Organic compounds -- part of the class 532-570 series – Organic compounds – Polycyclo ring system containing anthracene configured ring...
Reexamination Certificate
2001-11-13
2003-01-21
Pryor, Alton N. (Department: 1616)
Organic compounds -- part of the class 532-570 series
Organic compounds
Polycyclo ring system containing anthracene configured ring...
Reexamination Certificate
active
06509486
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for the synthesis of 2-carboxyanthraquinone from 2-ethylanthraquinone by oxidation of the said ethyl group by means of a nitric acid solution.
BACKGROUND OF THE INVENTION
Anthraquinones are used in the manufacture of oxygen-absorbing films which make possible the preparation of packagings suited to the preservation of oxygen-sensitive products, such as foodstuffs.
This is because numerous foodstuffs decompose on contact with oxygen. A packaging comprising a multilayer structure is generally used for their preservation. This multilayer structure comprises, inter alia, an oxygen-barrier film and an oxygen-absorbing film. These films are positioned so that the oxygen-barrier film is in contact with the air external to the sealed packaging and the oxygen-absorbing film is positioned in contact with the food found inside the sealed packaging.
While the aim of the barrier film is to provide for protection against the entry of oxygen inside the sealed packaging, the oxygen-absorbing film provides for the absorption of the oxygen which has possibly remained trapped inside the packaging during the closure of the latter or which is given off by the foods themselves.
The multilayer structure also comprises other films, for example made of polyethylene or of polypropylene, which provide for the mechanical strength of the structure and protection against moisture.
Several processes for the preparation of 2-carboxyanthraquinone are already described by oxidation of anthraquinone or anthracene derivatives. Patent JP 50047964 discloses the preparation of 2-carboxyanthraquinone by oxidation of 2-methylanthraquinone by oxygen in the presence of cobalt and manganese in acetic acid.
However, the known processes for the preparation of 2-carboxyanthraquinone make use of oxidizing agents which are highly toxic to the environment, such as, for example, chromium, manganese and cobalt, or else of techniques or of reactants which are difficult to employ, such as, for example, UV radiation or chlorine.
Furthermore, these processes for the manufacture of 2-carboxyanthraquinone have the disadvantage of using expensive starting materials which are mainly available in small amounts, such as anthracene derivatives or 2-methylanthraquinone.
The invention is thus targeted at providing a solution to these disadvantages.
DETAILED DESCRIPTION OF INVENTION
The invention relates to a process for the synthesis of 2-carboxyanthraquinone from 2-ethylanthraquinone by oxidation with nitric acid.
According to one embodiment of the invention, the oxidation with nitric acid is carried out using an aqueous nitric acid solution at a concentration of between 1 and 20% by weight and preferably between 3 and 15% by weight.
According to one embodiment of the invention, the proportion of 2-ethylanthraquinone to be treated is between 2 and 20% by weight of nitric acid solution and preferably between 5 and 12% by weight.
According to one embodiment of the invention, the reaction temperature is between 120 and 220° C. and preferably between 160 and 200° C.
According to one embodiment of the invention, the pressure at which the reaction is carried out is between 6 and 80 bar and preferably between 15 and 20 bar.
According to one embodiment of the invention, the pressure is kept constant throughout the reaction.
According to one embodiment of the invention, the nitrogen oxide vapours produced during the reaction are recycled as nitric acid.
The process for the manufacture of 2-carboxyanthraquinone will now be described.
The principle of the reaction consists in bringing together 2-ethylanthraquinone and an aqueous nitric acid solution under hot conditions and at a certain pressure. The reaction products are 2-carboxyanthraquinone, carbon dioxide and nitrogen oxides.
The reaction temperature, for its part, is between 120 and 220° C. It is preferably between 160 and 200° C.
The pressure, for its part, is greater than or equal to the saturated vapour pressure of the nitric acid solution at the reaction temperature. If no degassing is carried out, the pressure is greater than the saturated pressure since the reaction generates gaseous compounds, which are carbon dioxide and nitrogen oxides. The reaction is carried out at a pressure which can be between 6 and 80 bar. The pressure is advantageously between 15 and 20 bar, with one or more manual or automatic degassings during the reaction, for a reaction temperature of between 180 and 200° C.
The concentration of the aqueous nitric acid solution, for its part, is from 1 to 20% by weight and it is preferably between 3 and 15% by weight.
The amount of 2-ethylanthraquinone introduced into the reaction medium, for its part, is between 2 and 20% by weight of nitric acid solution and preferably between 5 and 12% by weight.
The reaction can be carried out:
by a batchwise method, that is to say by charging the reactants and discharging the products in a batchwise fashion;
by a semicontinuous method, that is to say by continuous charging of the reactants and batchwise discharging of the products; or alternatively
by a continuous method, that is to say by charging the reactants and discharging the products in a continuous fashion.
A batchwise method is preferably used for small amounts of reactants and products. For implementation on an industrial or semi-industrial scale, the semicontinuous or continuous methods are preferred, the semicontinuous method having the advantage of making possible good control of the exothermicity of the reaction and of the concentration of nitric acid and easy discharging of 2-carboxyanthraquinone.
During the reaction, the nitric acid is preferably introduced into the reactor in the form of a concentrated solution of 58 to 60% by weight. This makes it possible to maintain a strength of 3 to 15% by weight of nitric acid in the reaction medium.
The duration of the reaction depends on the temperature at which the reaction is carried out. When the reaction is carried out at 190° C. under the conditions set out above, the reaction lasts between 30 minutes and 1 hour.
It is important for the stirring to be efficient in order to ensure good emulsification of the molten 2-ethylanthraquinone (example: 2-ethylanthraquinone melts at approximately 110° C.) in the aqueous nitric acid solution and good entry into suspension of the 2-carboxyanthraquinone formed, which is solid at the reaction temperature (M.p.≅290° C.).
The reactor can be made of stainless steel or of enamelled steel.
During the reaction, nitrogen oxides given off can either be removed or recycled as nitric acid after oxidation using air or oxygen under pressure.
On completion of the reaction, the 2-carboxyanthraquinone is isolated by filtering the reaction medium. The filtrate, which is a relatively pure nitric acid solution, can be reused after adjusting its nitric acid strength by addition of concentrated nitric acid. The amount of aqueous effluents is thus substantially reduced.
The 2-carboxyanthraquinone produced is very pure, at approximately 99%, and only requires washing with water, preferably tepid water, until the pH is neutral, the sign of the removal of any residual nitric acid.
The melting point of the 2-carboxyanthraquinone is subsequently measured, which melting point must be between 287 and 297° C., ensuring a satisfactory degree of purity, and preferably between 292 and 296° C.
REFERENCES:
patent: 662 139 (1951-12-01), None
patent: 1 425 692 (1976-02-01), None
patent: 50-047964 (1976-10-01), None
Porshakova et al, Alkylation of anthracene with alcohols, Oct. 23, 1972, Chem. Abs., vol. 77 No. 17, p. 424.*
Chemical Abstracts, vol. 77, No. 17, Oct. 23, 1972 Columbus, Ohio, US; abstract No. 114111g, K.I. Porshakova et al. “Alkylation of anthracene with alcohols in the presence of zinc chloride” p 424.
Atofina
Pryor Alton N.
Smith , Gambrell & Russell, LLP
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