WO1993017787A1 - Catalyseur et procede de production de pyrrolidones d'alkyle - Google Patents

Catalyseur et procede de production de pyrrolidones d'alkyle Download PDF

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Publication number
WO1993017787A1
WO1993017787A1 PCT/US1993/001397 US9301397W WO9317787A1 WO 1993017787 A1 WO1993017787 A1 WO 1993017787A1 US 9301397 W US9301397 W US 9301397W WO 9317787 A1 WO9317787 A1 WO 9317787A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
alcohol
pyrrolidone
copper
mixture
Prior art date
Application number
PCT/US1993/001397
Other languages
English (en)
Inventor
Lowell R. Anderson
Ratan K. Chaudhuri
Robert B. Login
Waldo De Thomas
Original Assignee
Isp Investments Inc.
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 Isp Investments Inc. filed Critical Isp Investments Inc.
Publication of WO1993017787A1 publication Critical patent/WO1993017787A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C07D211/76—Oxygen atoms attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2

Definitions

  • This invention relates to catalysts and more particularly to catalysts for producing alkyl substituted pyrrolidones from alcohols and 2-pyrrolidone.
  • N-substituted 2-pyrrolidones are produced by the reaction of butyrolactone with the corresponding amine.
  • amines are more costly than corresponding alcohols since they are prepared from the alcohols, requiring an extra processing step.
  • the amines are produced in less than quantitative yields due to the formation of secondary and tertiary amines. Consequently, it would be economically desirable- to prepare N-substituted pyrrolidones directly from alcohols and 2- pyrrolidone, providing the yields are sufficiently high.
  • a method which utilizes copper catalysts in a hydrogen atmosphere at temperatures of 180 to 450°C to react various alcohols with 2-pyrrolidone.
  • the catalysts discussed are copper, copper-chromium, copper- rhenium, copper-silver, copper-nickel, copper-molybdenum, copper-manganese, copper-tungsten, and a copper-chromium- manganese catalyst. These were found to provide satisfactory selectivity relative to alcohol and pyrrolidone, however the yields were fairly low.
  • a catalyst for converting various alcohols and cyclic lactams to N-substituted cyclic lactams in a hydrogen environment comprises from 10 to 15% cooper, 0.01 to 0.15% palladium disposed on a carrier. Utilizing a copper-palladium catalyst produces noticeable improvements in yield and selectively over other catalysts, including those disclosed in the Japanese Application, particularly in the production of N-octyl 2- pyrrolidone. DETAILED DESCRIPTION OF THE INVENTION
  • the active catalytic components according 'to the present invention are copper and palladium deposited on a substrate support material. While various substrates could be used, a manganese silicate support substrate is preferred.
  • the active catalytic material copper and palladium
  • the active catalytic material are deposited on the substrate material by any conventional method.
  • metal salts are dissolved in either aqueous or organic solvents and dried on a substrate and then treated with hydrogen to form metal crystallites. While metal deposition from the nitrates is preferred, any acceptable route to form the metal crystallites on the substrate material may be used, such as hydrogen reduction of the salt to form the metal crystallites or oxidation of the salt in air followed by reduction in hydrogen.
  • the amounts of copper and palladium used may vary somewhat but are generally used in amounts based on catalyst plus support materials of 10 to 15% by weight copper, 0.01 to 0.15% palladium. Preferably, 10 to 12% copper and 0.09 to 0.13% palladium are used.
  • the catalyst is usable at temperatures of from about 150° to 400°C.
  • the inventive catalyst provides improved conversion and selectively in the conversion of alcohols and cyclic lactams of the Formula I to produce N-substituted lactams of the Formula II:
  • n is an integer from 2 to 20.
  • 2-pyrrolidone of Formula III is used, to produce the N-substituted pyrrolidones of Formula IV:
  • R', R" and R 1 are H or lower alkyl
  • R IV is
  • n 2 to 20.
  • the reactions described in the example can be varied to alter the characteristics of the catalyst. Longer reaction times and higher temperatures may produce catalysts which have an increase in effectiveness as it was found that during the initial reaction with copper nitrate, the longer reaction times, higher temperatures and higher acid levels may result in the production of a catalyst which has copper disposed deeper in the substrate. This tends to induce a stronger interaction of the copper with the substrate which increases the efficiency of the catalyst when used in the reaction of the invention.
  • a reaction was also carried out as described in example 2 using copper chromite and ruthenium catalysts as described in Table II which follows. Conditions such as pressure, temperature and time were also varied. The best results were obtained at a hydrogen pressure of 1,000 psi where the selectively was 50% and the yield was 39.7%. In addition, Raney copper, and copper-bismuth were also utilized, none of which were as effective as even the copper chromite catalyst.
  • inventive catalyst economic conversion of alcohols and 2-pyrrolidone or cyclic lactams to corresponding alkyl pyrrolidones and alkyl substituted lactams are achieved.
  • inventive process processing costs are reduced through the reduction in cost of raw materials for producing the finished product. For example, octylamine sells for approximately $2.50/pound while octyl alcohol sells for approximately $.83/pound.
  • the invention offers significant improvements over the prior art processes for producing N-substituted pyrrolidones. While preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes and modifications could be made without varying from the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Pyrrole Compounds (AREA)

