WO2005097753A1 - Method for producing perylene tetracarboxylic diimide derivatives - Google Patents

Method for producing perylene tetracarboxylic diimide derivatives Download PDF

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WO2005097753A1
WO2005097753A1 PCT/FR2005/000668 FR2005000668W WO2005097753A1 WO 2005097753 A1 WO2005097753 A1 WO 2005097753A1 FR 2005000668 W FR2005000668 W FR 2005000668W WO 2005097753 A1 WO2005097753 A1 WO 2005097753A1
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formula
compound
carbon atoms
perylene tetracarboxylic
iii
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PCT/FR2005/000668
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French (fr)
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Jean-Charles Mossoyan
Mireille Mossoyan
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Universite De Provence Aix-Marseille 1
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings

Definitions

  • the present invention relates to a process for the preparation of derivatives of 1.8 naphthalimide or of its polymeric forms such as perylene tetracarboxylic diimide.
  • Perylene tetracarboxylic diimide (hereinafter PTCDI) is a widely used compound. In its uses in electronics, it is necessary to have this compound in a quality of very high purity.
  • PTCDI perylene tetracarboxylic diimide
  • alkaline fusion of naphthalimide at a temperature above 200 ° C. followed by oxidation.
  • the PTCDI is prepared by reaction between 280 and 300 ° C of a mixture of naphthalene-1,8-dicarboxylic imide, potassium hydroxide and a small amount of water.
  • the PTCDI is prepared by alkaline fusion of the naphthalene-1,8-dicarboxylic imide in a mixture of sodium hydroxide, potassium hydroxide and sodium acetate at a temperature of 190 to 220 ° C, then oxidation of the compound obtained.
  • US-A-4,588,814 describes a comparable process implemented in a mixture of dried potassium hydroxide and sodium acetate, for example under vacuum or in the absence of oxygen.
  • US-A-6 372 910 describes the preparation of 1, 8 naphthalimide from 1, 8 naphthalic anhydride using an aqueous solution of ammonia at 29% as an imidation agent.
  • Processes for preparing 1, 8 naphthalimide are also described in Israeli patent 38,952, in US-A-4,892,950 and in SU 491,631.
  • the molten alkaline salts are very corrosive and damage the material as described in particular by Desilets et al. in Can. J. Chem., 1995, 3, 325).
  • the isolation of the final product requires multi-stage purification processes.
  • N-substituted products methylamine, chloromethane, ethylamine, chloroethane, phenylamine etc.
  • the compounds used to prepare N-substituted products are affected by one or more of the following defects: extremely flammable, harmful by inhalation and / or ingestion, irritating to the eyes and respiratory tract.
  • the reactions involved are polluting because alkaline mists are formed during the synthesis and the washings produce large quantities of strongly alkaline waste water.
  • PTCDI by condensation of perylene tetracarboxylic dianhydride with ammonia in the presence of alkaline salts, as described for example in DE-A-1 619 531. But the yield is in particular very low.
  • dialkylated and diarylated PTCDIs are essentially prepared from the above dianhydride by reaction with an alkyl- or arylamine.
  • dialkylated PTCDI N, N'- di C ⁇ -C alkyl perylene tetracarboxylic diimides from PTCDI by reaction with an alkyl halide as described for example in US-A-3,331,847.
  • Ri and R 2 independently of each other, represent hydrogen or an alkyl radical containing from 1 to 8 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 12 carbon atoms, characterized in that the perylene tetracarboxylic dianhydride is reacted
  • Ri and R 2 independently of each other, represent hydrogen or an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 10 carbon atoms, said reaction being carried out in the absence of solvent, then the desired compound of formula I is isolated.
  • Ri and R 2 represent in particular an alkyl radical.
  • R 1 or R 2 represents an alkyl radical containing from 1 to 8 carbon atoms, it is a branched radical or not, particularly an n-butyl or n-propyl radical and preferably an ethyl or methyl radical .
  • R 1 or R 2 represents an aryl radical containing 6 to 10 carbon atoms, it is preferably a phenyl radical.
  • R 1 or R 2 represents an aralkyl radical containing from 7 to 12 carbon atoms, it is preferably a phenylethyl or benzyl radical.
  • Ri and R 2 have the same meaning.
  • Ri and R 2 represent a hydrogen atom or a phenyl radical.
  • Ri and R 2 independently, are both different from hydrogen.
  • Ri and R 2 represent an alkyl radical containing from 1 to 6 carbon atoms or a phenyl radical.
  • the reaction is carried out at a temperature greater than or equal to the melting point of the compound of formula (III), for example at a temperature ranging from 130 ° C. to 320 ° C, in particular from 130 ° C to 280 ° C, preferably from 150 ° C to 260 ° C, in particular from 180 ° C to 260 ° C, and particularly from 210 ° C to 260 ° C.
  • the process is rapid, and does not use an alkaline base.
  • the process does not use an organic solvent, such as nitrobenzene, xylene or trichlorobenzene, which are aromatic solvents of high cost, toxic and difficult to remove, on the contrary, according to the invention, the urea used as solvent can be easily removed by washing with water and then drying with water. It does not form a leuco form during the process and therefore there is no need for further oxidation.
  • the reaction does not require the presence of a catalyst and can be carried out at atmospheric pressure.
  • the reaction which takes place in one step is carried out according to the same protocol, whether one seeks to obtain a compound of formula (I) substituted or not.
