CS263193B1 - 4, S-Disubstituted-2-azoarfuranane perchlorates and a process for their preparation - Google Patents

Abstract

The method for the preparation of new substances 4,5-disubstituted-2-azoarenefuran-bisperchlorates of the formula I, where Ar is nitrophenyl and Nu/+/ is a tri-Ci_2 alkylammonium, pyridinium, methylpyridinium or triphenylphosphonium group, consists in treating the vinamidine salt of furan of the formula II, where Nu/+' has the above meaning, with arene diazonium sulfates of the formula III, where Ar has the above meaning, in water. The products can be used in the preparation of biologically active substances and synthetic dyes.

Description

263193

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

C10 (-) (1) wherein Ar is nitrophenyl, and

Nu ^ + ^ is a tri C1-4alkylammonium, pyridinium, methylpyridinium or trimethylphosphonium group, and processes for their preparation. The compounds of the invention have not been described in the literature so far.

The nature of the preparation of these compounds is based on the 4-substituted-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium salt of the formula (II).

Nu '

CgH5 - <HCH, CH, / + /

CH = N CH,

2 CIO / - / / 11 /

where Nu '' is as defined above, it is treated with arndiazonium sulfates of formula III (+) (c) - (III), wherein Ar is as defined above, in water at 20 to 80 ° C.

Arndiazonium sulfates are prepared in situ by diazotizing the appropriate aniline in an aqueous solution of sulfuric acid by treatment with sodium nitrite at 0-5 ° C. An advantage of the method of preparing the compounds of the present invention is that the syntheses are single-stage, starting with the relatively readily available vinamidinium salts. The products are obtained in high yields and purity and represent a novel group of aza-analogues of vinamidinium salts of furan which, due to their high reactivity to the nucleophilic agents at the 5-position of the furan nucleus and the good leaving trialkylammonium group, give the possibility of using as a synthetic intermediate (4 carbon building block) in the preparation of biologically active pyridazine derivatives and synthetic furan type dyes and surfactants. In the following, the invention is illustrated by the following examples without being limited thereto. Example 1 4- (1-Phenyl-1-trimethylammonium) -methyl-5- (N, N-dimethylamino) -2-azo / 4-nitrobenzene / furan-bisperchlorate To a solution of 4- (1-phenyl-1-trimethylammonium) n-methyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bisperchlorate (1.54 g) in 10 ml of water with 20 min. -nitrobenzenediazonium sulfate in water, prepared in situ by diazotization / 0.5 g / 4-nitroaniline in sulfuric acid / 0.42 ml, water / water (3 ml) / sodium nitrite / 0.25 g / v 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. N, 11.65; Cl, found: 11.23% N, 11.72% Cl. 1 H NMR Spectrum (measured in acetone-dg): 11.02 (s, 1H, NH), 8.10 (d, J = 9 Hz, 2H, H-, enzyme, 7'51, s, 5H)

