Method of simultaneous production of acetophenone and α-phenylpropionic aldehide

FIELD: chemistry.

SUBSTANCE: invention relates to method of simultaneous production of acetophenone and α-phenylpropionic aldehide, which are aromatic substances. Method lies in oxidation of α-methylstyrole with air in presence of highly-silicious zeolite catalyst of pentasyl type with molar ratio SiO2/Al2O3=120 in H-form, in amount of 2-6 weight %, at the rate of air supply of 20-40 l/h, reaction temperature of 80-100°C during 3-5 hours. The method allows for obtaining acetophenone with selectivity of 41.6-58.9% and α-phenylpropionic aldehide with selectivity of 37.9-54.7%, with α-methylstyrole conversion of 54.1-73.0 weight %.

EFFECT: ensuring possibility of simultaneous production of acetophenone and phenylpropionic aldehide.

1 tbl, 5 ex

 

The invention relates to the field of organic chemistry, in particular to the way the joint production of acetophenone and α-phenylpropionamide aldehyde.

The acetophenone - fragrant substance (the smell of cherry) - used for perfuming Soaps and in the production of pharmaceuticals, α-phenylpropionic aldehyde is an aromatic substance with a smell of hyacinth. As he α-phenylpropionic aldehyde and its derivatives (acetals, alcohols and esters) used for making perfumes and as a flavoring in the food industry [Brutus I.N. Chemistry of fragrant substances. M.: Chemistry. 1979].

In industry, the acetophenone (1) receive liquid-phase oxidation of ethylbenzene with oxygen of air at 115-120°and the pressure of 5-10 ATS in the presence of benzoate Co, Cu, Mn, Ni, Pb or Fe:

The yield of ketone is about 60%, the main by-product - α-phenethyl alcohol (2), by catalytic dehydrogenation of which it is possible to increase the yield of acetophenone to 70-80% [Chemical encyclopedia. T.1 M.: Soviet encyclopedia. 1988. 624 S.].

The disadvantages of this process are the low selectivity of the formation of acetophenone, work under pressure, several stages of the process.

Another known method of producing acetophenone is the acylation of benzene from the reaction Friedel-in Pris is accordance aluminium chloride. AlCl3is taken as the equivalent amount of chloride to the anhydride (or acetic anhydride) [Chemical encyclopedia. T.1 M.: Soviet encyclopedia. 1988. 624 C.]:

The disadvantages of this process: a) the use of AlCl3, the use of which is associated with a number of difficulties. Complexes of aluminum chloride with aromatic hydrocarbons is very corrosive and cause severe corrosion of the equipment. Aluminium chloride is partially dissolved in the products, so they should be cleaned, resulting acidic wastewater; b) the catalyst is used in large quantities.

α-Phenylpropionic aldehyde (3) in the industry is produced by condensation of acetophenone with ethyl ether monochloracetic acid in the presence of alkaline agents and subsequent saponification of the resulting ethyl ester α,β-epoxy-β-methylβ-phenylpropionic acid [Brutus I.N. Chemistry of fragrant substances. M.: Chemistry. 1979]:

You know the obtaining of acetophenone and formic acid by ozonation α-methylstyrene in the presence of aliphatic carboxylic acids C1-C4[AU CZECHOSLOVAKIA NO. 249239, 1985]. Solution α-methylstyrene in the acid in a thin film is treated with a mixture of ozone with oxygen or air at a molar ratio of α-methylsterol: 3=0,95÷1,5:1. The reaction temperature 60°C, pressure of 0.14÷0,50 MPa. After ozonation product emuleret in water and passed through a film reactor at a temperature of 70÷120°and a pressure of 0.1-0.5 MPa, and then produce acetophenone and formic acid.

The disadvantages of this method are multi-stage, the use of organic acids, the use of ozone.

In [Rec. trav. chim. Pays. - Bos., 1990, 109, No. 2, R] described a method of producing acetophenone, benzaldehyde (4) and cinnamic aldehyde (5) gas-phase oxidation of styrene in the presence of catalysts Vakker-process are the oxides of aluminum or titanium, coated with a monolayer of V2O5coated with PdCl2and LiCl. The reaction proceeds at a temperature of 75÷180°and the pressure of 0.11 MPa. The selectivity of the formation of acetophenone is 45%, benzaldehyde - 55%.

This process does not allow you to earn both acetophenone and α-phenylpropionic aldehyde.

The proposed simultaneous production of acetophenone and formaldehyde oxidation α-methylstyrene air in the liquid phase at 60÷150°at atmospheric pressure, in the presence of Olkiluoto ester of boric acid (Tripropylamine) or phosphoric acid (tri-p-propylphosphine):

The concentration of the catalyst which is 5÷ 11 mol.% in the calculation of acid. The air is blown at a rate of 30 l/h over 240 minutes of low Molecular weight oxygenated products are extracted with methanol or ethanol. Formaldehyde is captured in the cooling system in the form of formaldehyde or proforma. The reaction product contains, in addition to acetophenone, unreacted α-methylsterol (10%), oxide α-methylstyrene (10÷32%), tropanol and tropical (3,2÷4,4%) [AC NRB No. 30236, 1980].