  • the compound of formula (I) obtained is of high purity and therefore finds its use in particular as a laser dye, as an organic photoconductor and photoreceptor, in lithography, in microelectronics and, after treatment, as a pigment. This is why the present application also relates to a derivative of perylene tetracarboxylic diimide of formula (I) obtained by the implementation of the process described above and a derivative of perylene tetracarboxylic diimide of formula I whose infrared spectrum is in accordance with that described in the figures below concerning the products of the examples.
  • Example 1 Perylene tetracarboxylic diimide 2 g of perylene tetracarboxylic dianhydride are mixed in a reactor with 4.6 g of urea, the temperature is brought to 175 ° C. for 2 h. The expected product is isolated.
  • Example 2 Perylene tetracarboxylic diimide 51.6 g of perylene tetracarboxylic dianhydride are mixed in a reactor 51 with 115 g of urea, the mixture is brought to the temperature of 220 ° C. in 30 min with stirring and then the reaction is allowed to continue for 90 min. . The mixture is allowed to cool to 80 ° C. and is washed with hot water until the excess urea is completely eliminated. After drying in an oven for 12 h, 50.4 g of the expected product are isolated, in the form of crystalline powder.
  • Elementary analysis 51.6 g of perylene tetracarboxylic diimide are mixed in a reactor 51 with 115 g of urea, the mixture is brought to the temperature of 220 ° C. in 30 min with stirring and then the reaction is allowed to continue for 90 min. . The mixture is allowed to cool to 80 ° C. and is washed with hot water until the excess urea is completely eliminated. After drying in an oven for
  • Example 3 N, N'-dimethyl perylene tetracarboxylic diimide 3.0 g of perylene tetracarboxylic dianhydride are mixed in a reactor with 6.8 g of N, N'-dimethylurea, a small amount of water is introduced to form a paste and the temperature is brought to 249 ° C for 2 h.
  • Example 4 N, N'-diethyl perylene tetracarboxylic diimide The procedure is as in Example 3, without water, from 1 g of dianhydride and 4.44 g of N, N'-diethylurea for 1 h at 170 ° C. . 1.11 g of the expected product are isolated in the form of a crystalline powder. The infrared spectrum of the product obtained is reproduced in FIG. 3.
  • Example 5 N.N'-diphenyl perylene tetracarboxylic diimide The procedure is as in Example 3 by mixing 2.0 g of dianhydride and 10.55 g of N, N'-diphenylurea and a small amount of acetic acid. It is heated for 2 h at 249 ° C. Washing is carried out using concentrated and hot acetic acid. 2.60 g of the expected product are isolated in the form of a crystalline powder. The infrared spectrum of the product obtained is reproduced in FIG. 4.
  • Example 7 N-phenyl-1, 8-naphthalimide
  • 2 g of the anhydride 1, 8-naphthalic (1.10 “2 M) are mixed with 3.20 g of diphenylurea (1, 5 10 " 2 M ), i.e. 3 times the stoichiometric quantity.
  • the oven is heated to 250-260 ° C for 30 min.
  • the reactor is then introduced into the oven and left for 1.5 h with stirring. After cooling, the solid product obtained is washed cold with anhydrous ether.
  • Example 8 N-methyl-1.8-naphthalimide
  • 3 g of the 1,8-naphthalic anhydride (1, 5.10 "2 M) are mixed with 2.73 g of dimethylurea (3.10 10 " 2 M ), i.e. 4 times the stoichiometric quantity.
  • the oven is heated to 280 ° C for 30 min.
  • the reactor is then introduced into the oven and left for 45 min with stirring at 260 ° C. It is allowed to cool slightly and a few ml of hot water are added just after the mixture has solidified.
  • the product is washed hot with a mixture of 12 ml of concentrated hydrochloric acid in 100 ml of water and then rinsed with 150 ml of hot water. 3.05 g of N-methyl-1,8-naphthalimide are obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Indole Compounds (AREA)

Abstract

The invention relates to a method for preparing a compound of formula (I), wherein R and R2 = hydrogen or alkyl C1-C6, aryl C6-C10 or aralkyl C7-C12, consisting in reacting perylene tetracarboxylic dianhydride or naphtalic anhydride with a compound of formula (III), wherein R1 and R2 have the said meanings, in the absence of a solvent and, afterwards in isolating the desired compound of formula (1).

