CS265307B1 - Substituted 3-dithiolcarbamate tributyltin propionates - Google Patents

Abstract

The solution concerns substituted 3-dithiocarbamate-tributyltin propionate compounds of the general formula I. These compounds can be used as bactericidal agents for disinfection and sanitation of premises and equipment.

Description

The invention relates to substituted 3-dithiocarbamate-tributyltin propionate compounds. Said compounds have bactericidal effects.

Some organotin compounds, such as bis-tributyltin oxide, tributyltin acetate or tributyltin benzoate, are known as substances with bactericidal effects.

The series of these substances is extended by the substituted 3-dithiocarbamate - tributyltin propionate according to the invention of general formula I,

R-CS-S-CH ₂ -CH ₃ -COOSn(nC ₄ H ₉ ) ₃ (I) where R means /ch ₃ / ₂ n-, /c ₂ h ₅ /n-, /nC ₃ H _? / ₂ N-, /nC ₄ H _g / ₂ N- ₍

O-· Oor

These substances are prepared by condensation of the corresponding sodium salt of dithiocarbamidopropionic acid with the sodium salt of 3-chloropropionic acid to form the sodium salt of the propionic acid derivative. The action of hydrochloric acid on the sodium salt of 3-dithiocarbamidopropionic acid liberates 3-dithiocarbamidopropionic acid. Esterification of 3-dithiocarbamidopropionic acid with bis-tri-n-butylene oxide produces the corresponding 3-/dithiocarbamido/propionate of tri-n-butylane.

The reactions that occur in the preparation of the compounds of the invention can be represented by the following equations (A, B).

R-CSSNa + Cl-CH ₂ -CH ₂ COONa ——-> R-CS-S-CH ₂ -COOH + 2NaCl A ^Sn/nC ,H„/,

2R-CS-S-CH--COOH + 0 -> 2R-CS-S-CH„CH,-COOSn/n-C.Η./, + Η,Ο B

Sn/nC ₄ H ₉ / ₃ where R is the same as above.

These substances have the same or higher bactericidal activity than known substances. They are odorless, non-volatile and do not decompose at ordinary temperatures or under the influence of light, they are very effective even at very low concentrations, especially against gram-positive bacteria such as Bacillus subtilis, Staphylococcus aureus, which are very dangerous.

Example

The corresponding sodium salt of dithiocarbamide acid and the sodium salt of 3-chloropropionic acid are dissolved in ethanol in a molar ratio of 1:1. The reaction mixture thus obtained is heated to boiling ethanol and boiled under a reflux condenser for 4 hours. After the reaction is complete and the reaction mixture is cooled to room temperature, an equal amount of distilled water is added to it and the corresponding 3-/dithiocarbamido/-propionic acid is released by acidification with dilute hydrochloric acid, which, after washing with water, is dried to a constant weight. The yields range from 95 to 98% of theoretical. The 3-dithiocarbamido/-propionic acid thus obtained is dissolved in benzene together with bis-tri-n-butylene oxide in a molar ratio of 2:2. The resulting mixture is refluxed and the water formed during the reaction is azeotropically distilled off. The reaction lasted 1 hour. After the reaction was complete, benzene was distilled off under reduced pressure and a crystalline portion of the corresponding tri-n-butyltin 3-dithiocarbamidopropionate was obtained in a yield of approximately 98% of theory.

The substances according to the invention were identified by elemental analysis by determining carbon, hydrogen, nitrogen, sulfur and tin by NMR spectroscopy and their melting points were determined, which are listed in Table 1.

The bactericidal activity of the newly synthesized organotin compounds is demonstrated in the following examples, without referring to them exclusively.

Example 2

We determined the bactericidal effectiveness of these substances using the so-called roller (chimney) method.

This method consists in placing ground aluminum or duralumin cylinders 1 cm high with an internal diameter of 6 to 8 mm at appropriate distances on the surface of the inoculated suitable culture medium. A solution of the test substance is filled into the cylinder with a pipette, and the Petri dishes with the inoculated culture medium are incubated with the filled cylinders. The substance from the solution in the cylinders diffuses into the culture medium and, if it is effective against microorganisms, it inhibits their growth and reproduction, and a clear zone uninfested by microorganisms is formed around the cylinder.

