Method of producing organic sulfides

专利摘要:
A process for preparing organic thioethers of formula R-S-R, in which R is an aliphatic, aryl, arylaliphatic or heterocyclic radical and R1 is an aliphatic or arylaliphatic radical, from organic dithiocarbonates and organic halides or sulphonates, in the presence of an aqueous alkaline base and a phase transfer catalyst, at a temperature of between 50° and 100°C for a time of 10-60 minutes. The process allows the preparation of large classes of products used as dyestuff and pharmaceutical intermediates, and as pesticides herbicides, oxidation inhibitors, lubricating oil additives and the like.
公开号:SU1230465A3
申请号:SU823425400
申请日:1982-04-16
公开日:1986-05-07
发明作者:Дегани Йакопо；Фоки Рита；Регонди Валерия
申请人:Консильо Национале Делле Ричерке (Фирма)；
IPC主号:

专利说明:

 "
This invention relates to a process for the preparation of organic sulphides of the formula (I)
Rs -r (i)
where R is alkyl with 1-8 carbon atoms, chlorinated paraffins, nitrophenyl, phenyl-lower alkyl, benzothiazolyl group or a group of the formula
 R, j, is lower alkyl;
R ,, - lower alkyl or lower 13)
alkoxy-lower alkyl;
R /,) is alkyl with 1-8 carbon atoms or phenyl-lower alkyl, which is found in -1 change in medicine, agriculture, oil industry.
The purpose of the invention is to intensify the process, increase the yield and quality of the target product,
PRI and MER 1. Methyl sulfate sulfide creep. 2.97 g of octyl chloride (mol) and 1.34 g of 5,8-dimethyldithiocarbonate (0.011 mol) are mixed with 0.05 g of Aliguat 336 (tricaprilmethyl-, t-1H) and 10 ml of 30% KOH
The mixture is heated at slight boiling in a ycjroBHHX vigorous stirring for 15 minutes. The mixture is cooled, the coziness of petrol ether and the solution is filtered through silica gel (petroleum ether is used as eluent) to remove the catalyst. The resulting solution is evaporated in vacuo and the residue is collected. By NMR and gas chromatography analysis (condition: S E 30.5% at varaport 30; a programmatic temperature rise from 100 to 250 ° C), 3.20 g of the residue was found to be pure methyl octyl sulfide. The output is the amount.
Prepared in a manner similar to the previous one, but using 0.05 g of hexadededtributylphosphonium oromide, pure methyl octyl sulfide in quantitative yield.
Prepared in a manner similar to the previous one, but using tetrabutylammonium bromide and discharging the product by simple extraction with a solvent without passing the solution through a silnagel, 304652
methyl octyl sulfide in quantitative yield.
In tab. I shows sulfides paramilitary under conditions similar to
5 example 1 (but sometimes with different amounts of catalyst). Only varying parameters are given for each preparation (reagent composition, reaction time and yield).
1C The resulting sulfides are separated from the reaction mixture either by decantation or by filtration or solvent extraction, removing the catalyst, if it is soluble in the liquid phase, or by distillation in vacuum, recrystallization or filtration through silica gel, as is most appropriate for this product. Todu,
20 Example 2, Preparation of alkyl proton chlorinated paraffins. 3.50 g of commercial chlorinated paraffin containing 50% chlorine, 1.22 g S, H-dimethyldithiocarbo nath ,, 0.45 g of Aliguat 336 and 10 ml of 30% KOH are mixed together and heated under gentle boiling with vigorous stirring. The reaction is complete after 15-20 minutes.
thirty
The reaction mixture is cooled, concentrated and extracted with petroleum ether. After the solution has passed through the silica gel, the solvent is evaporated in vacuo. 35 mind I is left with 3.25 g of chloromethylthio-paraffin containing 52% Cf, 8% I, 29% C and 11% S,
The NMR method showed that the lines corresponding to S, S-dn-methyl dithiocarbonate disappear in this prod 5 kta.
and lines corresponding to appear. methylthioether groups.
Next, using 3.50 g of commercial chlorinated paraffin 45 on. containing 50% chlorine, 0.85 g of S5S-dimethyldithiocarbonate, 0.2 g of tetrabutylammonium bromide, and 7 tm of 30% KONJ; 3.40 g of chloromethylthioparaffin containing 51% SG, 7% N, is isolated by simple hot decantation, 32% C and 10% S.
About Next, by analogy, but using 3.50 g of commercial chlorinated paraffin containing 44% chlorine, 3.40 g of chloromethylthio-paraffin containing 53% C, 8% H, 29% C and 10% S are obtained.
.Further similarly, but using 3.50 g of commercial chlorinated paraffin containing 50% chlorine, 1.50 g of 8.5-diethyldithiocarbonate, 0.2 g of tetrabutylammonium bromide and 10 ml of 30% -% KOH , 3.50 g of chloroethylthioparaffin containing 54% C, 8% H, 26% C and 12% S is obtained. The NMR method showed the disappearance of lines corresponding to 8.8-diethyldithiocarbonate in the product and the appearance of lines corresponding to ethyl ester groups.
Example 3. Preparation of 2-methylthio-4-isopropylamino-6 - // 3-labels of sipropylamino / -5-triazine (metoprotrin). 2.60 g of 2-chloro-4-isopropyl-amino-b- (3-methoxypropylamino) -S-triazine (0.01 mol), 0.98 g of S, S-dimethyldithiocarbonate (0.008 mol), 0.25 g Aliguat 336 and 5 ml of 30% KOH are mixed together and heated up with a strong displacement, gradually raising the temperature to 15 minutes.
R-X + (R, -S) CO (I) (2)
Cjh
Br
sn
Br
Cl Br
S "5
CH,
CH,
-CgH ,,
OSOg -CHj
CH,
,
050, CHg
CsH.r I
CH,
Br
CH,
ten
304654
The initial solid mass passes into the oil, which is heated for another 15 minutes. After this, the reaction is completed. The mixture is cooled and extracted with carbon tetrachloride.
Gas chromatographic analysis (conditions: SE 30.5% on Varaport 30; programmed temperature rise from 100 to 25 ° C) and 5IMP analysis of the residue obtained by discharging the solvent show that conversion to metoprotrin is quantitative,
Metoprotrine is freed from the catalyst by recrystallization of the crude product from petroleum ether.
A similar procedure is repeated in the preparation of other thioalkyl triazine derivatives, which are commercially known products used as pesticides or herbicides.
In tab. 2 shows the parameters that vary in different experiments.
five
0
five
Table 1
R - S - R (3).
1: 0.55 17
Quantitative 96/16

