CS219447B1 - Process for the preparation of Fe (1H) -bis- (ansa-dioxy-diaminoisoindolino) -dioxy-diamino-diaza-cyclo-tetraisoindoles - Google Patents

Abstract

A method for preparing a hexaisoindoline iron complex by reacting phthalic anhydride, urea, ferrous sulfate and ammonium nitrate, whereby the reaction is carried out in an organic solvent environment at a temperature of 130 to 250 °C, catalyzed by ammonium molybdate or molybdenum oxide in an amount of 0.05 to 0.4 wt. % per phthalic anhydride.

Description

The invention relates to a process for the preparation of a hydroxyl-containing hexaisoindoline iron complex.

The porphyrin and tetrabenzoporphyrazine iron complexes exhibit catalytic activity resulting from the coordination bonding of the four pyrazole nitrogen atoms to the central Fe (II) or Fe (III) atom. These compounds, in particular iron phthalamine, catalyze, for example, the oxidation of organic compounds (Cook AH: J. Chem. Soc. 1938, 1774; Royals E.E., Upper SE: J. Am. Chem. Soc. 77, 187/1955 (Hock H., Kropf H .: J. Prakt. Chem. 9, 173 (1959); Uri N .: Nature 177, 1177 (1956)), peroxide decomposition (Cook AH: J. Chem. Soc. 1938, 1761) and act as oxidative catalysts - desiccants for drying oils (German Pat. No. 920,666). Due to the low solubility of iron phthalocyanine, in all cases the catalysis is heterogeneous. Efforts to improve its solubility and thus to increase its catalytic activity led to the preparation of iron phthalocyanine derivatives (Kaufmann, P., Bernard M., Fette, Seifen, Anstrichmittel 66, 613 (1964)) and structural modification of this compound - for the synthesis of the iron (III) hexaisoindoline complex (Kaufmann, P. P., Fleiter L., Fette, Seifen, Anstrichmittel 66, 819 (1964)).

Although the hexaisoindoline complex Fe (III) has been known since 1964, its synthesis has not been described in detail yet, and the general preparation process reported in the cited literature either results in undesirable iron phthalocyanine or yields of the complex are very low and therefore isolation from The reaction mixture is difficult and uneconomical.

Research has now found that hexa-indoline iron (III) complex of the formula C 18 H 30 QN 4 O 6 Fe can be prepared by the process of the invention, which comprises reacting phthalic anhydride, urea, ferrous sulfate and ammonium nitrate in an organic solvent at 130 to 250 DEG C., catalysed by ammonium molybdate or molybdenum oxide in an amount of 0.05 to 0.4 wt. air or oxygen are blown into the reaction mixture.

According to the invention, the process for the preparation of the hexaisoindoline complex Fe (III) is based on the reaction of phthalic anhydride, urea and anhydrous ferrous sulphate with the simultaneous oxidative action of ammonium nitrate and oxygen. The reaction is catalyzed by ammonium molybdate or molybdenum oxide in an amount of 0.05 to 0.4% by weight. to phthalic anhydride. Larger amounts of catalyst do not lead to an increase in yield but result in the formation of undesirable compounds.

According to the invention, the synthesis of the complex is carried out by suspending the individual components in an organic solvent, e.g. dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, nitrobenzene, etc. The suspension is heated to 130 to 250 ° C, preferably 160 to 190 ° C, and simultaneously injecting air or oxygen into the mixture. Perfect homogenization of the reaction mixture must be ensured by intensive air bubbling, possibly using a stirrer. The reaction is usually conducted for 2 to 8 hours.

After the reaction time, undissolved compounds are filtered from the reaction mixture and the hexaisoindoline Fe (III) complex is isolated from the filtrate. For example, isolation is carried out by distilling off the solvent and extracting the complex with carbon tetrachloride or chloroform from the crude product.

The hexa-indoline complex Fe (III) prepared according to the invention has the general formula CdsHssNuOgFe and according to the literature (Kaufmann, Fleiter: Fette, Seifen, Anstrichmittel 66, 819 (1964)) it is Fe (III) -bis- (anasadioxy- diaminoisoindolino) -dioxy-diamino-diaza-cyclo-tetraisoindoline. This compound contains 6 hydroxyl groups and is soluble in, for example, acetone, chloroform, carbon tetrachloride, nitrobenzene, drying oils, etc.

The example below illustrates an embodiment of the invention.

Exemplary embodiment

10 g of phthalic anhydride, 5.1 g of anhydrous iron sulphate, 20 g of urea, 4.1 g of ammonium nitrate and 0.06 g of ammonium molybdate are introduced into 300 g of nitrobenzene. The reaction mixture was heated to 170 ° C for 6 hours with stirring and air bubbling. The mixture is then filtered after cooling to 20 DEG C. and nitrobenzene is distilled off to dryness from the filtrate. The crude product was extracted with chloroform and Fe (III) -bis- (anasadioxy-diaminoisoindolino) -dioxy-diamino-diaza-cyclotetraisoindoline was precipitated with hexane from the solution. The complex obtained was brown in color and identified by elemental analysis and IR spectra.

Elemental analysis for C48H39NuO6Fe;

963.80

Calculated:

% H, 4.08;% N, 20.35;% Fe; 5.79;

Found:

% C, 59.65;% H, 4.19;% N, 20.41;

Claims (1)

A process for the preparation of Fe (III) -bis- (anasadioxy-diaminoisoindolino) dioxy-diamino-diaza-cyclo-tetraisoindoline of the general formula C48H39NnO8Fe by reaction of phthalic anhydride, urea, ferrous sulfate and ammonium nitrate. medium of an organic solvent at a temperature of 130 to 250 ° C, catalysed by ammonium molybdate or molybdenum oxide in an amount of 0.05 to 0.4% by weight per phthalic anhydride, whereby air or oxygen is injected into the reaction mixture.