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Preparation of Aromatic Carbonyl Compounds

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~" ' MM II II II Ml I III II II I Ml II I II J European Patent Office © Publication number: 0 178 184 B1 Office_„. europeen- desj brevets^ » © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 28.04.93 © Int. CI.5: C07C 45/45, C07C 49/76, C07C 51/58 © Application number: 85307320.3 @ Date of filing: 11.10.85 © Preparation of aromatic carbonyl compounds. © Priority: 11.10.84 US 659598 (73) Proprietor: RAYCHEM CORPORATION (a Dela- ware corporation) @ Date of publication of application: 300 Constitution Drive 16.04.86 Bulletin 86/16 Menlo Park, California 94025(US) © Publication of the grant of the patent: @ Inventor: Horner, Patrick James 28.04.93 Bulletin 93/17 139 Buckthorn Way Menlo Park California 94025(US) © Designated Contracting States: Inventor: Jansons, Vlktors AT BE CH DE FR GB IT LI NL SE 123 New York Avenue Los Gatos California 95030(US) References cited: Inventor: Gors, Helnrlch Carl EP-A- 0 024 286 EP-A- 0 069 598 2508 Mardell Way DE-A- 2 014 514 GB-A- 1 420 506 Mountain View California, 94043(US) GB-A- 2 103 604 US-A- 1 874 580 US-A- 3 282 989 Representative: Jay, Anthony William et al Raychem Limited Intellectual Property Law Department Faraday Road Dorcan Swindon Wiltshire (GB) 00 00 00 Note: Within nine months from the publication of the mention of the grant of the European patent, any person ® may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition CL shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee LU has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3. 10/3.5x/3.0. 1) EP 0 178 184 B1 Description This invention relates to the preparation of aryl carbonyl compounds, and in particular to para substituted aryl carbonyl compounds. 5 Aryl carbonyl compounds are useful in the preparation of poly(arylene ether ketones). In the preparation of these polymers it is essential that the monomers used be in a highly pure state to prevent undesirable side reactions. Furthermore, the polymers obtained should be stable enough to survive extrusion without undue deleterious effects on their physical properties. The substitution pattern of the monomers used can control the properties of the polymers synthesised, and it is generally recognised that the highest melting io points and glass-rubber transition temperatures are obtained with all para linked polymers. Mixtures of substitution isomers are used when polymers of reduced crystallinity or lowered Tg are required, but the all para substituted polymers are most preferred. When mixtures of monomers are used, known ratios of the different isomers are needed, necessitating the use of pure starting materials. The present invention relates to a process for the preparation of aryl carbonyl compounds that improves outstandingly the degree of 75 purity of the product and/or the degree of para substitution. Aryl carbonyl compounds are also useful as chemicals and chemical intermediates, for example, in the pharmaceutical and agricultural chemicals, dyestuffs and general chemical additives area. Here too it is frequently found that the all para substituted carbonyl compounds are the most useful. Avoidance of concurrent formation of other isomeric by products in the synthesis of such compounds is always beneficial 20 economically and in some instances is essential because some isomeric compounds which are different to remove have been found to be toxic or even carcinogenic. A known method of producing aryl carbonyl compounds by Friedel Crafts condensation using a Lewis acid catalyst is described in GB-A-21 03604. In accordance with the present invention, the Friedel-Crafts condensation of appropriate reactants is 25 controlled to suppress side reaction including alkylation and/or ortho acylation by the addition of a controlling agent, such as a Lewis base, to the reaction medium. Thus the invention provides a process for the preparation of a para-substituted aromatic carbonyl compound which is not an oligomer or polymer, by a Friedel Crafts condensation of (1) an aromatic compound containing at least one activated hydrogen atom with (2) phosgene or an acyl compound in the 30 presence of (3) a Lewis acid, characterised in that any aromatic ring which contains an activated hydrogen atom also contains less than 2 alkoxy groups, and the condensation is controlled by the addition of at least 0.1 equivalents of Lewis base per equivalent of acid, ester of acid halide groups in the reactants, plus an additional equivalent of Lewis acid per equivalent of Lewis base. One aspect of this invention provides a process for the preparation of an aromatic carbonyl compound 35 having the formula (R)sArDCOY, (R)sArDCOBD(R')t, (R)sArDCOBDCOArD(R)s or (R)sArDCODAr(R)s wherein each s and t independently is 1 , 2 or 3 and each R, Ar, B, D, Y and R' independently is as defined 