RU2084455C1 - Dibenzo(b,e)-pyrano(3,2-b)-benzopyrilium salts and method of their synthesis - Google Patents

Abstract

FIELD: organic chemistry and technology. SUBSTANCE: product: compounds of the general formula (I)

where: R₁= - hydrogen or halogen atom, C₁-C₆-alkyl, C₁-C₆-alkoxy or nitro-group; R₂ - hydrogen or halogen atom or allyl; R₃= - hydrogen atom, C₁-C₆-alkyl, C₁-C₆-alkoxy, di-(C₁-C₆)-alkylamino or nitro-group; R₄ - halogen atom; R₅, R₆-C₁-C₆-alkyl.Methodofsynthesisinvolvesinteractionof2-R₄-5,5--R₅, R₆-cyclohexene-1,3-diones with salicylic aldehyde or its substituted derivatives in the presence of perchloric acid and triethyl-ortho-formate. Given: N; R₁, R₂, R₃, R₄, R₅, R₆; yield (%); m. p. (C); UV-spectrum (L max - E, nm): 1a; H, H, H, Br; CH₃; CH₃; 55.1; 308-310; 548.2-33.51. 1b; CH₃,, H, H, Br; CH₃,; CH₃;; 43.6; 305-307; 555.6-82.78. 1c; H, CH₃,, CH₃,, Br; CH₃; CH₃;; 41.0; 303-305; 563.1-40.11. 1d; OCH₃, H, H, Br; CH₃,; CH₃;; 53.5; 307-309; 573.4-85.61. 1e; NO₂,, H, H, Br; CH₃,; CH₃;; 54.5; 342-344; 548.2-57.57. 1f; Cl, H, H, Br; CH₃; CH₃; 51.8; 322-324; 553.1-87.65; 1g; Br, H, H, Br; CH₃,; CH₃; 63.2; 301-304; 555.6-102.17. 1h; Br, Br, H, Br; CH₃,; CH₃;; 69.0; 341-343; 558.0-44.92. 1i; Br, Br, OCH₃,, Br; CH₃,; CH₃;; 42.5; 345-347; 573.4-113.65. 1j; H, CH₂OH=CH₂,, H, Br; CH₃,; CH₃;; 87.2; 219-220; 550.7-105.13. 1k; CH₃,, H, NO₂,, Br; CH₃,; CH₃;; 45.7; 348-350; 553.1-90.34. 1l; H, H, N(CH₃)₂, Br; CH₃,; CH₃;; 41.4; 318-320; 698.3-81.72. Synthesized compounds exhibit high spectral properties and can be used as fluorescent dyes for anion-modified fibers and films staining. EFFECT: improved method of synthesis, enhanced quality and properties. 2 cl, 2 tbl

Description

где R₁ атом водорода или галогена, C₁-C₆ алкил, C₁-C₆ алкокси или нитро-группа;
R₂ атом водорода или галогена или аллил;
R₃ атом водорода, C₁-C₆ алкил, C₁-C₆ алкокси-, ди(C₁-C₆)алкил-амино- или нитро-группа;
R₄ атом галогена;
R₅, R₆ C₁-C₆ алкил;
которые проявляют флуоресцентные свойства и могут быть использованы как флуоресцентные красители для крашения аниономодифицированных волокон и пленок, и способу их получения.The invention relates to previously undescribed dibenzo [b; e] pyrano [3,2-b] -1-benzopyrilium perchlorates of the general formula (I),

where R _{1 is} a hydrogen or halogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or nitro group;
R _{2 is} a hydrogen or halogen atom or allyl;
R _{3 is} a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, di (C ₁ -C ₆ ) alkyl amino or nitro group;
R _{4 is} a halogen atom;
R ₅ , R ₆ C ₁ -C ₆ alkyl;
which exhibit fluorescent properties and can be used as fluorescent dyes for dyeing anion-modified fibers and films, and the method for their preparation.

где R₁, R₂ атомы водорода или галогена, C₁-C₆ алкил, используемые в качестве флуоресцентных красителей для крашения аниономодифицированных волокон и пленок (DOS 2942931 (1980), BASF Erf. R.Schidt, V.Koch; C.A. 117065 (1980)).Dibenzo [b; e] pyrano [3,2-b] -1-benzopyrilium salts of the general formula (IIa, b) are known,

where R ₁ , R ₂ are hydrogen or halogen atoms, C ₁ -C ₆ alkyl, used as fluorescent dyes for dyeing anion-modified fibers and films (DOS 2942931 (1980), BASF Erf. R. Schidt, V. Koch; CA 117065 ( 1980)).

Compounds (II) have L _max (nm): 11a -549 (R ₂ H, R ₁ Br); 11b 552 (R ₁ R ₂ Br). The extinction coefficient (E) and the data of the luminescence spectra (quantum yield) are not given.

The method of obtaining compounds (IIa, b) consists in the interaction of the sodium salt of 2-methyldimedone (IV), previously obtained by deprotonation of 2-methyldimedone (III) with sodium hydride in a nitrogen atmosphere at ^o C in excess GMF, further processing with butyl lithium at 20 ^o C, heating with the sodium salt of salicylic aldehydes Va, b in excess of hexametapol, as well as with perchloric acid.

