DE102012007529B4 - Imido-s-heptazine derivatives - Process for their preparation and their uses - Google Patents

Abstract

Imidio-s-heptazine derivatives represented by the formula (1): wherein Ra, Rb and Rc are independently indicated with the provisos that at least one of Ra, Rb and Rc is an imido radical, not the radicals -NH2 and -Cl are contained together and that the radicals R 1 and R 2 in the imido radical independently of one another are alkyl radicals, aryl radicals, phthal radicals, tetrafluorophthalene radicals, pyromellitrites

Description

The present invention relates to a novel, stable class of compounds of heptazine or tri-s-triazine derivatives [1], which are obtained by reacting carboxylic acid halides or anhydrides with melem (C ₆ N ₇ (NH ₂ ) ₃ ) and their Use as luminescent dyes, optical brighteners, laser dyes, components of optoelectronic components (eg OLEDs), homogeneous or heterogeneous (photo) catalysts, flame retardants, fire-extinguishing agents, plastic additives, or the like, and as starting material for further heptazine derivatives.

Amides derived from melem (C ₆ N ₇ ) (NH ₂ ) ₃ and imides, in particular triimides derived from phthalic acid and derivatives thereof, are hitherto unknown.

For the heptazine core - consisting of three fused s-triazine units ( shows the basic structural motif of the class of s-heptazines of melem, melon and the claimed here tri (imido) -, di (imido) - and mono (imido) -s-heptazine derivatives) - can be found in the Chemical Abstracts Registry File (Strukturfragment - or substructure research) 390 results [2]. An analogous structural formula search for "triimido-s-heptazine" derivatives, ie after the fragment C ₆ N ₇ [N (COR) ₂ ] ₃ gives no results, apart from those mentioned in theoretical work [3] and a patent specification [4] Trinitro compound C ₆ N ₇ (NO ₂ ) ₃ , which does not belong to the substance class according to the invention. Similarly, no results are obtained for the "monoimido-s-heptazine" derivatives (Comparisons ).

If one searches in the bibliographic part of the Chemical Abstracts databases, one finds a total of 533 references which refer to the s-heptazine fragment C ₆ N ₇ [5]. Among them are a large number of patents and patents relating to applications in the field of flame retardants, but also some recent evidence aimed at exploiting the optical, electronic and catalytic properties of s-heptazine derivatives.

With regard to possible use as flame retardants, for example, some phosphorus-containing heptazine derivatives [6] may be mentioned. In the Russian patent [6b] melem phosphate (C ₆ H ₆ N ₁₀ × H ₃ PO ₄ ) and Melempyrophosphat (C ₆ H ₆ N ₁₀ × H ₄ P ₂ O ₇ ) are described as "useful as fireproofing agents". In addition, melem phosphate (C ₆ H ₆ N ₁₀ × H ₃ PO ₄ ) is mentioned in a Japanese patent and claimed as a component for epoxy refractory formulations and electronic circuit adhesives [7]. Other typical applications are in the plastics, wood and textile industries. Many flammable materials are stabilized by flame-retardant additives. As flame-retardant additives many halogen-containing substances are still used today. These are harmful to health and pollute the environment. Therefore, they have been trying for a long time to replace them with halogen-free flame retardants. Melemphosphoranylidene [8] and silylcyamelurate are suggested [9].

Most s-heptazine derivatives are characterized by a very high temperature resistance to over 500 ° C in air. For example, the so-called cyamelurates, salts of cyameluric acid H ₃ [C ₆ N ₇ O ₃ ] are stable up to 550 ° C, while the closely related cyanuric salts M ₃ ¹ [C ₂ N ₃ O ₃ ] are much more unstable [10]. The same applies to melonates [C ₆ N ₇ (NCN) ^3- ] [11], s-heptazine chloride (cyameluric chloride) C ₆ N ₇ Cl ₃ [12], cyameluric acid amides [13] and melem [14] as well as by condensation from melem producible polymeric melon [15].