Description

PROCEDE DE PREPARATION DE DERIVES DU PERYLENE TETRACARBOXYLIQUE DIIMIDE PROCESS FOR THE PREPARATION OF DERIVATIVES OF PERETLAC TETRACARBOXYLIC DIIMIDE
La présente invention concerne un procédé de préparation de dérivés du 1 ,8 naphthalimide ou de ses formes polymères comme le pérylène tétracarboxylique diimide. Le pérylène tétracarboxylique diimide (ci-après PTCDI) est un composé très utilisé. Dans ses utilisations dans l'électronique, il est nécessaire de disposer de ce composé dans une qualité de très haute pureté. Actuellement, on sait préparer le PTCDI par fusion alcaline du naphtalimide à température supérieure à 200°C suivie d'une oxydation. Dans DE-A-276 357, le PTCDI est préparé par réaction entre 280 et 300°C d'un mélange de naphtalène-1,8-dicarboxylique imide, d'hydroxyde de potassium et d'une faible quantité d'eau. Dans EP-A-0 054 806, le PTCDI est préparé par fusion alcaline du naphtalène-1,8-dicarboxylique imide dans un mélange d'hydroxyde de sodium, hydroxyde de potassium et d'acétate de sodium à une température de 190 à 220°C, puis oxydation du composé obtenu. US-A-4 588 814 décrit un procédé comparable mis en œuvre dans un mélange d'hydroxyde de potassium et d'acétate de sodium desséchés, par exemple sous vide ou en absence d'oxygène. De même, par exemple US-A-6 372 910 décrit la préparation du 1 ,8 naphthalimide à partir d'anhydride 1 ,8 naphtalique en utilisant une solution aqueuse d'ammoniac à 29% comme agent d'imidation. Des procédés de préparation du 1 ,8 naphtalimide sont également décrits dans le brevet israélien 38 952, dans US-A-4 892 950 et dans SU 491 631. Mais les sels alcalins fondus sont très corrosifs et endommagent le matériel comme décrit notamment par Desilets et Al. dans Can. J. Chem., 1995, 3, 325). En outre, l'isolation du produit final nécessite des procédés de purification en plusieurs étapes. De plus les composés utilisés pour préparer des produits N-substitués (méthylamine, chlorométhane, éthylamine, chloroéthane, phénylamine etc) sont affectés d'un ou plusieurs des défauts ci-après : extrêmement inflammables, nocifs par inhalation et/ou ingestion, irritants pour les yeux et les voies respiratoires. Enfin, les réactions mises en jeu sont polluantes car il se forme des brouillards alcalins pendant la synthèse et les lavages produisent de grandes quantités d'eau usées fortement alcalines. On sait également préparer le PTCDI par condensation du pérylène tétracarboxylique dianhydride avec l'ammoniac en présence de sels alcalins, comme décrit par exemple dans DE-A-1 619 531. Mais le rendement est en particulier très faible. Pour leur part, les PTCDI dialkylés et diarylés sont essentiellement préparés à partir du dianhydride ci-dessus par réaction avec un alkyl- ou arylamine. On sait également préparer des PTCDI dialkylés N,N'- di Cι-C alkyl pérylène tétracarboxylique diimides à partir du PTCDI par réaction avec un halogénure d'alkyle comme décrit par exemple dans US-A- 3 331 847. La synthèse de 1,4,5,8-naphtalènetétracarboxydiimides par réaction entre l'anhydride correspondant et l'urée en présence de 1,3,5-trichlorobenzène est décrite dans l'article Y.Suga et al., Journal of Oleo Science, 2001 , 50, 527. Par ailleurs, le Chemical abstract n°1975 .458167, XP002303271, décrit la synthèse d'amides cycliques par réaction d'anhydrides d'acides carboxyliques avec l'urée, en solution dans le xylène. Après de longues recherches, la demanderesse a découvert un procédé de préparation simple et rapide du pérylène tétracarboxylique diimide ou du 1,8 naphtalimide et de certains de leurs dérivés N-substitués conduisant à des composés de très haute pureté avec de bons rendements. C'est pourquoi la présente demande a pour objet un procédé de préparation d'un composé de formule (I)
Figure imgf000005_0001
The present invention relates to a process for the preparation of derivatives of 1.8 naphthalimide or of its polymeric forms such as perylene tetracarboxylic diimide. Perylene tetracarboxylic diimide (hereinafter PTCDI) is a widely used compound. In its uses in electronics, it is necessary to have this compound in a quality of very high purity. Currently, it is known to prepare PTCDI by alkaline fusion of naphthalimide at a temperature above 200 ° C. followed by oxidation. In DE-A-276 357, the PTCDI is prepared by reaction between 280 and 300 ° C of a mixture of naphthalene-1,8-dicarboxylic imide, potassium hydroxide and a small amount of water. In EP-A-0 054 806, the PTCDI is prepared by alkaline fusion of the naphthalene-1,8-dicarboxylic imide in a mixture of sodium hydroxide, potassium hydroxide and sodium acetate at a temperature of 190 to 220 ° C, then oxidation of the compound obtained. US-A-4,588,814 describes a comparable process implemented in a mixture of dried potassium hydroxide and sodium acetate, for example under vacuum or in the absence of oxygen. Likewise, for example US-A-6 372 910 describes the preparation of 1, 8 naphthalimide from 1, 8 naphthalic anhydride using an aqueous solution of ammonia at 29% as an imidation agent. Processes for preparing 1, 8 naphthalimide are also described in Israeli patent 38,952, in US-A-4,892,950 and in SU 491,631. However, the molten alkaline salts are very corrosive and damage the material as described in particular by Desilets et al. in Can. J. Chem., 1995, 3, 325). In addition, the isolation of the final product requires multi-stage purification processes. In addition, the compounds used to prepare N-substituted products (methylamine, chloromethane, ethylamine, chloroethane, phenylamine etc.) are affected by one or more of the following defects: extremely flammable, harmful by inhalation and / or ingestion, irritating to the eyes and respiratory tract. Finally, the reactions involved are polluting because alkaline mists are formed during the synthesis and the washings produce large quantities of strongly alkaline waste water. It is also known to prepare PTCDI by condensation of perylene tetracarboxylic dianhydride with ammonia in the presence of alkaline salts, as described for example in DE-A-1 619 