40 below, which comprises reacting a first reactant consisting of a substituted or unsubstituted aromatic compound containing at least one activated hydrogen atom of the formula (R)sArDH 45 with a second reactant consisting of phosgene or a mono-functional acyl compound of the general formula YCOBD(R'), or 0(COBD(R'),)2 50 or a di-functional acyl compound of the general formula YCOBDCOY in a reaction medium comprising: 55 A) a Lewis acid in an amount of one equivalent per equivalent of carbonyl or other basic species in the reactants plus one equivalent per equivalent of Lewis base plus an amount effective to act as a catalyst for the reaction; 2 EP 0 178 184 B1 B) a Lewis base in an amount of from 0.1 to 4 equivalents per equivalent of acid, ester or acid halide group in the reactants; and C) a non-protic diluent in an amount from about 20 to about 93% by weight, based on the weight of the total reaction mixture, 5 wherein: (a) Ar is a homo or hetero-aromatic mono-, di- or tri- cyclic moiety or a fused homo-aromatic ring system containing less than 20 aromatic carbon atoms or a hetero-aromatic system containing less than 8 nitrogen atoms; (b) D is -(ZAr)n-(ZAr)m-(ZAr)p- io wherein n, m, and p are each independently 0, 1, 2 or 3, provided that n + m + p is less than 4, and Z -CO- or -SO2- when linking two Ar moieties which are both 4-phenoxyphenyl, or Z is -CO-CgH^-CO-, -0- (CF2)qO-, or V, provided that when n + m + p > 0 any Ar group comprising an activated hydrogen atom is also linked to a V group, where V Is a divalent radical of the formula 15 -0-, -S-, -N = N-, -(CF2)q-, -(CH2)q- or -C(CH3)2- wherein q is 1 to 20; (c) B is independently a divalent substituted or unsubstituted aliphatic or cycloaliphatic group or Ar; 20 (d) R and R' which may be the same or different are H, Br, CI or F atom or a hydroxy, alkoxy, alkyl, aralkyl, unsubstituted or mono- or disubstituted amino, nitro, ester, acid, or acid halide, amide or imide group; and (e) Y represents a Br, CI or F atom or a hydroxy or alkoxy group; subject to the proviso that any aromatic ring which contains an activated hydrogen atom also contains less than 2 alkoxy groups, and 25 the resulting aromatic carbonyl compound contains less than 2 identical directly linked sequences containing at least one -CO- or -S02 -group and at least one -V-group. Pendant substitutents which can be present on B or Ar groups include, for example, lower alkyl, cyano, halogen, nitro, benzoyl or any other atom or group which will not interfere with the reaction by virtue of either its chemical nature or its location in the reactant from which the B group is derived. 30 The term "activated hydrogen atom" refers to a hydrogen atom displaceable under the electrophilic (Friedel-Crafts) reaction conditions employed in the reaction. Aromatic compounds suitable for acylation according to the process of the instant invention exhibit carbon-13 nuclear magnetic resonance (C-13 NMR) chemical shifts at the ring site where acylation is desired at least 2.1, preferably at least 2.4 and most preferably at least 2.8 parts per million (ppm) less than 35 that exhibited by benzene. For a listing of C-13 NMR chemical shifts of monosubstituted benzenes see M. Mishima et al (Memoirs of the Faculty of Science, Kyusuu Un., Ser. C, Vol. 11 No. 1, 1978). Table 2 of this reference lists C-13 NMR chemical shifts of a variety of mono-substituted benzenes measured in solution in carbon tetrachloride. Benzene in this solvent is stated to have a chemical shift of 128.04 ppm. The aromatic compounds useful in the instant invention may, but preferably do not, form additional complexes with Lewis 40 acid under the reaction conditions. Those skilled in the art will readily recognize that when an addition complex is formed, it should not substantially deactivate the molecule to acylation. Thus such complexes, for example, should still exhibit C-13 NMR chemical shifts which are at least 2.1 ppm less than that of benzene or sufficient uncomplexed aromatic compound is present to enable the reaction to proceed at the desired rate. 45 Illustrative aromatic compounds of the general formulas (R)sArDh are: toluene, ethyl benzene, fluorobenzene, anisole, ethoxy benzene, 3-chloroanisole, naphthalene, anth- racene, and compounds of the formulas 50 55 3 EP 0 178 184 B1 0~0 0-*0 000 0^> o-~o-!-o--o O-O-fO-O O^C o*o*o Illustrative mono or di-acyl compounds of the general formula YC0BD(R'),,0(C0BD(R')t)2 or YCOBDCOY are: acetic anhydride, acetyl chloride, adipoyl dichloride, benzoyl chloride, 4-fluorobenzoyl chloride, 4- chlorobenzoyl chloride, 3-nitrobenzoyl chloride, phthaloyl chloride, pthalic anhydride, naphthoyl chloride, tetrabromophthaloyl chloride, and compounds of the following formulas EP 0 178 184 B1 ' II II 0 0 o 0 20 25 30 35 wherein each V is independently as defined above, a is 0, 1 or 2 and Z is as defined above.
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