"benzene 7 '' 51 's' 5H, 1' benzene 7 '7', 42 '(d, J = 9 Hz, 2H', benzene, 7 ', 35' s, 1H 'furan', 5,31 / s, 1H , CH (3.65) s, 3H, CH3, 3.62 (s, 9H, CH3), 3.61 (s, 3H, CH3). 1-Trimethylammonium / -methyl-5- (N, N-dimethylamino) -2-azo / 4-nitrobenzene / furan-bisperchlorate 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 is added with a solution of 4-nitrobenzenediazonium sulphate in the water prepared in water for 10 min at 20-25 ° C. by "diazotization / 0.5 g (4-nitroaniline in sulfuric acid solution / 0.42 ml) and water (3 ml) with sodium nitrite (0.25 g) in 2 ml of water at 0 ° C. The reaction mixture is stirred for 3 h at 20-25 ° C. The precipitated solid is filtered off with suction and washed with water. The 95: 5 acetic acid-water carbon black is crystallized. Yield 76%. Mp 118-124 ° C. For C 25 H 33 Cl 2 N 5 ° 11 / mol. wt. N, 10.90; Cl, found: 10.52% N, 10.84% Cl. &Lt; 1 &gt; H NMR spectrum (measured in acetone-dg): 11.03 (s, 1H, NH), 8.10 (d, J = 9 Hz, 2H, H) -enzene-7,7,60 (s, 5H, benzene), 7.52 (d, J = 9 Hz, 2H, Hbenzene), 7.42 (s, 1H, Hfuran), 5.78 (8, 1H, CH), 3.65 (s, 3H, CH3). 61 (s, 3H, CH 3), 3.00 / m, 1 CH, C 2 H 5 3 N). Example 3 4- [1-Phenyl-1-pyridinium / methyl-5- [N, N-diethylamino] -2-azo] -4-nitrobenzene / furan-bisperchlorate To a 4- (1-phenyl-1-pyridinium / methyl) suspension -5- / N, N-Dimethylamino / -2-furfurylidene - N, N-dimethylimidium bis (chloroform) (1.6 g) in 10 ml of water is added with a solution of 4-nitrobenzenediazonium sulphate in 10 ml of water at 25-25 ° C water which had been prepared in situ by diazotization / 0.5 g / 4-nitroaniline in sulfuric acid solution / 0.42 ml / and water / 3 ml / sodium nitrite / 0.25 g / v 2 ml water at 0 ° C . The reaction mixture is stirred for 3 h at 20-25 ° C. The precipitated solid is filtered off with suction and washed with water. The 95: 5 acetic acid-water carbon black is crystallized. Yield 69%. Mp 133-138 ° C. For C 24 H 23 Cl 2 N 5 ° 11 / mol. wt. N, 11.28; Cl, found: 10.98% N, 11.13% Cl. 1 H NMR Spectrum: measured in acetone-dg: 11.02 (s, 1H, NH), 8.14 (d, J = 9 Hz, 2H, Hf-, enzyme / 7.50 / 8, 5H, Hben 1). [α] D = 7.32 (s, 1H, Hfuran), 6.16 (s, 1H, CH, 3.49 (s, 3H, CH3); 3.43 (s, 3H, CH3). Example 4 $ 4- (1-Phenyl-l-carboxyl) pyridinium / methyl-5- (N, N-dimethylamino) -2-azo / 4-nitrobenzene / furanbisperchlorate To a 4- (1-phenyl-l-trimethylammonium) suspension / Methyl-5- [N, N-dimethylamino] -2-fufrurylidene-N, N-dimethylimidium bisperchlorate (1.73 g) in 10 mL of water is added with stirring over 10 min at 20-25 ° C. 4-nitrobenzenediazium sulfate in water, prepared by "diazotizing" (0.5 g) 4-nitroaniline in a sulfuric acid solution (0.42 ml) in water (3 ml) with sodium nitrite (25 g) in 2 ml of water 0 ° C. The mixture is stirred for 4 h at 20-25 ° C. The precipitated solid is filtered off with suction and washed with water. The 95: 5 acetic acid-water carbon black mixture crystallizes. Yield 82%. Mp 140-145 ° C. For C25H23C12N4O33 / mol. N, 10.77%. Found: 8.59% N, 10.71% Cl. 1 H NMR spectrum (measured in acetone-dg): 11.12 / s, 1H, NH 4, 8.10 / d, J = 9 Hz, 2h Ht, enzyme 7 '7> 70 J = 9 Hz, 2H'"benzene7 * 7'50 7s * 5H 'benzene7 * 7'40 7m * 4H * pyridine7 * 7'33 7s * 1H * furan7 ** 6 * 02 / S, 1H, CH /, 3.59 / s, 3H , [Lambda], 3.57 (s, 3H, CH2). Example 4- (1-phenyl-1-triphenylphosphonium / methyl-5- [N, N-dimethylamino] -2-azo) 4-nitrobenzene / furan-bisperchlorate

Claims (2)

263193 To a suspension of 4- (1-phenyl-1-triphenylphosphonium) - 1-5 - (N, N -dimethylamino) -2-furfurylidene - N, N-dimethylimidium bispercorate (2.15 g / v 30 ml) of water, a solution of 4-nitrobenzenediazonium sulphate in water, prepared by diazothioic acid / 0.5 g (4-nitroaniline in sulfuric acid solution / 0.42 ml) and water was added in 30 min at 20-25 ° C with stirring. (3 ml) with 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 [deg.] C., a solid precipitates which is filtered off and washed with water. 95: 5 acetic acid-water was crystallized. Yield 79%. M.p. 120-125 ° C. For C ^ ^H ^ CICljN ^Oj · P / mol. wt. N, 8.75; Cl, sold: 7.1% N, 8.70% Cl. NMR Spectrum (DMSO-d6): 11.00 (s, 1H, NH), 7.92 (d, J = 9 Hz, 2H, benzene), 7.61 (m, 22H, benzene); 29 (s, 1H, Hfuran), 5.92 (s, 1H, CH), 3.59 (s, 3H, CH3), 3.55 (s, 3H, CH3). Example 4- (1-Phenyl-trimethylammonium) -methyl-5- (N, N-dimethylamino) -2-azo / 3-nitrobenzene / furan-bisperchlorate 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 is added with a solution of 3- nitrobenzenediazonium sulphate in water, prepared by "in situ" diazothioie / 0.5 g / 3-nitroaniline in sulfuric acid solution / 0.42 ml, conc. / water / 3 ml / sodium nitrite / 0.25 g / v 2 ml The mixture is stirred for 4 hours at 30 DEG-35 DEG C. The precipitated solid is filtered off with suction and washed with water and crystallized with 95: 5 acetic acid-water, 76% yield, mp 119 DEG-122 DEG. N, 11.65% Cl, found: 11.79% N, 11.52% Cl. SUBSTITUTE 1. 4,5-disubstituted Of 2-azoarfuran-bisperchlorates of general formula I Ar, 2 C1O4 (-) (1) wherein Ar is nitrophenyl and Nu ^ + ^ is tri C1-2alkylammonium, pyridinium, methylpyridinium or triphenylphosphonium. 2. A process for the preparation of compounds of the formula I according to claim 1, characterized in that the vinamidinium salts of the furan of the formula II are Nu1 C6H5 --CH2, + / CH. CH = N 2 CH 3 2 C 10/11 / Ar-N / + / HSO where Ar is as defined above, in water at 20 to 80 ° C. 1 drawing CH, as defined above, is treated with arndiazone SS sulfates of formula III / 111/263193 / + / Nu / 1 / / 11 / Λζ Ar - Ng Hso * / 111 /