SU956471A1 - Process for producing unsaturated esters of dithiocarbamic acids - Google Patents

Description

(54) METHOD FOR OBTAINING NONSATURATED ETHERS

one

The invention relates to a process for the preparation of unsaturated esters of dithiocarbamic acids, which can be used as pesticides and additives that do not contain chlorine to lubricating oils.

A known method for the preparation of dithiocarbamic acid esters by reacting halide compounds containing easily exchangeable halogen atoms with alkali metal dithiocarbamate in polar solvents for OO-C. In this case, chlorine-containing and relatively rarely bromine-containing compounds 1 are used.

However, it is not possible to obtain the esters of Dithiocarbamic acids with short S-substituted radicals (methyl, ethyl, allyl) by this method.

The closest to the invention in its technical essence and the achieved result is a method for producing S-allyl dialkyldithiocarbamic acid by reacting metal dialkyldithiocarbamates and allyl bromide. The yield of the target product 78-73% 2.

However, organo-bromine compounds, including allyl bromide, DITIOCARBAMINE ACIDS

(much more expensive than the corresponding organochlorine compounds. In addition, they do not always provide a high yield of the target compounds. Therefore, the production of dithiocarbamic acid esters on an industrial scale from allyl bromide and dithiocarbamates of metals is expensive and economically impractical.

ten

The aim of the invention is to increase the yield of the target products.

The goal is achieved by the fact that the unsaturated esters of dithiocarbamic acids of the general form,

15: mules.

(H2 (lH- (iHa - $ - (

W

$

20

. Where K is alkyl or R and R

; together with the nitrogen atom form

piperidino or morpholino, obtained by the interaction of halide allyls with aqueous solutions or salts of 25 dithiocarbamic acids at 16 ° C.

Preferably, 3060% solutions of dithiocarbamic acid salts and allyl chloride are used in a sterile ratio or 2025% solutions of dithiocarbamic acid salts and 50% allyl chloride.

It is established that the yield of the target products p largely depends on the concentration of solutions

salts of dithiocarbamate and the ratio of initial reagents.

The dependence of the yield on the concentration of an aqueous solution of sodium dithiocarbamate (DTC Na) and the ratio of the initial reagents is presented in Table 1.

Table

1: 1

1: 1

1: 1

1: 1

1: .1

1: 1,1

1: 1.5

As follows from the table, at an equimolar ratio of the initial reagents, a high yield of ethers is provided only in the case of using sodium diethyldithiocarbamate (DTC Na) solutions with a concentration above 30%. The use of a 20% aqueous solution of DTKM with a solid ratio of reagents does not give a high yield of ether, even with a significant increase in the duration of the reaction. However, a 20% sodium diethyldithiocarbamate solution may also be used to produce S-allyl diethyl thiocarbamate in very high yield. This is achieved by reacting with an excess of allyl chloride.

Example. Getting S-allyldimethyldithiocarbamate

: ns

NjStiHidH dHg

SNS

To 2 kg of a 50% aqueous solution of sodium dimethyldithiocarbamate, at 1-3 ° C, 531 g of allyl chloride is added. As a result of exothermic

2

98 97 94 83 85 93 97

2

four

four

eight

four

2

the reaction temperature of the mixture rises to. The mixture is stirred at this temperature for another 1.5-2 hours, the organic layer is washed with water and dried under vacuum. The output of S-allyldimethyldithiocarbamate-1, 113 kg {99% of theoretical).

Example 2: Preparation of S-aplilpiperidindithiocarbamate

ABOUT

HC $ (H2 (

I

623 g of allyl chloride (8.6 mol) are added at 20 ° C to 5 kg of a 20% aqueous solution of sodium piperidine dithiocarbamate sodium (J5.45 mol). The temperature of the reaction mixture rises to 45 ° C. The mixture is then heated to and stirred for 1.5-2 hours. The organic layer is washed with water, the excess allyl chloride is distilled off and the floor is dried with vacuum. The output of S-allylpiperidine dithiocarbamate 1,097 g (99% of theoretical).

Claims (3)

The characteristics of some of the esters obtained by the proposed method are given in Table. 2. - Claim 1. The method of obtaining non-saturated dithiocarbamic acid esters of general formula. , (iH2 - $ - e- “; .-., where —C.-C-alkyl or R and R together with the nitrogen atom form piperidino or morpholino groups, by reacting alloyl halides with aqueous solutions of d salts of dithio-carbamic acids wherein, in order to increase the yield of the target products, allyl chloride is used as an allyl halide and the process is carried out with. Table2 2. A method according to claim 1, characterized in that 3060% solutions of dithiocarbamic acid salts and allyl chloride are used in a stoichiometric ratio. 3. The method according to claim 1, characterized in that they use 20- i 25% solutions of dithiocarbamic acid salts and 50% excess of allyl chloride. Sources of information taken into account in the examination 1. USSR author's certificate 363696, cl. C 07 C 155/08, 1970. 2. Lzerbaev, I.N., Tsoi, LA, Aitkhozhaeva, N.Zh., Dzhamatletdinova, M.K. Izv. AN of the Kazakh SSR, I 2, Ser, chemical, p. 67, 1969 (prototype).