DE1215844B - Process for the preparation of perimidon-6, 7-dicarboximides - Google Patents

Description

Process for the preparation of perimidone-6,7-dicarboximides The invention relates to the preparation of perimidon-6,7-dicarboximides, a previously unknown class of compounds of the general formula (R = H, aliphatic radical, aryl). Due to their excellent fastness properties, these compounds are eminently suitable as pigment dyes.

The new compounds are obtained by adding 4,5-diaminonaphthalic acid derivatives of the general formula in the X oxygen or where R is hydrogen, a low molecular weight aliphatic or aromatic radical, by reacting with derivatives of carbonic acid, e.g. B.

Phosgene or urea, which connects the two amino groups directly through a carbonyl group and, if X stands for an oxygen atom, this before, during or after the introduction of the carbonyl group by reaction with a compound of the formula R - NH2 or with formamide through the group replaced.

The following implementation scheme explains the implementation steps, for example 0 o R - NH2 1 phosgene H2N NH2 RI oXN <o 0 <0 0 IT o oc H2N NH2 HN NH II R III o- O / NO Phosgene or N ß 2 RNH2 urea HN NH R = H, alipha- K tic remainder, aryl O IV To prepare the new compounds, for example 4,5-diamino-naphthalic anhydride (I) is reacted in solvents with phosgene to give perimidone-6,7-dicarboxylic anhydride (III) and converted into the corresponding perimidone-6,7 with ammonia or primary amines -dicarboximides (IV). The solvents used are primarily high-boiling aromatic compounds, such as nitrobenzene, di- and trichlorobenzene, naphthalene, alkyl- and chloronaphthalenes or their mixtures; into consideration. The compound of the formula 1 is expediently introduced into this and phosgene is then allowed to flow in at 50 to 250.degree.

Instead of naphthalic anhydride, naphthalic acid can also be used in the reaction mixture, since they are already in. at low temperatures the anhydride passes over. For the production of perimidone-6,7-dicarboximide (IV, R. = H) from the perimidone-6,7-dicarboxylic acid anhydride (III) this is dissolved, for example at temperatures below 30 ° C in aqueous ammonia and heats the solution Temperatures above 40 ° C. The perimidone-6,7-dicarboximide separates (IV) in a very fine distribution.

Perimidon-6,7-dicarboximide (IV, R = H) can also be used directly from 4,5-diamino-naphthalic anhydride (1) by reaction in a urea melt obtained in excellent yield. The reaction takes place at temperatures between 100 and 160 "C almost quantitative, being carried out simultaneously with the carboxylation Imide formation takes place with the ammonia split off in the process.

The cooled melt is expediently extracted with water. The perimidon-6,7-dicarboxylic acid (1V) remains as an insoluble residue.

But you can also initially from 4,5-diaminonaphthalic anhydride (I) and ammonia or primary amines 4,5-diamino-naphthalic acid imide (II) and this by reaction with phosgene into the perimidone-6,7-dicarboximide (IV) convict.

Instead of ammonia or amines, formamide can also be used at higher levels Use temperatures, e.g. B. between 100 and 195 "C.

In the manufacture of perimidone-6,7-dicarboxylic acid N-alkylimides from perimidon-6,7-dicarboxylic acid anhydride (III) and alkaylmine it is often achieved excellent yields useful when you consider the reactions in anhydrous agents executes. Particularly favorable results are achieved with nitrobenzene as the solvent, but especially with acid amides such as dimethylformamide, N-methylpyrrolidone and the like polar solvents. If the aliphatic amine to be reacted is a has a sufficiently high boiling point or, if you work in closed vessels, leaves it the reaction can also be carried out without further solvents, provided one is from the aliphatic Amin takes an excess.

For the implementation of the perimidone-6,7-dicarboxylic acid anhydride (III) with ammonia and aliphatic amines, even very mild ones are generally sufficient Conditions, on the other hand, the arylamines require much harsher reaction conditions, z. B. quinoline as a solvent, zinc chloride as a condensing agent and temperatures around 200 "C.

