CS252122B1 - Method of aminonanaphtho-(2,1-d)thiazole's sulphonated derivatives preparation - Google Patents

Abstract

The method of preparation consists in being to a sulfonated derivative of ammonium naphthalene of Formula II, wherein R 1 = H, SO-1 H Rg = H, SO2H, OH R 3 = H, SO 2 H sodium or potassium rhodanide in the presence of hydrogen peroxide in aqueous alcoholic environment with 40 to 70% wt. alcohol with a number of carbon atoms 1 to 3. The substances obtained are significant intermediates for dyeing purposes.

Description

The present invention relates to a process for the preparation of sulfonated aminonephrto [2,1-d] thiezol derivatives, which are important intermediates for berveral purposes.

Compounds of this type, for example 1-aminonephrto [2,1-d] thiazole sulfoacids, have been disclosed as diazotizing components in NDR Pat. 113 760. Their preparation has not yet been specifically described.

The process according to the invention consists in treating a sulphonated aminonaphthalene derivative of the general formula II, wherein R ^ represents H, SO ,H, Rg represents H, SO ^H, OH and R ^ represents H, SO ^H, with sodium rhodanide or % potassium hydroxide in the presence of hydrogen peroxide in an aqueous alcoholic medium with 40 to 70 wt. alcohol having a carbon number of 1 to 3.

The object of the invention is a technologically simple process for the preparation of 2-aminonaphtho [2,1-d] thiezol-mono- or disulfonic acids and their hydroxy derivatives, which are formed in one step in good yield and good quality. The starting products for this preparation are manufactured on a technical scale and do not contain any proportions of carcinogenic substances, such as 2-naphthylamine, due to the production process.

As starting products and e, 2-amino-naphthalenesulfonic acid derivatives are used which, in the non-amino-containing cycle, have one or more aulfo-acyl groups, respectively. or starting from those 2-eminonephthalenesulfonic acids having a sulfo group at the 1 and 5 position.

Thus, they utilize and are technically based on starting compounds which, due to the content of a plurality of hydrophilic groups, for example OH-, SO4H and the production process, cannot contain harmful additives.

A further advantage is that when 2-eminone-phthalenedi- or -trisulfonic acids are used in which the sulfo group at the 1-position is adjacent to the amino group at the 2-position, the ring closure eliminates the sulfo group at the 1-position.

The reaction is carried out within a short period of 15 to 20 minutes, heating at a relatively low temperature of 60 to 65 ° C. The reaction product is formed in high yield and satisfactory purity.

The preparation process is illustrated in the following examples.

Example 1

(a) 2-Aminonephrto [2,1-d] thiazole-6-aulfocyeeline

To a solution of 30 g of potassium rhodanide in 300 ml of methanol was added 25 g of conc. hydrochloric acid and 31.7 g (0.1 mol) of 2-eainonaphthalene-1,5-disulfonic acid. A solution of 30 ml conc. hydrogen peroxide in 40 ml of methanol and the reaction mixture is heated to 60-65 ° C. After cooling, the pH of the reaction mixture was adjusted with conc. ammonium hydroxide solution to pH 8 to 9 and the reaction solution filtered. By acidifying the filtrate with conc. hydrochloric acid and precipitated the product which was suctioned off and dried.

Yield: 90%.

(280.2 (mex ^{) nm} / ship) in 0.1 N KOH: 236 (3.95), 267 s (4.48), 271 (4.50), 294 (3.39), 306 (3) , 40 (344) (3.04).

b) Non-betting of 22.3 g (0.1 mol) of 2-aminonephthalene-5-sulfoacid gave the product described in Example 1a in a yield of 90% of theory.

Example 2

2-Amino-naphtho [2,1-d] thiazole-7-sulfonic acid

a) Using 22.3 g (0.1 mol) of 2-aminonaphthalene-6-sulfonic acid as the starting product analogously to Example 1, except that sodium rhodanide was used in place of potassium rhodanide and 60% ethanol was used in place of methanol, the desired heterocyclic compound, in 85% yield.

C _n HGN ₂ S ₂ O ₃ / 280.2 / max ^{/ nm /} ° ^{e L} £ ° · ^Z 'K® ^M "' 245 / 4.50 / 269 and / 3.42 / 296/3, 60), 336 s (3.04).

b) Using 31.7 g (0.1 mol) of 2-aminonaphthalene-1,6-disulfonic acid, the thiazole sulfoacid is obtained in a yield of 85%.

Example 3

2-Aminonaphtho [2,1-d] thlazole-9-sulfonic acid

Using 22.3 g (0.1 mol) of 2-aminonaphthalene-8-sulfonic acid gave 54% yield as described in Example 1.

