SU419022A3 - - Google Patents

Description

(54) METHOD FOR OBTAINING SUBSTITUTED a-ARYLOXYLES and a-ARYLTI-ALKANE ACIDS OR THEIR ETHERS,

AMIDOV, SALTS

nyem, easily soluble - by evaporation of the solvent.

Example 1. 3.4 g (9.0 mmol) of 2- (6,7,8,9-tetrahydrodibenzofuran-2-ylokoi) -2-hexylmalonic acid are boiled for 30 minutes in 34 ml of xylene under reflux, evaporated to dryness in iBaKyyMe, the oily residue is recrystallized twice from hexane to obtain pure 2- (6,7,8,9-tetrahydrodibenzofuran-2-yloxy) -octanoic acid, white needles, t.ol. 99-100 ° C.

Similarly, receive:

from 1.20 g (4.0 mmol) 2- (6,7,8,9-tetrahydrodibenzofuran-2-yloxy) -2 - methylmalonic

acids 2- (6,7,8,9-tetrahydrodibenzofuran-2yloxy) -propionic acid, so pl. 128-

129 ° C (methanol-water);

: from 1.45 g (3.0 mmol) of 2- (6,7,8,9-tetrahydrodibenzofuran-2-yloxy) -2 - tetradecylmalonic acid of 2- (6,7,8,9-tetrahydrodibenzofuran-2-yloxy ) -hexadecano: vuyu acid, so pl. 55-56 ° C (hexane);

from 2.25 g (6.0 mmol) of 2- (6,7,8,9-tetrahydrobenzofuran-3-yloxy) -2-hexyl.malonO | Howl of acid 2- (6,7,8,9-tetrahydrodibenzofuran- Z-yloxy) -octanoic acid, so pl. 78-79 ° C (hexane);

from 1.95 g (5.0 mmol) of 2- (6,7,8,9-tetrahydrodibenzofuran-2-ylthio) -2-hexylmalonic acid 2- (6,7,8,9-tetrahydrodibenzofuran-2-ylthio) - octanoic acid, t. pl. 92-93 ° C (hexane);

from 1.95 g (5.0 mmol) of 2- (6,7,8,9-tetrahydrodibenzofuran-3-ylthio) -2-hexylmalonic acid 2- (6,7,8,9-tetrahydro-1benzofuran-3-ylthio) - octanoic acid, t. pl. 62-63 ° C (hexane);

from 2.23 g (5.0 mmol) of 2- (6,7,8,9-tetrahydrodibenzofuran-3-ylthio) -2-decylmalonic acid 2- (6,7,8,9-tetrahydrodibenzofuran-3- Ilthio) dodecanoic acid, m.p. 73.5-74.5 ° C (hexane);

from 0.80 g (2.0 mmol) of crude 2- (6,7,8,9 tetrahydrodibenzothiophen-2-ylthio) -2 - hexylmalonic acid 2- (6,7,8,9-tetrahydrodibenzothiophen-2-ylthio) - octanoic acid, so pl. 91-92 ° C (hexane);

from 1.20 g (0 mmol) of crude 2- (6,7,8,9 tetrahydrodibenzothiophen-3-ylthio) -2 - hexylmalonic acid 2- (6,7,8,9-tetrahydrodibenzothiophen-3-Ilthio) -octane acid, p 1.5718 (for chromatographic purification on silica gel, eluent benzene and benzene – acetic acid mixture, 49: 1).

Example 2. 0.78 g (-2.0 mmol) of crude 2- (6,7,8,9-tetrahydro-dibenzothiophen-2-yloxy) 2-hexylmalonic acid “agate for 30 minutes under nitrogen at 150 ° C. The decarboxylated crude product is chromatographed on silica gel (eluent benzene and benzene – ice / acetic acid, 19: 1). After recrystallization from hexane, 2- (6,7,8,9-tetrahydrodibenzothiophen-2-Iloxy) -octanoic acid is obtained, m.p. 90-91 ° C.

Example 3. 0.78 (2.0 mmol) of crude 2 (6,7,8,9-tetrahydrodibenzothiophen-3-yloxy) 2-hexylmalonic acid is heated for 5 minutes to 240-250 ° C, treated as in Example 2, and get 2- (6,7,8,9-tetrahydrodibenzothiophen-3-yloxy) -octanoic acid, so pl. 106-107 ° C (hexane).

Example 4. 1.1 g (3.5 m, mol) 2- (6,7,8,9-tetrahydrodibenzofuran-2-yloxy) - heptane

The acid is dissolved in 20 ml of absolute ethanol, a solution of 69 mg (3.0 mmol) of sodium IB is added to 5 ml of absolute ethanol, the solvent is evaporated to dryness and the white solid is triturated with 20 ml of ether. Then sucked off, additionally washed with a simple

ether and get pure sodium salt in

a white powder, so pl. 290-308 ° С

(different).

Similarly, get from 3.465 g (10.0 mmol)

2- (6,7,8,9-tetrahydrodibenzothiophen-3-yloxy) octanoic acid sodium salt of 2- (6,7,8,9 tetrahydrodibenzothiophen-3-yloxy) - octanoic acid, so pl. 320-322 ° C. Example 5. To a suspension of calcium hydroxide prepared from 110 mg (2.75 mmol) of calcium and 10 ml of WATER in a nitrogen atmosphere, was added 2.05 g (6.22 mmol) of 2- (6,7,8,9- tetrahydrodibenzofuran-2-loxy) octanoic acid in 50 ml of methanol and boil for 15 minutes under reflux. After cooling, the resulting white suspension is evaporated to 20 ml, the calcium salt is filtered off with suction, washed with a small amount of ether, and extracted with LC, 120 ml of boiling methanol. The combined extracts are filtered, evaporated to 20 ml, diluted with 30 ml of ether, the crystals are filtered off with suction and washed with ether. After drying in a high vacuum, pure calcium salt of 2- (6,7,8,9-tetrahydrodibenzofuran-2yloxy) -octanoic acid is obtained, m.p. 305-315 ° C (decomp.).

Example 6. To a suspension of calcium hydroxide obtained from 137 MG (3.42 mmol) of calcium in 15 ml of water, a solution of 2.50 g (7.2 mmol) of 2- (6.7.8 , 9-tetrahydrodibenzothiophen-2-yloxy) -octanoic acid in 80 ml of methanol, boiled for 15 minutes with a reflux condenser, evaporated to a small volume, the calcium salt is filtered off, washed with ether and recrystallized twice from absolute methanol. Get the pure calcium salt of 2- (6,7,8,9-tetrahydrodibenzothiophen-2-yloxy) -octanoic acid, so pl. 290-305 ° C (decomp., The salt turns brown).

Subject invention

A process for the preparation of substituted a-aryloxyly a-arylthioalkanoic acids or their esters, amides, salts of the general formula

where Ri is GI-CI-alkyl or Cs-Su-cycloalkyl;

R2 is hydroxyl, in which a hydrogen atom can be replaced by an alkali metal or alkaline earth metal atom, Ci-Cz-alkoxygrume, aiMHHorpynna;

X and Y are independently of each other oxygen or sulfur, characterized in that the corresponding substituted malonic acid of the general formula

B, -1x-C-SOKg

Cun

where Hb R2, X, and Y are as defined above, heated at the cleavage temperature of an equimolar amount of carbon dioxide, followed by isolation of the target product or its conversion into the corresponding derivatives by known methods.