CS263193B1 - 4,5-disubstituted-2-azoarenfuran bisperchlorates and process for preparing them - Google Patents

Abstract

A way of preparing new substances 4.5- -disubstituted-2-azoarfuran-bisperchlorates of formula I wherein Ar is nitrophenyl and Nu (+) is tri C 1-2 alkylammonium, pyridinium, methylpyridinium or the triphenylphosphonium group rests in that the vinamidine salts of the furan of formula II wherein Nu / + 'is as defined above arndiazonium sulfates act as meaning of formula III wherein Ar is as defined above meaning in water. Products are usable in the preparation of biologically active substances and synthetic dyes.

Description

The present invention relates to 4,5-disubstituted-2-azoarenofuran-bisperchlorates of formula I

CIO (-) (Ar) wherein Ar is nitrophenyl, and

Nu ^ ⁺ ^ is C ^ _ three ₂ alkylammonium, pyridinium, methylpyridinium, or trimethylphosphonium group, and minded to their preparation. The compounds of the invention have not been described in the literature.

The process for the preparation of these compounds is characterized in that the 4-substituted-5- (N, N-dimethyl amino) -2-furfurylidene-N, N-dimethylimmonium salt of the general formula II, (+)

Nu ¹

CGH ₅ - <H CH

CH, / + /

CH = N

CH,

CIO (-) (11) where Nu '' is as defined above, is treated with arenediazonium sulphates of formula III (+) - (/ 111), where Ar is as defined above, in water at 20 to 80 ° C.

Arendiazonium sulfates are prepared in situ by diazotization of the corresponding aniline in aqueous sulfuric acid by treatment with sodium nitrite at 0-5 ° C.

An advantage of the process for the preparation of the compounds according to the invention is that the syntheses are one-stage, starting from relatively readily available vinamidinium salts. The products are obtained in high yields and purity and represent a new group of aza-analogues of the furamidine vinamidinium salts, which, due to the high reactivity to nucleophilic craft at the 5-position of the furan nucleus and good leaving trialkylammonium group, biologically active pyridazine derivatives and synthetic dyes; and furan type surfactants.

In the following, the subject matter of the invention is illustrated by way of example without being limited thereto.

Example 1

4- / l-l-phenyl-trimethylammonium / methyl-5- / N, N-dimethylamino / 2-azo / 4-nitrobenzene / furan-bisperchlorát

To a solution of 4- (1-phenyl-1-trimethylammonium) -methyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bisperchlorate (1.54 g) in 10 ml of water was stirred with stirring A solution of 4-nitrobenzenediazonium sulphate in water which was prepared in situ by diazotization (0.5 g) of 4-nitroaniline in sulfuric acid solution (0.42 ml, conc.) And water (3 ml) was added at 20-25 ° C for 10 min. (sodium nitrite) 0.25 g / 2 ml of water at 0 ° C. The mixture was stirred at 20-25 ° C for 4 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5. Yield 69%. Mp 110-115 ° C. For ^< -22 ^Η 27 ^< '^' 2 ^Ν 5θ11 ^7mo ^ ·· 1 ™ ° !. N, 11.65%. Found: N, 11.23; Cl, 11.72. ^X H-NMR / measured in acetone-d / 11.02 / s, 1 H, NH /, 8.10 / d, J = 9 Hz, 2 H, ^H j, _enz en ^ ^{'7' 7 S 51 <5 H} 'benzene ⁷ ' ^{7 '51 / s} ' ^5H < ^H benzene ⁷ ' ⁷ < ^{42 / d} < ^J = ^{9 Hz} < ^2H '' benzene '' ⁷ < ^{35 / s} ' ^1H '' furan '5,31 / s, 1 H, CH 3, 3.65 (s, 3H, CH 3), 3.62 (s, 9H, CH ₃ ), 3.61 (s, 3H, CH 3).

