CS271506B1 - 5-substituted and 4,5,-disubstituted-2-2-azoarene furan hydrobromides or hydrogen perchlorates and method of their preparation - Google Patents

Abstract

The solution concerns new 5-Substituted and 4.5-disubstituted 2-azoarenfuran-hydrobromides and hydrogen perchlorates of the formula I, where Ar is nitrophenyl, 4-acetamidophenyl, R<1> is hydrogen, brome, 1-phenyl-1-methoxymethyl, NR<2>R<3> is dialkylamino-group C1 to C3, morpholino group and X is Br or C1O4. The method of their production consists of the fact that the vinamidinium salts of furan of formula II, where R, NR<2>R<3> and X have the above mentioned meaning, are treated with arenediazonium sulfates of the general formula III, where Ar has the above mentioned meaning, in water at a temperature of 10 to 20 degrees C. The substances are analogues of vinamidinium salts that are a synthetic intermediate product for the production of biologically effective pyridarine derivates and for the preparation of synthetic colour agents and superficially active agents.<IMAGE>

Description

(57) The invention relates to novel 5-substituted and 4,5-disubstituted 2-azoarfenofuran hydrobromides and hydrogen perchlorates of formula I, wherein Ar is nitrophenyl, 4-acetamidophenyl, R1 is hydrogen, bromo, 1-phenyl-1-methoxymethyl, NR ² R ³ is a dialkylamino group C to C, morpholino, and X is Br or C 10. The preparation of these is based on the furamidine vinamidinium salts of formula II, wherein R, NR 1, R 3 and χ are as defined above, The compound of formula III, wherein Ar is as defined above, is treated with water in a temperature of 10 to 20 ° C. The substances are analogues of vinamidinium salts, which are a synthetic intermediate for the preparation of biologically active pyridarine derivatives and for the preparation of synthetic dyes and surfactants.

and

CS 271506 31

Л / / - /

N. HSO A 4

Ar / Ш /

CS 271 506 Bl

The present invention relates to 5-substituted and 4,5-disubstituted 2-azoarenfuran hydrobromides, respectively. -hydrogen perchlorates of the formula I

wherein Ar is nitrophenyl, 4-acetamidophenyl, is hydrogen, bromo, 1-phenyl-1-methoxymethyl,

NR ² R ³ is di-C ^ ^ až.C, morpholino а X is Br or C1O ₄ and their preparation.

Of similar compounds, the preparation of 5- (N, N-dimethylamino) -2-azoarenfuran hydrochloride is described in the literature, wherein the arene is benzene, 4-methoxybenzene, 4-nitrobenzene, by reaction of 5- (N, N-dimethylamino) -2- furaldehyde and arendiazonium chlorides / Chim. Geterosikl. Soedin. 1324 (1974) and 4-N (N, N-dimethylamino) -azoarenbenzenes, by reaction of 4- (N, N-dimethylamino) -benzaldehyde and arendiazonium salts (2). Org. Chim. 24, 1233 (1954).

The process for the preparation of the substances according to the invention consists in

wherein R 1, NR ² R ² and X are as defined above, are treated with arendiazonium sulphates in water at a temperature of 10 to 20 ° C.

Arendiazonium sulfates are prepared in situ by diazotizing the appropriate aniline in sulfuric acid and water with sodium nitrite at 0-5 ° C.

An advantage of the process for the preparation of the compounds according to the invention is the one-step synthesis starting from the furanamidinium salts which are intermediates in the preparation of the respective

5- (N, N-dialkylamino) -2-furaldehydes / Chim. Geterosikl. Soedin. 586 (1969), Sollect. Czech. Chem. Commun. 49, 1600 (1984)] and 4-substituted 5- (N, N-dialkylamino) -2-furancarbaldehydes (Collect.). Czech. Chem. Commun. 50, 675 (1985)] and the possibility of preparing a wide variety of 5-substituted and 4,5-disubstituted-2-azoarenofuran hydrobromides, respectively. -hydrogénperchlorátov. The compounds of the invention are aza analogues of vinamidinium salts, which are synthetic intermediates for the preparation of biologically active pyridazine derivatives and for the preparation of furan-type synthetic dyes and surfactants due to the increased reactivity to the nucleophilic agents at the 5-position of the furan nucleus.

