JPS6219571A - Manufacture of n-alkyl- or n-arylsulfonyloxynaphthalimides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing N-furkyl- or N-arylsulfonyloxynaphthalimides using naphthalic anhydride as a starting material.

N-Furkyl- or N-arylsulfonyloxynaphthalimides are important dye intermediates and can be synthesized via the corresponding naphtolactams [N-, L-, placidine (U,
L-Plalcidin) and co-researchers J, Q
Chem, USSR 10 (1974), Part 2, p. 2249], which is useful in the production of naphthostyryl dyes. Such dyes and methods for their production are disclosed, for example, in German Patent No. 1917456.

The conventionally well-known method for producing 1,8-naphtholactam (naphthostyryl) uses naphthalimide as a starting material. This naphthalimide is obtained by heating naphthalic anhydride and aqueous ammonia [Ullmann (Ul 1
Mann), 4th edition, Volume 9 (1975) '153
page], this naphthalimide is converted to naphthostyryl by Hofmann decomposition [F, Ullmann
) and collaborators, Chem, Ber, 43.
439 (1910)). The disadvantage of this method is that the desired product is obtained only in relatively low yields.

Furthermore, a method for producing N-furkyl- or N-arylsulfonyloxynaphthalimide is well known and can be similarly obtained using naphthalic anhydride as a starting material. In this process, naphthalic anhydride is first reacted with hydroxyl-amine to give naphthalic hydroxyimide, and the N-hydroxy group is subsequently acylated with a sulfochloride, for example benzene sulfochloride (DE 2417789). issue). The reaction between naphthalic anhydride and hydroxylamine is carried out in a protic solvent such as water or propionic acid, whereas the subsequent acylation reaction is carried out in an organic solvent such as methanol or pyridine. It will be done. This method is relatively uneconomical because the reaction of the acid anhydride and hydroxylamine and the subsequent acylation are carried out in different solvents, and there is an intermediate step to separate the naphthalic acid hydroxyimide formed. It is.

Currently, efforts are being made to further simplify the intermediate synthesis method carried out in large-scale production, and it has become possible to achieve a production method that is as streamlined as possible by simplifying the synthesis process. . A simple process for the preparation of N-alkyl- or N-arylsulfonyloxynaphthalimides was sought in which naphthalic anhydride was reacted with hydroxylamine or hydroxylammonium salts, followed by naphthalic acid, using water as the reaction medium. It has been found that the hydroxyimide can be reacted directly with the sulfochloride in the same reaction vessel to the desired final product without separating it. Considering that the reaction is carried out in suspension and the extracts and products are virtually insoluble in water, this reaction proceeds extremely homogeneously and with good yields, and the use of water as the reaction medium can also be achieved. , it can be seen that there is no appreciable sulfochloride hydrolysis. An additional advantage is that since the reaction takes place in water, there is no need to recover the solvent.

The object of the present invention is thus a process for the preparation of N-furkyl- or N-arylsulfonyloxynaphthalimides of the formula:

0-R ■ Here, R is an alkyl- or arylsulfonyl group, R' and R'' are unrelated to each other, and are hydrogen, alkyl, alkoxy, halogen, N.

means N-dialkylamino or nitro group,
Starting from the corresponding naphthalic anhydride, using water as reaction medium, the naphthalic anhydride is reacted with hydroxylamine or a hydroxylammonium salt to give naphthalic hydroxyimide, without intermediate separation. It is characterized by reacting with an alkyl- or arylsulfochloride to form N-furkyl- or N-arylsulfonyloxynaphthalimide.

This reaction proceeds according to the following reaction formula.

As a reaction example, naphthalic anhydride is reacted with hydroxylamine sulfate and benzene sulfochloride to produce °N-phenylsulfonyloxynaphthalimide.

Naphthalic acid hydroxyimide Besides naphthalic anhydride, substituted naphthalic anhydrides can also be used as starting materials. The substituents R' and R'' mentioned above are of course primarily hydrogen, but can also be, for example, alkyl, in particular lower alkyl of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl or , and also isopropyl or sec-butyl groups; further alkoxy, especially lower alkoxy of 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy,
Butoxy or isopropoxy or tertiary butoxy radical rings; further possible halogens are, for example, fluorine, chlorine or bromine, or nitro groups or N,N-dialkylamino groups, such as N,N-dimethylamino groups. .

Naphthalic anhydride or the corresponding derivative is first reacted with hydroxylamine, expediently with an aqueous solution, or with a hydroxylammonium salt. Suitable hydroxylammonium salts are, for example, hydroxylamine hydrochloride, -sulfate or mononitrate, especially hydroxylamine sulfate. The intermediate naphthalic acid hydroxyimide is R-8O! α Acylated with a furkyl- or aryl sulfochloride of the formula.

The group R here is an alkyl group, in particular a lower alkyl group having 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tertiary-butyl group. be. Alkyl is also to be understood as meaning a phenyl-substituted alkyl group, such as a benzyl group or a phenylethyl group. R furthermore denotes an aryl group, in particular an unsubstituted phenyl group or a phenyl group which can also be substituted, for example by a methyl, ethyl, chlorine, bromine or nitro group. Such sulfochlorides include, for example, 2-methylbenzenesulfochloride, 3-methylbenzenesulfochloride, 4-methylbenzenesulfochloride, 2,3-dimethylbenzenesulfochloride, 3.4
-dimethylbenzole sulfochloride, 2,6-dimethylbenzole sulfochloride, 3,5-dimethylbenzole sulfochloride, 2-ethylbenzole sulfochloride, 3-ethylbenzole sulfochloride, 4-ethylbenzole sulfochloride, 3-diethylbenzole Sulfochloride, 3.4-diethylbenzole sulfochloride, 2.6-diethylbenzole sulfochloride, 15-diethylbenzole sulfochloride, 2-nitrobenzole sulfochloride, 3-nitrobenzole sulfochloride, and 4-nitrobenzole sulfochloride, etc. It is. A preferred acylating agent in the method of the invention is benzene sulfochloride.