531. But the yield is in particular very low. For their part, the dialkylated and diarylated PTCDIs are essentially prepared from the above dianhydride by reaction with an alkyl- or arylamine. We also know how to prepare dialkylated PTCDI N, N'- di Cι-C alkyl perylene tetracarboxylic diimides from PTCDI by reaction with an alkyl halide as described for example in US-A-3,331,847. The synthesis of 1, 4,5,8-naphthalenetetracarboxydiimides by reaction between the corresponding anhydride and urea in the presence of 1,3,5-trichlorobenzene is described in the article Y.Suga et al., Journal of Oleo Science, 2001, 50, 527. In addition, Chemical abstract no. 1975 .458167, XP002303271, describes the synthesis of cyclic amides by reaction of anhydrides of carboxylic acids with urea, in solution in xylene. After lengthy research, the applicant has discovered a simple and rapid process for the preparation of perylene tetracarboxylic diimide or 1,8 naphthalimide and of some of their N-substituted derivatives leading to very high purity compounds with good yields. This is why the present application relates to a process for the preparation of a compound of formula (I)
Figure imgf000005_0001
ou de formule (!')or formula (! ')
Figure imgf000005_0002
Figure imgf000005_0002
dans laquelle Ri et R2, indépendamment l'un de l'autre, représentent l'hydrogène ou un radical alkyle renfermant de 1 à 8 atomes de carbone, un radical aryle renfermant de 6 à 10 atomes de carbone ou aralkyle renfermant de 7 à 12 atomes de carbone, caractérisé en ce que l'on fait réagir le pérylène tétracarboxylique dianhydridein which Ri and R 2 , independently of each other, represent hydrogen or an alkyl radical containing from 1 to 8 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 12 carbon atoms, characterized in that the perylene tetracarboxylic dianhydride is reacted
Figure imgf000005_0003
Figure imgf000005_0003
ou l'anhydride naphtaliqueor naphthalic anhydride
Figure imgf000005_0004
avec un composé de formule (III)
Figure imgf000005_0004
with a compound of formula (III)
R NH-CO-NH-R2 (III)R NH-CO-NH-R 2 (III)
dans laquelle R-i et R2, indépendamment l'un de l'autre, représentent l'hydrogène ou un radical alkyle renfermant de 1 à 6 atomes de carbone, un radical aryle renfermant de 6 à 10 atomes de carbone ou aralkyle renfermant de 7 à 10 atomes de carbone, ladite réaction étant réalisée en l'absence de solvant, puis l'on isole le composé de formule I désiré. Ri et R2, représentent particulièrement un radical alkyle. Lorsque Ri ou R2 représente un radical alkyle renfermant de 1 à 8 atomes de carbone, il s'agit d'un radical ramifié ou non, particulièrement d'un radical n-butyle ou n-propyle et de préférence un radical éthyle ou méthyle. Lorsque Ri ou R2 représente un radical aryle renfermant de 6 à 10 atomes de carbone, il s'agit de préférence d'un radical phényle. Lorsque Ri ou R2 représente un radical aralkyle renfermant de 7 à 12 atomes de carbone, il s'agit de préférence d'un radical phényléthyle ou benzyle. Dans des conditions préférentielles de mise en œuvre de l'invention, Ri et R2 ont la même signification. Dans d'autres conditions préférentielles de mise en œuvre de l'invention, Ri et R2 représentent un atome d'hydrogène ou un radical phényle. Selon un autre aspect préférentiel, Ri et R2, indépendamment, sont tous les deux différents de l'hydrogène. En particulier, Ri et R2 représentent un radical alkyle renfermant de 1 à 6 atomes de carbone ou un radical phényle. Dans d'autres conditions préférentielles de mise en œuvre de l'invention, la réaction est effectuée à une température supérieure ou égale à la température de fusion du composé de formule (III), par exemple à une température allant de 130°C à 320°C, notamment de 130°C à 280°C, de préférence de 150°C à 260°C, notamment de 180°C à 260°C, et particulièrement de 210°C à 260°C. Dans encore d'autres conditions préférentielles de mise en œuvre de l'invention, on met en œuvre de 1 à 20 moles, de préférence de 1 à 15 moles, notamment de 5 à 15 moles, particulièrement de 8 à 12 moles et tout particulièrement environ 10 moles de composé de formule (III) pour une mole de pérylène tétracarboxylique dianhydride ou d'anhydride naphtalique. Dans toujours d'autres conditions préférentielles de mise en œuvre de l'invention, on opère à la pression atmosphérique. L'isolation du composé de formule (I) obtenu peut être réalisée très simplement, par exemple par lavage dans un solvant approprié, de préférence à chaud, pour éliminer l'excédent du composé de formule (III). De manière générale, on peut opérer à température plus basse lors de la préparation de dérivés du 1 ,8-naphtalimide que lors de la préparation de ses formes polymères comme les dérivés du pérylène tétracarboxylique diimide. Le procédé objet de la présente invention est doué de nombreuses qualités. Il permet de préparer un produit de haute pureté, avec un rendement élevé, en utilisant seulement deux réactifs : le dianhydride et l'urée éventuellement substituée. En effet, on observe sur les spectres infra rouges des composés obtenus selon le procédé ci-dessus en particulier deux bandes d'absorption vers 1770-1780 cm"1 qui n'avaient jusqu'à présent pas été décrites sur les spectres des produits obtenus par les procédé antérieurs car leur intensité était bien trop faible par rapport au bruit de fond. Le procédé est rapide, et n'utilise pas de base alcaline. Avantageusement, le procédé n'utilise pas de solvant organique, tel que le nitrobenzène, le xylène ou le trichlorobenzène, qui sont des solvants aromatiques d'un coût élevé, toxiques et difficiles à éliminer. Au contraire, selon l'invention, l'urée utilisée comme solvant peut être éliminée facilement par lavage à l'eau puis séchage à l'étuve. Il ne se forme pas de forme leuco pendant le procédé et il est donc inutile d'avoir recours à une oxydation ultérieure. La réaction ne nécessite pas la présence d'un catalyseur et peut se faire à pression atmosphérique. La réaction qui se fait en une étape est effectuée selon le même protocole, que l'on cherche à obtenir un composé de