DE151017C - - Google Patents

Description

PATENT OFFICE.

M 151017 CLASS 22 a.

in Basel.

The present invention aims to produce previously unknown azo dyes, which bezw from Amidoarylacidylamidonaphtholsulfoäuren. Amidoarylamidoacidylamidonaphthol sulfonic acids derive and - are characterized by excellent developer properties.

The substances colored with these new developer dyes can be processed after

ίο Diazotize with the most diverse Amines and phenols combine further, producing colorations which are mutually exclusive not only because of its excellent wash fastness, but also because of its intensity and beauty the nuance.

The amidoarylacidylamidonaphtholsulfonic acids used as starting material can be represented by the action of Nitro- or. Acetamidoaryl acid chlorides Amidonaphtholsulfonicäuren and treatment of the resulting condensation products with Reducing agents respectively. saponifying agents. If you combine these amidoarylacidylamidonaphtholsulfonic acids in alkaline solution with diazo compounds, only the amidonaphthol residue is combined, during the Amidoarylacidylrest remains intact, whereby azo dyes arise that differ from the previously differentiate known developer dyes from amidonaphtholsulfonic acids by that they are not the diazotizable amido group in which the oxy or. Containing azo group Radical, but in a form independent of this chromophore, namely in the amidoarylacidyl radical that acts as a pure monamine contain. The effect of this heteronuclear amido group is quite striking. Because while using the diazotization dyes derived from amidonaphtholsulfonic acids (such as diamine black, Oxamine violet, etc.) by developing with β-naphthol or m-tolylenediamine only dark, d. H. blue up. Allow black tones to be generated, provide those according to the present Process available dyes light, clear shades of predominantly orange-red to blue-red nuances.

The same dyes can also be used in the Ways to be obtained that the acetyl derivatives of these dyes - are the same now represented by combining the acetylamidoarylacidylamidonaphtholsulfonic acids with diazo bodies or by the action of acetylamidoaryl acid chlorides on the azo dyes of the corresponding amidonaphtholsulfonic acids - partially saponified by heating with alkalis, thereby adding the acetyl group is more easily split off than the arylacidyl group.

The procedure is illustrated by the following examples:

Example i.

9 T. m- amidobenzoylamidonaphtholsulfonic acid (2-5 -7), (represented by condensation of m-nitrobenzoyl chloride with 2-5-amido

naphthol- 7-sulfonic acid and reduction of nitro acid by means of iron) are approximately 150 T. water and 5 T. soda dissolved and the ice-cooled solution with a 2, + T. Aniline corresponding amount of diazobenzene solution is added.

The orange-red dye which forms immediately is in the usual way by warming up the reaction mass, salting out of the dye, pressing and drying obtained in solid form. The same stains unheated ones Cotton from neutral or alkaline salty bath orange-red, by diazotization and developing the fiber dyed in this way, the orange-red, slightly brownish orange-red nuances with diamine and excellent washfastness obtain.

If instead of diazobenzene o- and p-

if diazotoluene is also used, yellowish tinges are produced by means of diazoxylol and diazocumene scarlet red dyes with a bluish tinge due to diazoacetanilide and ß-diazonaphthalene, the real developer nuances when developing into lively, rich, yellow-red to blue-red be transferred.

In an analogous manner, red developer dyes are obtained from other primary aromatic amines, e.g. B. chloroaniline, m-nitroaniline, «- and ß-sulfonic acids of ß-naphthyl- 'amines,' a- and ß-sulfonic acids of α-naphthylamine; the latter acids give undeveloped blue red and with β-naphthol red, with diamine brown developer nuances.

If instead of the amidobenzoylamidonaphtholsulfonic acid (2 · 5 · 7) the ρ - amidobenzolamidocarbonylamidonaphtholsulf acid (2 x 5 x 7), which is obtained by the action of phosgene on a mixture of the same Molecules of 2 · 5-amidonaphthol-7-sulfonic acid and p-amidoacetanilide and treatment of acetamido acid with dilute alkali or by reduction of that from p-nitrophenyl isocyanate and 2 · s-amidonaphthol ^ sulfonic acid obtained condensation product, then similar red developer dyes are formed.

The same can be used instead of the m-Amidobenzoylamidonaphtholsulf oic acid (2-5-7) the p- and o-amido compound, as well as the Methyl, halogen, alkyloxy and nitro substitution products of amidobenzoylamidonaphthol sulfonic acid Use (2 x 5 x 7). Due to the purity of the developer nuances, those of the amidoanisic acid amidonaphthol sulfonic acids are particularly special derived dyes excellent.

Example 2.

To a solution of 9.5 T. m-amidobenzoylamidonaphthol monosulfonic acid (2 x 8 x 6) in about 500 T. water and 5 T. soda is made in a known manner from 8.5 T. dehydrothiotoluidinsulfonic acid shown diazo compound entered.

The dye combination is warmed up and the dye is precipitated using common salt.

It dyes unheated cotton bluish-red and can be diazotized using β-naphthol to a dark red, develop to a brownish red using diamine.

