SU1502564A1 - Method of producing alkyl esters 4.6-dithia-5-methylenondiene-2.7-dio acid - Google Patents

Abstract

SUBSTANCE: invention relates to sulfur-containing nitriles, in particular, to the preparation of alkyl esters of 4,6-dithia-5-methylennonadiene-2,7-diethoic acid form (NC) C (R ₁ ) = ROOC-CH = CH-SCS-CH = CH-COOR, where R is lower alkyl, R _{1 is} cyano-, aminocarbonyl or lower alkoxycarbonyl, which exhibit fungicidal activity. The goal is to get new connections in a new way. Obtaining the target compounds are from the salt of 1,1-vinylidendithiol Formula (NC) (R ₁ ) C = C (SM) (SM), where R _{1 is} indicated above, the M-cation of an alkali metal or ammonium and the propiolic ester -lly HC = C-COOR, where R is as indicated above, in the presence of an equimolar amount of an acidic agent, preferably CH ₃ COOH, or HCl, or AICI ₃ ^. 6H ₂ O in a polar organic solvent, preferably a lower alcohol, or benzene, or acetonitrile. 1 hp f-ly.

Description

The invention relates to organic chemistry, specifically to a new method for the preparation of new compounds, esters of 4,6-dithia-5-methylenesnadien-2,7-diic acid of the formula

ROOC-CH CH- - C-S-CH CH-COOR

II

/ C NC E, (I)

where R is lower alkyl;

R, is a cyano, aminocarbonyl or lower alkoxycarbonyl group that exhibits fungicidal activity and can be used in agriculture.

The aim of the invention is to develop a new method for the preparation of previously unknown compounds - esters of 4,6-dithia-5-methylenone-2,7-bottom acid of formula (I), possessing valuable properties.

The method consists in the interaction of salts of 1,1-vinylidenethiols of formula

NCv / SM

/

where R has the indicated meanings; M - alkali metal or ammonium cation, with propioloric acid esters of the formula

sl o ka ate

O5 4

HC C-COjR (III)

where R is HT-ieer the indicated values, in the medium ort of the polar polar diluent D in the presence of equimolar KojiHMecTJ a acidic agents at boiling point.

Example 1. Preparation of dimethyl ester A, 6-dithia-5- (cyanocarbamoylmethylene) nonadiene-2,7-diic acid. 0.6 ml was added to a solution of 0.68 g of propiolic acid methyl ester in 10 ml of methanol. glacial acetic acid and then with stirring 0.80 g of the ammonium salt of 2-cyano--2-carbamoyl-1, 1-dime rcaptoethylene. The reaction mixture is heated to boiling and lumps for 10 minutes. The precipitate formed after cooling (the precipitate is filtered off, washed with 50% aqueous methanol and water. 11 0.78 g (60%) of colorless crystals are obtained; 1X crystals with (from methanol).

m.p. 180-183 seconds

IR spectrum (): 2215 (CN); 1690 (GS ef.); 1665, Ij655 (amide); 1602 ().

Spectrum Ø EP (au, eTOH-dt) S ppm :

Calculated,%: C 49.98; H 5.24; N 7.28; S 16.67.

C, 6l4oNiOjSa

Found,%: C 50.33; H 5.46;

VjlieKlp Jirir V clLl.f. 1 Ull u u M.A -on

3.74 s and 3.77 C (6H, 2 OC1C); 6.15 d S 17.25.

and 7.59 d (J 10.2 Hz); 6.23 d and 7.40 dSample 4. Synthesis of Dnispro (J 9.9 Hz) C4H, 2 (Z) -C-CH CH-SJcn-4,6-dithia-5- ester (dicyano7, 19 s ( 2H, TCs).

Calculated,%: C 43.90; And 3.05; N 8.53; S 19.51.

35

1. It is 1) nonadiene-2,7-dioic acid. To a solution of 0.56 g of propionic acid isopropyl ester in 50 ml of isopropanol, 0.26 g of AICI-0, 0, and then 0.80 g trigsh, rata sodium 2,2-diciano-1,1-dimercaptoethylene. The irarper.aror reaction mixture was boiled and boiled for 30 minutes. The cooled reaction mixture is fed into 200 ml of water, the precipitated precipitate is taken off. Obtain 0.68 g d5 (73%) best; white crystals with t. Nl.

Found,%: C 43.59; P 3.44; N 8.46; S 19.24.

Example 2. Preparation of diethyl 1) ester of 4, 6-dithia-5- (cyano-carbamo-1 methylene) nonadien-2,7-di-ACID. Similarly, from 0.40 g of ethyl ester ipa. Proniolic acid, 0.25 ml of glacial acetic acid and 0.40 g of salt in 10 ml of ethanol, 0.62 g (86%) of colorless crystals are obtained.

m.p. (from 50% aqueous ethanol).

IR: 1 Spectrum (cm): 2213 (CN); 1709 (ate, ef.); 1685, 1662 (C-0 amide); 1590 (C-C).

PMR spectrum (acetone-dg) S ppm: 1.30 t and 1.32 t (J 7 Hz, 6P, 2SI,); 4.20 KB and 4.22 kV (J.7 Hz, 4H, 20CHj); 6.15 d and 7.59 d (J 10.3 Hz); 6.20 d and 7.38 d (J 9.9 Hz) 4Z,: (2) - C-SP SI G) 1; 7.18 with (2P, NH).

N

ten

025644

Calculated,%: C 47.19; H 4.55; N 7.89; S 17.96.

C ,, H, f,

Found,%: C, 47.02; And 4.59; 7.95; S 18.46.