formule (I) substitué ou non. Le composé de formule (I) obtenu est de grande pureté et trouve de ce fait son utilisation notamment comme colorant laser, comme photoconducteur et photorécepteur organique, en lithographie, en microélectronique et, après traitement, comme pigment. C'est pourquoi la présente demande a aussi pour objet un dérivé du pérylène tétracarboxylique diimide de formule (I) obtenu par la mise en œuvre du procédé ci-dessus décrit et un dérivé du pérylène tétracarboxylique diimide de formule I dont le spectre infra rouge est conforme à celui décrit dans les figures ci-après concernant les produits des exemples.in which Ri and R 2 , independently of each other, represent hydrogen or an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 10 carbon atoms, said reaction being carried out in the absence of solvent, then the desired compound of formula I is isolated. Ri and R 2 , represent in particular an alkyl radical. When R 1 or R 2 represents an alkyl radical containing from 1 to 8 carbon atoms, it is a branched radical or not, particularly an n-butyl or n-propyl radical and preferably an ethyl or methyl radical . When R 1 or R 2 represents an aryl radical containing 6 to 10 carbon atoms, it is preferably a phenyl radical. When R 1 or R 2 represents an aralkyl radical containing from 7 to 12 carbon atoms, it is preferably a phenylethyl or benzyl radical. Under preferential conditions for implementing the invention, Ri and R 2 have the same meaning. In other preferential conditions for implementing the invention, Ri and R 2 represent a hydrogen atom or a phenyl radical. According to another preferred aspect, Ri and R 2 , independently, are both different from hydrogen. In particular, Ri and R 2 represent an alkyl radical containing from 1 to 6 carbon atoms or a phenyl radical. In other preferred conditions for implementing the invention, the reaction is carried out at a temperature greater than or equal to the melting point of the compound of formula (III), for example at a temperature ranging from 130 ° C. to 320 ° C, in particular from 130 ° C to 280 ° C, preferably from 150 ° C to 260 ° C, in particular from 180 ° C to 260 ° C, and particularly from 210 ° C to 260 ° C. In yet other preferential conditions for implementing the invention, use is made of 1 to 20 moles, preferably from 1 to 15 moles, in particular from 5 to 15 moles, particularly from 8 to 12 moles and very particularly about 10 moles of compound of formula (III) for one mole of perylene tetracarboxylic dianhydride or naphthalic anhydride. In always other preferential conditions for implementing the invention, the operation is carried out at atmospheric pressure. The isolation of the compound of formula (I) obtained can be carried out very simply, for example by washing in an appropriate solvent, preferably hot, to remove the excess of the compound of formula (III). In general, it is possible to operate at a lower temperature during the preparation of derivatives of 1, 8-naphthalimide than during the preparation of its polymeric forms such as derivatives of perylene tetracarboxylic diimide. The process which is the subject of the present invention is endowed with numerous qualities. It makes it possible to prepare a high purity product, with a high yield, using only two reagents: dianhydride and optionally substituted urea. Indeed, one observes on the infrared spectra of the compounds obtained according to the above process in particular two absorption bands around 1770-1780 cm "1 which had hitherto not been described on the spectra of the products obtained by the previous processes because their intensity was far too low compared to the background noise. The process is rapid, and does not use an alkaline base. Advantageously, the process does not use an organic solvent, such as nitrobenzene, xylene or trichlorobenzene, which are aromatic solvents of high cost, toxic and difficult to remove, on the contrary, according to the invention, the urea used as solvent can be easily removed by washing with water and then drying with water. It does not form a leuco form during the process and therefore there is no need for further oxidation. The reaction does not require the presence of a catalyst and can be carried out at atmospheric pressure. The reaction which takes place in one step is carried out according to the same protocol, whether one seeks to obtain a compound of formula (I) substituted or not. The compound of formula (I) obtained is of high purity and therefore finds its use in particular as a laser dye, as an organic photoconductor and photoreceptor, in lithography, in microelectronics and, after treatment, as a pigment. This is why the present application also relates to a derivative of perylene tetracarboxylic diimide of formula (I) obtained by the implementation of the process described above and a derivative of perylene tetracarboxylic diimide of formula I whose infrared spectrum is in accordance with that described in the figures below concerning the products of the examples.
Les conditions préférentielles de mise en œuvre des procédés ci- dessus décrites s'appliquent également aux autres objets de l'invention visés ci- dessus, notamment aux dérivés de formule (I) obtenus par la mise en œuvre du procédé ci-dessus décrit. Les exemples qui suivent illustrent la présente demande.The preferential conditions for implementing the methods described above also apply to the other objects of the invention referred to above, in particular to the derivatives of formula (I) obtained by the implementation of the method described above. The following examples illustrate the present application.
Exemple 1 : Pérylène tétracarboxylique diimide On mélange dans un réacteur 2 g de pérylène tétracarboxylique dianhydride avec 4,6 g d'urée, on porte à la température de 175°C pendant 2 h. On isole le produit attendu.Example 1: Perylene tetracarboxylic diimide 2 g of perylene tetracarboxylic dianhydride are mixed in a reactor with 4.6 g of urea, the temperature is brought to 175 ° C. for 2 h. The expected product is isolated.
