WO2006016197A1 - Procédé catalytique à base de zéolite pour la préparation d’éthers aromatiques acylés - Google Patents

Procédé catalytique à base de zéolite pour la préparation d’éthers aromatiques acylés Download PDF

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WO2006016197A1
WO2006016197A1 PCT/IB2004/002443 IB2004002443W WO2006016197A1 WO 2006016197 A1 WO2006016197 A1 WO 2006016197A1 IB 2004002443 W IB2004002443 W IB 2004002443W WO 2006016197 A1 WO2006016197 A1 WO 2006016197A1
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zeolite
veratrole
anisole
aromatic ether
catalyst
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PCT/IB2004/002443
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English (en)
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Raksh Vir Jasra
Beena Tyagi
Yogiraj Mansukhlal Badheka
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Council Of Scientific & Industrial Research
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Priority to EP04744096A priority Critical patent/EP1786749A1/fr
Priority to PCT/IB2004/002443 priority patent/WO2006016197A1/fr
Publication of WO2006016197A1 publication Critical patent/WO2006016197A1/fr

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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to an improved zeolite based catalytic process for the preparation of acylated aromatic ethers and more particularly, the invention relates to catalysed acylation of anisole (methoxybenzene) and veratrole (1,2- dimethoxybenzene) for the preparation of acylated aromatic ether, namely, p-methoxyacetophenone and 3,4-dimethoxyacetophenone respectively using microporous alumino-silicates solids like zeolites.
  • acylated aromatic ethers are of commercial importance in the fine chemicals industries, as many synthetic fragrances and pharmaceutical contains an acyl group, and these ethers are useful intermediates.
  • Acylated anisole is used for synthesis of 2-(4-Methoxybenzoyl) benzoic acid, the sodium salt of which is used as sweetening agent.
  • acyf ⁇ ted veratrole is a synthon for preparation of vesnarinone l-(3,4-Dimethoxybenzoyl)-4(l,2,3,4-tetrahydro-2-oxo-6-quinolinyl) piperazine which is a cardiotonic drug.
  • Aromatic ethers are particularly acylated by using Friedel- Crafts acylation reaction.
  • German patent (DE 3809260, 1989, Botta A., et al.) wherein anisole and acetic anhydride were stirred for 3 hours with Mordenite zeolite catalysts at 160 0 C under 20 bar of nitrogen pressure to give 75% conversion with 98% selectivity for p-methoxyacetophenone.
  • This process has disadvantage of operating at high temperature and very high pressure and also needs a solvent.
  • the reported process is multi-step process wherein separation of the product with very high recovery is a limitation.
  • the main object of the present invention is to provide an improved zeolite based catalytic process for the preparation of acylated aromatic ethers, which obviates the drawbacks as detailed above.
  • Another object of the present invention is to develop crystalline micro porous alumino-silicate catalyst based acylation process for aromatic ethers, which operates at moderate conditions of pressure, temperature and without the requirement of any solvent and yields high conversions for veratrole and anisole.
  • Yet another object of the present invention is to provide a process for acylation of aromatic ethers using solid acid heterogeneous catalysts, which are environmentally friendly and safe in handling.
  • Still another object of the present invention is to provide a process for acylation of aromatic ether selectively at para position.
  • a further object of the present invention is to provide a process for acylation of aromatic ethers wherein the acylating agent used does not generate any hazardous by-product.
  • a further more object of the present invention is to provide a process where acylation of aromatic ether is carried out catalytically with high atom economy without giving rise to by ⁇ products.
  • the present invention provides an improved zeolite based catalytic process for the production of acylated aromatic ethers, which comprises the steps of:- a) reacting an aromatic ether selected from a group comprising of anisole and veratrole with an acylating agent at temperature in the range of 80-120 0 C for time period in the range of 1 to 8 hours without using any solvent, in the presence of rare earth exchanged zeolite catalyst having general formula:
  • M2 ⁇ 1O . AI2O3 . xSi ⁇ 2 . WH2O wherein: M is an alkali and/or lanthanide cation or proton; n is the valency of the metal M which may be alkali and/or lanthanide cations or protons; x is the SiO 2 / Al 2 O 3 ratio which may vary from 3 to 24 and W is the weight percentage of water adsorbed in the pores which may vary from 1 to 20% depending upon the relative humidity, temperature and zeolite type; Si/ Al ratio is in the range of 5.5 to 20; aromatic ether to catalyst ratio is in the range of 1:3 to 1:5; to form an acylated aromatic ether in reaction mixture; b) separating the zeolite catalyst from the reaction mixture of step (a); and c) separating the acylated aromatic ether from the mixture of step (b).
