CS256172B1 - 5-substituted and 4,5-disubstituted 2-azoarenfurane hydrogentetrafluoroborates and method of their preparation - Google Patents

Description

The invention relates to 5-substituted and 4,5-disubstituted 2-azoarenfuran hydrogen tetrafluoroborates of formula I

... 4 areas of the electron spectrum indicate the possibility of use as detergents, synthetic intermediates and dyes with the possibility of biodegradation of the furan nucleus.

R ² R ³ N

..... I.

Ό N ~ EXAMPLE 1

5- (Ν, Ν-dimethylamino) -2-azo (4-nitrobenzene) furan hydrogen tetrafluoroborate (I) wherein Ar is phenyl, nitrophenyl, 4-methylphenyl, or 4-carbethoxyphenyl; R ¹ is hydrogen, halogen, acetyl, or (Tmethoxy-1-phenyl) methyl, and NR ² R ³ is dimethylphimino or morpholino.

Of similar compounds, the preparation of 5- (Ν, Ν-dimethylamino) -2-azoarenfuran hydrogen chloride is described wherein arene is benzene, 4-methoxybenzene, 5-nitrobenzene, by reacting 5-N, N-dimethylamino-2-furaldehyde with arendiazonium chloride [ Chim. Geterosikl. Soedin. 1325 (1974)], 4- (Ν, Ν-dimethylamino) azoarenbenzenes, by reaction of 4- (N, N-dimethylamino) azoarenbenzenes, by reaction of 4- (N, N-dimethylaminobenzaldehyde with arendiazonium salts [Ž. Org. Chim. 24, 1233 (1954)].

SUMMARY Methods for making compounds according to the invention is that the furan vinamidinium salt of formula II (II) wherein R ¹ and NR ² R ³ is as defined above, is treated with diazonium tetrafluoroborates of formula III

Ar — N2 < ⁺⁾ BFP ^-1 (ΙΠ) where Ar is as defined above in water at –5 to 50 ° C.

An advantage of said process for the preparation of the derivatives of formula I is the one-step synthesis starting from the furan vinamidinium salts, which are intermediates in the preparation of the corresponding 5- (N, N-dialkylamino) -2-furaldehydes [Chim. Geterosikl. Seedin. 586 (1969) Collect. 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-azoarenfuran hydroxenetetrafluoroborates. Ionic character and visible absorption

To a solution of 5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylammonium bromide (0.795 g) in 10 mL of water was stirred with stirring for 30 min. a solution of 4-nitrobenzenediazonium tetrafluoroborate (0.721 g) in 15 ml of water was added at 0-5 ° C. After stirring for 1 hour at 20 to 50 ° C, the orange solid is filtered off with suction, washed with water and dried. Yield 84%. T. t. Mp 229-231 ° C.

For C12H13BF.1N4O3 calculated:

% C, 41.40;% H, 3.76;% N / 16.09;

H, 3.77; N, 16.05.

¹ H NMR Spectrum (DMSO-D):?

8.08 (d, J 5.3 Hz, 1H, H 3 furan),

7.38 (d, J 5.3 Hz, 1H, H ₄ furan),

3.62 (s, 3H, CH 3),

3.57 (s, 3H, CH 3);

7.58 (d, J 7.6 Hz, 2H, benzene H);

7.42 (d, J 7.6 Hz, 2H, benzene H)

Example 2

5- (Ν, Ν-dimethylamino) -2-azo (4-carbetoxybenzene) furan hydrogen tetrrafluoroborate

To a solution of 5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium bromide (0.795 grams) in 10 mL of water was stirred with stirring for 50 min. A solution of 4-carbethoxybenzenediazonium tetrafluoroborate (0.972 g) in 20 ml of water is added over a temperature range of -5 to 0 ^° C. After stirring at 20-40 ° C for 2 hours, the solid is filtered off with suction, washed with water and dried. Yield 42%. T. t. 232-236 ° C.

For C15H18BF4N3O3 calculated:

% C, 48.02;% H, 4.83;% N, 11.20.

H, 4.78; N, 11.16.