In addition to the particular thermal stability, the heptazine derivatives are characterized by further highly interesting and useful properties. For example, it has recently been discovered that certain melon and related materials are organic (photo) semiconductors [16, 17]. In addition, catalytic [18] and photocatalytic [16,19] activity could be detected. Because of their UV absorption properties and presumably because of further application-relevant characteristics of s-heptazine derivatives such as toxicological safety, solubility properties in aqueous and organic media, a large range of melem derivatives has been claimed as UV absorbers for sun creams [20]. Recently, a similar class of s-heptazine derivatives has been patented by Australian researchers for organic electroluminescent devices [21]. The company Merck patented s-heptazine derivatives for organic-electronic applications [22].

The compound melem C ₆ N ₇ (NH ₂ ) ₃ can be easily and in large quantities from inexpensive C / N / H compounds such as melamine C ₃ N ₃ (NH ₂ ) ₃ or dicyandiamide H ₂ N-CNH (NH) Generate CN by thermal aging [23].

It is therefore an object of the invention to provide novel compounds based on melem C ₆ N ₇ (NH ₂ ) ₃ .

bereitgestellt, wobei R_a, R_b und R_c unabhängig voneinander

-NH₂ oder Cl bedeuten mit den Maßgaben, dass mindestens ein Rest von R_a, R_b und R_c ein Imido-Rest ist, die Reste -NH₂ und -Cl nicht gemeinsam enthalten sind und dass die Reste R₁ und R₂ im Imido-Rest unabhängig voneinander Alkylreste, Arylreste, Phthalreste, Tetrafluorphthalreste, Pyromellitreste sind.According to the invention the object is achieved by the compounds listed in claim 1. There are imidio-s-heptazine derivatives represented by the formula (1):

provided, wherein R _a , R _b and R _c independently

-NH ₂ or Cl with the provisos that at least one radical of R _a , R _b and R _{c is} an imido radical, the radicals -NH ₂ and -Cl are not jointly contained and that the radicals R ₁ and R ₂ in the imido radical independently of one another are alkyl radicals, aryl radicals, phthal radicals, tetrafluorophthalene radicals, pyromellitrites.

Melem can be used as the starting compound for the novel class of compounds of the "triimido-s-heptazines". Attempts to synthesize the target compounds from phthalic anhydride or phthaloyl chloride in common organic solvents have not been successful. Only the use of special high-boiling solvents, in particular ortho-dichlorobenzene, decalin, nitromethane, xylene, or as solid phase reaction led to success. shows the synthesis of the inventive tri (imido) -s-heptazine derivatives of type 1.1 from a) melem and dicarboxylic acid anhydrites and b) from melem and dicarboxylic acid dichlorides. In addition to this route, a second, completely different way to represent the new substance class can be used. In this case, imides or their salts are reacted with s-heptazine chloride. shows the synthesis of the inventive molecular tri (imido) -s-heptazine derivatives of the type 1.1 from Cyamelursäurechlorid and dicarboxylic acid imide salts.

The imido-s-heptazine derivatives of the type 1.1a according to the invention are generally of molecular structure, stable in air and intensely yellow to colorless. Oligomers or polymers of type 1.1b can be prepared by reacting melem with pyromellitic anhydride or by reacting the imide salts of pyromellitic acid with cyameluric chloride. shows the preparation of polymeric tri (imido) -s-heptazine derivatives of the type 1.1b from a) melem and carboxylic acid derivatives, and b) from cyameluric chloride and imide salts.

In addition to the trifunctional imide derivatives, monofunctional and difunctional melem imides of the 1.2a and 1.3a types can also be prepared by adjusting the stoichiometry and the synthesis parameters. shows the basic structural motif of the class of s-heptazines of melem, melon and the claimed tri (imido), di (imido) and mono (imido) -s-heptazine derivatives. shows the representation of the molecular di (imido) -s-heptazine derivatives of the invention of the type 1.2a and mono (imido) -s-heptazine derivatives 1.3.aa) from melem and carboxylic acid derivatives and b) from Cyamelursäurechlorid and imide salts. In a manner similar to the abovementioned molecular compounds, oligomeric and polymeric compounds 1.2b and 1.3b can also be produced here, as in US Pat . and is shown. shows the representation of "dimeric" di (imido) -s-heptazine derivatives of the type 1.2b from a) melem and carboxylic acid derivatives and from b) cyameluric chloride and imide salts. shows the preparation of polymeric or oligomeric di (imido) -s-heptazine derivatives of the type 1.3b from melem and carboxylic acid derivatives and from Cyamelurchlorid and imide salts.