The derivatives of amidobenzoylamidonaphtholsulfonic acid mentioned in Example 1 can also be used (2 · 5 · 7) use the generally purer, more yellowish red, deliver more direct and developed nuances than the corresponding derivatives of 2 »8« 6-amidonaphtholsulf acid.

Example 3.

The neutral solution of 10 T. m-Amidobenzolsulfamidonaphtholsulfonic acid (2 · 5 · 7) or (2 · 6 · 8), represented by condensation of m-nitrobenzenesulfochloride with 2 · 5 · 7- or 2 · 6 · 8 - amidonaphtholsulfonic acid and reduction of nitro acid in about 200 T. Water is mixed with 9.2 T. benzidine, 20 T. hydrochloric acid, 6.9 T. sodium nitrite and 7.5 T. Salicylic acid in soda-alkaline solution, available as an intermediate product go_ registered.

The dyes dye unheated cotton from dark red to burgundy red and can be used by diazotizing and developing with ß-naphthol and diamine in analogous, something develop more yellowish, intense and real tones.

As in Example 2, the derivatives of 2 · 5 · 7-amidonaphtholsulfonic acid also show here purer, less bluish nuances.

Instead of m-amidobenzenesulfamidonaphtholsulfonic acid In this example, chloro-, methyl-, nitro- and alkyloxy-amidobenzenesulfamidonaphtholsulfonic acids can be used use in a completely analogous manner, as well as the amidobenzamidonaphthol derivatives mentioned in Examples 1 and 2.

Instead of benzidine and salicylic acid, the intermediates can be made from other p-diamines and oxycarboxylic acids are used, as well as diazotized dehydrothiotoluidinsulf acid.

Example 4.

The amount of tetrazodiphenyl solution corresponding to 18.4 T. benzidine is added to a well cooled dissolution of 4.8 T. amido-ptoluolsulfamidonaphtholdisulfosaures Soda (ΐ · 8 · 3 · 6) was quickly added to 500 tons of water and 40 tons of soda and the instantly formed Intermediate then with a neutral solution of 25 T. Amidonaphtholmonosulfo-

acid (2 x 8 x. 6) reacted. After stirring for twelve hours, the dye becomes liquid warmed up and felled with table salt.

The dye dyes unheated cotton black-violet and can be diazotized on the fiber and combining with toluene diamine to an intense washable Develop black with blue outline.

If in the above example instead of amidonaphtholsulfonic acid (2 · 8 · 6) phenol, If phenol carboxylic acid or metadiamine are used, this creates developer dyes that can be used Let develop brown nuances with m-toluenediamine.

Example 5.

52 T. Amidonaphtholsulfosäure (a 68 percent) are in 300 T. water and the necessary Soda dissolved and then with 20 T.

lot

Sodium acetate is added and this solution is added at normal temperature by means of about 40 T. Acetsulfanilic acid chloride is treated until the amido group disappears, then with Soda neutralized and an equivalent amount of a diazo compound added, e.g. B. off Dehydrothiotoluidine sulfonic acid. The dye formed is used for splitting off the acetyl group saponified by heating with about 5 percent sodium hydroxide solution.

In an analogous manner, dyes are made from the condensation product of acetamidobenzoyl chloride and amidonaphtholsulfonic acids obtained.

The table below shows a larger number of those that can be represented using this method Azo dye combinations with regard to their properties and their technical dyeing properties Characterized behavior in more detail:

, 1. 1 η (j. 45 9 · Dye au diazotized
Amine solution
in solution
in
concentrate coloring
on unheated cotton with ß- with 4 ° trotter Naphthol
developed Toluene
. diamine 35 ² 7 · 10. component aniline water sulfur
acid developed 30th I I. direct Red orange brownish 3 · 8th. m-amidobenzoyl-2 s- ο -Toluidine orange orange orange 50 12. Amidonaphthol-7-sulfonic acid orange yellowish brownish- 4 · the same p-toluidine orange yellow Red Scarlet fever" Scarlet fever ■ 3 · yellowish yellowish brownish- the same Xylidine Orange red cherry red Red Scarlet fever Scarlet fever Ι4 yellowish bluish tint brownish- the same p-nitroaniline Red bluish tint Red Scarlet fever Scarlet fever 55 'δ Red Scarlet fever brownish brownish the same p-amidoacet- wine red violet orange orange ι 6. anilide Orange red blue red bordeaux desgL ο - chloraniline bluish tint bluish tint ¹ I- Red Red blue red brownish - the same m-chloroaniline brownish cherry red orange 5ο ^lS orange brownish brownish - the same ρ - chloroaniline brownish cherry red orange orange orange brownish yellowish - , the same p-amidophenol orange cherry red orange Red o-anisidine Orange red bordeaux Brown the same blue red blue red Scarlet fever. - the same Amidocresol bluish tint red-violet blue red methyl ether Red bluish tint bluish tint - the same α-naphthylamine bluish tint violet Red Scarlet fever Red bluish tint cloudy - ' the same ß-naphthylamine bluish tint blue Red red-violet Red red-violet Scarlet fever cloudy the same ι -4-naphthyl- yellowish violet Scarlet fever aminesulfonic acid Red Scarlet fever Red brownish red the same ι ■ 5-naphthyl wine red blue aminesulfonic acid blue red Red brownish red the same ι ■ 8 - naphthyl wine red violet aminesulfonic acid blue red Scarlet fever yellowish the same Dehydrothio-p-
toluidine Orange red cherry red Scarlet fever Scarlet fever blue red the same blue red violet blue red

