SU1006432A1 - Process for preparing 2-methylquinoline - Google Patents

Abstract

. one . WAYS OF OBTAINING 2-ME-THILHINOLINE by catalytic alkylation of quinoline on a nickel-containing catalyst in the gas phase with an alkylating agent, with the aim that, in order to increase the yield of the target product and simplify the process, they use alkolium as an alkylating agent The catalyst is a nickel-aluminum catalyst and the process is carried out in the presence of hydrogen and an inert diluent. 2. A method according to claim 1, characterized in that n is used. Kelumuminium catalyst with a nickel content of 20.5-30.0 wt.%, Zo The method according to claim, 1, tl and h and y and the fact that the process is carried out at a partial pressure of hydrogen of 0.03-0, 06 MPa, i. The way to pop, 1, I write u. and with the fact that nitrogen, argon or helium with a partial pressure is used as an inert diluent. by the amount of 0.005-0.05 MPa.

Description

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4 00 ts9 The invention relates to an improved method for producing 2-methylquinoline (quinaldine), which can be used as a starting material in the synthesis of drugs, paints and varnishes, herbicides. The known method of producing alkylquinoline in gas phase is the interaction of quinoline with carbon monoxide (or a mixture of CO; and H). Metals 1B, OB, tlA (CuO, Znp, or СGdO3) are used as catalysts. The yield of alkylquinolines, for example methylquinolines, does not exceed 50 mas. The disadvantage of this method is the low yield of the target product. The method for producing 2-alkylquinoline by alkylating quinoline in the gas phase with an alkylating agent is the closest to the invention. It is known as a compound of the general formula R -k and Rc- o -R 0-R O (1) where or alkyl; R is alkyl, or 1, in the presence of a catalyst, namely nickel on nickel oxide at. The method of producing 2-methylquinoline is that quinoline is alkylated in the gas phase with methanol in the presence of a catalyst, namely nickel on nickel oxide (L1 / K | 20z) at 150 - 00 ° C, contact time 0.5-50 s Exit 2 -methylquinoline equals b5masD 2 The disadvantage of this method is the low yield of 2-methylquinoline, as well as the difficulty of obtaining and isolating the target product, because when using such oxygen-containing methylating agents as alcohols, the hydrocarbon layer of the reaction products contains up to 30 wt.%. water due to the mutually soluble solubility of water and HYNOLINOV1X bases The latter form azeotropic mixtures with water in an 1: 1 ratio by weight. The aim of the invention is to increase the yield of the target product and simplify the process. The delivered wele is achieved by the fact that quinoline is catalytically alkylated in the gas phase with alkane C-C on a nickel-aluminum catalyst In the presence of hydrogen and an inert diluent at 150 - 00 ° C. The process is preferably carried out with a nickel content of 20.5-30.0 masD on a nickel-aluminum catalyst. The process is preferably carried out at a partial pressure of 0.01-0.06 MPa. Nitrogen, argon or helium with a partial pressure of 0.005-0.05 MPa is used as an inert diluent. The yield of the target product to 80 mol. from theory. Example 1c The process for the preparation of 2-methylquinoline is carried out on a flow-type plant. The quinoline products are converted to methane and hydrogen to the reaction temperature and are fed into the reactor with 50 ml of a heterogeneous nickel-aluminum catalyst (AM-1 grade TU-03-237-b9o) Nickel content of at least 25.5 May.). The reaction temperature is 300 ° C. Volumetric rate 0.4 / Lat-h, partial pressures, MPa: quinoline 0.02, methane 0.01, hydrogen 0.03, inert (gels. 0.04. Missing quinoline 129 g (1, 0 mol), methane 11.2 l (0.5 mol) and 33 l (1.5 mol) of hydrogen. The reaction products are condensed with cooled water. 116 g of condensate are obtained, which is analyzed by gas chromatography, for example, with a thermal conductivity detector ChL- chromatograph; Benzidine (5 wt.) and Tween 60 (7.5 wt.) on celite are used as the stationary phase. The column length is k, 2 m, diameter is 0.005 m, the temperature of the column is 11 ° Co The content of the main products in the condensate, by weight, is: quinoline 50.0; 2-methylquinoline 2.2} 2,3-dimethylpyridine 3,6, 3-methylpyridine 4.2. Conversion of the starting quinoline 43.8%, yield 2methylquinoline The flow rate is 35.1 mol, which is 80.2 mol. of theory. The extraction of the desired 2-methylquinoline from condensate is easily accomplished by rectification on a column with an efficiency of 50 mt. 2-methylx + 1Noline concentration 99 wt.%, Synthesized 2 -methylquinoline has a high degree of purity, boiling point 246 ° C,, 051. Literature data: boiling point 2k6-2k7 ° Cf, 059. Found:: g: C 84, Q7; H 6.31; N 9.62 Calculated,%: C, 83.87; H 6.35; N 9.78. Example 2-6, Process wire as in Example 1, Process parameters and yield of the target product are summarized in Table. G, P im ep 7-t2. The process is carried out analogously to example 1. The starting product is hino / uiH. The process parameters and the yield of the target products are summarized in Table 2,234 Example 13-1. The process is carried out analogously to Example 1, Partial pressure, MPa: quinoline 0.02; alkanes 0.01; hydrogen 0.03 inert Cr% li) 0.0, Temperature. The results of the syntheses are summarized in m1bl, 3. EXAMPLE 15-17 ° The process is carried out analogously to example 1, MPa partial pressures: quinoline 0.02} alkanes 0.01; hydrogen 0.03, inert (helium 0.0, Temperature 300 ° C. The results of the experiments are summarized in tab.

Quinoline 2-Methylquinoline 0.8 20.3

Quinoline 2-methylquinolium 1.0

76.1 20.1 72.3

, 0 30.0 0.67 33.2 7.3 NI / AljOj 28.5 0, H 36.6 76.7 Nl / Al20j 20.5 0.5 25.6 69.1

Claims (4)

.1- METHOD OF PRODUCING 2-ME-TILKHINOLINE by catalytic alkylation of quinoline on a nickel-containing catalyst in the gas phase with an alkylating agent at 150–400 ° С, which consists in that, in order to increase the yield of the target product and simplify the process, as an alkylating Alkanes C ^ -C ^ are used as the agent, a nickel-aluminum catalyst is used as the nickel-containing catalyst, and the process ^ is driven in the presence of hydrogen and an inert diluent. 2. The method according to p. 1, characterized in that they use a nickel-aluminum catalyst with a nickel content of 20.5 "30.0 wt.%. 3 "The method according to π. 1, with the fact that the process is carried out at a partial pressure of hydrogen of 0.03 * 0.06 MPa. ₍ 4. The way to pop. 1, distinguishes 1st and th with the fact that as I inert diluent, nitrogen, 1 argon or helium with a partial pressure is used, | by 0.005-0.05 MPa. |