The compound of formula 1 can be obtained, for example, by reduction of 4,5-dinitro-naplitha1 acid anhydride, the compound of formula II except from the compound of formula 1 also through Reduction of the 4,5-dinitro-naphthalic acid imide, which can be substituted on the imide nitrogen. Especially the one on the imide nitrogen atom Diaminonaphthalimides substituted by aryl radicals are expediently prepared by reducing the corresponding dinitroniaphthalic acid imides. The dinitroimides can be done catalytically or with iron-hydrochloric acid in the presence of an organic solvent to reduce. For the production of diamino compounds from the corresponding dinitro compounds no protection is claimed under this property right.

The aliphatic radicals R are those with 1 to 6 carbon atoms preferred, especially the methyl, ethyl, propyl and butyl radicals. You can in turn be substituted, for example by hydroxyl groups. As aromatic The phenyl and naphthyl radicals are preferred.

These radicals can in turn be substituted, e.g. B. by Halogen.

The perimidone-6,7-dicarboximides which can be prepared according to the invention are yellow and greenish yellow compounds and in appropriately cleaned and nd finely divided form valuable pigment dyes.

Particularly advantageous measures for fine distribution are sulphate precipitations, wet and dry salt grinding and swelling in solvents such as aromatic ones Compounds, glycol ethers, alcohols, esters, ketones, and especially in acid amides such as dimethylformamide or N-methylpyrrolidone.

The swellings are generally at temperatures between 20 and 250 "C, preferably at 100 to 210" C. The remedy for the swelling may also contain emulsifiers and dispersants. Fine distribution is common associated with a change in the shade of the compound obtained by the synthesis.

For the use of perimidone-6,7-dicarboximides as pigments Average particle sizes of 0.05 to 20 µ, preferably 0.1 to 2, are desired.

The pigments are extremely resistant to diluted acids and weak alkalis, excellent lightfast, solventfast and thermostable as well as extremely strong and brilliant.

The new pigments can be used in doughs, flush pastes, Preparations, printing inks, glue paints, binder paints and varnish paints of all kinds. The Pigments can be present in synthetic or natural macromolecular substances, such as polyvinyl chloride, polystyrene, polyamide, polyethylene, polypropylene, polyesters, Phenolic pastes, aminoplasts and rubbers. The pigments can also be used for bulk coloring of fibers made from acetyl cellulose, polyacrylonitrile, polyester, polyurethane and polyvinyl chloride use. They are also suitable for bulk coloring paper or for dyeing inorganic substances, e.g. B. cement.

In all of these substances the new pigment dyes predominantly result yellow, strong colors of excellent durability to external ones Influences such as light, temperature and weather.

The parts and percentages given in these examples are weight units.

Example 1 23 parts of 4,5-diamino-naphthalic anhydride are used in 4500 Parts of nitrobenzene dissolved at 150 "C. In the solution, which has been cooled to 1000 C, 30 minutes, then another 30 minutes each at 130, 160 and 190 "C. drier Phosgene stream initiated. It is then flushed with nitrogen, cooled, filtered off with suction and washed the yellow residue with a little methanol. Yield 21 parts (83 0 in theory) Perimidon-6,7-dicarboxylic anhydride, yellow crystals of strong color, melting point above 350 "C.

20 parts of perimidone-6,7-dicarboxylic anhydride are used at room temperature dissolved in 1500 parts of 5% ammonia. The solution will be used within an hour heated to a low boil. After a further two hours it is cooled, suctioned off and dried.

Yield 18.1 parts (90.5% of theory) of perimidone-6,7-dicarboximide, olive-yellow powder, melting point above 350 "C. The conversion of perimidone-6,7-dicarboxylic acid anhydride with aqueous ammonia can also be in heterogeneous phase or at high concentrations it can be carried out with liquid or gaseous ammonia in the pressure vessel.

