SU1016277A1 - Process for preparing mono- or diarylketones - Google Patents

Abstract

1. METHOD OF OBTAINING MONOILS OF DIARYLKETONES by the interaction of an aromatic hydrocarbon with carboxylic acid halide at 110-120 C in the presence of a complex catalyst — onium salt and zinc or iron chloride, so that, in order to intensify the process, As a catalyst, use is made of a compound of the general formula Illes, i., where Me is zinc or iron / n 2-3; X is the number determined by the valency of the metal; R, -Ce, H5, R -CH-C, H, hcSbN -cNe-cn2. CbH2 - (fn. 2. The method according to claim 1, which is also different from the fact that the process is carried out at a molar ratio of aromatic hydrocarbon (halo-danhydride and catalyst, respectively, 3: 1: CO, 05-0.01). o: IsD

Description

The invention relates to an improved process for the preparation of mono or diaryl ketones-which are used in the manufacture of intermediate products and dyes, for example, b-eantron and dibenzpyren-quinone. A known method for producing mono-ketones by condensation of aromatic hydrocarbons, in particular isomeric xylenes, with anhydride-benzoyl chloride in the presence of a zinc chloride catalyst. The process is carried out at a molar ratio of xylene: benzoyl chloride: a catalyst of 1: 0.1; (0.01-0.05), the reaction time is 6 hours at an output of 36-72% of theoretical 1, the disadvantage of this The method is a relatively low yield of the target product. There is also known a method for producing a diaryl ketone, 1,4-bys-dimethyldibeno-zoylbenzene, consisting in that toluene is condensed with terephthaloyl chloride in the presence of AECEs catalyst, at 30-ZO C and molar ratio of toluene: terephthaloyl-chloro catalyst equal to 2: 1: 1,2 . The yield of the target product is 60-80, the reaction time is 6-8 hours. The disadvantage of this method is that the method requires a considerable consumption of catalyst, which is not regenerated and is lost irretrievably. The closest to the invention to the technical essence and the achieved result is a method for producing monoaryl ketones, which means that aromatic carbon is hydrogen (toluene, xylene isomers, naphthalene is condensed with acetyl chloride benzyl chloride at 110-120 ° C in the presence of a catalyst-complex compound on the basis of metal chlorides and tetra-substituted ammonium salts of the general formula MeCEj R NCe-A, where A is PNSH at H 0.5-2.0 or MeC-, where MeCKU MCt-t,, VeCH,, XH СЪ ,, R - hydrocarbon radical. Target product yield kta 65-90%, reaction time up to 30 h, Molar ratio aromatic hydrocarbon: halo: dan hydride: catalyst: 10: 1: 10.05-0.1) C3 and G. The H-state of a known method consists in the duration of the process as well as the thermal instability of the catalyst, which causes a decrease in the activity of the catalyst. In as little as 2-3 hours, there is a decrease in the reaction rate of the yield of the target product due to the decomposition of the catalyst. The aim of the invention is to intensify the process. The aim is achieved in that according to the method of producing mono- or diaryl ketones by the interaction of an aromatic hydrocarbon with a carboxylic acid halide at 110-120 s in the presence of a complex catalyst-onium salt and zinc or iron chloride, the catalyst used is compound of general formula imese. h , where Ri SbH5-, K-CH2C H5-, -CH2. SbH4. CH, - CHjCfeH C CH) ,,, Me zinc or iron, X is the number determined by the valence of the metal,. Preferably, the process is conducted at a molar ratio of aromatic hydrocarbon, acid halide and catalyst, respectively, 3: 1: {0.050, 017. The proposed method allows to intensify the process, since the reaction time is 0.68 - 4 hours, while the consumption of the catalyst in some cases also decreases, and the yield of the desired product remains at the level of the known method and is 72-85%. Changing the ratio of reactants, such as increasing the concentration of hydrocarbons, does not require additional consumption of the catalyst. At the same time, the proposed catalyst is resistant to the action of moisture in the air and a higher temperature. It retains activity with repeated use without reducing the yield of the target product, as shown in Table. 2 Example. A mixture of naphthalene, benzoyl chloride and a catalyst of composition) P (,, x xBFeCK-i, taken in a molar ratio of 3: 1: 0.01, is refluxed at 120 ° C with HCf absorption. Reaction time is 50 min. The yield of phenyl naphthylketone is 80% from theoretical. Isomeric composition — 73.5% ci-isomer and 6.5% E-isomer-determined chromatographically. Example 2: Mixture of o-xylene, terephthaloyl chloride and catalyst 1 (C (, H;) D. CH SbNdSNeSse 3-ZSSR:;, taken in a molar ratio of 3: 1: 0.01 is heated, as in Example 1, at 120. The reaction time is 4 hours, the yield of 1.4 bis-dimethyldibenzoylbenzene is 82.0% of the theoretical. EXAMPLE 3 A mixture of toluene, benzoyl chloride and catalyst Pca2., (Dus). Ces-sase, taken in a molar ratio of 3: 1: 0.01, is heated as in Example 1 at. Reaction time 3 h. The yield of dimethylbenzophenone is 78.0% of the theoretical one.

, 31016277

In tab. Figure 1 shows the synthesis of diaryl hydrocarbons with benzoyl chloride in wowel ketones by the interaction of the aromatic absence of complex catalysts.

Table

3CCSbN.5) zR-sn2 -c H4. -SNz1se-1Rezezn, 10

4t ((, H4-cH,

P5: (C (, H5) 5P-cH2.-Ct, H4-CH, 3Ct-3ihce, j

1 (.SbI5) zR CH1-C (, H4-CH ZSg: 31iSe2.120P-Xylene

tCCe, H5), P-CW, .- CH% a ° m-Xylene

IbN5, Pn, 27SbN4-CH 1se-31 1se2120-o-xylene

CtC H54 l 6V 3 2 ° Toluene

C (Gj, H5), P-cH, j: CjjHjJce Fece ,. 120 toluene

iSnb) -} P-SNgSbN4SNzSse-zrese: 120toluene

CCCbHsV-c aCbHs ce - iFece ,,

12

120 Naphthalene 120 LL-Xylene

120 o-xylene

120 Toluene

. Continuation of the table. one

Claims (2)

1. METHOD FOR PRODUCING MONOIL DIARYL KETONES by reacting an aromatic hydrocarbon with a carboxylic acid halide at 110-120 ° C in the presence of a complex catalyst — an onium salt and zinc or iron chloride, with the aim of intensifying of the process, as a catalyst, a compound of the general formula and h \ ece * R are used. ' _% R.pcg, where Me is zinc or iron, ⁴ and = 2-3; X is the number determined by the valency of the metal compounds', -C ₆ H ₅ , R -CH_C, H-, CH _g C ₆ H ₄ -CH _e , -CH ^ H ^ - (CH ^ L ⁶ 2. The method according to π. 1, distinguished by the fact that the process is conducted at a molar ratio of aromatic hydrocarbon (halide anhydride and catalyst, respectively, 3: 1; (0.05-0.01). Oh ^ ^ 4 ^ 4