Vа,б; IIа,б:а R₁ Br, R₂ H; б R₁ R₂ H
Недостатком способа является многостадийность процесса, необходимость проведения первой стадии процесса в инертной атмосфере и при 0^oC, использование пожароопасных реагентов (гидрид натрия, бутиллитий) и растворителей (гексан), использование большого количества (до 500 г на 5 г целевого продукта) гексаметапола, низкие выходы целевого продукта (10-15%), невозможность получения соединений с R₄= галоген, так как при введении в реакцию соответствующих 2-галогендимедонов, они разлагаются под действием гидрида натрия и/или бутиллития, и не дают в конце реакции целевой продукт общей формулы I (где R₄=галоген).

Va, b; IIa, b: a R ₁ Br, R ₂ H; b R ₁ R ₂ H
The disadvantage of this method is the multi-stage process, the need for the first stage of the process in an inert atmosphere and at 0 ^o C, the use of fire hazardous reagents (sodium hydride, butyl lithium) and solvents (hexane), the use of a large amount (up to 500 g per 5 g of the target product) of hexametapol, low yields of the target product (10-15%), the impossibility of obtaining compounds with R ₄ = halogen, since when the corresponding 2-halogenatedones are introduced into the reaction, they decompose under the action of sodium hydride and / or butyl lithium and do not give the reaction of the target product of General formula I (where R ₄ = halogen).

The aim of the invention are new compounds of the series of dibenzo [b, e] -prano [3,2-b] -1-benzopyrilium salts having high spectral characteristics, having, in comparison with known compounds of this series (DOS 2942931, (1980), BASF, Erf. R. Schmidt, V. Koch; CA 95, 117065 (1980)) absorption of l _max in the longer wavelength region of the UV spectrum and a high extinction coefficient sufficient to be used as fluorescent dyes for dyeing anion-modified fibers and films similar to those used for this purpose, the described compounds of General formula IIa, b (compounds Izh, h, which are R ₄ -bromosubstituted analogues of the described compounds of formula IIa, b according to the UV spectrum have: Izh - l _max 555.6 nm; IIa l _max 549.0 nm; 1z l _max 558, 0 nm; IIb l _max 552.0 nm, respectively), as well as the method for their preparation.

The goal is achieved by compounds I, as well as by the fact that in the known method for producing compounds of the dibenzo [b, e] pyrano [3,2-b] -1-benzopyrilium salt series, comprising reacting substituted salicylic aldehydes with substituted 2-R ₄ -5, 5-R ₅ , R ₆ -cyclohexane-1,3-dione in the presence of perchloric acid, the difference is that, as substituted salicylic aldehydes, compounds of the general formula VII are used, as 2-R ₄ -5,5-R ₅ , R ₆ -cyclohexane-1,3-diones, compounds of general formula VI, and the process is conducted in the additional presence trietilortofo Miata.

The method of obtaining compounds 1A-m is that 2-R ₄ -5,5-R ₅ , R ₆ -cyclohexane-1,3-dione of general formula VI, where R have the above meanings, are reacted with substituted salicylic aldehydes of general formula VII, where R have the above meanings in the presence of perchloric acid and triethyl orthoformate. The latter is taken in excess sufficient to absorb water released as a result of the reaction, and water contained in perchloric acid.

Соединения I, а также способ их получения обладают изобретательским уровнем, так как наличие высоких флюоресцентных характеристик у соединений I, а также возможность их получения в присутствии триэтилортоформиата и хлорной кислоты в столь мягких условиях является неочевидными.

Compounds I, as well as the method for their preparation, have an inventive step, since the presence of high fluorescence characteristics of compounds I, as well as the possibility of their preparation in the presence of triethyl orthoformate and perchloric acid under such mild conditions, are not obvious.

 The combined effect of triethylorthoformate and perchloric acid on a mixture of o-hydroxybenzaldehydes and cyclic 1,3-diketones (in particular, dimedones) was previously studied.

 It is known that under the action of triethyl orthoformate and perchloric acid on o-hydroxyalkones (VIII), 4-ethoxy flavilium (XI) perchlorates are formed.

(Дорофеенко Г.Н. Ткаченко В.В. ЖОрХ, 10,2188-2191, 1972).

(Dorofeenko G.N. Tkachenko V.V. ZhORKh, 10.2188-2191, 1972).

 The effect of triethylorthoformate and perchloric acid on ketones of the aromatic fatty series (X) was also studied. It was found that the reaction cannot be stopped at the monoadduct stage of the ketone and triethyl orthoformate (XI) and, as a result of the condensation of two ketone molecules with the orthoester, 1,5-diketone (XII) is formed, which cyclizes during the reaction to the pyrilium cation (XIII).

(Дорофеенко Г.Н. Межерицкий В.В. Олехнович Е.П. Вассерман А.Л. ЖОрХ, 9, 395, 1973).