Dye off diazotized
Amine solution solution
in
1 <· 4 * ~ \ 4 "* '' r / ~ h V ^ 'Coloring
on unheated cotton with ß- with in concentrate Naphthol
developed Toluene
diamine Dehydrothio-p- trotter developed component toluidine sulfo- water sulfur
acid direct bluish tint yellowish acid Red Scarlet fever IC). m - amidobenzoyl- 2 · 5 - Between brownish- red-violet bluish tint Amidonaphthol-7-sulfonic acid product from Red Red bordeaux bordeaux Benzidine and 20th the same Salicylic acid
aniline orange blue bordeaux Orange red p-toluidine 21. ρ - amidobenzoyl - 2 · 5 - m-xylidine orange yellow Red orange Scarlet fever - Amidonaphthol-7-sulfonic acid bluish tint 22nd the same ß-naphthylamine Orange red cherry red yellowish Scarlet fever 23- the same Red blue red bluish tint bluish tint - Amidocresol Scarlet fever Scarlet fever 24. the same methyl ether yellow Red violet bluish tint bluish tint - aniline Scarlet fever Scarlet fever 25th the same blue red violet blue red brownish red Brown Dehydrothio-p- 26th 1-3-5 -nitroamidobenzoyl- toluidine sulfo- orange yellow Red brownish bordeaux Brown 2 5-amidonaphthol-7-sulfo-
Q "ill Vf acid orange 27 Ci el LIl C
the same aniline brownish violet bordeaux Red brownish- Brown yellow Red 28. 1-2-5 -nitroamidobenzoyl- Dehydrothio-p- orange bordeaux orange 2 · 5-amidonaphthol-7-sulfo- toluidine sulfo- Scarlet fever cloudy acid acid Scarlet fever 29 m - amidobenzenesulfamido- Benzidine Red red-violet bluish tint naphthiol sulfonic acid (2-5-7) Salicylic acid Red yellow yellowish Dehydrothio-p- bordeaux bordeaux 3 ° the same toluidine sulfo- wine red blue blue red blue red - acid 3 ¹ · Diamidotoluene sulfamido aniline yellow Red red-violet blue red naphthol sulfonic acid (2-5-7) Orange red Xylidine 3 ² Amidomethoxybenzoyl-2 · 5- orange yellow Red orange bluish tint - Amidonaphthol-7-sulfonic acid ß-naphthylamine
Xylidine Scarlet fever 33 the same Red cherry red bluish tint blue red - ß-naphthylamine Scarlet fever yellowish - 34 · the same m-xylidine Red blue-violet blue red Red 35 · Amidochlorobenzoyl - 2 · 5 - bluish blue red bluish tint cloudy - Amidonaphthol-7-sulfonic acid ß-naphthylamine Red Red UldUrOL
bluish tint 36. the same aniline orange blue-violet cloudy red Red 37- 0 - amidobenzoyl - 2 · 5 - Orange red blue red Red bluish tint - "- .. Amidonaphthol-7-sulfonic acid Dehydrothio-p-
toluidine sulfo- Red
Red yellow Red 38. the same acid Red blue-violet Red 39 · m-amidobenzoyl- 2 8- Between bluish tint yellow Red bluish tint blue red bordeaux Amidonaphthol-6-sulfonic acid product from Red Red 40. the same Benzidine and
^^ oll ^ Irlf ^ nii 1 * f \ wine red red-violet blue red bordeaux bordeaux oaüzyisaure
Dehydrothio-p- 41. the same toluidine sulfo- wine red blue-violet bordeaux acid bordeaux brown Benzidine bordeaux 42. m - amidobenzenesulfamido- Salicylic acid wine red blue-violet bordeaux naphthol sulfonic acid (2-8-6) 0-amido-p- cloudy red brownish red Chloranisole 43 · - the same wine red dirty blue red yellowish - blue red Scarlet fever 44 · m - amidobenzoyl - 2 · 5 - bluish tint violet yellowish Amidonaphthol-7-sulfonic acid Red Red

Claims (2)

Ρλ τ ε ν τ - A ν S ρ R υ C Η: Process for the preparation of developer dyes, which an amidoarylacidyl- respectively Amidoarylamidoacidyl radical, consisting in that one i. Amidoarylacidylamidonaphthol respectively. Amidoarylamidoacidylamidonaphthol derivatives combined with aromatic diazo bodies respectively 2. Acetylamidoarylacidylamidonaphtholsulfonic acids with aromatic diazo bodies combined and the azo dyes obtainable in this way with splitting off the acetyl group Agents dealt with.