Exemple 2 : Pérylène tétracarboxylique diimide On mélange dans un réacteur 51 ,6 g de pérylène tétracarboxylique dianhydride avec 115 g d'urée, on porte à la température de 220°C en 30 min sous agitation puis on laisse la réaction se poursuivre pendant 90 min. On laisse refroidir à 80°C et on lave à l'eau chaude jusqu'à élimination complète de l'excès d'urée. Après séchage à l'étuve pendant 12 h, on isole 50,4 g du produit attendu, sous forme de poudre cristalline. Analyse élémentaireExample 2: Perylene tetracarboxylic diimide 51.6 g of perylene tetracarboxylic dianhydride are mixed in a reactor 51 with 115 g of urea, the mixture is brought to the temperature of 220 ° C. in 30 min with stirring and then the reaction is allowed to continue for 90 min. . The mixture is allowed to cool to 80 ° C. and is washed with hot water until the excess urea is completely eliminated. After drying in an oven for 12 h, 50.4 g of the expected product are isolated, in the form of crystalline powder. Elementary analysis
Calculé % C: 71 ,91 , H: 2,55, N: 7,14, O: 17,42 Obtenu % C: 73,80, H: 2,56, N: 7,18, O: 16,40 Le spectre infrarouge du produit obtenu est reproduit sur la figure 1. On observe sur ce spectre deux bandes d'absorption que l'on n'avait jusqu'à présent jamais pu observer sur les spectres du pérylène tétracarboxylique diimide obtenu par les procédé antérieurs (voir bandes aux environs de 1756 et 1716 cm"1 identifiées par une flèche sur la figure 1). Le spectre infrarouge du composé décrit par K. Akers et al. dans Spectrochimica Acta Vol. 44A, n° 11, pp. 1129-1135, 1988 est reproduit sur la figure 5 et celui récemment décrit par Takaaki Sakamoto et al dans J. Org. Chem. 2001 , 66, pp. 94-98 sur la figure 6.Calculated% C: 71, 91, H: 2.55, N: 7.14, O: 17.42 Obtained% C: 73.80, H: 2.56, N: 7.18, O: 16.40 The infrared spectrum of the product obtained is reproduced in FIG. 1. Two absorption bands are observed on this spectrum, which until now has never been observed on the spectra of perylene tetracarboxylic diimide obtained by the previous processes ( see bands around 1756 and 1716 cm "1 identified by an arrow in FIG. 1). The infrared spectrum of the compound described by K. Akers et al. in Spectrochimica Acta Vol. 44A, n ° 11, pp. 1129-1135 , 1988 is reproduced in FIG. 5 and that recently described by Takaaki Sakamoto et al in J. Org. Chem. 2001, 66, pp. 94-98 in FIG. 6.
Exemple 3 : N,N'-diméthyl pérylène tétracarboxylique diimide On mélange dans un réacteur 3,0 g de pérylène tétracarboxylique dianhydride avec 6,8 g de N,N'-diméthylurée, on introduit un faible quantité d'eau pour former une pâte et on porte à la température de 249°C pendant 2 h.Example 3: N, N'-dimethyl perylene tetracarboxylic diimide 3.0 g of perylene tetracarboxylic dianhydride are mixed in a reactor with 6.8 g of N, N'-dimethylurea, a small amount of water is introduced to form a paste and the temperature is brought to 249 ° C for 2 h.
On laisse refroidir et on élimine l'excès de diméthylurée par simple lavage à l'eau chaude. On isole 3,0 g du produit attendu sous forme de poudre cristalline. Le spectre infrarouge du produit obtenu est reproduit sur la figure 2. On observe sur ce spectre deux bandes d'absorption que l'on n'avait jusqu'à présent jamais pu observer sur les spectres du N,N'-diméthyl pérylène tétracarboxylique diimide obtenu par les procédé antérieurs (voir bandes aux environs de 1765 et 1732 cm"1 identifiées par une flèche sur la figure). Le spectre infrarouge du composé décrit par K. Akers et al. dans Spectrochimica Acta Vol. 44A, n° 11 , pp. 1129-1135, 1988 est reproduit sur la figure 7. Dans une variante, on a opéré de même, mais sans eau, à 180- 220°C. On a isolé un produit analogue. L'utilisation d'un peu d'eau permet cependant notamment une limitation des pertes d'urée avant le début de la réaction et limite les pertes en évitant l'adhérence des produits de la réaction aux parois.The mixture is allowed to cool and the excess dimethylurea is removed by simple washing with hot water. 3.0 g of the expected product are isolated in the form of a crystalline powder. The infrared spectrum of the product obtained is reproduced in FIG. 2. Two absorption bands are observed on this spectrum which, until now, have never been observed on the spectra of N, N'-dimethyl perylene tetracarboxylic diimide obtained by the previous processes (see bands around 1765 and 1732 cm "1 identified by an arrow in the figure). The infrared spectrum of the compound described by K. Akers et al. in Spectrochimica Acta Vol. 44A, n ° 11, pp. 1129-1135, 1988 is shown in Figure 7. In a variant, the same operation was carried out, but without water, at 180-220 ° C. A similar product was isolated. The use of a little water however makes it possible in particular to limit the losses of urea before the start of the reaction and limits the losses by avoiding the adhesion of the products of the reaction to the walls.
Exemple 4 : N,N'-diéthyl pérylène tétracarboxylique diimide On opère comme à l'exemple 3, sans eau, à partir de 1 g de dianhydride et 4,44 g de N,N'-diéthylurée pendant 1 h à 170°C. On isole 1 ,11 g du produit attendu sous forme de poudre cristalline. Le spectre infrarouge du produit obtenu est reproduit sur la figure 3.Example 4: N, N'-diethyl perylene tetracarboxylic diimide The procedure is as in Example 3, without water, from 1 g of dianhydride and 4.44 g of N, N'-diethylurea for 1 h at 170 ° C. . 1.11 g of the expected product are isolated in the form of a crystalline powder. The infrared spectrum of the product obtained is reproduced in FIG. 3.
