SU1482919A1 - Method of producing acetyl derivatives of benzocroun esters - Google Patents

Abstract

The invention relates to the production of benzocrown ethers — macrocyclic heterocyclic compounds, in particular the preparation of: a) 4.4 x (5 ^b ) -diacetyldibenzo-18-crown-6

b) 4-acetylbenzo-15-crown-5

c) 4-acetylbenzo-18-crown-6, which can be used as an extractant of alkali metals or as an antihypoxic agent in medicine. The goal is to simplify the process. The latter is carried out by acetylating the benzocrowune ester with a 2-4 fold excess of acetic anhydride at 30–50 ° C in a chlorine-containing solvent (CHCL ₃ ) in the presence of a catalyst with 50–60% perchloric acid, which is used in an amount of 1–10 wt.%. Chloroform is used in an amount of 2-5 liters per mole of benzocrown ether. Output, %

mp, ° s

gross la: a) 51,8-93,5

195-200

C ₂ 4H ₂ 8O ₈

b) 85.2

76-77

C ₁ 8H ₂ 6O ₇

c) 88.7

95-96

C ₁ 6H _{2 2} O _6. These conditions simplify the process by eliminating the use of large quantities of freshly prepared polyphosphoric acid and reducing the amount of wastewater. 1 hp f-ly, 4 tab.

Description

Note. Synthesis conditions: solvent - chloroform (4 l / / mol DB18K6); 3-fold excess (CHiCO) aO; temperature 40 ° С „

Note. Synthesis conditions: catalyst - 57% HC104 (4 wt.% To DB18C6), solvent — chloroform (4 l / mol DB18C6), temperature 40 C.

Note. Synthesis conditions: catalyst - 57% HC10j | (4 wt.% To DB18K6); the solvent is chloroform (4 l / mol DB18C6), 3-fold excess (CH3CO) gO,

PRI mme R 2. Obtaining diacetyl DB18K6.

A mixture of 3.6 g of dibenzo-18-crown-6, 10 ml of acetic anhydride and 0.15 g of 57% is stirred at 40 ° C for 3 hours. The reaction mixture is poured into 100 ml of water, the precipitated product is filtered, washed on filter with water until neutral wash water, then washed with 10 ml of acetone and dried on the filter. 2.9 g of a solid black product are obtained, from which it is not possible to isolate diacetyl DB18Kb.

PRI me R 3. Obtaining 4-acetyl benzo-15-crown-5 (ha 1, q 1).

A mixture of 2.7 g (0.01 mol) of benzo-15-crown-5, 25 ml of chloroform, 3.1 g (0.03 mol) of acetic anhydride and

0.1 g of 57% HC10,) is stirred at 40 ° C for 4 hours. After cooling, 20 ml of water is added, stirred, the organic layer is separated and washed with water. Chloroform is distilled off and the product obtained is recrystallized from heptane.

Obtain 2.75 g of the final product, yield 88.7% theoretical., So pl. 95-96 ° C.

Found,%: C 61.98; H 7.10.

S (6 N Si About.

Calculated,%: C, 61.92; H 7.15.

IR spectrum (KBG), cm 1: 1680 () 1280 (CQp -0-Sol); 1150 (C-O-C); 880-820 (1,2,4-substituted benzene).

PRI me R 4. Getting 4-acetyl benzo-18-crown-6 (t 0, q 2),

A mixture of 3.1 g (0.01 mol) benzo-18-crown-6, 25 ml of chloroform, 3.1 g

35

482919b

(0.03 mol) of acetic anhydride and 0.1 g of 57% HC104 are stirred at 40 ° C for 4 hours. After cooling

, add 20 ml of water, mix,

five

the organic layer is separated and washed with water. Chloroform is distilled off, the resulting product is recrystallized from heptane.

10 Obtain 3.0 g of the final product, yield 85.2% theoretical., So pl. 76-77 ° C. Found,%: C 61.07; H 7.25. C / a Ng60t. Calculated,%: C 61.00; H 7.39.

15 IR spectrum (KBG), 1680 (); 1270 (Sar-0-Sal); 1145 (C-O-C); 880-820 (1, 2,4-substitutable benzene).

Claims (2)

1. A process for the preparation of acetyl derivatives of the benone amine esters of the formula thirty 40ts p 5 X0. o-% -s-sn5 BUT where t is 0.1; q 1,2-interaction of benzocrown ether with 2-4-fold excess of the acetylating agent in the presence of a catalyst in a solvent medium when heated, characterized in that, in order to simplify the process, 50-60% perchloric acid is used as a catalyst in an amount of 1-10% by weight with respect to to benzocrown ether, acetic anhydride is used as acetylating agent 714829198 and the process is carried out in a chloro-containing solvent medium. holding solvent at 30-50 ° C. chloroform in the amount of 2-5 l n 2. The method according to claim 1, I distinguish (the MOLE of the benzocrown-ether “i and the fact that as chlorine