DD271512A1 - PROCESS FOR THE PREPARATION OF ARYLIDENE KETONIUMINES PRIMAERER AMINE - Google Patents

Abstract

The invention relates to a process for the preparation of arylidene ketone imines of primary amines. Such compounds have significance as synthesis building blocks for nitrogen-containing heterocycles, which in turn can be used for example as pharmaceuticals, dyes or dye intermediates, for catalytically active metal complexes and the intermediates for optical sensitizers. According to the invention, the process is based on the reaction of α-methylene ketones with primary amines and aromatic aldehydes in or without a solvent to give the arylidene ketone imines of primary amines of the type. IV

Description

wherein R ¹ and R ¹ aryl or alkyl radicals or together may denote a Cycloalkylidenrest, R ² also Wasserstott, with primary amines of the type Il

R ³ -NHj II ₍

wherein R ^{3 represents} an aryl or alkyl radical in the presence of equimolar amounts of an aromatic aldehyde of type III

Ar-CHO III

without or in a solvent to the Arylidenketoniminen primary amines of the general formula IV

^IV f

wherein R ¹ , R ² , R ³ and Ar have the abovementioned meaning, are reacted.

The invention will be explained with reference to the embodiments shown in Table 1, the following Variants were presented.

option A

0.01 mole of a primary amine type II-type α-methylene ketone and 0.01 mole of a type III aromatic aldehyde are dissolved or suspended together in 50-15 μmol of toluene, benzene or chloroform and optionally heated in the presence of catalytic amounts of an auxiliary base, such as triethylamine, sodium acetate or potassium tert-butoxide or in the presence of catalytic amounts of 4-toluenesulfonic acid on a water for 4-18 hours until 3.6ml H ₂ O have deposited. Thereafter, the mixture is cooled, filtered off with suction solid product and recrystallized from the indicated solvent; liquid products are fractionated in vacuo.

Table 1 Prepared Arylldenketone Lines of Primary Amines

R ¹ R ² R ³ Ar % Yield. variant Mp / ° C CH ₃ H iso-propyl phenyl 40 A oil CH ₃ H phenyl phenyl 42 A 45 CH ₃ H n-butyl phenyl 56 A oil CH ₃ H allyl phenyl 81 A oil Ph H n-b- Wl phenyl 43 A oil Ph H iso-propyl phenyl 40 B 135 Ph H allyl phenyl 62 B oil - (CH ₂ J ₄ - n-butyl phenyl 100 A 107 - (CH ₂ J ₄ - phenyl phenyl 100 B 118 - (CH ₂ J ₄ - iso-propyl phenyl 85 A 113 - (CH ₂ I ₄ - allyl phenyl 95 B oil

- (CHj) ₄ -phenyl-4-anisyl 95 A 143

Variant B

Analog variant A, it is worked without solvent and auxiliary base. The products are made by recrystallization from the

purified solvent or by fractional distillation in vacuo.

Claims (1)

Process for the preparation of arylidene ketone imines of primary amines, characterized in that a-methyl ketones of type I l M 2 R ¹ - C - CH ₂ - R in which R ¹ and R ^{2 may be} aryl or alkyl radicals or together may be a cycloalkylidene radical, R ^{2 is} also hydrogen, with primary amines of the type II R ³ -NH ₂ II, wherein R ^{3 represents} an alkyl or aryl radical, in the presence of equimolar amounts of an aromatic aldehyde type III Ar-CHO III without or in a solvent to the Arylidenketoniminen primary amines of the general formula IV Ψ
Ar wherein R ¹ , R ² , R ³ and Ar have the abovementioned meaning, are reacted. Field of application of the invention The invention relates to a process for the preparation of Arylidenketoniminen (Ci.alkoniminen) primary amines. Such compounds have meaning as synthetic building blocks for nitrogen-containing heterocycles, which in turn can be used for example as Pharmazeutikä and dyes or dye intermediates, for catalytically active metal complexes and as intermediates for optical sensitizers. Characteristic of the known technical solutions Arylidene ketone imines of primary amines have been previously synthesized only and in low diversity by reacting arylidene ketones with primary amines: A.T.MASON, Berdt. Chem. Ges. 20,270 (1887) 1; A. SENIER, P.H. GALLEGHER, J.Chem.Soc.113,28 (19'o; i, see summary in D.L.BOGER, [Tetrahedron 39, 2869 (1983)]. Object of the invention The aim of the invention is to represent the Arylidenketonimine primary amines in a new way in a large Viefalt from readily available starting materials and in good yield and high purity. Explanation of the essence of the invention The object of the invention is to make available the arylidene ketone imines of primary amines in great variety, good yields and high purity from readily available starting materials. According to the invention, this object is achieved in that a-methylene ketones of the type I. Rl-C-CH ₂ - R ²