The invention is explained in more detail by means of the following examples: All reactions were carried out under protective gas (argon) with the standard Schlenk technique and z. T. also under atmospheric normal conditions.

Commercially available starting materials were used and dried according to the appropriate laboratory regulations. Heptazine chloride (cyameluric acid chloride) [12] and melem [23] were synthesized in accordance with the mentioned literature procedures.

Example 1:

Synthesis of 2,5,8-triphthalimido-tri-s-triazine starting from melem and phthaloyl dichloride variant 1

Under inert conditions, melem (3 g, 13.75 mmol) and phthaloyl dichloride (11.17 g, 55.03 mmol) in dry ortho-dichlorobenzene (200 mL) are refluxed for 22 h. After cooling to room temperature, the solid is separated and stirred in water (150 ml) for half an hour. After renewed separation of the solid and washing with ethanol, the crude product obtained is dried. An intensive Soxhlet extraction with nitromethane gives the desired imide as an intensely colored yellow solid as a 1: 1 adduct C ₆ N ₇ (C ₈ H ₄ NO ₂ ) ₃ CH ₃ NO ₂ . Fp> 300 ° C. IR (KBr): 3100, 3062, 2963 (v C _Ar H); 1804, 1742 (v C = O); 1618, 1610 (v _ass heptazine, v C = C _Ar); 1525 (v C = C _Ar ); 1470, 1329 (heptazine ring); 1395, 1112 (s, v CNC); 828, 812 (heptazine ring); 710 (δ C = O) cm ^-1 . C ₃₀ H ₁₂ N ₁₀ O ₆ , CH ₃ NO ₂ (669.54): calc .: C 55.61, H 2.26, N 23.01; Exp .: C 55.35, H 2.254, N 23.04%. ¹ H (DMSO-d ^6): δ = 8.06 - 7.96 (m, 12H, H-5, H-6); 4.41 (s, 3H, CH ₃ NO ₂ ) ppm. ¹³ C (DMSO-d ⁶ ): δ = 163.94 (C-3); 163.13 (C-2); 161.46 (C-1); 136.12 (C-6); 131.41 (C-4); 124.68 (C-5); 63.69 (CH ₃ NO ₂₎ ppm. ¹³ C CP / MAS NMR 166.2, 164.1, 161.9, 160.3 (C = O, C ₆ N ₇ ); 142.2, 138.1, 135.3, 131.4, 129.7, 127.2, 126.1, 123.4 (phenylene unit); 63.4 CH ₃ NO ₂ ) ppm. The UV / Vis spectrum ( ) of the compound in nitromethane shows a shoulder at 394 nm (ε = 314 l · mol ^-1 · cm ^-1 ) and a band at 413 nm (ε = 339 l · mol ^-1 · cm ^-1 ). shows the spectra of 2,5,8-triphthalimido-tri-s-triazine in nitromethane at 298 K, normalized to 1, absorption (dashed line) and emission (solid line). The fluorescence spectrum gives a signal at 487 nm.

Example 2:

Synthesis of 2,5,8-triphthalimido-tri-s-triazine starting from melem and phthaloyl dichloride variant 2

Under an argon stream, melem (3 g, 13.75 mmol) and phthaloyl dichloride (11.17 g, 55.03 mmol) are heated in an open flask to 190 ° C for 30 min. During the reaction, the HCl is driven out of the reaction mixture by the argon stream and the solid turns intense yellow. Cooling, washing with water and ethanol (10:90) and subsequent drying gives the corresponding product. Fp> 300 ° C. IR (KBr): 3102, 3060, 2961 (v C _Ar H); 1803, 1741 (v C = O); 1619, 1612 (v _ass heptazine, v C = C _Ar); 1525 (v C = C _Ar ); 1471, 1328 (heptazine ring); 1394, 1111 (s, v CNC); 826, 810 (heptazine ring); 712 (δ C = O) cm ^-1 .