The 4,5-diamino-naphthalic anhydride is z. B. manufactured after J. Honda and M. Okazaki, 'J.

Soc. Org. Synthetic. Chem. (Japan), 7, pp. 25-29 (1950), and Chem. Abstracts, 47, p. 6922b.

Example 2 5.1 parts of perimidone-6,7-dicarboxylic acid anhydride are dissolved in the cold in 150 parts of 100 /, the aqueous methylamine solution, heated within one hour to low simmer, cools after 30 minutes, sucks off and dries. Yield 4.3 parts (81% of theory) of perimidone-6.7-dicarboxylic acid-N-methylimide, yellow powder, melting point above 350 "C.

- Example 3 A mixture of 5.8 parts of 4,5-diamino-naphthalic anhydride with 58 parts of urea is heated to 150 "C within 30 minutes and 2 hours stirred at 150 "C. The cooled melt is pulverized, mixed with water, Sucked off, washed with water and dried. Yield 5.8 parts (1000 /, of theory) Perimidone-6,7-dicarboximide.

For cleaning and fine division 7.9 parts of perimidone-6,7-dicarboxylic acid, ureimide in 120 parts. Dissolve concentrated sulfuric acid and add 40 parts of water to the solution move, suction off the resulting precipitate and add 50 parts of 600 /, sulfuric acid to wash.

The residue is decomposed with ice-ammonia, with water and then washed with methanol. Yield 6.8 parts (8601, of theory) perimidone-6,7-dicarboximide, Particle size will be about 0.05 to 0.5 parts 5.4 parts of the pigment thus obtained for swelling in 80 parts of N-methylpyrrolidone for 5 hours at reflux temperature heated, filtered off with suction at 50 ° C., washed with methanol and dried. Yield 51 Parts (94.5% of theory) of perimidone-6,7-dicarboximide, particle size 0.1 up to 0.3, exceptionally brilliant and strongly colored yellow pigment. Particularly beneficial it is to use the paste, which is still wet with methanol, for the re-swelling. Through longer Particle sizes of any size can be produced by swelling times.

One rubs 20 parts of the prepared according to the previous embodiment yellow pigment and 20 parts of alumina hydrate on a three-roll mill in the usual way If you use 60 parts of linseed oil varnish to produce a printing ink, the processing results brilliant yellow prints with excellent fastness properties in the letterpress or offset printing process, especially very good lightfastness and great color strength.

A yellow gravure printing ink that can be used to produce light and solvent resistant Suitable prints are obtained by using a nitrocellulose solution to add 10 parts Nitrocellulose, 5 parts of dibutyl phthalate, 80 parts of ethanol-ethylglycol mixture 9: 1 contains 5 parts of the pigment obtained according to the preceding paragraphs in one Ball mill drives.

By changing the recipe, printing pastes can also be used for others Purposes, e.g. B. for textile printing and screen printing. Brilliant yellow paintwork, the after. Hardening by baking is extremely weatherproof and resistant to overpainting can be made from a stoving enamel that you get when you turn 40 Parts coconut oil alkyd resin, 12 parts urea formaldehyde resin, 40 parts xylene and 8 parts. n-butanol with 8 parts of the pigment prepared according to the preceding paragraphs grinds on a hopper grinder.

Example 4 300 parts of formamide and 23 parts of 4,5-diaminonaphthalic anhydride are heated contained, 2 hours under reflux to boiling. Then the solution cooled, treated with 1000 parts of water, filtered off with suction and the residue with water and methanol washed. Yield 23 parts (10001, of theory) 4,5-diamino-naphthalic acid imide, yellow-brown powder, melting point above 350 "C.

8.7 parts of 4,5-diamino-naphthalic acid imide are in 150 parts of nitrobenzene solved. At 100 ° C., a weak stream of phosgene is passed into the solution.