(Dorofeenko G.N. Mezheritsky V.V. Olehnovich E.P. Wasserman A.L. ZhORKh, 9, 395, 1973).

 1,3-diketones (XIV) not containing terminal methyl groups under the action of triethyl orthoformate and perchloric acid form 1,3-diethoxy propenium cations (XV).

(Олехнович Е.П. Корбка И.В. ЖОрХ, 26, 213-214, 1990).

(Olehnovich E.P. Korbka I.V. ZhORKh, 26, 213-214, 1990).

 The effect of triethylorthoformate and perchloric acid on a mixture of o-hydroxybenzaldehydes and cyclic 1,3-diketones is not described.

Below are examples of the preparation of compounds 1a-m, their constants (R ₁ -R ₆ , melting points, elemental analysis and spectral characteristics) are given in tables 1 and 2.

Example 1. Obtaining perchlorate 6-bromo-13,13-dimethyl-13H (dibenzo [b, e] pyrano) [3,2-b] benzopyrilium (1a). The reaction mixture in a ratio of 2.2 g (0.001 mol) of 2-bromo-5,5-dimethylcyclohexane-1,3-dione (2-bromodimedone), 2.5 g (0.02 mol) of salicylic aldehyde, 20 ml of triethylorthoformate and 1 ml of 70% perchloric acid was incubated for 1 h. The precipitated crystals were filtered off and washed on the filter with ethyl acetate (2 times 5 ml) and ether (2 times 5 ml). Yield: 4.8 g (55.1%); Mp> 300 ^° C (from nitromethane; at 310 ^° C decomposition). Elemental analysis data and spectral characteristics are shown in Table 1.

 Compounds 1b-d, f, g were obtained without heating the reaction mixture similarly to compound 1a (example 1).

 Example 2. Obtaining perchlorate 2,2-dinitro-6-bromo-13,13-dimethyl-13H (dibenzo [b, e] pyrano) [3,2-b] benzopyril (1e).

To 2.2 g (0.01 mol) of 2-bromo-5,5-dimethylcyclohexane-1,3-dione and 3.4 g (0.02 mol) of p-nitrosalicylic aldehyde are added 20 ml of triethylorthoformate, 1 ml of 70% perchloric acid and heat the reaction mixture until boiling begins (about 60 ^o C). It is kept at this temperature for 5 minutes, cooled to room temperature, and after 1 hour, the released red-brown crystals are filtered off. Washed on a filter with ethyl acetate and ether, as in Example 1. Yield: 2.0 g (54.5%); Mp> 300 ^° C (from nitromethane).

Compounds 1z-m were obtained by briefly heating the reaction mixture before boiling (about 60 ^° C) similarly to compound 1e (example 2).

All described compounds (1a-m) were obtained with a yield of 50-90%
All described compounds (1a-m) in a solution of polar solvents (chloroform, nitromethane, acetonitrile, etc.) have intense orange-red fluorescence. Fluorescence characteristics (data from the UV spectra of compounds 1a-m, which prove the possibility of using compounds 1a-m as fluorescent dyes for anion-modified fibers, are given in Table 2.

 Thus, compounds I are obtained in higher yield (50-90%) and in a simpler way than the method for producing compounds II, which in turn can also be obtained by the proposed method. Compounds 1a-m have sufficiently high fluorescence characteristics sufficient to allow the use of these compounds as fluorescent dyes for dyeing anion-modified fibers. Compound 1k is an allyl derivative capable of photo- and electropolymerization and copolymerization, which makes it possible to synthesize polymer phosphors based on it.

Claims (2)

1. Dibenzo (c, f) pyrano (3,2-c) -benzopyrilium salts of the general formula I

where R _{1 is} a hydrogen or halogen atom, C ₁ C ₆ is alkyl, C ₁ C ₆ alkoxy or nitro;
R _{2 is} a hydrogen or halogen atom or allyl; R _{3 is} a hydrogen atom; C ₁ C ₆ alkyl; C ₁ C ₆ alkoxy; di (C ₁ C ₆ ) alkylamino or nitro;
R _{4 is} a halogen atom;
R ₅ and R ₆ C ₁ C ₆ alkyl. 2. A method of producing dibenzo (c, e) pyrano (3,2-c) 1-benzopyrilium salts of the general formula I

where R _{1 is} a hydrogen or halogen atom, C ₁ C ₆ is alkyl, C ₁ C ₆ alkoxy or nitro;
R _{2 is} a hydrogen or halogen atom or allyl;
R _{3 is} a hydrogen atom, C ₁ C ₆ alkyl, C ₁ - C ₆ alkoxy, di (C ₁ C ₆ ) alkylamino or nitro;
R _{4 is} a halogen atom;
R ₅ and R ₆ C ₁ C ₆ alkyl,
characterized in that 2-R ₄ -5,5-R ₅ , R ₆ -cyclohexane-1,3-dione of formula VI

where R ₄ , R ₅ and R ₆ have the above meanings,
subjected to interaction with salicylic aldehyde or its substituted General formula VII

where R ₁ , R ₂ and R ₃ have the above meanings,
in the presence of perchloric acid and triethyl orthoformate.

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