SU763346A1 - Copper chelates of beta-aminovinylketones as catalysts of trimerization of perfluorocarboxylic acid nitriles to triazones - Google Patents

Description

The invention relates to organic synthesis and relates to compounds which are not described in the literature, namely, copper chelates of polyfluorinated fi-aminovinyl ketones of the general formula (l (RH (CP2l2-C0. HC bue. CH) where R CH3, H-C4H9, C (CH2 ;, С.Н; "2 H or CHjiH that exhibit catalytic activity and can be used as catalysts for the trimerization of nitrites of perfluorocarboxylic acids into the corresponding triazines. Metal acetyl acetonates of variable valence are known, which exhibit catalytic properties in the trimerization reaction of nitrile per fluorocarboxylic acids into triazines. According to known data, 100% conversion of nitrile to triazine is achieved at 190 ° C, the reaction time is (1) 2 h and the catalyst: nitrile molar ratio is 0.033: 1 Shch However, these acetylacetonates are insoluble in perfluorocarboxylic acid nitriles, which requires the use of relatively large amounts of catalyst, since the reaction proceeds on its surface. In addition, it is impossible to obtain cross-linked polymers from oligomers, since the surface of the catcher is very quickly covered with a film of insoluble material Leamer, curing oligomer is suspended. The purpose of the invention is the synthesis of a catalyst with higher activity and soluble in nitrites of perfluorocarboxylic acids. These properties are determined by the new structure of the proposed compounds of general formula (1). The structure of the synthesized chelates of b-aminovinyl ketones was established using elemental analysis and data from IR and electron spectroscopy (Table 1). In the IR spectra of copper chelates there is an intense band of chelated carbonyl Q 16001630 cm, and in the electronic spectra

a band of 0 (1d, 2.2-2.7) is observed, due to a copper transition and a band of 1 - ft transitions of the pseedo-aromatic metal-chelate ring, 290-330 (igE 4.2-4.6). In addition, copper chelates were obtained from the corresponding (L-aminovinyl ketones, the structure of which was unambiguously established with the elemental element analysis, IR, PMR, and mass spectroscopy.

The synthesized compounds differ from structural analogues by the nature of the coordination unit (nitrogen atom instead of oxygen), as well as by the structure of organic radicals. Upon the appearance of new structural features in them, this leads to a higher catalytic activity and solubility in perfluorocarboxylic acid nitriles.

Compounds of formula (I) are obtained by reacting the corresponding jb-aminovinyl ketone with copper acetate. The reaction is carried out at reflux in benzene, methanol or ethanol. Copper acetate is used in a calculated amount or in insignificant isohydrate. The reaction temperature is determined by the boiling point of the solvent. Purification of the reaction product is performed by reprecipitation of methanol or ethanol solution with distilled water. Proposed

The method can be used to prepare compounds characterized by the general formula (1). Example 1. Preparation of -medium bis- (1,1,2,2, tetrafluoro-5-aminohex 4-e "-3-onat).

To a solution of 1.85 g (0.01 mol) 1,1,2,2, -tetraLuoro-5-amino-hex-4-en-3-one in 30 ml of benzene was added 0.91 g (0.005 m) copper acetate. The mixture was boiled for 0.5 h, the solvent was distilled off, the solid residue was distilled with distilled water from ethanolic solution and 1.95 g of chelate was obtained, yield 92%.

Example 2. Getting copperbis (1,1,2,2-tetrafluoro-5-phenylaminohex-4-en-3-onat) ..

To a solution of 2.60 t (0.01 m) 1,1,2,2. Tetrafluoro-5-phenylaminohex-4-en-3-it in 30 ml of benzene was added 0.91 g (0.005 m) of copper acetate. The mass is boiled for 0.5 h, the solvent is distilled off. The solid precipitate is reprecipitated with distilled water from ethanol solution. 2.65 g of chelate are obtained, yield 91.3%.

Similarly, the remaining compounds listed in Table 1 are prepared and 0 are tested in the trimerization reaction of perfluorocarboxylic acid nitriles.

The catalytic ability of polyfluorinated 5-aminovinyl copper ketonates is estimated by the triazine yield of nitrile conversion, the formation of impurity products using GLC, NMRG and IR spectroscopy.

The reaction is carried out by heating the nitrile in a sealed evacuated vial at ISO-IO C in the presence of catalytic amounts of copper chelates (L-amino vinyl ketones.

Example 3. Preparation of 2,4,6-tris-perFethexyl-1, 3,5-triazine .. 1.92 g (5.56 "10 perfluoro-enanthanum nitrile and 0.01 g {1, 9810

copper bis (1,1,2,2-tetra ") tor-5-phenylaminonan-4-en-3-onat) in a molar ratio of 1: 0.0033, respectively. The catalyst is completely dissolved in the perL-enanthic acid nitrile. The ampoule was evacuated, sealed and kept at 150 ° C for 10 hours. The reaction mixture was analyzed using GLC, IR and spectroscopy. The yield of 2,4,6-tris-perFethexyl-1,3,5-triazine 70%, conversion of the nitrile 70%. Table 2 presents data on the use of copper chelates (b-aminovinyl ketones as catalysts for the trimerization of perfluorocarboxylic acid nitriles.

Trimerization of perfluoroenanthic acid nitrile in the presence of p-aminovinyl ketones

0

; c (sn

N. 0 С (СР, ЬН

table 2

V ..

/ N - with

Example 4. Obtaining cross-linked polymers from perfluorodicarboxylic dinitriles. In a vial with a capacity of 3 cm is placed 1 g (1/0710)

1 C-CP lOCP Crl OiCPglsOCP - CN

since

CP,

CP

and 0.0037 g (7,) copper-bis (1,1,2,2, -tetrafluoro-5-aminononan-4-en-3-onat), which was completely dissolved in the dinitrile. Vacuum ampoule, sealed and hold for 2 h at. The result is a crosslinked iolimer with a gel fraction of 94% (extraction in Soxhlet apparatus),

Thus, from the above materials it follows that copper chelates. 1-aminovinyl ketones have a higher catalytic activity than transition metal valence acetylacetonates, i.e. they cause trimerisation of perfluorocarboxylic nitriles at a lower temperature (150-180 ° C), shorter reaction time (1-5 h) and amount of catalyst (0.0033 m). In addition, (L-aminovinyl ketonates of the formula (1 well solution in mono- and dinitriles, perfluorocarboxylic acids, and they can be used to prepare cross-linked polymers using nitrile-terminated oligomers.

It should be noted that the use of p-aminovinyl ketone chelates

allows to expand the raw material base for the production of catalysts while simultaneously disposing of the little-used raw material. 2,2,3,3-Tetrafluoropropionic acid, the esters of which are deposited in the synthesis of the starting material (b-aminovinyl ketones, is obtained by oxidation of 2,2,3,3, -tetrafluoropropyl alcohol (telomere-nl alcohol), which is formed in a significant amount at industrial tetrafluoroethylene tegshomerization. Currently, ti -1 alcohol telomere is not widely used and is an illiquid raw material.

five

Claims (1)

1. Patent IT 3728344, cl. 260-248, publ. 1973.