JPS6117559A - Triamine and its preparation - Google Patents

Abstract

NEW MATERIAL:The triamine of formula I (m and n are 3-5). USE:Useful as an intermediate raw material of pharmaceuticals, agricultural chemicals and other industrial chemicals. PREPARATION:The compound of formula I can be prepared by the intermolecular condensation reaction of 2-(w-aminoalkyl)-1-azacycloalkane of formula II under heating. The reaction can be carried out either in vapor phase or in liquid phase. When an inert solvent is used in the reaction, it is preferably to carry out the reaction in the presence of benzene, toluene, etc. at the boiling point of said inert solvent. The reaction is carried out preferably in the presence of a catalyst to promote the reaction, and a compound having ammonia-removing activity or hydrogenation activity, preferably a compound containing the VIII-group metal of the periodic table, e.g. Raney catalyst such as Raney nickel, etc. or a noble metal catalyst such as palladium carbon, platinum black, etc. is used suitably as the catalyst. The compound of formula II can be prepared by the decarbonation condensation reaction of alpha-pyrrolidone followed by the hydrogenation of the product.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a triamine represented by the following formula and a method for producing the same. The compound of the present invention can be produced, for example, by heating 2-(ω-aminoalkyl)-1-azacycloalkane represented by the following formula I.

(Formula I) (Formula ■) (m and n are each an integer of 3.4.5) Triamine, which is the object of the present invention, is a new metal compound and is useful as an intermediate raw material for pharmaceuticals, agricultural chemicals, and other industrial chemicals. It is a compound.

<Prior Art and Problems to be Solved by the Invention> Conventionally, there is no known method for producing a dimer by subjecting a primary amine having a secondary amino group in the same molecule to an intermolecular deammonia condensation reaction.

Means and action for solving the problems> The present inventors provide a new compound, and a general method for synthesizing the new compound using as a starting material a compound that can be manufactured from industrially easily available raw materials. As a result of various studies aimed at providing the following, we have arrived at the present invention.

That is, the present invention is a triamine represented by the following first part, and further a 2-(=--aminoalkyl)-1-azacycloalkane (m and n are each 3) represented by the following formula I.
．． A triamine is obtained by heating a compound (an integer of 4 or 5) to cause an intermolecular condensation reaction.

2-(ω-Aminoalkyl 1) which is the starting material of the present invention
-1-Azacycloalkane is a compound that can be synthesized in high yield by decarboxylating and condensing α-pyrrolidone, a-piperidone, or ε-caprolactam, which are easily available industrially, and then hydrogenating it. Kosho 41-1
It is described in Publication No. 8096. As described above, the starting material of the present invention is a compound that is much easier to synthesize than conventional production methods, and is advantageous both technically and economically.

Thus, in the present invention, the starting material 2-(ω-aminoalkyl)-1-azacyclo, alkali/ is subjected to an intermolecular condensation reaction by heating.

The reaction can be carried out in either a gas phase or a liquid phase, and the raw material 2-(ω-aminoalkyl)-1-azacycloalkane may be heated in the presence or absence of a catalyst. The heating temperature is 50 to 250°C, and the reaction is completed within several tens of hours.

The reaction in the present invention is expressed by the following formula: [1) %formula% The reaction can also be carried out in an inert solvent.

Examples of such inert solvents include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, and ethers, and specific examples include benzene, toluene, xylene, chlorobenzene, cyclohexane, and decalin. Can be mentioned.

When using an inert solvent, the reaction is preferably carried out at the boiling point F of the inert solvent.

It is preferable to use a catalyst to accelerate the reaction. As the catalyst, a compound having Kaye deammonization activity or hydrogenation activity is used, and a compound containing a group metal of the periodic table, such as a Raney catalyst such as Raney nickel or Raney cobalt, or a noble metal catalyst such as palladium charcoal or platinum black. is preferred.

The amount of catalyst to be used should be several percent or more (it can be determined as appropriate based on various reaction conditions. Since the intermolecular condensation reaction ends after ammonia is produced, ammonia is produced as the reaction progresses. By detecting the amount of ammonia, the reaction rate can be adjusted by adjusting the amount of catalyst.

The compound of the present invention can be separated from the reactant by conventional separation means such as distillation.

<Examples> The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 2-(5-aminopentyl)-1-azacyclohebutane 1oOf (0.54 mol) Oraneninkel 351 C
The mixture was heated under reflux in 330 ml of xylene under a nitrogen gas atmosphere and stirred in the presence of water. After about 6 hours, the production of ammonia stopped and the catalyst content was reduced to 11 by distillation.
32.5 g of a fraction of 0 to 114° C. (+9 flHg) and a residue of 58.2 f were obtained.

The residual content is molecule m351 < mass spectrum), original purple analysis value (C + 74.1%, H + 12.8%, N; 1, 169
6), infrared absorption spectrum, and NIVLR spectrum, it was confirmed that it was bis(5-(2-perhydroazepinyl)pentyl)amine.

Examples 2 to 6 Table 1 shows the results of carrying out the same reaction as in Example 1 by changing the proportions of 2-(5-aminopentyl)-1-azacyclohebutanetranene and xylene. 1st
In the table, the reaction rate and yield are values determined by gas chromatography analysis of the reaction mixture.

Table 1 *) Bis[5-(2-perhydroazepinyl)pentyl]amine Examples 7 to 8 Types of metal catalysts in xylene for 2-(5-aminopentyl)-1-azacyclohebutane Example 1 by changing
Table 2 shows the results when reacting in the same manner as above.

Table 2 *) Bis[5-(2-perhydroazepinyl)pentyl]amine <Effects of the invention> According to the present invention, it is possible to provide a novel triamine, and it is also technically economical. It can also be produced by advantageous methods.

Claims (3)

[Claims] (1) Triamine represented by the following formula II. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...II (2) A method for producing a triamine represented by the following formula II, which comprises heating a 2-(ω-aminoalkyl)-1-azacycloalkane represented by the following formula I to cause an intermolecular condensation reaction. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... I ▲There are mathematical formulas, chemical formulas, tables, etc.▼...II (m, n are integers of 3, 4, and 5, respectively) (3) The method for producing triamine according to claim 2, characterized in that a metal catalyst containing at least one metal of Group VIII of the Periodic Table is used as a catalyst.