CS266981B1

CS266981B1 - 2,5,6,8,11,12-Hexasubstituted 4,10-di- (N, N-disubstituted N'-thioureido) -1,3,7,9-tetraoxacyclododanes and their preparation

Info

Publication number: CS266981B1
Application number: CS879923A
Authority: CS
Inventors: Juraj Doc Rndr Csc Bernat; Ladislav Ing Csc Kniezo; Dana Rndr Petercakova; Jan Rndr Csc Imrich
Original assignee: Juraj Doc Rndr Csc Bernat; Ladislav Ing Csc Kniezo; Dana Rndr Petercakova; Jan Rndr Csc Imrich
Priority date: 1987-12-27
Filing date: 1987-12-27
Publication date: 1990-01-12
Also published as: CS992387A1

Abstract

Sú popísané nové 2,5,6, 8,11,12-hexasubstituované 4,10-di-(N,N-disubstituované Ν'-tioureido)-1,3,7,9-tetraoxacyklododekány obecného vzorca I, kde R^ znamená metyl alebo etyl, R2 znamená atom vodíka alebo metyl, etyl, resp. R^ s R^ je morfolínoskupina a R^ znamená etyl n-butyl, fenyl, benzyl, 4-totyl. Podstata ich přípravy spočívá v tom, že izotiakyanáty obecného vzorca III, kde R^ a R2 znamená to isté ako vo vzorci I reagujú s primárnými alebo sekundárnými amínmi za vzniku tiomočovín obecného vzorca II, kde R^, R2, r3 a R^ znamenajú to isté ako vo vzorci I, pričom pri teplotách od 10 °C až do teploty varu rozpúštadla za vzniku látok I.New 2,5,6,8,11,12-hexasubstituted 4,10-di-(N,N-disubstituted Ν'-thioureido)-1,3,7,9-tetraoxacyclododecanes of the general formula I are described, where R^ means methyl or ethyl, R2 means a hydrogen atom or methyl, ethyl, respectively. R^ with R^ is a morpholino group and R^ means ethyl n-butyl, phenyl, benzyl, 4-totyl. The essence of their preparation lies in the fact that isothiocyanates of the general formula III, where R^ and R2 mean the same as in formula I, react with primary or secondary amines to form thioureas of the general formula II, where R^, R2, r3 and R^ mean the same as in formula I, at temperatures from 10 °C to the boiling point of the solvent to form substances I.

Description

CS 266 981 B1

The present invention relates to novel compounds of the substituted 1,3,7,9-tetraoxacyclododecanes of the general formula I, R4R3N-CS-NHv / " - > 100- < - > wherein R is methyl or ethyl, R is hydrogen, or methyl, R is hydrogen, 4, 4 methyl, ethyl, or methyl; R 5 is R is morpholino and R is ethyl, n-butyl, phenyl, benzyl or 4-methyl, and a method for their preparation. The substances according to the invention have not been described in the literature so far.

The principle of their preparation is that the isothiocyanate of the formula III P- / nl / n

(III)

NCS12n where R and R are the same as in Formula I, are reacted with primary or secondary amine of the general formula NR3R4, where R3 and are the same as in Formula I, to give the thiourea of Formula II,

Wherein R 2 R 2 R 3 and R 4 are the same as in Formula I, wherein the thioureas of Formula II undergo in solution self-dimerization at temperatures of from 10 ° C to the boiling point of the solvent to form compounds of Formula I .

Dimerization can be carried out by dissolving the substance in a suitable solvent such as chloroform, dichloromethane, acetone, acetonitrile, methanol and the like. at temperatures up to 10 ° C up to the solvent temperature of the solvent. The reaction time depends on the solvent used and the temperature, and the possibility is preferably determined by thin layer chromatography. An advantage of the process for the preparation of the substituted 1,3,7,9-tetraoxacyclododecanes of the general formula I according to the invention is the easy availability of the starting materials, the simple working procedure and the self-dimerization of the compounds of the formula II in a high-yield solution.

The use of the compounds of formula I prepared according to the invention is that they form + + 2+ complexes with metal cations such as Li, Ag, Cu

The following examples illustrate, but do not limit, the invention. Example 1 Preparations of 4- (N-phenyl-N'-thioureido) -2,6-dimethyl-1,3-dioxane I, R 1 = CH 3, R 2 = R 3 = H, R 4 = Ph). To a solution of 1.73 g (0.01 mol) of 4-isothiocyanato-2,6-dimethyl-1,3-dioxane in 25 ml of ether at -10 DEG C. ethereal solution of 0.93 g (0.01 mol) of aniline and the reaction mixture was stirred at room temperature for 5h. The precipitate was filtered off and, after crystallization from chloroform-ether, 2.04 g (77%) of the product was obtained with mp 142-144 ° C.

Claims

SUBJECT OF THE INVENTION

1. 2,5,6,8,11,12-hexasubstituted 4,10-di-(Ν,Ν-disubstituted N-thioureido)-1,3,7,9-tetraoxacyclododecanes of the general formula I,

Ί 2 3 where R represents methyl or ethyl, R represents a hydrogen atom or methyl, R represents a hydrogen atom, 3 4 4 methyl, ethyl, or R with R is a morpholino group and R represents ethyl, n-butyl, phenyl, benzyl or 4-tolyl.

2. A method for preparing substances according to item 1, characterized in that the isothiocyanates of the general formula III,

(III)

CS 266 981 Bl

1 2 where R and R mean the same as in formula I react with primary or secondary amines of the general formula NR^R ⁴ , where R^ and R ⁴ mean the same as in formula I, to form thioureas of the general formula II, R ⁴ ¹¹¹¹

1 2 3 4 R ² NH-CS-NR ³ R ⁴ where R , R , R and R have the same meaning as in formula I, whereby the thioureas II undergo spontaneous dimerization in solution, preferably in acetone, at temperatures from 10 °C to the boiling point of the solvent to form substances of the general formula I.