¹ H NMR Spectrum (DMSO-D 6):

8.05 (d, J 5.2 Hz, 1H, H 3 furan),

7.62 (d, J 5.2 Hz, 1H, H _{fui. N)}

3.58 (s, 3H, CH 3),

3.52 (s, 3Η, CH 3),

7.96 (d, J 8 Hz, 2H, H _{11b remains} ), 7.40 (d, J 8 Hz, 2H, H _{b: 1; Zen} ), 4.28 (q, J 7 Hz, 2H , CHa),

4.32 (t, J 7 Hz, 3H, CH 3).

Example 3

4-fluoro-1-methoxymethyl) -5- (N, N-dimethylamino-1H-azo (4-nitrobenzene) furetrafluoroborate

To a solution of 4- (1-phenyl-1-methoxymethyl) -5 (N, N-dimethylamino-2-furfurylidene-N, N-dimethylammonium perchlorate (1.1 g) in 10 mL of water was stirred for 40 min. A solution of 4-nitrobenzenediazonium tetrafluoroborate (0.721 g) in 15 ml of water was added at 0-10 ° C. After stirring for one hour at 20-25 ° C, the solid was filtered off with suction, washed with water and dried in a yield of 94 percent. 125 DEG -128 DEG C. with decomposition.

For C20H2! BF4N1O4 calculated:

% C, 51.30;% N / 4.52;% N, 11.96.

% C, 51.45;% H, 4.53;% N, 11.73.

^X H-NMR (DMSO-d):

7.93 (d, J = 9 Hz, 2H, H _bl! ^).

7.22 (s, 5H, benzene H),

6.63 (d, J 9 Hz, 2H, H '_{(j; 1} zen),

5.23 (s, 1H, C H),

3.18 (s, 3H, CH 3),

2.56 (s, 3H, CH 3),

2.43 (s, 3 HCHe).

Example 4

4-Bromo-5- (Ν, Ν-dimethylamino) -2-azo- (4-nitrobenzene) furanotetrafluoroborate

To a solution of 4-bromo-5- (N, ^N-d! Methylamino) -2-furfurylidene-N, N-dimeíalimónium chloride (0.84 g) in 10 mL of water was stirred for 40 minutes. a solution of 4-nitrobenzenediazonium tetrafluoroborate (0.721 g) in 15 mL of water was added between 0-10 ^° C. After stirring at 20-25 ° C for one hour, the solid is filtered off with suction, washed with water and dried. Yield 72%. T. t. 205 DEG-208 DEG.

Calculated for:

% C, 33.75;% H, 2.83;% N, 13.12;% Br, 18.71.

% C, 33.69;% H, 2.89;% N, 13.25;

¹ H NMR Spectrum (DMSO-D 6):

8.00 (d, J 9 Hz, 2H, benzene H)

6.70 (d, 9 Hz, 2H, benzene H)

6.55 (S, 1H, H furan) j

2.76 (s, 3H, CH 3), 2.73 (s, 3H, CH 3).

Example 5

4-Acetyl-5- (Ν, Ν-dimethylamino) -2-azo- (4-nitrobenzene) furan hydrogen tetrafluoroborate

To a solution of 0.92 g of 4-acetyl-5- (N, N-dimethylamino) -2-furfurylidene-N, N-dimethylimmonium (II) perchlorate in 10 ml of water is stirred at a temperature ranging from 0 to 20 C was added a solution of (0.721 g) t-Nitro tetrafluoroborate in 15 ml of water. After stirring at 20-50 C the solid was filtered off with suction, .premyje water and dried. Yield 93%. mp. 130 ^C C at ( dec).

For CuH ^BF / NiOt calculated:

% C, 43.10;% H, 3.87;% N, 14.36.

% C, 43.72;% H, 3.91;% N, 13.75.

