Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Halogen or compound containing same
Reexamination Certificate
1998-12-11
2001-01-30
Wood, Elizabeth D. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Halogen or compound containing same
C502S226000, C502S227000, C502S229000, C502S231000
Reexamination Certificate
active
06180557
ABSTRACT:
This invention relates to a novel supported catalyst useful for Friedel-Crafts reactions and process for the preparation of aralkylated aromatic compounds using the catalyst. This invention particularly relates to a novel supported catalyst, containing mixed metal oxides or halides deposited on porous catalyst carriers or supports useful for the heterogeneously or solid catalyzed Friedel-Crafts reactions, and a process for the preparation of the catalyst and also to a catalytic process for the preparation of aralkylated aromatic compounds by the aralkylation of aromatic compounds with aromatic aralkylating or alkylating agent, using the supported catalyst.
The catalyst preparation process of this invention could be used for the preparation of solid catalysts useful in the Friedel-Crafts reactions. The catalytic process for this invention could also be used for the preparation of aralkylated aromatic compounds, which are fine chemicals and/or intermediates used in the preparation of fine chemicals.
BACKGROUND OF THE INVENTION
A number of homogeneous and heterogeneous acidic catalysts useful for the Friedel-Crafts reactions, for examples alkylation, polyalkylation, aralkylation, acylation, aroylation and the like, are known in the prior art. Aralkylated aromatic compounds are useful fine chemicals and these are also used as intermediates in a member of organic syntheses. Both the homogeneous and heterogeneous catalysed liquid phase processes for the preparation of aralkylated aromatic compounds are known in the prior art,
Homogeneous Catalysts for Friedel-Crafts Reactions
The acylation and benzoylation of aromatic compounds and related Friedel-Crafts type reaction using homogeneous lewis acid catalysts are well-known in the prior art [ref G. A. Olah, in Friedel-Crafts and related reactions: vol. III, Acylation and related reactions, Wiley-Interscience Publ., New York, 1964].
A use of CuCl
2
as a homogeneous catalyst in the benzylation of benzene or substituted benzenes by benzyl chloride is disclosed in two U.S. patents, U.S. Pat. No. 3,678,122 (1972) and U.S. Pat. No. 3,679,760 (1972), A French patent, Fr. Demande 2,144,578 (1973), disclosed benzylation of p-substituted phenols by benzyl halides in the presence of homogeneous ZnCl
2
catalyst. A USSR patent, U.S.S.R. 394,353 (1973), disclosed a use Of SnSO
4
or SnCl
2
as homogeneous catalyst for the benzylation with benzyl chloride of m-dimethoxy benzene, A Japanese patent, Japan Kokai 7399,154 (1973), disclosed preparation of dibenzyl benzene derivatives by benzylation of benzene or substituted benzenes using AlCl
3
, FeCl
3
and 98% H
2
SO
4
. A use of H
2
SO
4
or H
3
PO
4
and optionally 4-CH
3
C
6
H
4
SO
3
H, ZnCl
2
, BF
3
, etc. in the preparation of o-benzyltoluenes by the reaction of &agr; o-chloromethyltoluene with a benzene derivative is disclosed in a German patent, Ger. Offen 2,456,747 (1976). A use of phosphoric acid and optionally H
2
SO
4
or a Friedel-Crafts type metal halide in the benzylation of benzene with benzylether is disclosed in a U.S. patent, U.S. Pat. No. 4,049,733 (1977).
A German patent, Ger.offen 2,451,037 (1976), disclosed the use of HF as a catalyst for the benzoylation of aromatic compounds.
A French patent, Fr. Demande FR 2,496,097 (1982) disclosed the acylation of benzene by phthaleic anhydride using HF—BF
3
mixture.
More recently, an European Patent, Eur.Pat.Appl.FP 538,704 (1993), disclosed a process for the preparation of p-substituted o-benzylphenols by treating phenols, p-R′C
6
H
4
OH (R′=halo, alkyl, OH, alkoxy, alkylmercapto, aryl, aryloxy or arylmercapto), with ArCH
2
X (Ar=corresponding aryl nucleus; X=halo, arylcarboxy, phenylsulfatoxy, hydroxy, alkoxy etc.) in a continuously functioning distillation apparatus in the presence of dissolved acid catalyst.
The main disadvantages of the use of homogeneous acid catalyst for the Friedel-Crafts processes are as follows:
1) The separation and recovery of the dissolved acid catalysts from the liquid reaction mixture is difficult.
2) The disposal of the used acid catalysts creates environmental pollution.