Abstract

L'invention se rapporte à un catalyseur et à un procédé de production de pyrrolidones substituées par N. Ce procédé met en oeuvre un catalyseur de cuivre-palladium placé sur un support et mélangé à un alcool désiré et à 2-pyrrolidone. On effectue une réaction dans une atmosphère d'hydrogène, de préférence de 50 à 1000 psig, et à une température s'élévant jusqu'à 400 °C. En utilisant un catalyseur de cuivre-palladium, on obtient des résultats supérieurs au niveau de la sélectivité et du rendement par rapport aux catalyseurs précédents.
PCT/US1993/001397 1992-03-06 1993-02-18 Catalyseur et procede de production de pyrrolidones d'alkyle WO1993017787A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84713592A 1992-03-06 1992-03-06
US847,135 1992-03-06

Publications (1)

Publication Number Publication Date
WO1993017787A1 true WO1993017787A1 (fr) 1993-09-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/001397 WO1993017787A1 (fr) 1992-03-06 1993-02-18 Catalyseur et procede de production de pyrrolidones d'alkyle

Country Status (1)

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WO (1) WO1993017787A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0794176A1 (fr) * 1996-03-05 1997-09-10 Nippon Shokubai Co., Ltd. Procédé pour la préparation d'amines tertiaires
EP1067114A1 (fr) * 1999-07-05 2001-01-10 Atanor S.A. Méthode de préparation d'acide amino-, imino-, et nitrilocarboxyliques; catalyseur à base de cuivre activé à l'argent pour ledit procédé
WO2015158794A1 (fr) 2014-04-15 2015-10-22 Byk-Chemie Gmbh Préparations à base d'urée stables au stockage utilisables comme modificateurs de rhéologie

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU264249A1 (ru) * Катализатор для конверсии водяного газа
US2674602A (en) * 1954-04-06 Production of n-alkyl lactams
US3767644A (en) * 1970-12-30 1973-10-23 Asahi Chemical Ind Process for the preparation of n-alkyl substituted lactams
US3865814A (en) * 1972-07-28 1975-02-11 Inventa Ag Process for preparing n-substituted lactams
WO1980002023A1 (fr) * 1979-03-28 1980-10-02 Gallaher Ltd Procedes catalytiques et catalyseurs
US4845065A (en) * 1986-03-27 1989-07-04 Topy Industries, Ltd. And Japan Tobacco, Inc. Carbon monoxide oxidizing catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU264249A1 (ru) * Катализатор для конверсии водяного газа
US2674602A (en) * 1954-04-06 Production of n-alkyl lactams
US3767644A (en) * 1970-12-30 1973-10-23 Asahi Chemical Ind Process for the preparation of n-alkyl substituted lactams
US3865814A (en) * 1972-07-28 1975-02-11 Inventa Ag Process for preparing n-substituted lactams
WO1980002023A1 (fr) * 1979-03-28 1980-10-02 Gallaher Ltd Procedes catalytiques et catalyseurs
US4845065A (en) * 1986-03-27 1989-07-04 Topy Industries, Ltd. And Japan Tobacco, Inc. Carbon monoxide oxidizing catalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0794176A1 (fr) * 1996-03-05 1997-09-10 Nippon Shokubai Co., Ltd. Procédé pour la préparation d'amines tertiaires
US5847213A (en) * 1996-03-05 1998-12-08 Nippon Shokubai Co., Ltd. Process for production of tertiary amine compound
EP1067114A1 (fr) * 1999-07-05 2001-01-10 Atanor S.A. Méthode de préparation d'acide amino-, imino-, et nitrilocarboxyliques; catalyseur à base de cuivre activé à l'argent pour ledit procédé
WO2015158794A1 (fr) 2014-04-15 2015-10-22 Byk-Chemie Gmbh Préparations à base d'urée stables au stockage utilisables comme modificateurs de rhéologie
US9796860B2 (en) 2014-04-15 2017-10-24 Byk-Chemie Gmbh Storage-stable urea preparations which are suitable as rheology control agents

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