SU511008A3 - The method of obtaining 3- / dialkylaminoethyl / -4-alkyl7-carboethoxymethoxycoumarin - Google Patents

Description

hydrolysis of phosphorus trihalides with a calculated amount of water. The resulting 3- (p-haloethyl) -4-alkyl-7-oxycum rin in

CHiCH.X

where Ti has the indicated values, and X denotes a chlorine or bromine atom, is treated with ethyl ester-halogen of acetic acid XCHjCpjC jHy, where X denotes a chlorine or | bromine atom, in ace- | g tone in the presence of alkali metal carbonate or catalyst (dimethylformamide, water , potassium iodide) at the boiling point of the reaction medium.

Thus obtained 3- (p-ha 20 logenethyl) -4-apkyl-7-carboethoxymethoxycoumarin IV

sn.xn

CiHtOiCCHtO

where K and X are indicative, treated with an excess of dialkylamine IjRjNH, where R and Rj have the indicated values, in the presence of a hydrogen halide acceptor, after which the desired product is isolated. Pyridine or an alkali metal carbonate is used as an acceptor of a hydrogen halide. The reaction is carried out at elevated temperature, isolating the desired product as a complex with zinc chloride. The complex is decomposed with an aqueous alkaline solution, for example, ammonium alkali metal carbonate solution.

Example 1, K9,5 weight.h. red phosphorus and 182 weight.h. acetic acid added 10, -4 weight.h. water, and then for 1 h at room temperature and constant stirring 52.4 weight.h. bromine. The reaction mixture is stirred for 0.5 h, the excess phosphorus is filtered off, and 11 parts by weight are added to the filter. resorcinol, cool the solution to 10 ° C and add 10.9 parts by weight. “1-acetyl-Tbutirolactone. The reaction mixture is boiled for 2 hours, cooled to room temperature, 55 parts of water are added with constant stirring. The product crystallizes out and is filtered off and washed with water to pH 7. 22.6 parts by weight are obtained. 3- (| u-bromoethyl) -4-mwtll-7 hydroxycoumarin, m.p. 177-180 C (96% of theoretical).

22.6 parts by weight 3- (p-bromoethyl) -4-methyl-7-oxcoumarin is dissolved in 76 parts by weight. boiling acetone, salt of 0.5% water, add 2 weight, h. activated carbon and stirred at boiling point for

15 minutes. The hot solution is filtered from charcoal. The filtrate is heated to reflux temperature, add

23.7 parts by weight anhydrous potassium carbonate was boiled for 10 minutes; 0.03 pbw added. potassium iodide and 14.4 weight.h. ethyl ester with, - chloroacetic acid.,

10 The reaction mixture is maintained at a CyPeny temperature of 10 minutes, cooled to room temperature, and the product is precipitated with water. The precipitate is filtered off; and washed with water to pH 7. 28.7 parts by weight are obtained. 3- (p - bromine, thyl) -4-methyl-7-carboethoxycoumarin, so pl. 118-120С (98% of the theoretical).

28.7 parts by weight 3- (p-bromoethyl) -4-methyl-7-Kap6o3TOKCHMeT6kcT KyMapHHa per 100 weight.h. ; benzene is added to 13 parts by weight. anhydrous potassium carbonate AND 10 weight.h. diethylamine, incubated for 5 hours, at boiling point, cooled, washed twice with 25 ml of water. The benzene layer is evaporated to dryness in a vacuum. The residue is dissolved in ethyl alcohol .4i and 15.2 parts by weight is added to the solution. anhydrous zinc chloride in 117 weight.h. ethanol. A camplex compound of zinc chloride with 3-diethylaminoethyl) -4-methyl-7-carboethoxymethoxycoumarin is precipitated, which after cooling; the reaction mixture is filtered off.

The complex compound is decomposed with an aqueous solution of potassium carbonate in the presence of 100 parts by weight benzene. The benzene layer containing 3- (p-diethylaminoethyl) -4-methyl-7-carboethoxymethoxycoumarin is evaporated to dryness. The residue is dissolved in ethyl acetate and the solution is saturated with hydrogen chloride. Precipitated 25.5 parts by weight. hydrochloride salt of 3- (i-diethylaminoethyl) -4 methyl-7-carboxethoxymetoxymympine, m.p. 161-1b2 ° C.

Example 2. 22.6 wt.h. The 3- (f-bromoethyl) -4-methyl-7-hydroceicumarin prepared in Example 1 is dissolved in 80 parts by weight. 24 parts by weight of hot acetone are added. anhydrous potassium carbonate i is stirred at boiling point for 10 minutes. Next, add 0.5 weight.h. dimethylformamide.and

16webs. ethyl ester "(. -bromoacetic acid and stirred at a temperature.: K | 1pe nor for 1 h. Get 3- (| -bromoethyl-7-Carboethoxycoumarin; to which Yuves.h Liethylamine in 100 parts by weight of toluene with

Claims (1)

9. weight.h. pyridine and the reaction are boiled for 2 hours. The solution is then washed with water and the toluene layer is evaporated in vacuo. The residue is 120 parts by weight of ethyl alcohol and 15.2 parts by weight is added. anhydrous zinc chloride in 117 weight, h. ethanol. The reaction mixture is saturated with hydrogen chloride at room temperature. After cooling to a precipitate of the complex compound of zinc chloride with 3- (L-diethylamino-ethylamino) -4-methyl-7-carb ethoxymethoxycoumarin, it is filtered, decomposed with an aqueous solution of ammonia aka. 3- (p) -diethylaminoethyl) -4-methyl-7-carboethoxymethoxycoumarin is obtained, which is filtered and dried. The dried substance is dissolved in ethyl acetate and the solution is saturated with hydrogen chloride. 25 weight parts precipitate. the hydrochloride salt of 3- (p-diethylamine ethyl) -4-methyl-7-carboethoxymethoxycoumarin, so pl. 160-162 ° C. The invention of the method for the preparation of 3- (b-dialkylaminoethyl), 4-alkyl-7-carboethoxymethoxycum; .OZS SN, " CH COOCjH, where 1., K, and mean lower alkl containing 1–3 carbon atoms, as well as the hydrohalides of the compound of formula I, by the interaction of resorcinol with the derivative –butyrol actone,; IMS is different, that, in order to increase the yield of the target product, the interaction of resorcinol with the y-butyrolactone derivative of general formula II ;-and. Here, the indicated values are carried out in anhydrous acetic acid. YN | CH, X thirty HaCOsC Hj where l has the indicated values, is treated with a dialkylamine of the formula Kj, T {, NH where Cr Rj have the indicated values, in benzene or toluene, in the presence of pyridine or alkali metal carbonate at a molar ratio of reagents li 1.2-2, after which the reaction mixture is heated with water t, the solvent is evaporated, the residue is dissolved in ethyl alcohol, zinc chloride is added and cooled / the complex compound of the product with zinc chloride is separated, which is decomposed with an aqueous solution of alkali metal carbonate or ammonia and the target product is isolated rimmed or converted into a hydrohalogen salt, an acid in the presence of hydrogen halide and phosphorous acid, forming 3- (p) -haloethyl) -4 alkyl-7-hydroxycoumarin of the formula III ,, 1n, d where T has the above value and X represents a chlorine atom or bromine, treated with halogenoacetic acid ester of the formula X CHjCooCjHy, where X denotes a chlorine or bromine atom, in an acetone in the presence of an alkali metal carbvnate and, as a catalyst, 0.2-2% dimethylformamide or water and potassium iodide, obtained 3- (p- haloethyl} 4-alkyl-7-2 arboethoxymethoxy Arin Formula And