  • the acylated aromatic ether obtained is p-acyl veratrole when the aromatic ether used is veratrole.
  • the acylated aromatic ether obtained is p-acyl anisole when the aromatic ether used is anisole.
  • the zeolite catalyst used is selected from the group comprising of Zeolite - Y, Zeolite - B, mordenite, and ZSM-5. In still another embodiment of the present invention, the zeolite catalyst used has crystallinity in the range of 65 to 99%.
  • the amount of rare earth metals incorporated in the zeolite catalyst is in the range of 10 to 30% by wt.
  • the rare earth metals incorporated in the zeolite are selected from lanthanum, cerium, neodymium, praseodymium and samarium.
  • the acylating agent used is a chloride or anhydride of acetic acid.
  • step (c) wherein in step (c), the acylated aromatic ether is separated from the reaction mixture by distillation.
  • the zeolites prepared were characterized for crystallinity by using X-ray powder diffraction using Philips X'perts MPD model and for BET surface area using Micromeritics ASAP-surface area analyzers.
  • CSTR continuous stirred tank reactor
  • the flask was kept in an oil bath whose temperature was slowly raised to desired reaction temperature.
  • the content of the flask were analyzed by gas chromatography at different time intervals ranging from 1 to 8 hours.
  • the yield was followed over time by taking aliquots which were analyzed by Gas Chromatography HP model 6890 using capillary column HP-5.
  • zeolite based solid acid catalysts can be used both for anisole and veratrole acylation to produce selectively the desired p-acylated ether.
  • zeolite- ⁇ shows highest yields for both the compounds followed by zeolite Y.
  • Zeolite ZSM-5 and mordenite show very poor activity for this conversion. This probably is due to smaller cavity size of these zeolites compared to Zeolite ⁇ and Y which offers diffusional resistance to acylated products.
  • the various zeolite ⁇ studied the one modified by incorporating cerium into it showed highest yields both for anisole and veratrole.
  • Zeolite- beta and zeolite-Y are modified with rare earth in the range of 10 to 30 weight % to make the catalysts more compatible with acylation reactions.
  • the acylation reaction is carried out in single step so that the multi-step process can be avoided.
  • the lower temperature and pressure favours the selectivity for para position, which is desired.
  • the catalytic reaction proceeds at relatively moderate temperature of 100 0 C and at atmospheric pressure, which obviates the need of high temperature and pressure.
  • EXAMPLE 1 10 grams of sodium zeolite Beta was refluxed with 100 ml of IM aqueous solution of ammonium chloride for 6 hours at 80°C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was- dried over night at HO 0 C. The dried sample was calcined at 550 0 C in air for removing ammonia and the calcined solid was termed as zeolite H-Beta.
  • EXAMPLE 3 1Og of zeolite H- Beta prepared by the process described in Example- 1 was refluxed with 100 ml of IM aqueous solution of Cerium nitrate for 6 hours at 80°C. (The Cerium nitrate solution used was prepared by treating cerium oxide with nitric acid). This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550°C in air and the calcined solid was termed as zeolite Ce- Beta .
  • zeolite H- Beta prepared by the process described in Example-1 was refluxed with 100 ml of IM aqueous solution of Cerium nitrate for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at HO 0 C. The dried sample was calcined at 550 0 C in air and the calcined solid was termed as zeolite Ce- Beta. Acylation of veratrole (or anisole) was carried out following the procedure as described in Example-1 using Ce- Beta as a catalyst instead of H- Beta.
  • zeolite H- Beta prepared by the process described in Example-1 was refluxed wich 100 ml of IM aqueous solution of Cerium nitrate for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride tree as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550 0 C in air and the calcined solid was termed as zeolite Ce- Beta. Acylation of veratrole (or 7anisole) was carried out following the procedure as described in Example- 1 using Ce- Beta as a catalyst instead of H- Beta.
  • EXAMPLE 7 1Og of zeolite H- Beta prepared by the process described in Example- 1 was refluxed with 100 ml of IM (aqueous solution of Neodymium nitrate for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 55O 0 C in air and the calcined solid was termed as zeolite Nd- Beta. Acylation of veratrole (or anisole) was carried out following the procedure as described in Example- 1 using Nd- Beta as a catalyst instead of H- Beta. Same amounts of veratroleor anisole, acetic anhydride and catalyst were used . The percent yield of p-acyl veratrole obtained as shown in Table 1 varies from 66 to 73% and 33 to 64% respectively.