15 15 15 15 15
90/20 97/16 97/16 97/16 97/16
1: 0.55
thirty
94
97/23

权利要求:
Claims (3)
[1]
1. METHOD FOR PRODUCING ORGANIC SULFIDES of the general formula
R-S-R where R is alkyl with 1-8 carbon atoms, chlorinated paraffins, nitrophenyl, phenyl lower alkyl, benzothiazolyl-group or a group of the general formula
N ^ -N η ₂ ΗΝ- Λ · ΝΗ-Η ₃ where R ₂ is lower alkyl;
R ₃ is lower alkyl or lower alkoxy lower alkyl;
R ₄ is alkyl with 1-8 carbon atoms or phenyl lower alkyl, using a sulfur-containing compound, an organic halogen and a base when heated and the desired product is isolated, which is characterized by the fact that, in order to intensify the process, increase the yield and the quality of the target product, a general formula dithiocarbonate is used as a sulfur-containing compound.
(R, S) ₂ with where R is as defined above, which is reacted with an organic halide or sulfonate of the general formula
RX where R has the above meanings;
X - iodine, bromine, chlorine, - SO ^ CH ^ or S0 ₃ -C _b H _c -CH, in the presence of a 30% sodium hydroxide solution as the base and tricaprilmethyl ammonium chloride as the catalyst. or tetrabutylammonium bromide, or hexadecyl tributylphosphonium bromide when boiling.
[2]
2. The method according to p. 1, with the fact that, in the case of using a water-soluble catalyst, the target product is isolated by decantation and, if necessary, further subjected to purification by distillation in vacuum or recrystallization.
[3]
3. The method according to π. 1, the fact that in the case of using a catalyst soluble in the organic phase, the target product is isolated by extraction with an organic solvent, followed by evaporation of the solvent and further distillation in vacuo or recrystallization.
SU 1230465 A 3

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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IT21263/81A|IT1136581B|1981-04-17|1981-04-17|PROCESS FOR THE PREPARATION OF ORGANIC SULPHURES|

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