Example 2

4/1-trimethylammonium-feny1-1 / methyl-5- / N, N-dimethylamino / 2-azo / 4-nitrobenzene / furan-bisperchlorát

To a solution of 4- (1-phenyl-1-trimethylammonium) -methyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bisperchlorate (1.66 g) in 10 ml of water was stirred under stirring A solution of 4-nitrobenzenediazonium sulphate in water, prepared in situ by diazotization (0.5 g) of 4-nitroaniline in sulfuric acid solution (0.42 ml) and water (3 ml) with sodium nitrite, was added at 20-25 ° C for 10 min. (0.25 g) in 2 ml of water at 0 ° C. The reaction mixture was stirred at 20-25 ° C for 3 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5. Yield 76 4. Mp 118-124 ° C. For ^C 25 ^H 33 ^Cl 2 ^N 5 ° 11 / mol. wt. 650.5 / calculated: 10.76% N, 10.90 4 Cl, found: 10.52% N, 10.84% Cl.

³ H NMR Spectrum (measured in acetone-dg): 11.03 (s, 1H, NH), 8.10 (d, J = 9 Hz, 2H, ^H ) Jenzene ⁷ '7.60 (β, 5H, Hbenzene) (7.52 (d, J = 9 Hz, 2H, _benzene H), 7.42 (s, 1H, _furan ), 5.78 (8, 1H, CH), 3.65 (S, 3H), CH ₃ ), 3.61 (s, 3H, CH ₃ ), 3.00 (m, ICH, C ₂ H ₅ N).

Example 3

4- / l-phenyl-pyridinium / methyl-5- / N, N-diiuetylamino / 2-azo / 4-nitrobenzene / furan-bisperchlorát

To a suspension of 4- (1-phenyl-1-pyridinium) methyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bisperchlorate (1.6 g) in 10 ml of water was stirred under stirring for 10 minutes. A solution of 4-nitrobenzenediazonium sulphate in water, which was prepared in situ by diazotization (0.5 g) of 4-nitroaniline in a sulfuric acid solution (0.42 ml) and water (3 ml) with sodium nitrite, was added at 20-25 ° C for min. 0.25 g / v of 2 ml of water at 0 ° C. The reaction mixture was stirred at 20-25 ° C for 3 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5. Yield 69 4. Mp 133-138 ° C. For ^C 24 ^H 23 ^Cl 2 ^N 5 ° 11 / mol. wt. N, 11.28%. Found: N, 10.98; Cl, 11.13.

³ H-NMR / measured in acetone-d / 11.02 / s, 1 H, NH /, 8.14 / d, J = 9 Hz, 2 H, N- ^H, _{Step enz} /

7.50 ( _8.5H , H _benJ , _en ), 7.32 (s, 1H, H _furan ), 6.16 (s, 1H, CH), 3.49 (s, 3H, CH3), 43 (s, 3H, CH3).

Example 4 $

4- / l-l-phenyl-o-carboxyl / pyridlnium / methyl-5- / N, N-dimethylamino / 2-azo / 4-nitrobenzene / furánbisperchlorát

To a suspension of 4- (1-phenyl-1-trimethylammonium) methyl-5- (N, N-dimethylamino) -2-furyrurylidene-N, N-dimethylimmonium bisperchlorate (1.73 g) in 10 ml of water was stirred in a solution of 4-nitrobenzenediazine sulphate in water prepared by diazotization (0.5 g) of 4-nitroaniline in sulfuric acid solution (0.42 ml) in water (3 ml) with nitrite was added over 10 min at 20-25 ° C. sodium (25 g) in 2 ml of water at 0 ° C. The mixture was stirred at 20-25 ° C for 4 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5. Yield 82 4. Mp 140-145 ° C. For? 25? 23? ^ 2? 4? 13 / mol. wt. 658.4 / calculated: 8.51 4 N, 10.77% Cl, found: 8.59% N, 10.71 4 Cl. ^X H-NMR / measured in acetone-d? / 11,12 / s, 1 H, NH /, 8.10 / d, J = 9 Hz, 2 H ^H t _{enz Step} / ^{»7> 70} / ^d r J = 9 Hz, ^2H '' benzene ^{7, 7 '50 7 S} * ^5H' 'benzene ⁷ * ^{7 "40 7 m} * ^{4 H} *' pyridine ⁷ * ^{7" 33 7 S} * ^{1 H H} -furan ^{7 '6' 02/8,} 1 H CH, 3.59 (s, 3H, CH3), 3.57 (s, 3H, CH3).