Example 1

5 / N, N-Dimethylamino / 2-azo / 4-acetaminobenzén / furan hydrobromide

A solution of 5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylammonium bromide (1.6 g) in 10 ml of water was added with stirring over a period of 10 min at 0-5 ° C. Of 4-acetaminobenzenediazonium sulfate in water, which was prepared in situ by diazotization (1.1 g) of 4-aminoacetanilide in solution (0.84 ml) of concentrated sulfuric acid and (6 ml)

CS 271 506 B1 water with sodium nitrite (0.5 g) in 3 ml water at 0 ° C. The reaction mixture was allowed to stand overnight in the refrigerator. A violet solid formed which was filtered off with suction and washed with water. Crystallize in acetic acid-water (95: 5). . Yield 55%. MP: Mp 240-246 ° C.

^C i4 to i7 ^{H BrN} 4 ° 2 ° ⁱⁿ yP read: 17% N, 24.29% Br Found: 16.85% N, 24.32% Br.

NMR Spectrum (measured in DMSO-d6): 11.52 (s, 1H, NH), 9.98 (s, 1H, NH), 7.95 (d),

J = _5.2 Hz, 1H, H ( _furan ). 7.57 / d, J = 9 Hz, 2H, H _benzene // 7.48 / d, J = 5.2Hz, 1H, ^H 4furan ^Z ' ^{7.28 Zd} ' ^{J = 9Hz} ' ^2H ' ^H Benzene ^Z ' ^{3.52 Zs ( 3H,} CH3), 3.45 ^Zs ( ^3H, CH3 ⁾ .

1.97 (s, 3H, CH3). UV spectrum (measured in acetone): 483 nm (λ _max ) · 3.44 (log 4).

Example 2

5- (N, N-D.methylamino) -2-azo- (3-nitrobenzene) furan hydrobromide

A solution of 5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bromide (1.6 g) in 10 ml of water was added with stirring over a period of 5 min. At a temperature of 10-15 ° C. Of 3-nitrobenzene diazonium sulfate in water, which was prepared in situ by diazotization (1 g) of 3-nitroaniline in solution (0.84 ml) of concentrated sulfuric acid and 6 ml of water (0.5 g) of sodium nitrite in 3 ml water at 0 ° C. The reaction mixture was stirred at room temperature for 2 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water (95: 5); Yield 93%. T. t. Mp 241-245 ° C. For C ₂ ^H 4 ^BrN j3 ° 3 Calculated: 16.42% N, 23.44% Br Found: 16.02% N, 23.31% Br.

NMR / measured in DMSO-d /: 11.81 / s, 1 H, NH /, 8.05 / d, J = 5.2 Hz, 1 H, ^{н з} п ^ £ ^{иг? //} 7.88 / m, 4H, Hbenzene], 7.65 (d, J = 5.2 Hz, 1H, H 4 _-furan ), 3.6 (s), 2H, CH ₃ /, 3.5 / s, 3H,

CH -> /. UV spectrum (measured in acetone): 432 nm (L), 3.05 (log).

J ΙΐΐαΧ t /

Example 3

5-Morpholino-2-azo / 4-nitrobenzene / furan hydrobromide

To a solution (2.09 g) of 5-morpholino-2-furfurylidene-N-morpholinium bromide in 15 ml of water is added a solution of 4-nitrobenzenediazonium sulphate in water over 20 minutes at 0-5 ° C, with stirring, which was prepared in situ by diazotization (1 g) of 4-nitroaniline in solution (0.84 ml) of concentrated sulfuric acid and 6 ml of water (0.5 g) of sodium nitrite in 3 ml of water at 0 ° C. The reaction mixture was stirred at room temperature for 2 h. Standing in the refrigerator overnight a solid precipitated which was aspirated and washed with water. Crystallize from acetic acid-water (95: 5). Yield 66%. T. t. 205-209 ° C. For ₅ BrN ₄ O _4, calculated: 14.62% N, 20.86% Br Found: 14.43% N, 19.30% Br.

