Process for producing perylene-3, 4-dicarboxylic acid imides

Details Process for producing perylene-3, 4-dicarboxylic acid imides Process for producing perylene-3, 4-dicarboxylic acid imides

1998-12-07

2000-10-24

Rotman, Alan L.

Organic compounds -- part of the class 532-570 series

Organic compounds

Nitrogen attached directly or indirectly to the purine ring...

544318, 544319, 546 39, C07D47100, C07D40112, C07D40312, C07D23928

Patent

active

061369764

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a novel process for preparing perylene-3,4-dicarboximides of the formula I ##STR2## where R.sup.1 is hydrogen; C.sub.1 -C.sub.8 -alkyl; C.sub.5 -C.sub.8 -cycloalkyl; or phenyl or naphthyl, each of which can be substituted by C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.6 -alkoxy or cyano; and -alkyl; or aryloxy, arylthio, hetaryloxy or hetarylthio, each of which can be substituted by C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.6 -alkoxy or cyano.
Perylene-3,4-dicarboximides of the formula I are known to be important intermediates in preparing pigment additives, fluorescent dyes and fluorescent pigments (EP-A-636 666; EP-A-596 292), but are also suitable themselves with advantage as fluorescent dyes and pigments (EP-A-657 436; nonprior-published DE-A-195 01 737).
To prepare perylene-3,4-dicarboximides I whose perylene framework is unsubstituted (R.sup.2 .dbd.H) a range of complex multistage processes have been described which start from perylene-3,4,9,10-tetracarboxylic dianhydride and which yield the compounds I in usually unsatisfactory yields and in such poor purity that complex purification methods, such as extraction and column chromatography, are required.
For instance, unsubstituted and N-alkyl-substituted perylene-3,4-dicarboximides (where alkyl is methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl or n-dodecyl) are obtained by alkaline decarboxylation of the perylene-3,4,9,10-tetracarboxylic imide anhydride intermediates at .gtoreq.220.degree. C. under superatmospheric pressure in reaction times of 18 h (DE-C-486 491; Bull. Chem. Soc. Jap. 54 (1981) 1575-1576; EP-A-596 292). This process, however, is suitable only for base-stable aliphatic imides.
To prepare the N-methyl- and N-ethyl- (and also N-phenyl-, N-tolyl- and N-anisyl-)substituted perylene-3,4-dicarboximides, the initially prepared unsubstituted perylene-3,4-dicarboximide is sulfonated with oleum and then converted with potassium hydroxide solution into the sulfonated anhydride, which is then reacted with the appropriate primary amine to form the sulfonated N-substituted imide, which finally is desulfonated using sulfuric acid to give the desired perylene-3,4-dicarboximide (Bull. Chem. Soc. Jap. 52 (1979) 1723-1726, Shikizai Kyokaishi 49 (1976) 29-34 = Chemical Abstracts 85:209285). This process is extremely laborious and can only be used for sulfuric-acid-stable imides.
In EP-A-657 436, unsubstituted, N-alkyl-, N-cycloalkyl- and N-phenyl-substituted perylene-3,4-dicarboximides with an unsubstituted perylene framework are obtained by condensing perylene-3,4,9,10-tetracarboxylic dianhydride with 2,5-di-tert-butylaniline in the presence of water, zinc acetate dihydrate and imidazol, by alkaline hydrolysis of the chromatographically purified N-2,5-di-tert-butylphenylperylenedicarboximide, to give the perylene-3,4-dicarboxylic anhydride, which is then reacted with the appropriate primary amine.
Another process described in EP-A-657 436 for preparing N-alkyl-substituted perylene-3,4-dicarboximides starts from the unsubstituted perylene-3,4-dicarboximide, which initially, as described above, can be prepared from perylene-3,4,9,10-tetracarboxylic dianhydride and is reacted with the appropriate alkyl bromide in the presence of a strong base and of a dipolar-aprotic solvent. In this case too the reaction products are chromatographed.
Finally, N-1-hexylheptyl- and N-1-octylnonyl-perylene-3,4-dicarboximide can in accordance with EP-A-657 436 also be obtained, by analogy with the N-2,5-di-tert-butylphenylperylene-3,4-dicarboximide intermediate, directly from perylene-3,4,9,10-tetracarboxylic dianhydride.
However, the preparation processes known from EP-A-657 436 as well are highly complex and produce only low overall yields of the N-substituted perylene-3,4-dicarboximides.
A process which is suitable inter alia for preparing perylene-3,4-dicarboximides which are substituted in the perylene framework is described in nonprior-published DE-A-195 01 737. Here, the imides I are obtained by direct reaction of pe

REFERENCES:
patent: 5405962 (1995-04-01), Mullen et al.
patent: 5650513 (1997-07-01), Langhals et al.
patent: 5808073 (1998-09-01), Bohm et al.
patent: 5981773 (1999-11-01), Langhals et al.
patent: 5986099 (1999-11-01), Mullen et al.

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