  • zeolite H- Beta prepared by the process described in Example- 1 was refluxed with 100 ml of IM aqueous solution of Praseodymium nitrate for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110°C. The dried sample was calcined at 550°C in air and the calcined solid was termed as zeolite Pr- Beta.
  • zeolite Sm- Beta 55O 0 C in air and calcined solid was termed as zeolite Sm- Beta.
  • Acylation of veratrole (or anisole) was carried out following the procedure as described in Example- 1 using Sm- Beta as a catalyst instead of H- Beta (same amounts of veratrole or anisole, acetic anhydride and catalyst were used).
  • the percent yield of p-acyl veratrole and p-acyl anisole obtained as shown in Table 1 varies from 36 to 60% and 26 to 47% respectively.
  • EXAMPLE 10 10 grams of zeolite, NaY, was refluxed with 100 ml of IM aqueous solution of Ammonium chloride for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550 0 C in air for removing ammonia and the calcined solid was termed as zeolite HY.
  • zeolite LaY 55O 0 C in air and the calcined solid was termed as zeolite LaY.
  • Acylation of veratrole (or anisole) was carried out following the procedure as described in Example- 1 using LaY as a catalyst instead of H ⁇ (same amounts of veratrole, acetic anhydride and catalyst were used).
  • zeolite CeY 550 0 C in air and the calcined solid was termed as zeolite CeY.
  • Acylation of veratrole ( or anisole) was carried out following the procedure as described in Example- 1 using CeY as a catalyst instead of H-Y. Same amounts of veratrole or anisole, acetic anhydride and catalyst were used. The percent yield of p-acyl veratrole and p-acyl anisole as shown in Table 1 from 56 to 79 and 34 and 62% respectively were obtained.
  • EXAMPLE 13 1Og of zeolite HY prepared by the process described in Example- 10 was refluxed with 100 ml of IM aqueous solution of Neodymium nitrate for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solutions thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550 0 C in air and the calcined solid was termed as zeolite NdY.
  • zeolite HY prepared by the process described in Example- 10 was refluxed with 100 ml of IM aqueous solution of Praseodymium nitrate for 6 hours at 80°C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550 0 C in air and the calcined solid was termed as zeolite PrY.
  • zeolite SmY 55O 0 C in air and the calcined solid was termed as zeolite SmY.
  • Acylation of veratrole (or anisole) was carried out following the procedure as described in Example- 1 using SmY as a catalyst instead of H-Y (same amounts of veratrole or anisole, acetic anhydride and catalyst were used).
  • the percent yield of p-acyl veratrole and p-acyl anisole obtained as shown in Table 1 varies from 39 to 61% and 7 to 35% respectively were obtained.
  • EXAMPLE 16 10 grams of zeolite sodium mordenite, NaM, was refluxed with 100 ml of IM aqueous solution of ammonium chloride for 6 hours at 80 0 C. This was followed by filtration, washing with hot distilled water till the filtrate became chloride free as checked by silver nitrate solution. Solid thus obtained was dried over night at 110 0 C. The dried sample was calcined at 550 0 C in air for removing ammonia and the calcined solid was termed as zeolite HM.
  • Regeneration of the catalyst used in Example-3 was done using filtration, washing with polar solvent like acetone or ethyl alcohol followed by drying at 110 0 C and activation at 400-500 0 C.
  • the catalyst thus regenerated gave 90% and 88% yields for veratrole acylation under acylating conditions described in Example-3 after first and second regeneration.
  • Atom utilization is calculated by dividing the molecular weight of the desired product by the sum of the all substances produced in the stoichiometric equation, i.e. if we consider the acylation of the anisole and veratrole by acetic anhydride by using zeolite, reactions are represented as under.
  • Catalyst being solid in nature can be easily separated the reaction mixture by filtration or centrifuge.
  • Zeolites being highly crystalline and thermally stable can be regenerated by thermal treatment and re-used.
  • Zeolite based catalysts are easy in handling in comparison conventional Friedel-Craft acylation catalysts like H 2 SO 4 , HF, AlCl 3 and other Lewis acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un procédé catalytique amélioré à base de zéolite pour la préparation d’éthers aromatiques acylés et plus particulièrement, l’invention porte sur l’acylation catalysée d’anisole (méthoxybenzène) et de vératrole (1,2- diméthoxybenzène) pour la préparation d’un éther aromatique acylé, à savoir un p-méthoxyacétophénone et un 3,4-diméthoxyacétophénone respectivement, à l’aide de solides d’aluminosilicates microporeux comme les zéolites.
PCT/IB2004/002443 2004-08-02 2004-08-02 Procédé catalytique à base de zéolite pour la préparation d’éthers aromatiques acylés WO2006016197A1 (fr)