Exemple 5 : N.N'-diphényl pérylène tétracarboxylique diimide On opère comme à l'exemple 3 en mélangeant 2,0 g de dianhydride et 10,55 g de N,N'-diphénylurée et une faible quantité d'acide acétique. On chauffe pendant 2 h à 249°C. Le lavage est effectué à l'aide d'acide acétique concentré et chaud. On isole 2,60 g du produit attendu sous forme de poudre cristalline. Le spectre infrarouge du produit obtenu est reproduit sur la figure 4. On observe sur ce spectre deux bandes d'absorption que l'on n'avait jusqu'à présent jamais pu observer sur les spectres du N,N'-diphényl pérylène tétracarboxylique diimide obtenu par les procédés antérieurs (voir bandes aux environs de 1770 et 1730 cm"1 identifiées par une flèche sur la figure). Le spectre infrarouge du composé décrit K. Akers et al. dans Spectrochimica Acta Vol. 44A, n° 11 , pp. 1129-1135, 1988 est reproduit sur la figure 8. Exemple 6 : 1 ,8-naphtalimide On mélange dans un réacteur 2 g de l'anhydride 1 ,8-naphtalique avec 3,0 g d'urée, et porte à la température de 175°C pendant 2 h. On lave à l'eau chaude et on isole le produit attendu.Example 5: N.N'-diphenyl perylene tetracarboxylic diimide The procedure is as in Example 3 by mixing 2.0 g of dianhydride and 10.55 g of N, N'-diphenylurea and a small amount of acetic acid. It is heated for 2 h at 249 ° C. Washing is carried out using concentrated and hot acetic acid. 2.60 g of the expected product are isolated in the form of a crystalline powder. The infrared spectrum of the product obtained is reproduced in FIG. 4. Two absorption bands are observed on this spectrum which, until now, have never been observed on the spectra of N, N'-diphenyl perylene tetracarboxylic diimide obtained by the previous processes (see bands around 1770 and 1730 cm "1 identified by an arrow in the figure). The infrared spectrum of the compound described K. Akers et al. in Spectrochimica Acta Vol. 44A, n ° 11, pp 1129-1135, 1988 is shown in Figure 8. Example 6: 1,8-naphthalimide 2 g of 1,8-naphthalic anhydride are mixed in a reactor with 3.0 g of urea, and brought to the temperature of 175 ° C. for 2 h. Wash with hot water and isolate the expected product.
Exemple 7: N-phenyl-1 ,8-naphtalimide Dans un réacteur, on mélange 2 g de l'anhydride 1 ,8-naphtalique (1.10 "2 M) avec 3,20 g de diphénylurée (1 ,5 10 "2 M), soit 3 fois la quantité stoechiométrique. Le four est mis à chauffer à 250-260 °C pendant 30 min. On introduit alors le réacteur dans le four et on le laisse 1 ,5 h sous agitation. Après refroidissement, on lave à froid le produit solide obtenu à l'éther anhydre. Une évaporation lente du filtrat contenant le produit désiré dans l'éther donne de beaux monocristaux brillants dont la maille cristalline mesurée par diffraction aux rayons X correspond à celle du N-phényl-1 ,8-naphtalimide publiée par Y. Dromzee et al. (Zeitschrift fur Kristallographie (1995), 210 (10), 760).Example 7: N-phenyl-1, 8-naphthalimide In a reactor, 2 g of the anhydride 1, 8-naphthalic (1.10 "2 M) are mixed with 3.20 g of diphenylurea (1, 5 10 " 2 M ), i.e. 3 times the stoichiometric quantity. The oven is heated to 250-260 ° C for 30 min. The reactor is then introduced into the oven and left for 1.5 h with stirring. After cooling, the solid product obtained is washed cold with anhydrous ether. Slow evaporation of the filtrate containing the desired product in ether gives beautiful shiny single crystals whose crystal lattice measured by X-ray diffraction corresponds to that of N-phenyl-1, 8-naphthalimide published by Y. Dromzee et al. (Zeitschrift fur Kristallographie (1995), 210 (10), 760).
Exemple 8: N-methyl-1.8-naphtalimide Dans un réacteur, on mélange 3 g de l'anhydride 1 ,8-naphtalique (1 ,5.10 "2 M) avec 2,73 g de diméthylurée (3,10 10 "2 M), soit 4 fois la quantité stoechiométrique. Le four est mis à chauffer à 280 °C pendant 30 min. On introduit alors le réacteur dans le four et on le laisse 45 min sous agitation à 260°C. On laisse refroidir légèrement et on ajoute quelques ml d'eau chaude juste après que le mélange se soit solidifié. On lave à chaud le produit avec un mélange de 12 ml d'acide chlorhydrique concentré dans100 ml d'eau puis on rince avec 150 ml d'eau chaude. On obtient 3,05 g de N-méthyl-1,8- naphtalimide. Example 8: N-methyl-1.8-naphthalimide In a reactor, 3 g of the 1,8-naphthalic anhydride (1, 5.10 "2 M) are mixed with 2.73 g of dimethylurea (3.10 10 " 2 M ), i.e. 4 times the stoichiometric quantity. The oven is heated to 280 ° C for 30 min. The reactor is then introduced into the oven and left for 45 min with stirring at 260 ° C. It is allowed to cool slightly and a few ml of hot water are added just after the mixture has solidified. The product is washed hot with a mixture of 12 ml of concentrated hydrochloric acid in 100 ml of water and then rinsed with 150 ml of hot water. 3.05 g of N-methyl-1,8-naphthalimide are obtained.

