DEP0032243DA - Process for the preparation of chromium-containing monoazo dyes - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Pofentanwalf

Dlp!. ° lng. E. Splonemann

Hambu.g36

Hg6 _u . _ _e

Neuer Wall 10, 4. Stocfe ,, ^H ™! "Gff, * & Jflft

äarui 347900 ^ ^{9USr Wa! 11Ü} ' ⁴ ' ^ltedl

Germany

Process for the production of chromium-containing monoazo fars.

It has been found that new, valuable chromium-containing monoazo dyes! * Can be obtained by using moaoazo dyes <2-general formula

0-A-, HO
i ^l I
R ₁ -N = NR ₉ ,

0-A ₂

in vjelcher R ₁ a sulfur-free aromatic radical of the benzene series in which the substituents -K = N-, -0-A, and -O-Ap are in the 1,2,5-position to one another, A _{1 (} and A ₂ each an alkyl radical, preferably a methyl radical each and R _{2 is} a naphthalene radical which contains one or preferably two sulfonic acid groups and which is in the 2-position on the azo group and in the 1-position on the hydroxyl group or preferably in the 1-position on the azo group and In the 2-position bonded to the hydroxyl group i & c, under conditions in which the Α group is split off, allows chromium-donating agents to act.

The monoazo dyes corresponding to the above formula and used as starting materials in the present process can

be prepared by adding a dlazo compound of an amine of the general formula

Q-A,

5 1

R ₁ -NH ₀
1 ²

where R-, a sulfur-free aromatic radical of the benzene series,

JL

In animal; (Uf- Sub ftItu enters -Yn ₂ , -! W ^, ~ ° "* ^A 2 are ^{in 1χ2ί} 5-position to one another and. A ₁ and A ₀ each denote an alkyl radical,

J C.

with a 2-xynaphthalene-mono- or disulfonic acid coupling in the! -position or with a 2-xynaphthalene-monO7 coupling in the 2-position or -el isu If on acid combined.

In the amines serving here as Dlazc ^ f components ae>? given formula, the radical R. can be free of further substituents or it can contain further substituents, which, however, must be free of sulfur. Ais such come into consideration, for example; Nitro, acylamino or A Iky! Groups, halogen atoms, fluorine or bromine and especially chlorine,

The two alkyl groups A ₇ and A ₀ can be identical or different. Aside from straight aliphatic hydrocarbons, the term alkyl radical here also includes branched aliphatic; see hydrocarbon radicals and cycloalkyl radicals, which in turn can be free of substituents or also substituted. In general, particularly good results are achieved with those amines of the formula mentioned at the outset in which the alkyl radicals A and A ₀ contain only a few, for example 2 to 4 carbon atoms each.

As examples of such amines are to be mentioned ·.

l-Amino-2,5-olemethoxybenzene, 1-amino-2, S-dimethoxy - ^ - chlorobenzene, l ~ amino-2,5-dlmethoxy -4 = rdrobenzene, 1-amino-2,5 ~ dimethoxy-4- siefchy! benzene, l-amino ^ S-dimethoxy - ^ - benzoylaminobenzene, 1-amino-2-methoxy-5-ethoxybenzene, 1-amino-2-methoxy-5-allyloxybenzene, 1-amino-2,5-dlaethoxybenzene, 1-Amino-2-methoxy-5-butyloxybenzene, 1-vftmino-SjS-diaethoxy - ^ - nitrobenzene, 1-amino-2,5-diaethoxy - ^ - chlorobenzene. As a k th ompone η η example, the following come into consideration Oxynaphthalinsulfonsäuren% l-oxynaphthalene-3- ,, -4- or -5-sulf oic acid, 1-oxynaphthalene-3 ^ 6 -, - 3,8- or -4,8 -disuifonic acid, '2-0xynaphthalene' 4-, -5-, -6-, -7- or -8-suH.fonsäure, 2-0xynaphthalin-3,6-dlsulfonsäurej also oxynaphthalenesulfonic acids with further substituents such as l-oxynaphthalene- S-sulfonic acid-S-sulfonic acid amide, 1-oxynaphthalene-8-sulfonic acid-3-sulfonic acid-n-butylamide, 1-oxyn-8-sulfonic acid -3 -sinifonic acid ~ N -methyl

The Diazotierving the amines of the above-mentioned formula can be applied in customary, bekanntej "se _e eg using Jiatriumnitrit and hydrochloric acid. The coupling of the diazo compounds with the oxynaphthalenonono- or disulphonic acids takes place in two cases in an alkaline medium, for example a sodium carbonate-alkaline medium. If appropriate, the coupling can also be carried out in the presence of suitable solvents, such as alcohol or pyridine.

Among the monoazo dyes corresponding to the general formula mentioned at the outset, there are in particular those

valuable chromium-containing dyes, which in the rest

0-A,

R «N« N I ¹

in the para »position on the -N-N- group contain one of the substituents listed above, preferably a chlorine atom, so z.I. Monoaso dyes of the formula

0 "alkyl

HO I • N * N -R "

0-alkyl

where the AIky! groups A. and A _{2 can be,} for example, ethyl or, preferably, methyl groups.