Priority Applications (2)

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EP04744096A EP1786749A1 (fr) 2004-08-02 2004-08-02 Procédé catalytique à base de zéolite pour la préparation d"éthers aromatiques acylés
PCT/IB2004/002443 WO2006016197A1 (fr) 2004-08-02 2004-08-02 Procédé catalytique à base de zéolite pour la préparation d’éthers aromatiques acylés

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2592039A1 (fr) * 1985-12-23 1987-06-26 Centre Nat Rech Scient Procede d'acylation d'hydrocarbures aromatiques
DE3809260A1 (de) * 1988-03-19 1989-09-28 Bayer Ag Verfahren zur herstellung von in 4-stellung veretherten phenylketonen
US4960943A (en) * 1988-03-19 1990-10-02 Bayer Aktiengesellschaft Process for the preparation of phenylketones etherified in the 4-position
US6013840A (en) * 1995-05-12 2000-01-11 Rhodia Chimie Process for the acylation of aromatic ethers
EP1138662A1 (fr) * 2000-03-31 2001-10-04 Council of Scientific and Industrial Research Procédé pour la préparation de 4'-isobutylacétophénone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2592039A1 (fr) * 1985-12-23 1987-06-26 Centre Nat Rech Scient Procede d'acylation d'hydrocarbures aromatiques
DE3809260A1 (de) * 1988-03-19 1989-09-28 Bayer Ag Verfahren zur herstellung von in 4-stellung veretherten phenylketonen
US4960943A (en) * 1988-03-19 1990-10-02 Bayer Aktiengesellschaft Process for the preparation of phenylketones etherified in the 4-position
US6013840A (en) * 1995-05-12 2000-01-11 Rhodia Chimie Process for the acylation of aromatic ethers
EP1138662A1 (fr) * 2000-03-31 2001-10-04 Council of Scientific and Industrial Research Procédé pour la préparation de 4'-isobutylacétophénone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAARE K ET AL: "MODIFIED ZEOLITES AS CATALYSTS IN THE FRIEDEL-CRAFTS ACYLATION", JOURNAL OF MOLECULAR CATALYSIS. A, CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 109, no. 2, 1996, pages 177 - 187, XP000946681, ISSN: 1381-1169 *

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