SU1351933A1 - Method of obtaining polyfunctional sulfur-containing spiro lactones - Google Patents

Abstract

The invention relates to poly-functional sulfur-containing spiro-cyclic lactones, in particular to the preparation of 3-methoxycarbonylmethylene 2, 2,6,6-tetramethyl (la) or 3-methoxycarbonylmethylene-2,6-dimethyl-2,6-diethyl (1b ) 1,7-dioxa-4-thiaspiro () nonan-8-one and 1 8-methoxycarbo G nsh1methylene-7,11-dioxa-I9-tynrispiro (5,3,1,5,2) nedecan-8 -on C1B), which can be used in fine organic synthesis. The goal is to develop a new method of obtaining new compounds. The compounds 1a-1b are prepared from acetylenic hydroxy acid ester and Na sulfide at 20-50 ° C in an aqueous medium. Yield,%: mp; amp C; gross l: 1 and 57.1; 157-158; С „Н, 16 50i 50 С, К ,, 0 ,; 1 to 43.3; 183-184; C ,, A new one-step method has been developed for the preparation of isomerically pure 3-methoxy-carbonylmethylene-2,2,6, b-tetraalkyl-1,7-dioxa-4 thia-spnro (4,4) non-8-ones Z-configuration . (L with cd with so with

Description

This invention relates to a new process for the preparation of polyfunctional sulfur-containing spirocyclic lactones, namely 3-methoxycarbonylmethylene-2,2,6,6-tetraalkyl-1,7-diox-4-thiaspiro (4,4) nonane -8-onam general formulas:

  - R./OOc,

where E, or R, CH, E (E

or R ,, R - - (CHjj- which can find a variety of practical applications, in particular as fine organic reagents (

ABOUT

he

OSI

Where. R -Rj-CH, or R, -CH ,; . or R, R - - (CH) j-.

The possibility of the formation of polyfunctional sulfur-containing spirocyclic lactones by the reaction of acetylene hydroxy acids with a 1-base metal sulphide is apparently due to the configuration features of the resulting intermediate product.

The method is extremely simple to perform: an acetylene hydroxy acid ester, taken in stoichiometric

amount, added to an aqueous solution of alkali metal sulphide at the indicated temperature. The mixture is stirred for 4 hours. The crystalline non-water soluble substances that form the desired product are easily separated from the reaction mixture by filtration.

Changing the reaction temperature does not improve the results. By lowering and increasing the reaction temperature the yield of the target product decreases.

The structure of the synthesized compounds was proved by IMP and IR spectra, the composition was confirmed by elemental analysis.

The synthesized compounds are isomerically pure. According to

synthesis and precursors for the production of materials with desired properties, since they have in their composition an active exocyclic double bond (a fragment of acrylic acid), a lactone and ester group, and a sulfur atom in the oxothiolane cycle.

The aim of the invention is to develop a new method of producing new compounds in a number of polyfunctional sulfur containing spirocyclic lactones based on functional functions.

and; enue acetylenes.

The proposed method is based on a new unexpected reaction of heterocyclization of acetylene hydroxyacid esters with sodium sulfide in an aqueous medium at 20-50 C.

ABOUT

 OST, S, + G1AON-1-SNZON

VII with the rule of trans-nucleophilic attachment, the exocyclic ethylene structural element has a Z-configuration. Thus, heterocycling proceeds stereospecifically.

The invention is illustrated by the following examples.

Example 1. Synthesis of 3-methoxy-carbon-1-methylene-2,2,6,6-tetramethyl-1,7-diox-4-thia-spiro (4,4) non-8-one

. ABOUT

NZS

DOS

in a three-necked flask, equipped with an eshalka and a thermometer, placed

1.2 g (0.005 mol) and 1.4 g (0.01 mol) of methyl 4-methyl-4-hydroxy-2-pentinatoate is added at 20 ° C.

The reaction mixture is stirred

 h at the same temperature. The precipitated white crystals are filtered, repeatedly washed with water, and dried. Obtain 0.8 g (57.1%) of the desired product. M.p. 157-158 C.