The reaction of unsubstituted or substituted naphthalic anhydride with hydroxylamine or hydroxylammonium salt is preferably carried out at a temperature in the range from 10°C to the boiling point of the reaction mixture, especially in the temperature range from 60°C to 100°C. The pH is preferably around the neutral point, especially between 6.5 and 7.
5 is preferred.

The acylation of naphthalic acid hydroxyimide is expediently carried out at a temperature of 10 to 50° C. and a pH of 8 to 13.5.

In the case of reacting hydroxylamine or hydroxylammonium salts and also in the case of the subsequent acylation, the required PM adjustment is usually achieved by aqueous solutions of alkali metal or alkaline earth metal hydroxides or carbonates. , or suspensions, or tertiary amines such as triethylamine or piperidine are used. In particular, it is suitable to adjust the pH with an aqueous sodium hydroxide solution.

The reaction time varies from 3 to 10 hours, depending on the reaction temperature and the quantitative scale of the reactants. The processing method has an additional advantage over the above-mentioned method, and is extremely simple.
This is because the product is substantially insoluble in the reaction medium and can therefore be easily separated by filtration, centrifugation or decantation. Subsequently, the product is expediently washed with water and dried. N-furkyl- or N
-Arylsulfonyloxynaphthalimides can be further reacted directly to the corresponding naphtholactams. Pre-purification operations are generally unnecessary.

The process according to the invention is carried out, for example, as follows: naphthalic anhydride is suspended in water, expediently in such a way that 1 mol of naphthalic anhydride is suspended in about 1 liter of water. The suspension is clouded and an approximately equimolar amount of a hydroxylammonium salt, such as hydroxylamine sulfate, is added to this suspension. It is preferable to add the hydroxylammonium salt in a small excess, particularly in 10% excess compared to the equimolar amount. The reaction mixture was then heated to about 90°C.
and adjust the pH to about 6.5 to 7.5 by adding an aqueous sodium hydroxide solution. After about 1 to 3 hours of reaction time, the reaction mixture is allowed to cool to room temperature and aqueous sodium hydroxide solution is added to raise the pn to >10, preferably about 13. The sulfochloride, for example benzene sulfochloride, is then added, again preferably in an excess of about 10% compared to the equimolar amount. As the acylation proceeds, the pH value of the reaction mixture falls to less than pnlQ, approximately pn 9.

After about 2 to 5 hours, the reaction is complete and the product is filtered off. The O-7 silnaphthalic acid hydroxyimide is then washed with lake water and then dried. The yield obtained with this method is generally greater than 90%.

The following examples serve to illustrate the invention, in which parts are parts by weight and percentages are percentages by weight.

Example: 99.1 parts of naphthalic anhydride are suspended in 500 parts of water and then 45.1 parts of hydroxylamine sulfate are added to this suspension. This suspension is heated to 90°C, and about 60 parts of 50% aqueous sodium hydroxide solution is added dropwise to adjust the pH value to 6.5-7. Adjust to -5. After continuing stirring at 90° C. for 1 hour, the reaction mixture is cooled to 25° C. and about 44 parts of 50% aqueous sodium hydroxide solution are added dropwise to bring the pH number to about 13.5.

Then, within 1 hour, 98 parts of benzene sulfochloride are added dropwise at room temperature. During this acylation, the pH value drops to about 9 after a further hour. The reaction is virtually complete at this point. The product is taken from house to house, washed with water and then dried. 163 parts of N-phenylsulfonyloxynaphthalimide were obtained, corresponding to a yield of 92%. The melting point of the product is 206°C.

Claims (1)

[Claims] 1. N-alkyl or N-arylsulfonyloxynaphthalimide of the following formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (Here, R is an alkyl- or arylsulfonyl group, and R' and R '' independently represents hydrogen, alkyl, alkoxy, halogen, N, N-
It means dialkylamino or nitro group. ) starting from the corresponding naphthalic anhydride, in which the naphthalic anhydride is reacted with hydroxylamine or hydroxylammonium salt to form naphthalic acid-hydroxyimide using water as the reaction medium; A process characterized in that it is reacted with an alkyl- or arylsulfochloride to give the N-alkyl- or N-arylsulfonyloxynaphthalimide without intermediate separation. 2. Reaction of unsubstituted or substituted naphthalic anhydride with hydroxylamine or hydroxylammonium salt at a temperature ranging from 10° C. to the boiling point of the reaction mixture with a pH value near the neutralization point. Method 3 according to claim 1, characterized in that the method 3 is carried out at a temperature in the range of 60°C to 100°C and a pH value of 6.
．． 5. The method according to claim 2, characterized in that the method is carried out at a temperature of 5 to 7.5. 4. Naphthalic acid hydroxyimide is alkyl- or
2. A process according to claim 1, characterized in that the reaction with the aryl sulfochloride is carried out at a temperature of 10 to 50 DEG C. and a pH value in the range of 8 to 13.5. 5. Starting from naphthalic anhydride, this is reacted with hydroxylamine sulfate and then with benzene sulfochloride to obtain N-phenylsulfonyloxynaphthalimide. Claim 1 The method described in any one of paragraphs to paragraphs 4 to 4.