Example 3:

Synthesis of 2,5,8-tri (2,3,4,5-tetrafluorophthalimido) tri-s-triazine starting from melem and tetrafluorophthalic anhydride variant 2

Melem (0.33 g, 1.5 mmol) and tetrafluorophthalic anhydride (1 g, 4.5 mmol) are heated in an open flask to 190 ° C for 12 min. During the reaction, the water is driven out of the reaction mixture and the solid turns pale yellow. Cooling, washing with water and ethanol (10:90) and subsequent drying gives the corresponding product.

The irradiation with daylight shows as well as the irradiation with UV light strong photoluminescence in the blue range.

Example 4:

Reaction of melem and pyromellitic anhydride variant 2

Melem (3 g, 13.75 mmol) and pyromellitic anhydride (12 g, 55.03 mmol) are heated in an open flask at 190 ° C for 12 min. During the reaction, the water is driven out of the reaction mixture and the solid turns yellow. Cooling, washing with water and ethanol (10:90) and subsequent drying gives the corresponding product.

The irradiation with daylight shows as well as the irradiation with UV light strong photoluminescence in the blue range.
IR (KBr): 3094 (v C _Ar H); 1803, 1741 (v C = O); 1620, 1611 (v _ass heptazine, v C = C _Ar); 1523 (v C = C _Ar ); 1470, 1331 (heptazine ring); 1397, 1115 (s, v CNC); 826, 797 (heptazine ring); 712 (δ C = O) cm ^-1 . Exp .: C 51.39, H 2.808, N 21.86%.

Literature:

• [1] Synonyms: Tri-s-triazine, sym-heptazine, s-heptazine, heptazine, 1,3,4,6,7,9,9b-heptaaza-phenalene, 1,3,4,6,7,9 -hexaazacycl [3.3.3] azine or cyamelurin.
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Claims (10)

Imidio-s-heptazine derivatives represented by the formula (1):

wherein R _a , R _b and R _c independently

with the provisos that at least one radical of R _a , R _b and R _{c is} an imido radical, the radicals -NH ₂ and -Cl are not jointly contained and that the radicals R ₁ and R ₂ in the imido radical is independent alkyl radicals, aryl radicals, phthal radicals, Tetrafluorphthalreste, Pyromellitreste are Process for the preparation of imido-heptazine derivatives according to formula (1) by reacting melem with carboxylic acid halides. Process for the preparation of imido-heptazine derivatives according to the formula (1) by reacting melem with carboxylic acid anhydrides. Process for the preparation of imido-heptazine derivatives according to the formula (1) by reacting heptazine chloride (cyameluric acid chloride) with one or two chlorine atoms on the C ₆ N ₇ unit with carboxylic acid imides or salts of carboxylic acid imides. Use of the imido-heptazine derivatives according to the formula (1) for the preparation of further s-heptazine derivatives. Use of the imido-heptazine derivatives according to the formula (1) as flame retardants for plastics, textiles, wood products, paper, cardboard, plastering, insulating materials and building material composites. Use of the imido-heptazine derivatives according to the formula (1) for the production of materials in which optical, acoustic, magnetic or (opto) electronic properties are harnessed. Use of the imido-heptazine derivatives according to the formula (1) for the preparation of luminescent dyes, optical brighteners, laser dyes and electroluminescent materials. Use of the imido-heptazine derivatives according to the formula (1) for the preparation of OLEDs (Organic Light Emitting Diodes). Use of the imido-heptazine derivatives according to the formula (1) for the preparation of (photo) catalytically active materials or material components (heterogeneous catalysis) and for the preparation of homogeneous (photo) catalysts.

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