³ H-NMR / DMSO-measured in _dg / 11.27 / s, 1 H, NH /, 7.83 / d, J = 9 Hz, 2H, H _{of benzene} /.

7.66 (d, J = 5.4 Hz, 1H, H 3 _-furan ). 7.40 (d, J = 9 Hz, 2H, H at the _base ), 6.68 (d, J = 5.4 Hz),

Example 4

4- / l-phenyl-l-methoxy / methyl-5- / N, N-dimethylamino / 2-azo / 4-nitrobenzene / furan-hydrogénperchlorát

To a suspension of (2.2 g) 4- (1-phenyl-1-methoxy) methyl / -5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium perchlorate in 10 ml of water was stirred with stirring a solution of 4-nitrobenzenediazonium sulfate in water, which was prepared in situ by diazotization (0.5 g) of 4-nitroaniline in solution (0.42 ml) of concentrated sulfuric acid and 6 ml of water, was added over a period of 20 min. sodium nitrite (0.25 g) in 3 mL of water at 0 ° C. The reaction mixture is stirred for 3 h at room temperature. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water (95: 5). Yield 87%. T. t. Mp 140-145 ° C.

NMR Spectrum (measured in DMSO-d6): 11.34 (s, 1H, NH), 7.89 (d, J = 9 Hz, 2H, H.). ], benzene

CS 271 506 B1

7.66 (s, 1H, H 3 _-furan ), 7.20 Zs, 5H, _benzene H, δ 61 (d, J = 9 Hz, 2H, H 2 O), 5.20 (s, 1H, N); 3.19 (s, 3H, CH3 ⁾ , 2.56 (s, 3H, CH3 ⁾ , 2.45 (s, 3H, CH3 ⁾ . UV spectrum / measured in acetone / 456 nm / Д / _max / ^{3 '40} / I, 5 ° 9 / · ^{C for} 20 ^H 21 ^CIN 4 ° ^to 8 ° yp ^read: * ^N

Cl, 7.57. Found: N, 11.3; Cl, 7.62.

Example 5

4-Bromo-5 / N, N-dimethylamino / 2-azo / 3-nitro-benzene / furan-hydrogénperchlorát

To a solution of (1 g) 4-bromo-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium perchlorate in 15 ml of water was stirred for 10 min at 0-10 ° C. add a solution of 3-nitrobenzenediazonium sulfate in water which was prepared in situ by diazotization (0.5 g) of 3-nitroaniline in solution (0.42 ml) of concentrated sulfuric acid and 6 ml of water with sodium nitrite (0.25 g) in 3 ml water at 0 ° C. After stirring for 2 h, the precipitated solid was filtered off with suction and washed with water. Crystallize from acetic acid-water (95: 5). Yield 76%. T. t. Mp 170-178 ° C. NMR Spectrum (measured in DMSO- d 6): 11.76 (s, 1H, NH), 7.56 (m, 4H, _benzene H), 7.02 (s, 1H _furan ), 2.62 (s), 3H, CH3 ₎ , 2.45 (s, 3H, CH3), 2.45 (s, 3H, CH3). UV spectrum (measured in acetone): 450 nm ( _max ) 3.65 (log). For ^C ₁₂ ^H 12 ^C2BrN 4 ° 7 N Calculated 12.75%, 18.2% Br, 7.9% Cl; found: 13.02% N, 26.4% Hal.

Claims (2)

OBJECT OF THE INVENTION 1. 5-Substituted and 4,5-disubstituted 2-azoarenofuran hydrobromides respectively. -hydrogen perchlorates of the formula I wherein Ar is nitrophenyl, 4-acetamidophenyl, R ² is hydrogen, bromo, 1-phenyl-l-methoxymethyl, 2 3 NR R is C 1-4 -C 6 dialkylamino, morpholino and X is Br or Cl 10. 2. A process for preparing compounds of the formula I defined in claim I, characterized in that the furan všeobený vinamidínové salt of formula II wherein R ^1, NR ² R ³ and N are as defined above, the arendiazonium sulphate of formula (III) is used. Ar - N HSO of 4 wherein Ar is as defined above (III) in water at a temperature of 10 to 20 ° C.