Petri dishes with a diameter of 180 mm filled with 150 ml of massopept agar were used. 8 cylinders were placed on the surface of the solidified inoculated medium, into which 0.2 ml of a 0.01 M solution was pipetted into four and 0.2 ml of a 0.001 M solution of the test substances in dimethyl sulfoxide into the other four. As a control for comparison,

(a) tributyltin acetate

(b) pure dimethyl sulfoxide.

The following bacteria were used as test microorganisms: Bacillus subtilis, Staphylococcus aureus, Proteus mirabilis, Micrococcus albidus, Pseudomonas sp. and Escherichia coli. The substances were tested three times in three parallel rows.

The results are shown in Table 2. The agent used was ineffective against the bacteria Proteus mirabilis, Micrococcus albidus, Pseudomonas sp. and Escherichia coli.

Example 3

The procedure was the same as in Example 2, active substance concentration 0.001 mol/liter in dimethyl sulfoxide.

The following bacteria were used as test microorganisms: Bacillus subtilis, Staphylococci aureus, Proteus mirabilis, Micrococcus albidus, Pseudomonas sp. and Escherichia coli. The substances were tested three times in three parallel rows.

The results are shown in Table 3. The agent used was ineffective against the bacteria Proteus mirabilis, Microcococcus albidus, Pseudomonas sp. and Escherchia ooli.

These substances can be used primarily for disinfection, sanitation of premises, floors, walls, for disinfection of equipment, or devices, but also for disinfection of linen in hospitals, for the needs of the food industry for disinfection of filling equipment and other equipment, especially for breweries and dairies. These substances are highly effective even at very low concentrations, especially against gram-positive bacteria such as Bacillus subtilis, Staphylococci aureus, which are very dangerous.

Table 1

R Melting point (°C) /CH ₃ / ₂ N- 57.5 to 53.5 /c ₂ h ₅ / ₂ n- 49.0 to 50.0 /c ₃ h ₇ / ₂ n- 61.0 to 62.0 /c ₄ ^h 9/ ₂ n- 59.5 to 60.5 o- 61.5 to 62.5 About- 63.0 to 64.0 r~\ 0 N\/ 55.5 to 56.5 Table 2 R Bacillus subtilis Staphylococcus aureus /ch ₃ / ₂ n- ++++ ++++ ^{/ C2H5Z2N- ​ ​} +++ ++++ /c ₃ h ₇ / ₂ n- +++ ++++ /c ₄ h ₉ / ₂ n- ++++ o- ++++ ++++ r~\ 0 N- ++++ ++++ About- ++++ ++++ CHjCOOSn/C^Hg/j Standard ++++ ++++ dimethyl sulfoxide pure - - ++++ very high inhibition efficiency +++ high inhibition efficiency ++ medium efficiency of inhibition + visible inhibition efficiency ineffective Table 3 R Bacillus subtilis Staphylococcus aureus /ch ₃ / ₂ n- +++ +++ ^ZC 2 ^H 5 ^/ 2 ^N - +++ +++ /c ₃ h ₇ / ₂ n- +++ +++ /c ₄ h ₉ / ₂ ⁿ - - -

Table 3 continued

R Bacillus subtilis

Staphylococcus aureus

G- +++ +++ About- ++ +++ z ^- λ ++ +++ _N- _{CH3COOSn / C4Hg} / ₃ +++ +++ dimethyl sulfoxide pure - -

++++ very high inhibition efficiency +++ high inhibition efficiency ++ medium inhibition efficiency + visible inhibition efficiency ineffective

Claims (1)

OBJECT OF THE INVENTION Substituted 3-dithiocarbamate-tributyltin propionates of formula I R-E-S-CH ₂ CH ₂ -COOSn / n-C ₄ H _9/3 (I) wherein R represents / CH ₃ / N _2, / n-C ₃ H _7/2 N, / n-C ₄ H _g / ₂ N-, N - or N -.