DD215311A1 - METHOD FOR PRODUCING TRITHIOOXALSAEUREAMIDE COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of trithiooxalic acid amide compounds which show as active substances such as first test results, e.g. in the photochemical industry, can gain meaning. The aim of the invention is to develop a simple process for the preparation of hitherto unknown Trithiooxalsaeureamidverbindungen of formula I. The essence of the invention is that halothioacetamides are reacted with elemental sulfur or polysulfides in the presence of bases, advantageously in a solvent and optionally with the addition of an alkylating agent.

Description

-7-

Process for the preparation of trithiooxalamide compounds

Field of application of the invention

The invention relates to a process for the preparation of trithiooxalamide compounds which are used as complexing agents and active substances, e.g. in the photochemical industry, can gain importance ·

Characteristic of the known technical solutions

Despite intensive efforts to prepare thioanalogenic oxalic acid esters and amides, trithiooxalamide compounds of formula I are poorly known. So far, only 2 representatives of the formula I (R = Me, X = SMe, SEt) succeeded by sulfurization of the corresponding 1,1-Dithiooxalsäureamide represent (H.Günther, University of Hamburg, Dissertation 1980). /

(D

Here, R = H, aliphatic or aromatic radical and X = SH, SR, S "Y ⁺ (Y = WH ^, HpUR ₁ HNRp, NlO.

-5,1111.1983 * 101324

    ·. - 2 τ. -

Attempts to represent compounds of the formula I (R = H, X = S-alkyl) by oxidation of chlorothioacetamide with elemental sulfur failed (W. Thiel, TU Dresden, Dissertation 1978)

Object of the invention

The aim of the invention is to develop a simple process for the preparation of previously unknown trithiooxalamide compounds of the formula I

Explanation of the essence of the invention

The object of the invention is Trithiooxalsäureamidderivate of general formula I (Realiphatic or aromatic radical) of Ν, ΪΤ-disubstituted Halogenthioacetamiden. to make accessible ·

According to the invention the object is achieved in that Ν, ΐΓ-disubstituted Halogenthioacetamide with elemental sulfur or polysulfides ^Ä in the presence of bases such as alkali and alkaline earth metal hydroxides, alkali metal and alkaline earth or preferably amines in solvents such as water, alcohols, ethers, aromatic Hydrocarbons or dimethylformamide and dimethyl sulfoxide or mixtures thereof, optionally with the addition of an alkylating agent. +

Since can not represent Trithiooxalsäureamidverbindungen with similar implementation of unsubstituted chlorothioacetamide, it is extremely surprising that ΙΤ, ϊΤ-disubstituted Chlorthioacetamide very smooth corresponding Trithiooxalamide. In addition, it is unusual that even with the use of secondary and primary amines not expected

r mi -in O O.,. 4 η -i Cf

Dithiooxalsäurediamide, but ammonium salts of trithiooxaluramides arise.

The latter ammonium salts can easily be converted into trithiooxalic acid ester amides with alkylating agents.

embodiments

Example 1 ·

Trithiooxalsäuremethylester-N-phenylanilid

2.62 g of Ν, Ν-diphenyl-chlorothioacetamide (II) are added at room temperature to 0.8 g of sulfur, 3 g of triethylamine and 20 ml of DMP. The mixture is stirred for a further 3 hours. Then, it is diluted with 20 ml of ethanol and filtered off with suction excess sulfur · After cooling to about 15 ⁰ C. 1.42 g of methyl iodide are added to the klaren.Lösung. The trithio compound is precipitated by addition of water. The pest substance obtained after the aspiration is recrystallised from ethanol. This gives 1.6-2.2 g of orange crystals, P. 97-99 ⁰ C.

Example 2

Piperidinium-, N-diphenylthiocarbamoyldithiocarboxylate]

To 3.5 g of sulfur, 12.8 g of piperidine and 65 ml of DMP are stirred at room temperature 13.1 g of Ν, Ν-diphenyl-chlorothioacetamide. After 2 h, methanol is slowly added and the incipient precipitation is completed by cooling with ice. The crystals are extracted μηά possibly with CS _? · 11.7 g of orange crystals are obtained,

p. 156-57 ° c. -

, _A «n λ η Ί Q 9. L

Example 3

Pyrrolidinium [hjn-diphenyltMocarbamoyldithiocarboxylat]

Analogously to Example 2, 0.8 g of sulfur, 2.15 g of pyrrolidine, 20 ml of DMP and 2.62 g of II 2.5 g of pyrrolidinium, salt, P. 141 -H ^{2 0} C, was obtained.

