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Procedure for the Photochlorination of Alkyl-Aromatic Compounds

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Procedure for the Photochlorination of Alkyl-Aromatic Compounds ~™ llll III II II II I II I II III II 1 1 (19) J European Patent Office Office europeen des brevets (11) EP 0 612 707 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int. CI.6: C07C 17/14, C07C 22/04, of the grant of the patent: C07C 25/02 18.06.1997 Bulletin 1997/25 (21) Application number: 94200350.0 (22) Date of filing: 16.02.1994 (54) Procedure for the photochlorination of alkyl-aromatic compounds Verfahren zur Photochlorierung von alkylaromatischen Verbindungen Procede pour la photochloration de composes alkylaromatiques (84) Designated Contracting States: • Contardi, Giuseppe AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL 1-20161 Milan (IT) PTSE • Messori, Vittorio 1-20129 Milan (IT) (30) Priority: 24.02.1993 IT MI930346 (74) Representative: Fusina, Gerolamo et al (43) Date of publication of application: Ing. Barzanb & Zanardo Milano S.p.A, 31.08.1994 Bulletin 1994/35 Via Borgonuovo, 10 20121 Milano (IT) (73) Proprietor: ENICHEM SYNTHESIS S.p.A. 1-90139 Palermo (IT) (56) References cited: DE-A- 3 320 020 DE-B- 2 530 094 (72) Inventors: GB-A- 928 693 • Ribaldo, Carlo 1-20131 Milan (IT) CO o Csl Note: Within nine months from the publication of the mention of the grant of the European patent, give CO any person may notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in ^ a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. Q. 99(1) European Patent Convention). Printed by Rank Xerox (UK) Business Services 2.14.7/3.4 1 EP 0 612 707 B1 2 Description does not form an explosive mixture with the organic compound to be chlorinated. Other problems related to The present invention relates to a procedure for the photochlorination methods of the known art consist in selective photochlorination in the side chain of alkyl-aro- the difficulties of thermal exchange, in that the heat of matic compounds. 5 the reaction is only exchanged through the reactor It is known that the chlorination in the side chain of jacket; the difficulty of regulating the temperature and alkyl-aromatic compounds is generally favored by rais- the ratio between chlorine and aromatic compound dur- ing the reaction temperature or, more commonly, by ing the reaction; the dirtying of the lamp immersed in the operating in the presence of free radical initiators such reaction mixture; the limited operating pressures due to as light radiation or peroxides. 10 the glass seal of the lamp-holder; and the difficulty in Particularly known in the art is the chlorination in providing a system which completely satisfies security the side chain of toluene, and its chlorine-substituted regulations. derivatives in the nucleus, to benzyl chloride, benzal The purpose of the present invention is to over- chloride and benzotrichloride. These compounds are come the disadvantages of the known art related to pro- useful intermediates which can be transformed into 15 cedures for the photochemical chlorination of alkyl- other chemical products, especially by reactions involv- aromatic compounds. ing chlorine substituents in the side chain. In this way In particular it has been found, in accordance with benzyl chloride can be used in the production of benzyl the present invention, that it is possible to photochlorin- butyl phthalate, a plasticizer for vinylic resins, benzal ate alkyl-aromatic compounds with practically total con- chloride can be hydrolyzed to benzaldehyde and benzo- 20 versions of the reagents and with a high selectivity in trichloride can be transformed into benzoyl chloride. In the useful reaction product, operating with a batch circu- addition also some chlorine-substituted derivatives in lation system with the progressive chlorination of the the nucleus of the above compounds have a commer- alkyl-aromatic compound. It has also been found that cial value; for example p-chlorobenzotrichloride is an this photochlorination system is extremely safe and suit- important intermediate in the production of dinitroaniline 25 able for overcoming the disadvantages and limitations weed-killers. of the known art mentioned above. The basic problem related to procedures for the In accordance with this the present invention thermal and photochemical chlorination of alkyl-aro- relates to a procedure for the selective photochlorina- matic compounds consists in the limited selectivity of tion in the side chain of an alkyl-aromatic compound by the desired reaction product. For example in the produc- 30 contact with chlorine under the action of light radiation, tion of benzyl chloride there is normally only a partial characterized in that: conversion of the toluene, in order to minimize the for- mation of products with a degree of chlorination which is said alkyl-aromatic compound is continuously higher than that required. The same happens in the pro- removed from a