C ₁₁ H ₈ N ₂ S ₂ O ₃ (280.2) max ^{/ nm (1} β β) in 0.1 N KOH: 236 (4.14); 261 a (4.45), 270 (4.53), 289 s (3.67), 302 (3.66), 312 and (3.47), 347 (3.02).

Example 4

a) Using 31.7 g (0.1 mol) of 2-aminonaphthalene-1,7-disulfonic acid as the starting product and following the procedure of Example 1, the corresponding product is obtained in a yield of 77%.

b) Using 22.3 g (0.1 mol) of 2-aminonaphthalene-7-sulfonic acid according to Example 1 to give the desired product in 78% yield.

Example 5

2-Amino-naphtho [2,1-d] thiazole-6,8-disulfonic acid

a) Using 31.7 g (0.1 mol) of 2-eminonephthalene-5,7-disulfonic acid according to the procedure of Example 1, except that 70% propanol was used instead of methanol, the product was obtained in 62% yield.

b) Using 38.3 g (0.1 mol) of 2-aminonaphthalene-1,5,7-trisulfonic acid gave the product in 68% yield.

^C 11 ^H 8 ^{LT S} 2 ⁰ 3 ^{6/360 '4 /} max ^{/ nm} blogr / ⁱⁿ ° ^{»1N K0H:} 252 / 4.64 / 280 / 4,00 /, 293 / 3.66 / 356 (3.25).

Example 6

2-Aminonaphtho [2,1-d] thiazole-7,9-disulfoacid

AND

Using 31.7 g (0.1 mol) of 2-aminonaphthalene-6,8-dlaulfonic acid, the product was obtained in 43% yield according to the procedure of Example 1.

C 11 H ₂₅ N ₃ O ₆ ( _360.4 ) _mgx / nm (log) in 0.1 N KOH: 250 (4.62), 308 (3.82), 352 (3.53) .

Example 7

2-Amino-naphtho [2,1-d] thlazole-6-hydroxy-8-eulfonic acid

Using 23.9 g (0.1 mol) of 2-aminonaphthalene-5-hydroxy-7-sulfonic acid, the corresponding hydroxysulfoic acid is obtained according to Example 1 in a yield of 84%.

^C 11 ^H 8 ^N 2 ^S 2 ° 4 / 296.3 / _max / na / log 0.1 in KOH: 233 / 4.17 /, 250 s / 4.08 /, 262 / 4.07 / , 275 s (3.99), 290 s (3.88), 315 S (3.55), 362 s (3.32).

Example 8

2-Aminonaphtho [2,1-d] thiazole-4,7-disulfonic acid

Using 31.7 g (0.1 mol) of 2-aminonaphthalene-3,6-disulfonic acid in analogy to Example 1, the corresponding compound is obtained in a yield of 54%.

C _H H _g N ₂ S ₃ 0 ₇ / 376.4 / _max / nm / log / * / in 0.1 N KOH: 245 / 4.03 /, 275 s / 3.71 /, 308 / 3.82 (320), 3.75), 352 (3.53), 372 and (3.19).

Example 9

2-Amino-naphtho [2,1-d] thiezole-5,9-diaulfonic acid

Using 31.7 g (0.1 mol) of 2-aminonaphthalene-4,8-disulfonic acid, the corresponding thiazole disulfonic acid was obtained in a yield of 51% by the procedure of Example i.

CjjHgNgSjO? (376.4) mex ^{(nm) log} C v ^N Κ ⁸ : ²⁴⁵ (4.03), 275 and (3.71), 320 (3.75), 372 s (3.19).

Example 10

2-Aminonaphtho [2,1-d] thiazole-9-hydroxy-7-sulfonic acid

Using 23.9 g (0.1 mol) of 2-eminonaphthalene-8-hydroxy-6-sulfonic acid, hydroxyneftothiazolaulfonic acid was obtained according to Example 1 in a yield of 60.56.

C ,, H, ₈ N ₂ S ₂ O ₄ / 296.3 / AAX ^{/ n} "/ ^Io e £ ^Z 'o'^{'N 801.5 239} / 3,51 /. 329 (3.15), 359 and (2.85), 431 (2.03).

Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of sulfonated aminonaphtho (2,1-d) thiezol derivatives of the general formula I wherein kde, = H, SO ₃ H, R ₂ = H, SO-H, OH, B ₃ = H, SO ₃ H wherein Tih that the amlnonaftalenu sulfonated derivatives of formula II wherein R₁, Rg and R ₃ have the abovementioned meaning, has thiocyanate, sodium or potassium in the presence of hydrogen peroxide in aqueous alcoholic medium with 40 to 70% by weight. alcohol having a carbon number of 1 to 3.