3) The homogeneous acid catalysts also pose several other problems such as high toxicity, corrosion, spent acid disposal and use of more than the stoichiometric amount.
Heterogeneous Catalysts for Friedel-Crafts Reactions
A German patent, Ger.Offen 2,547,030 (1977), disclosed the preparation of o-benzyltoluenes by the reaction of o-methylbenzyl halides with substituted benzenes in the presence of Al-silicate. The 2-CH
3
C
6
H
4
CH
2
Cl was stirred with toltuene and Al-silicate (25%Al
2
O
3
) at 110° C. to give 81% 2-methylbenzyltoluene. According to a Japanese patent, Jpn. Kokai Tokkyo Koho JP 59,186,937 (1984), o-benzylphenol was prepared by the liquid phase reaction of benzyl alcohol with phenol in the presence of &ggr;-Al
2
O
3
. For example 7.5 g &ggr;-Al
2
O
3
was added to a mixture of 32.5 g benzyl alcohol and 47 g phenol at 190° C. under stirring to give a product containing 49.9% o-benzylphenol. A German Patent, Ger. Offen DE 3,700,917 (1988), disclosed the preparation of p-substituted o-benzylphenols by benzylation of p-substituted phenols with benzylalcohol in the presence of Na—Y type zeolite. A mixture of 0.5 mole 4-ClC
6
H
4
OH, 0 1 mole C
6
H
5
CH
2
OH and 0,6 g of Na-Y type zeolite was heated at 200° C. for 3 hrs to give 25.4% 2-benzyl-4-chlorophenol.
A French patent, Fr. Demande FR 2,667,063 (1992), disclosed the preparation of 4-substituted benzophenones by aroylation of substituted benzenes by substituted benzoic acid in the presence of HY and H&bgr; type zeolites. Accordingly 4-ClC
6
H
4
COOH and PhMe were heated 4 h at 200° C. under 2×10
5
Pa in the presence of calcined zeolite H&bgr; to give 84.4% 4-(4-ClC
6
H
4
CO) C
6
H
4
Me.
A recent paper by Vincent et al. (ref Tetrahedron Lett. 35, 1994, 2601), disclosed that H-ZSM-5 zeolite can catalyze the benzoylation by benzoyl chloride of phenol and anisole but not the benzoylation with benzoyl chloride of benzene, halobenzene and naphthalene, at 120° C. for 5 h.
A German patent, Ger. Offen DE 3,436,780 (1990), disclosed the process for the preparation of benzylbenzenes from benzenes and benzyl alcohols in the presence of activated bleaching earth and a diluent at 90-140° C. According to Japanese patent, Jpn Kokai Tokkyo Koho JP 03,170,442 (1991), benzylbiphenyls are manufactured by benzylating biphenyl and diphenylmethane with ≧1 compound from benzyl halides, benzyl alcohol, benzyl ether in the presence of a zeolite or silica-alumina catalyst. An European patent, Eur.Pat. appl. EP 428,081 (1991), disclosed a process of benylation of alkylbenzenes with benzyl chloride in the presence of H—Y or H—L zeolite catalyst. According to a German patent, Ger. Offen DE 4,038,933 (1992), disclosed a process for benzylation of aromatics using technical carbon catalysts.
Alkylation, aralkylation, acylation or aroylation of aromatic compound involves electrophilic substitution of H from the aromatic nucleus of the aromatic compound. It is well known in the prior art that the electrophilic substitution is favoured by the presence of electron donating groups, such as OH, alkyl, alkoxy, phenoxy, amine, alkyl amine, SH etc., in the aromatic compound. Whereas the electrophilic substitution is inhibited by the presence of electron withdrawing groups such as halo, nitro, cyano, carboxy, aldehyde, etc, in the aromatic compound, [ref, G. A. Olah, in Friedel-Crafts and related reactions, Wiley-Interscience Publ., New York, 1963].
Although some limitations of the homogeneous acid catalyzed processes are overcome in the prior art heterogeneous catalyzed processes described above, the alkylating, aralkylating, acylating or aroylating activity of the solid catalysts used in the prior art processes are low, particularly for alkylating, aralkylating, acylating or aroylating aromatic compounds containing electron withdrawing groups. Hence there is a great practical need for finding more efficient solid catalyst for the alkylating, aralkylatin
Choudhary Vasant Ramchandra
Jana Suman Kumar
Kiran B-Phani
Bednarek Michael D.
Council of Scientific & Industrial Research
Pittman Shaw
Wood Elizabeth D.
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