Example 4

Morpholinium fN, N-diphenylthio carbamoylthio carboxy lat]

From Example 2, 0.8 g of sulfur, 2.6 g of morpholine, 13 ml of DMP and 2.62 g of II 2.3 g of morpholinium salt, p. 141-45 ⁰ C, received.

Example 5 '

Cyclohexylammonium [H, N-diphenylthio carbamoyldithiocarboxy lat].

Analogously to Example 2, from 0.8 g of sulfur, 3 g of cyclohexylamine, 13 ml of DMP and 2.62 g of II 3.3 g of cyclohexylammonium salt, P 120-125 ⁰ G, received.

Example. 6

Di-n-propylammonium [H, H-diphenylthioearbamoyldithiocarboxy lat]

Analogously to Example 2 sulfur, 3 g of di-npropy lamin, J 3 ml DMP and 2.62 g are obtained 2.1 g ~ II Di-n-propylammoniumsalz, P · 145-47 ⁰ O, from 0.8 g ".

, Λ t \ Λ Ο Ο Λ

-5 -.

Example 7 '

Njn-Diphenylthiocarbamoyldithiocarbonsäureethylester

0.93 g of piperidinium [N, N-diphenylthiocarbamoyldithiocarboxy lat] are heated in 30 ml of ethanol and treated with a solution of 0.5 g of ethyl iodide in 10 ml of ethanol. Then it is boiled briefly. The crystalline ester is filtered off with suction and.recrystallized if necessary from ethanol. There are 0.8 g of orange crystals, mp 72-75 ⁰ C, obtained.

Example 8 ^, H-diphenylthiocarbamoyldithiocarboxylic acid propyl ester

Analogously to Example 7, 0.7 g of orange-colored crystals with propyl bromide, F. 100-101 ⁰ C is obtained.

Example 9 N, N-Diphenylthiocarbamoyldithiocarboxylic acid phenacyl ester

Analogously to Example 7 1.4 g of red ester, mp 147-49 ⁰ C, are obtained with phenacyl bromide.

Example 10 '

N, ¹ -diphenylthiocarbamoyldithiocarboxylic acid 4-nitrophen- ^1- acyl ester. '

Analogously to Example 7 are obtained with 4 ^ Nitrophenacylbromid dark brown crystals, mp 131-33 ⁰ O.

-S.1111

.1933 * 101324

ί - 6 - -

Example · 11 ''

^, N ^ Diphenylthiocarbamoyldithiocarbonsäure -phenylphenacylester

This ester is obtained analogously to Example 7 with 4-Phenylphenacylbromid in the form of red crystals, mp 166-68 ⁰ C, obtained ·

Example 12

N, aiocarbainoyldith.iocarbonsäure-4-N-iiitrobenzylester Diph'enylt]

This ester is formed analogously to Example 7 using 4-nitrobenzyl bromide as alkylating agent in the form of red crystals, F, 118-120 ⁰ C.

Example 13

] J, li-Diphenylthiocarbamoyldithiocarbonsäure-2,4-dinitrophenyl

Analogously to Example 7 are brown powder with 2,4-Dinitrochlorbenzen 1.1 g, Fv 147-150 ⁰ C is obtained.

- & JUL 19.83 * 101324

Claims (5)

ν "claim for invention 1. A process for preparing Trithiooxalsäureamidverbindungen of formula I, characterized in that Ν, ΪΤ-disubstituted Halögenthioacetamide be reacted with elemental sulfur or polysulfides in the presence of bases, advantageously in a solvent and optionally with the addition of an alkylating agent · 2 · Method according to item 1, characterized in that water, alcohols, ethers, aromatic • see hydrocarbons or preferably polar aprotic, such as dimethyl sulfoxide, dimethylformamide u.a ·, or mixtures thereof are used as the solvent. 3 · Method according to item 1, characterized in that alkali metal or alkaline earth metal alkoxides or hydroxides, ammonia, primary, secondary or tertiary amines and mixtures of the substances mentioned are used as bases. , '' 4. The method according to item 1, characterized in that as the alkylating agent, organic halogen compounds, such as alkyl or aralkyl halides, which may optionally contain further functional groups, or halogen-free alkylating agents, e.g. Dialkyl sulfates or sulfonic acid esters are used. 5. The method according to item 1, characterized in that the compounds d, he general formula I with X = SR (R: = aliphatic or aromatic radical) by alkylation of the Eeaktionsgemisches in a one-pot reaction or by alkylation of purely isolated compounds of formula I with X. = S ^- Y ⁺ (Y = NH ₃ , H NR-). -5 ^ 11983 * 101324 Formula I S \\ R-N Where R = aliphatic or aroinic radical and XeSH, SR, S-Y ⁺ (YeKH ₃ , H ₂ NR, HWR ₂ , M ₃ ). r 1111 4dftq * 1.Ol324;