Within an hour, the temperature is increased to 160 "C and one stirred for a further hour at 160 ° C., while phosgene was continuously introduced. The solution is then flushed with air, cooled, filtered off with suction and washed with methanol. Yield 7.8 parts (80.50% of theory) of perimidone-6,7-dicarboximide.

For cleaning and fine division, 10 parts of perimidone-6,7-dicarboximide are used with 100 parts of sodium chloride and 800 parts of porcelain balls for 24 hours in one Vibrating mill ground. The sodium chloride is washed out with water and washed with After methanol and dries. Yield 9.8 parts (98% theoretical), yellow pigment with a particle size of 0.2 to 0.5 p. By swelling the pigment obtained in this way with N-methylpyrrolidone a very strong and very opaque yellow can be obtained Prepare pigment with an average particle size of 1 p.

It is stained with 0.5 parts of that obtained in accordance with the preceding paragraphs Pigments on a rolling mill heated to 160 "C, in the usual way a mixture of 70 parts of polyvinyl chloride, 30 parts of diisooctyl phthalate and 1 Part of titanium dioxide (rutile type), you get a greenish yellow plastic mass, the z. B. can be used to produce films or profiles. The coloring draws are characterized by excellent plasticizer and lightfastness. Greenish yellow colored High lightfastness polystyrene moldings are obtained by mixing 100 parts Polystyrene granules with 1 part of the pigment prepared according to the preceding paragraphs in a mixing drum, homogenizing the mixture by means of a heated to 180 "C. Dyeing screw, comminuting the strand emerging from the nozzle of the screw a cutting machine and transferring the so obtained granules on an injection molding machine to form moldings.

Example 5 7.6 parts of perimidone-6,7-dicarboxylic acid anhydride are used in 80 parts of N-methylpyrrolidone dissolved at 1000 C. You lead within an hour 5 parts of gaseous ethylamine in the solution, which one at the same time to the weak Boiling heated. It is then cooled, neutralized with 2N acetic acid, filtered off with suction, washed with water and methanol and dried. Yield 7.4 parts (88% Theory) Perimidone-6,7-dicarboxylic acid-N-ethylamide, olive-yellow powder, melting point above 350 "C. Higher primary, aliphatic amines such as n-propyl- or n-butylamine are added to the reaction mixture in liquid form and also provide yields from 900/0 of theory, as well as substituted alkylamines such as ethanolamine.

Example 6 5 parts of 4,5-diamino-naphthalic acid-N-phenylimide become mixed with 60 parts of urea and, as described in Example 3, reacted. Yield 3.5 parts (640 /, of theory) perimidone-6,7-dicarboxylic acid N - phenylimide, greenish yellow powder, melting point above 3500 C.

Example 7 23 parts of 4,5-diamino-naphthalic anhydride are used in Suspended 250 parts of nitrobenzene and added 12 parts of carbamic acid chloride. The suspension is heated to 100 ° C. within one hour and then stirred in each case 1 hour at 100, 130, 160 and 190 "C. The perimidone-6,7-dicarboxylic acid anhydride obtained is filtered off with suction while cold, washed with methanol and dried. To transfer to the Imide can be proceeded according to example 1, paragraph 2.

Claims (2)

Claims: 1. Process for the preparation of perimidone-6,7-dicarboximides of the general formula in which R denotes a hydrogen atom, a low molecular weight aliphatic radical or an aromatic radical, characterized in that one in 4,5-diamino-naphthalic acid derivatives of the general formula in which X stands for an oxygen atom or the group stands, where R has the meaning given above, by reacting with derivatives of carbonic acid connects the two amino groups directly through a carbonyl group and, in the event that X stands for an oxygen atom, this before, during or after the introduction of the carbonyl group by reacting with a compound of Formula R - NH2 or with formamide through the group replaced. 2. The method according to claim 1, characterized in that one 4,5-diamino-naphthalic anhydride Reacts with urea.