • the gas phase reaction can be carried out at a relatively low temperature (250-400 ° C); (3) It is sufficient to use a very common solid acid catalyst as a catalyst. It is not necessary to use a catalyst supporting expensive noble metals or harmful heavy metals; (4) By selecting the raw material compounds appropriately, it is possible to produce various indoles. (5) N-substituted indole can be produced with high yield and high selectivity. Therefore, the method of the present invention is extremely excellent as a method for producing indole.
  • the method of the present invention will be described with reference to examples, but the present invention is not limited thereto.
  • quartz tubular reactor "eobead P" (Mizusawa Chemical Industry (lintel), chemical composition (Weight%); A1 2 0 3: Si0 2: Na 2 D two 8 8: 9: 3) was filled with 20 ⁇ and ripened in a tubular electric furnace. A mixture of aniline vapor, ethyl alcohol vapor, water vapor, nitrogen gas and Z or benzene vapor was introduced into the reactor under the following conditions. did.
  • a quartz tubular reactor with an inner diameter of 2 2-and a length of 30.0 mm was filled with the catalyst 30 ⁇ shown in Table 8 and heated in a tubular electric furnace.
  • a mixture of aniline vapor, ethylene glycol vapor, steam and nitrogen gas was introduced into this reactor under the following conditions. .
  • the chemical composition (weight / 0) of "Neobead P, C or D" (manufactured by Mizusawa Chemical Industry Co., Ltd.) used as the catalyst is as follows.
  • a quartz tubular reactor having an inner diameter of 22 and a length of 300 was filled with the catalyst 20 ⁇ shown in Table 10 and heated in a tubular electric furnace.
  • a mixture of aniline vapor, diethylene chloride vapor, steam and nitrogen gas was added under the following conditions.
  • N-ethylaniline and ethylene glycol are the first

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)

Abstract

Procede de preparation d'indoles representes par la formule generale suivante: (FORMULE) (ou R1 represente un atome d'hydrogene, un groupe alkyle, un groupe aryle, ou un groupe aralkyle, R2 represente un groupe alkyle ou un groupe alcoxy, R3 et R4, sont identiques ou differents, et representent chacun un atome d'hydrogene ou un groupe alkyle, R5 et R6, identiques ou differents representent chacun un atome d'hydrogene ou un groupe alkyle, et n represente un nombre entier de 0 a 4) consiste a faire reagir une aniline representee par la formule generale suivante: (FORMULE) avec un glycole ou un oxyde represente par la formule generale suivante: (FORMULE) a une temperature comprise entre 250 et 400 C en phase gazeuse en presence d'un catalyseur acide solide ayant une activite de deshydratation et de deshydrogenation.
PCT/JP1980/000146 1980-06-25 1980-06-25 Procede de preparation d'indoles WO1982000032A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP1980/000146 WO1982000032A1 (fr) 1980-06-25 1980-06-25 Procede de preparation d'indoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/JP1980/000146 WO1982000032A1 (fr) 1980-06-25 1980-06-25 Procede de preparation d'indoles
WOJP80/00146800625 1980-06-25

Publications (1)

Publication Number Publication Date
WO1982000032A1 true WO1982000032A1 (fr) 1982-02-07

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0069242A2 (fr) * 1981-06-12 1983-01-12 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation d'indoles
EP0075019A1 (fr) * 1981-03-25 1983-03-30 MITSUI TOATSU CHEMICALS, Inc. Procede de preparation d'indole et de derives d'indole
FR2529202A1 (fr) * 1982-06-24 1983-12-30 Mitsui Toatsu Chemicals Procede de preparation d'indoles
US4956174A (en) * 1986-03-06 1990-09-11 L'oreal Compositions for coloring the skin based on indole derivatives
US7612099B2 (en) 2005-12-01 2009-11-03 Hoffmann-La Roche Inc. Vinylogous acid derivatives
US7705034B2 (en) 2006-10-13 2010-04-27 Hoffmann-La Roche Inc. Vinylogous acid derivatives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4857968A (fr) * 1971-11-29 1973-08-14
JPS5188962A (ja) * 1975-02-03 1976-08-04 Indoorunoseizoho

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4857968A (fr) * 1971-11-29 1973-08-14
JPS5188962A (ja) * 1975-02-03 1976-08-04 Indoorunoseizoho

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075019A1 (fr) * 1981-03-25 1983-03-30 MITSUI TOATSU CHEMICALS, Inc. Procede de preparation d'indole et de derives d'indole
EP0075019A4 (fr) * 1981-03-25 1983-08-09 Mitsui Toatsu Chemicals Procede de preparation d'indole et de derives d'indole.
EP0069242A2 (fr) * 1981-06-12 1983-01-12 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation d'indoles
EP0069242A3 (en) * 1981-06-12 1983-04-27 Mitsui Toatsu Chemicals, Incorporated Process for the preparation of indoles
FR2529202A1 (fr) * 1982-06-24 1983-12-30 Mitsui Toatsu Chemicals Procede de preparation d'indoles
US4956174A (en) * 1986-03-06 1990-09-11 L'oreal Compositions for coloring the skin based on indole derivatives
US7612099B2 (en) 2005-12-01 2009-11-03 Hoffmann-La Roche Inc. Vinylogous acid derivatives
US7705034B2 (en) 2006-10-13 2010-04-27 Hoffmann-La Roche Inc. Vinylogous acid derivatives

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