Claims

REVENDICATIONS
1. Procédé de préparation d'un composé de formule (!)1. Process for the preparation of a compound of formula (!)
Figure imgf000012_0001
Figure imgf000012_0001
ou de formule (I')or of formula (I ')
Figure imgf000012_0002
Figure imgf000012_0002
dans laquelle Ri et R2, indépendamment l'un de l'autre, représentent l'hydrogène ou un radical alkyle renfermant de 1 à 8 atomes de carbone, un radical aryle renfermant de 6 à 10 atomes de carbone ou aralkyle renfermant de 7 à 12 atomes de carbone, caractérisé en ce que l'on fait réagir le pérylène tétracarboxylique dianhydridein which Ri and R 2 , independently of each other, represent hydrogen or an alkyl radical containing from 1 to 8 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 12 carbon atoms, characterized in that the perylene tetracarboxylic dianhydride is reacted
Figure imgf000012_0003
Figure imgf000012_0003
ou l'anhydride naphtalique
Figure imgf000013_0001
or naphthalic anhydride
Figure imgf000013_0001
avec un composé de formule (III) R NH-CO-NH-R2 (III)with a compound of formula (III) R NH-CO-NH-R 2 (III)
dans laquelle Ri et R2, indépendamment l'un de l'autre, représentent l'hydrogène ou un radical alkyle renfermant de 1 à 6 atomes de carbone, un radical aryle renfermant de 6 à 10 atomes de carbone ou aralkyle renfermant de 7 à 10 atomes de carbone, ladite réaction étant réalisée en l'absence de solvant, puis l'on isole le composé de formule (I) désiré. in which Ri and R 2 , independently of each other, represent hydrogen or an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical containing from 6 to 10 carbon atoms or aralkyl containing from 7 to 10 carbon atoms, said reaction being carried out in the absence of solvent, then the desired compound of formula (I) is isolated.
2. Un procédé selon la revendication 1 , caractérisé en ce que Ri et R2 ont la même signification. 2. A method according to claim 1, characterized in that Ri and R 2 have the same meaning.
3. Un procédé selon la revendication 1 ou 2, caractérisé en ce que Ri et R2 représentent un atome d'hydrogène ou un radical phényle. 3. A method according to claim 1 or 2, characterized in that Ri and R 2 represent a hydrogen atom or a phenyl radical.
4. Un procédé selon la revendication 1 ou 2, caractérisé en ce que Ri et R2, indépendamment, sont tous les deux différents de l'hydrogène. 4. A method according to claim 1 or 2, characterized in that Ri and R 2 , independently, are both different from hydrogen.
5. Un procédé selon la revendication 4, caractérisé en ce que Ri et R2 représentent un radical alkyle renfermant de 1 à 6 atomes de carbone ou un radical phényle. 5. A method according to claim 4, characterized in that Ri and R 2 represent an alkyl radical containing from 1 to 6 carbon atoms or a phenyl radical.
6. Un procédé selon l'une des revendications 1 à 5 , caractérisé en ce que la réaction est effectuée à une température supérieure ou égale à la température de fusion du composé de formule (III). 6. A method according to one of claims 1 to 5, characterized in that the reaction is carried out at a temperature greater than or equal to the melting temperature of the compound of formula (III).
7. Un procédé selon l'une des revendications 1 à 6 , caractérisé en ce que la réaction est effectuée à une température allant de 130°C à 320°C. 7. A method according to one of claims 1 to 6, characterized in that the reaction is carried out at a temperature ranging from 130 ° C to 320 ° C.
8. Un procédé selon l'une des revendications 1 à 7 , caractérisé en ce que l'on met en œuvre de 1 à 15 moles de composé de formule (III) pour une mole de pérylène tétracarboxylique dianhydride ou d'anhydride naphtalique. 8. A method according to one of claims 1 to 7, characterized in that 1 to 15 moles of compound of formula (III) are used for one mole of perylene tetracarboxylic dianhydride or naphthalic anhydride.
9. Un procédé selon l'une des revendications 1 à 8 , caractérisé en ce que l'on opère à la pression atmosphérique. 9. A method according to one of claims 1 to 8, characterized in that one operates at atmospheric pressure.
10. Un procédé selon l'une des revendications 1 à 9 , caractérisé en ce que l'isolation du composé de formule I est réalisée par lavage dans un solvant approprié à chaud, pour éliminer l'excédent du composé de formule (III). 10. A method according to one of claims 1 to 9, characterized in that the isolation of the compound of formula I is carried out by washing in an appropriate solvent under hot conditions, to remove the excess of the compound of formula (III).
11. Un dérivé du pérylène tétracarboxylique diimide de formule (I) obtenu par la mise en œuvre du procédé tel que défini à l'une des revendications 1 à 1 0. 11. A derivative of perylene tetracarboxylic diimide of formula (I) obtained by the implementation of the process as defined in one of claims 1 to 1 0.
12. Un dérivé du pérylène tétracarboxylique diimide de formule (I) telle que définie à la revendication 1 dont le spectre infra rouge est conforme à celui décrit dans l'une des figures 1 à 4. 12. A derivative of perylene tetracarboxylic diimide of formula (I) as defined in claim 1, the infrared spectrum of which conforms to that described in one of FIGS. 1 to 4.
PCT/FR2005/000668 2004-03-19 2005-03-18 Method for producing perylene tetracarboxylic diimide derivatives WO2005097753A1 (en)

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