container, mixed with chlorine in a duction of benzal chloride. Finally in the preparation of 35 static mixer, to obtain a homogeneous mixture, con- benzotrichloride, the product with a higher degree of taining from 0,02 to 2 parts by weight of chlorine for chlorination in the side chain, the selectivity of the reac- every 100 parts by weight of the alkyl-aromatic tion is reduced by the presence of by-products. All of compound, mixture which is fed to the foot of a this involves difficult operations for the separation and tubular-shaped reactor, without any mechanical purification of the useful products and for recycling the 40 stirring equipment, at least partially composed of unaltered reagents. material which is transparent at light radiation and With respect to the known photochlorination meth- externally equipped with a supply of light radiation, ods of organic compounds, either batch or continuous, said reactor being maintained under photochlorina- basically two types of reactors are used and more spe- tion conditions, to almost completely use up the cifically: a vessel reactor with one or more immersed 45 chlorine, and recover a mixture of the chlorinated lamps and a film reactor with an internal lamp. In the tra- alkyl-aromatic compound and hydrochloric acid by- ditional vessel reactors the stirring which is necessary product at the head of the reactor, to allow the chlorine to flow near the lamps and the said reaction mixture being continuously recycled organic compound to be effectively exchanged, is pro- to the container where the gaseous hydrochloric vided by bubbling the chlorine itself and hydrochloric so acid is separated from the chlorinated alkyl-aro- acid which is developed as a reaction by-product. This matic compound, causes a limited feeding flexibility of the chlorine which the alkyl-aromatic compound being partially chlo- can be partially remedied by connecting several reac- rinated at each recycling in the reactor, the number tors to each other in series, mainly to use up as much of recycles depending on the degree of chlorination chlorine as possible discharged from the photochlorina- 55 required, and further characterized in that in said tion. In the film reactor, this problem does not exist, but photochlorination reactor the linear rate of the reac- as the process is carried out in the presence of a radi- tion mixture is from 0,4 to 4 m/s, with a temperature ated gaseous phase, the use of these reactors in photo- at the inlet ranging from 0 to 150°C and maintaining chlorination is restricted to cases where the chlorine a difference of temperature between the inlet and 2 3 EP 0 612 707 B1 4 outlet at values of 1 to 35°C. namic conditions in the reactor, regardless of the quantity of chlorine fed; The alkyl-aromatic compounds which can be sub- the source of radiation external to the reactor and jected to the photochlorination process of the present the fact that the chlorine is dissolved or at least uni- invention are preferably toluene, monochlorotoluene s formly dispersed in the liquid phase enable the isomers, dichlorotoluene isomers trichlorotoluene, operation to be carried out without hot points, thus xylene isomers and mesitylene. The photochlorination avoiding the formation of explosive mixtures which products are those which are mono or polychlorinated are typical in the gaseous phase; in the side chain. For example in the case of toluene, the possibility of independently regulating the feed- benzyl chloride, benzal chloride or benzotrichloride can 10 ing of the chlorine and the reaction temperature, be obtained, depending on the reaction conditions. makes it possible to operate under excellent condi- According to an embodiment of the present inven- tions in relation to the depletion of the chlorine and tion, the alkyl-aromatic compound is removed from a selectivity of the reaction product desired, with a container and fed to the photochlorination reactor by a practically complete conversion of the alkyl-aro- suitable pump, after mixing with chlorine and homoge- is matic compound subjected to photochlorination; nizing the mixture by passing it through a static mixer. In there is no limitation relating to the thermal this phase of the procedure the ratio between chlorine exchange as the temperature of the reagent mix- and the alkyl-aromatic compound is such that the chlo- ture can be regulated to the most suitable value for rine, or a substantial quantity of this, is dissolved in the the particular reaction, with the consequent possi- liquid phase at the inlet of the photochlorination reactor. 20 bility of exploiting the fast kinetics to the utmost; Suitable concentrations of chlorine generally vary from there are no problems of the radiation lamps being 0.02 to 2 and preferably from 0.1 to 1 parts by weight for dirtied thus facilitating maintenance operations; every 100 parts by weight of the alkyl-aromatic com- finally there are no limitations deriving from the pound.
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