Example 3. Preparation of 4,6-dithia-5- (cyano-carbamoylmethylene) nonadien-2, 7-diic acid diisoprenyl ester. Similarly, 1.34 g (79%) of colorless crystals with a melting point of 1.34 g of propionic acid isopropyl ester, 0.70 ml of glacial acetic acid, and 1.00 g of salt in 20 ml of isopropanol. 159-160 ° С (from isopropanol)

IR spectrum (): 2215 (CN); 1692 (C-0 el. Ef.); 1660 (C-0 amide); 1587 ().

Spectrum PMR (aco gon-dg) S ppm: 1.32 d and 1.34 d (J 6.2 Gd, 12H, 4CH,); 5.02 septet and 5.05 septet (J 6.2 Hz, 2H, 20CFI); 6.09 d and 7.58 d (J 10.2 Hz); 6, 17 d and 7.37 d (J 9.9 Gc), 2 (Z) -C-CH CH-S; 7.17 with (2H, N11).

Calculated,%: C 49.98; H 5.24; N 7.28; S 16.67.

15

20

C, 6l4oNiOjSa

Found,%: C 50.33; H 5.46;

1. It is 1) nonadiene-2,7-dioic acid. To a solution of 0.56 g of propionic acid isopropyl ester in 50 ml of isopropanol, 0.26 g of AICI-0, 0, and then 0.80 g trigsh, rata sodium 2,2-diciano-1,1-dimercaptoethylene. The irarper.aror reaction mixture was boiled and boiled for 30 minutes. The cooled reaction mixture is fed into 200 ml of water, the precipitated precipitate is taken off. Obtain 0.68 g (73%) best; white crystals with t. Nl.

139-140 ° C (from 50% aqueous isopropanol).

IR spectrum (): 2220 (CN); 1697 (); 1600 ().

PMR spectrum (CDC1,) ppm: 1.21 d (J 6.5 Hz, 12H, 5.05 septet (J 6.5 Hz, 2P, 20CH), -6.17 d (J 0.0 Hz, 2H,); 7.11 d (J 10.0 Hz, 2H,).

Calculated,%: C 52.45; H 4.91; , S P, 49.

C, BP, LIE ,, 043

Found,%: C 52.47; And 4.90; S 17.89.

Example 5. Preparation of 4,6-dithia-5- (cyanoethoxycarbonylmethylene) 1gonadiene-2,7-dioic acid diethipic ester. To a solution of 0.60 g of ethyl propiolic ester in 10 ml of acetonitrile, with stirring, add 0.6 ml of concentrated HCl and then in small portions of 0.97 g of sodium salt 2-cyano-2-ethoxycarbonyl-1,1-dimer sodium pentahydrate captoethylene The reaction mixture is heated to boiling and boiled for 30 minutes. The solvent is removed in vacuo, the batch is chromatographed on silica gel (eluent-benzene). Obtain 0.85 g (84%) of a yellow slowly crystallizing oil, so pl. 102-106 ° C (from hexg on).

PC spectrum (cm): 2215 (CN); 1720, 1700, 1690 (); 1590 ().

PMR spectrum (acetone-dg) S ppm: 1.23 - 1.40 m (9H, CHS,); 4.12 - 4.31 m (6H, Zoa); 6.00 d and 6.07 d i (J 9.9 Hz, 2H,); 7.54 d and 7.69 d (J 9.9 Hz, 2H ,,).

In the PMR spectrum of the uncrystallized sample, signals (Z, E of the isomer: 6.14 d and 7.40 d (J 15.4 Hz)) of the (Z, E) -isomer are about 30%.

Calculated,%: C 49.84; H 4.97; S 16.61.

,,

Found,%: C 49.39; And 5.16; S 16.86.

Example 6. Preparation of 4,6-dithia-5- (cyano carbamosh chetilene) nonadien-2,7-diic acid diiso-. Prop saw ether. To a solution of 0.44 g of propiolic acid isopropyl ester in 20 MP of benzene, 0.4 ml of concentrated HCl and O, 44 g of the ammonium salt of 2-cyano-2- -carbamoyl-1, I-dimercaptratytene, are added with stirring. The reaction mixture is heated to boiling and the kitts are heated for 20 minutes. The solvent is removed in vacuo, the residue is crystallized from isopropanol. Obtain 0.42 g (59%) of colorless crystals with m. Pl.

G59-160 ° C (after recrystallization from isopropanol). The resulting compound does not depress the melting point of the mixed sample with the compound obtained g; example 3.

Thus, a new method of obtaining allows the synthesis of new compounds from the class of substituted sul-0 F ODD, which possess valuable properties, in particular, exhibiting fungicidal

act.

Claims (2)

Invention Formula I. Process for the preparation of alkyl esters from 4,6-dithia-5-methylenone-nadien-2,7-diic acid of the formula FJOOC-CH CH-S-C-S-CH CH-COOR 20 NC / E - lower alktsh; - cyano-, aminocarbonyl- or F de R RI lower al) oxycarbonate group, characterized in that 1,1-Vinylidendiol salt of the formula NC :: s-ss SM Bg 35 where RI has the indicated meanings; M is an alkali metal cation or ammonium is reacted with a propiolic ester of the formula  - COOR, where R has the indicated meanings, 40 in the presence of an equimolar amount of an acidic agent in a polar organic solvent at the boil. 2. The method according to p. I, is different from the fact that CH. COOH or HC1 or L1C1 is used as an acidic agent, and lower alcohol or benzene, 1-shee acetonitrile is used as a solvent.