Example

4- / l-l-phenyl-triphenylphosphonium / methyl-5- / N, N-dimethylamino / 2-azo / 4-nitrobenzene / furan-bisperchlorát

To a suspension of 4- (1-phenyl-1-triphenylphosphonium) methyl 1-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bisperchorate (2.15 g) in 30 ml of water and under stirring for 30 min at 20-25 ° C a solution of 4-nitrobenzenediazine sulphate in water, prepared in situ by diazotation (0.5 g) of 4-nitroaniline in a solution of sulfuric acid (0.42 ml) and water (3), is added. ml (sodium nitrite) (0.25 g) in 3 ml of water at 0 ° C. The mixture was stirred at 50-80 ° C for 2 h. After cooling to 5-10 ° C, a solid precipitates which is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5. Yield 79%.

Mp 120-125 ° C. For Cj ^H H jjCINjOj ^P / ^m ° ° · wt. 810.6 / calculated: 6.9% N, 8.75% Cl, soldered: 7.1% N, 8.70% Cl. NMR Spectrum (measured in DMSO-d6): 11.00 (s, 1H, NH), 7.92 (d, J = 9 Hz, 2H, _benzene H), 7.61 (m, 22H, _benzene H), 7.29 (s, 1H, _furan ), 5.92 (s, 1H, CH), 3.59 (s, 3H, CH3 ₎ , 3.55 (s, 3H, CH3 ₎ .

Example

4- / l-trimethyl-phenyl / methyl-5- / N, N-dimethylamino / 2-azo / 3-nitro-benzene / furan-bisperchlorát

To a solution of 4- (1-phenyl-1-trimethylammonium) -methyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylammonium bisperchlorate (1.54 g) in 10 ml of water was stirred with stirring a solution of 3-nitrobenzenediazonium sulphate in water prepared in situ by diazotization (0.5 g) of 3-nitroaniline in a solution of sulfuric acid (0.42 ml, conc.) and water is added over a period of 10 min at 30-35 ° C. (3 ml) sodium nitrite (0.25 g) in 2 ml water at 0 ° C. The mixture was stirred at 30-35 ° C for 4 h. The precipitated solid is filtered off with suction and washed with water. Crystallize from acetic acid-water 95: 5.

Yield 76%. MP: Mp 119-122 ° C. For C 13 H 14 Cl 3 N 6 O 4 / mol. wt. Found: 11.79% N, 11.52% Cl.

Claims (2)

OBJECT OF THE INVENTION 1. 4,5-Disubstituted-2-azoarenfuran-bisperchlorates of the formula I Ar 2 C1O ₄ ^{/ - /} / 1 / wherein Ar is nitrophenyl and Hu ^ ⁺ ^ a tri C ₁ _ ₂ alkyl ammonium, pyridinium, methylpyridinium or a triphenylphosphonium group. 2. A process for the preparation of the compounds of the formula I as claimed in claim 1, characterized in that, for the vinamidinium salts of furan of the formula II: Nu ¹ C ₆ H ₅ - CH, / + / CH. CH = N = ^{CH 3} 2 CIO / 11 / CH n where Nu (*) is as defined above, is treated with arendiazone SSsulfates of formula III Ar - N / + / HSO (111) wherein Ar is as defined above, in water at 20 to 80 ° C. 1 drawing / + / Nu / 1/3/11 Λζ Ar - Ng H _so *