Found,%: S. 11.23

p ff n h “l8

Calculated%: S 11.18

IR Spectrum, j 1590, 3050 (); H-spectrum, S, h (CH); -3.76 (OSI ;; II43 (CH,).

II p and me 2.

3 C 54.87; H 6.43;

C, 54.54; H 6.29;

 : 1190 (C-O-C); 1690, 1780 () per million: 5.76; 3.07 (CHj); one,

Synthesis of 3-methoxyIcarbonylmethylene-2, 6-cimethyl-2, b-di-ethyl-1,7-diox-4-thia-spiro (4,4) nonan-8-one

ABOUT

sn

HsCz Oh

f /

OSH

Uch. x

X / Sn,,

Out of 1.25

ABOUT

g (0,008

mol) methyl-4-ethyl-4-hydroxy-2-hexinoate and 1 g (0.004 mol) of Na; for 4 h, 0.6 g (50%) of the desired product is obtained, which is a white metallic substance. M.p. 50 C.

Calculated 10.19

WITH

%: C 57.63; H 7;

45

U ,, o, s

Found,%: C 56.8; H 7.3; S 9.45

IR, 1180 (C-O-C); 1590 (); 1780, 1690 (). SR-spectrum, S, hours per million; 5.7 (CH); 3.73 (axis,); 3.1 (fn,); 2.93, 1.72 (CH in); 1.44, 1.37, 0.93 (CKj).

PRI me R 3. Synthesis of 18-methoxy-carbonylmethylene-7, 11-diox-19-ti-atrispiro (5,3,1,5,2) nonadecan-8-one.

From 1.8 g (0.01 mol) of methyl 3- (1-hydroxycyclohexyl) -3-propionate and 1.2 g (0.005 mol) of Wa S-9H20 in 30 ml

Hjo

at 20 ° C, 0.87 g (43.3%) is obtained

the desired product as white crystals. M.p. 183-184 ° C.

Found,%: C 61.80; H 7.12; S 8.37

1351933

five

0

five

0

five

S

Calculated,%: C 62.02; H 7.1; 8.74.

IR spectrum, cm 1780 (); 200 (C-O-C); 1590 (). HMR spectrum, 8 ppm: 5.74 (CH); 3.75 (OCH,); 3.02 (CH); 1.72 (C, Hj.

EXAMPLE 4 Synthesis of 3-methoxy-carbonylmethylene-2,2,6,6-tetramethyl-1,7-dioxa-4-thia-spiro (4,4) nonan-8-one.

From 1.2 g (0.005 mol) of Na S-9H20 and 1.4 g (0.01 mol) of methyl 4-methyl-4-hydroxy-2-pentinoate at 50 ° C are obtained. 0.53 g (38%) of the desired product. M.p. 157-158 C.

EXAMPLE 5 Synthesis of 3-methoxy-carbonylmethylene-2,2,6,6-tetramethyl-1,7-dioxa-4-thia-spiro (4,4) nonan-8-one.

From 1.2 g (0.005 mol) &. and 1.4 g (0.01 mol) metsh1-4-methyl-4-hydroxy-2-pentinoate at 5 With receive 0.34 ir (25%) of the target product. M.p. 157 ° C.

Thus, a new one-step method has been developed for the preparation of isomerically pure 3 - metoxycarbonate and melenyl-2,2,6,6-tetraalkyl-j 7-diox-4-thia-spiro- (4,4) nonane-8-ones Z- KOH- figurations

F-Formula

The method of obtaining polyfunctional sulfur-containing spirocyclic lactones bps; her formula:

40

45

R

-ti 5 2. 2 С

R. - - (that

y th

Acetylene hydroxy acid ester is reacted with sodium sulfide at 20–50 ° C in an aqueous medium.

Claims (1)

Claim A method for producing polyfunctional sulfur-containing spirocyclic lactones of the general formula: where R ₍ -P ₂ -CH ₃ or% -STS, B ₂ -C ₂ H _f , or R ₍ , R ₂ - '- (CHj -this is that the acetylene hydroxy acid ester is reacted with sodium sulfide at 20 –50 ° C in the aquatic environment.