Example 6

5- (Ν, Ν-dimethylamino) -2-azobutane uranium hydrogen tetrafluoroborate

To a solution of 5- (N, N-dimethylamino) -2-fururylidene-N, N-dimethylimmonium bromide (0.795 g) in 10 mL of water was stirred with stirring for 30 min. at 0 ° C, a solution of benzenedtazonium tetrafluoroborate (0.57 g) in 10 ml of water was added. The mixture was stirred for 2 hours. at 20 to 25 ° C. A solid precipitated out overnight and was filtered off with suction and washed with water and dried. Yield 65%. T. t. Mp 235-238 ° C.

For C18H18FN5O5 calculated:

47.55% C, 4.65 «/ o Η, 13.86% N, found:

% C, 47.11;% N, 4.62;% N, 13.34.

¹ H NMR spectrum (DMSO-d 6):

7.85 (d, J 5.2 Hz, 1 H, Η3 f _ur u _e),

7.55 (d, J 5.2 Hz, 1H, 1H of _furan ),

7.40 (s, 5H, benzene H),

3.61 (s, 3H, CH _3),

3.53 (s, 3H, CH 3).

Example 7

5- (Ν, Ν-dimethylamino) -2-azo- (4-methylbenzene) furan hydrogen tetrafluoroborate

Κ of a solution of 5- (N, N-dimethylamino) -2-furfluididene-N, N-diethyliumium bromide (0.795 g) in 10 ml of water was stirred with stirring for 30 min. a solution of 4-methylbenzenediazonium tetrafluoroborate (0.61 g) in 15 ml of water was added at 0-5 ° C, and after stirring at 20-25 ° C for one hour, a solid formed which was filtered off with suction, washed with water and dried. 46 DEG C. ^, m.p. 195 DEG-198 DEG.

For CiHiBfhN / O

Example 8

5-Amino-2-azo (4-nitro-benzene) -furan-tetrafluoroborate

To a solution of 5-morpholino-2-furfurylidene-N-morpholinium bromide (2.09 g) in 15 mL of water was stirred for 30 min. a solution of 4-nitrobenzenediazonium tetrafluoroborate (0.721 grams) in 15 ml of water was added between 0-5 ^° C. After stirring at 20-25 ° C for one hour, a solid precipitated which was filtered off with suction and washed with water.

calculated:

C, 49.24; II, 5.09; N, 13.5.

H, 5.12; N, 12.94.

¹ H NMR Spectrum (DMSO-d 6):

7.76 (d, J 5.2 Hz, 1H, H _{3 Lur} / _n ), 7.38 (d, J 5.2 Hz, 1H, H 1), 7.35 (s, 4H, H _{1) (; nzuu} )

3.52 (s, 3H, CH 3),

3.42 (s, 3H, CH 3),

2.27 (s, 3H, CH 3).

For C 14 H 15 BF.NiO calculated:

% C, 43.11;% H, 3.87;% N, 14.36.

% C, 43.65;% H, 3.92;% N, 14.12.

Yield 63%. T. t. Mp 204-207 ° C

Ή NMR Spectrum (DMSO-d 6):

7.72 (d, J 5.3 Hz, ΙΗ, H3 turan L 7.04 (d,] 5.3 Hz, 11-I, 14 turan)),

7.80 (d, J 9 Hz, 2H, _benzene H),

7.42 (d, j 9 Hz, 2H, _benzene H),

4.12 (m, 8H, H).

Claims (2)

1. 5-substituted and 4,5-disubstituted 2-azoarenfuran hydrogen etrafluoroborates of formula I _with 5. n-i Β Β F, OJ kde Ar is phenyl, nitrophenyl, 4-methylphenyl, or 4-carbethoxyphenyl, R ¹ is hydrogen, halogen, acetyl, or (1-methoxy-1-phenyl) methyl and NR ² R ³ is dimethylamino or morpholino. 2: A process for the preparation of the compounds of the formula I according to claim 1, characterized in that for the furamidine salts of the formula II R 'Xx R ² R ³ N 4 O 4 CH = NR ² R ⁱ (+) Br (-) III) wherein R ¹ and NR ² R ³ as defined above are treated with diazonium tetrafluoroborates of the general formula Ar - N 2 ⁺ BF 4 wherein Ar is as defined above in water at a temperature of - 5 to + 50 ° C.