Further development of this method, see patent [AC NRB No. 35236, 1982]. α-Methylsterol oxidized by air at 60÷150°when the speed of the air flow 300÷700 liters per 1 kg α-methylstyrene/hour. The catalyst serve as Co or Mn salts of lower carboxylic acids or phosphates, in particular With(OON3)2or Co(O-PH-OR)2where R=alkyl, C1-C4. In oxidate contains the acetophenone (54÷83.8 percent), oxide α-methylstyrene (10÷32%) and unreacted α-methylsterol - 2÷10 wt.%

The disadvantages of these processes is the difficulty in separating the catalyst from the reaction mass and their regeneration. In addition, this method can not earn acetophenone and α-phenylpropionic aldehyde.

The present invention is to develop a method for simultaneous obtaining of acetophenone and α-phenylpropionamide aldehyde.

This is achieved by oxidation α-methylstyrene who is the ear in the presence of high zeolite catalyst of the type pentasil (VCC) with a molar ratio of SiO 2/Al2O3=120 in the protonated form at a temperature of 80÷100°and the amount of catalyst 2÷6 wt.%. The air supplied at a rate of 20÷40 l/h for 3÷5 hours

The reaction proceeds according to the scheme:

Conversion α-methylstyrene is 54,1÷73,0 wt.%, the selectivity of the formation of acetophenone - 41,6÷58,9%, α-phenylpropionamide aldehyde - 37,9÷54,7%. In addition to the products of oxidation in the reaction mass, there is a small number of products of the dimerization α-methylstyrene (1,5÷2,0%).

To obtain acetophenone and α-phenylpropionamide aldehyde using high-silica zeolite of the type pentasil with a molar ratio of (module) SiO2/Al2O3=120. On Pancasila with a smaller module main reaction products are dimers α-methylstyrene.

The catalyst is easily separated from oxidate by filtration and can be reused.

Zeolites of type pentasil due to the high chemical and thermal stability, resistance to coxworthy, stability properties and high catalytic activity are effective catalysts for oil refining and petrochemistry. They are used in processes for the alkylation of aromatic hydrocarbons with olefins, aromatization of olefins, C1-C4, isomerization of xylenes in the production of the e high-octane gasoline from methanol [Minachev oil on canvas, Kondrat'ev D.A. USP, 1983, t, No. 12, s-1973].

The proposed method is as follows.

The catalyst is a high-silica zeolite (VCC) is synthesized by the hydrothermal method from alkaline aljumokremnievykh using a diamine as organic additives. In the active H-form zeolite transfer processing to a 25%solution of ammonium chloride, followed by drying at 100°and annealing in the presence of air at 540°C for 6 hours.

Oxidation α-methylstyrene is carried out in a bubbling reactor type. Charged to the reactor the catalyst (2÷6 wt.% for raw materials) and 20 ml α-methylstyrene. When the reaction temperature purge air at a rate of 20÷40 l/h for 3÷5 hours Then the reaction mass is filtered from the catalyst and dispersed. The acetophenone and α-phenylpropionic aldehyde allocate by distillation in vacuum sampling fraction 98÷100°C/20 mm Hg Formaldehyde catch in the cooling system in the form of formalin.

The proposed method is illustrated by the following examples (table 1).

EXAMPLE 1. In a heated glass reactor bubble type load 20 ml α-methylstyrene and 0.36 g of zeolite type pentasil (SiO2/Al2O3=120). At the reaction temperature of 80°To blow air at a rate of 20÷40 l/h for 5 hours Then actionnow mass is filtered from the catalyst and obtain 18.2 g oxidate composition, wt.%:

α-methylsterol45,9
the acetophenone22,5
α-phenylpropionic aldehyde29,6
dimmers α-methylstyrene2,0

Conversion α-methylstyrene is to 54.1 wt.%, selectivity to acetophenone - 41,6%, α-phenylpropionamide the aldehyde - 54,7%.

EXAMPLES 2-5. Analogously to example 1. Conditions and results of examples shown in table 1.

Table 1

Oxidation α-methylstyrene in the presence of high zeolite type pentasil (SiO2/Al2O3=120)
no PPConc. Cat-RA, wt.%T °CT, hConversion α-MS, wt.%The selectivity for products, %
AFThe FCADM α-MS
12,080554,141,654,73,7
22,010461,349,446,7a 3.9
35,0 468,8of 58.9of 37.93,2
46,0803to 70.247,352,73,6
56,0100373,041,654,5a 3.9
AF - acetophenone;

The FCA - α-phenylpropionic aldehyde;

DM α-MS - dimer α-methylstyrene.

The way the joint production of acetophenone and α-phenylpropionamide aldehyde catalytic oxidation α-methylstyrene, characterized in that the catalyst used high-silica zeolite catalyst of the type pentasil with a molar ratio of SiO2/Al2O3=120 in the protonated form in the amount of 2-6 wt.% and the reaction is carried out at air speeds of 20-40 l/h, reaction temperature of 80-100°C for 3-5 hours



 

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