With regard to the radical R “, those dyes generally prove to be particularly valuable in which these

£ dah_e_r / naphthalene residue contains the hydroxyl group in the 1-position and / Ln 2-position is connected to the Aζobrücke »whereby especially Fär · substances with naphthalene radicals, which contain two sulfonic acid groups, see B, those of the formula

0-Ä

in particular

R ₁ --N = N -

ι J-

0-A ₂ "*

■ SO-H

provide valuable chromium-containing compounds.

The monoazo dyes used as starting materials in the present process can, if desired, be derived from the Coupling mixture isolated and freed from impurities. In general, however, can be used for treatment with the metal donors Averages the coupling compound to be used as a whole and without intermediate deposition. As a rule, it is necessary to the coupling mixture before carrying out the reaction with the metal-releasing agent to the one that is favorable for this reaction pH value, i.e. adjust to a weak mineral acid reaction.

In the present process, the salts of trivalent chromium such as chromium fluoride, chromium sulfate, chromium acetate and chromium formate come into consideration as ear-donating agents. The treatment with the chromium-releasing agents takes place under conditions under which the alkyl radical A _{1 is} split off. This splitting off with simultaneous formation of the complex chromium compound can be carried out according to a method known per se by treating with the chromium-bound agent, 2.B. with chromium formate or chromium sulfate in water!

The chromium-containing dyes obtainable by the present process are new. They are complex chromium compounds of the monoazo dyes of the general formula

OHH O

ι ι

R _n -N = NR

in which R, a sulfur-free aromatic radical of the benzene series, in dom the substituents -N = N-, -OH and -0-A _{2 are} in 1,2,5-Sfcellung to each other »A _{2 is} an alkyl radical and R _{2 is} a kaphthalene radical means which contains one to two sulfonic acid groups and is attached to the azo group in one of the positions 1 and 2 and to the hydroxyl group in the other of the positions 1 and 2

These pFodukto signs are mainly used to dye materials of animal origin such as silk, leather and in particular Wool, also for dyeing synthetic fibers made from super polyamides or super polyurethanes. The colorations obtainable with it stand out due to its good wash, milled and lightfastness. Also, these new stand out versus known ya rather composition, as a rule, mainly characterized by the fact that they result in uniform colorations of particularly pure tones, which maintain their purity even in artificial light.

The following examples serve to explain the invention "L-iIoll" '.

15? 3 parts of _2-P 5 Dlmethoxy-i ™ amlnobenzol are diazotized in a conventional manner in the presence of 30 parts of 30 $ strength by weight hydrochloric acid with 7 parts of sodium n ^ trJt. The filtered solution of the diazo compound / Tmte r thorough stirring to a cooled to 10 solution of 23 parts of 2-oxynaphthalene-4-sulfonic acid and 40 parts of anhydrous Nptrlumcarbonat ± n 400 parts of water zufHessen ^ "iswgpitf The resultant J ^ rb material falls to the largest

/ uxiu is filtered off./
Part of j »Dried, it represents a dark colored substance,

oy

which dissolves in dilute sodium carbonate solution with burgundy and in concentrated sulfuric acid with blue color and

oy

Dyes wool from an acid bath in bordaew ^ red tones.

This dye can, advantageously without prior drying, be converted into the complex chromium compound » For this purpose, the dye paste obtained according to the above information is mixed with 1000 parts of hot water and 10% sulfuric acid added until a weak mineral acid reaction. After adding an amount of chromium sulfate containing 5.7 parts of Cr

the reaction mixture is heated in the leaded

R-Ührautoklaven to 125-! Λϋ ° and stirred for 2Q hours at this temperature. The resulting C h romjverbindur.g falls largely ^m ell. It is filtered off after cooling to room temperature and re-washed with 10% sodium chloride solution. The pilter residue is dissolved in 1000 parts of water at 55-60 ° by adding 20 parts of 30% sodium hydroxide solution. The dye solution is mixed with dilute salt

acid added to the litmus-neutral reaction. D ^ r dyestuff is precipitated by addition of sodium chloride = It provides in dry Z ^ sta.nä a dark colored substance is, which dissolves in i / erdÜMitef sodium carbonate with violet-blue and in concentrated sulfuric acid green blue color and wool from sulphate B & de in real , very uniform blue tones: "ärbt, vrelohe show practically the same hue in artificial light as in daylight ,, / fj ^

A chromium-containing dye with similar properties is obtained if, instead of 15-3 parts of 2, 5-dimethoxy-1-aminobenzene, 18.1 parts of 2, S-k'i & efciioxy-1-aminobenzene are used and the rest of the information given above moves.

18.8 parts a ^ p

are diazofcated in the usual way in the presence of 30 parts of hydrochloric acid with 7 parts of sodium carbonate. The received,

A clear solution of the diazo compound w ^ rse ^ -f, with thorough stirring, to a solution, cooled to 10 °, of 31 parts of 1-oxynaphthalene-3,6-di ~ Sulphuric acid and 30 parts of anhydrous nafcrium carbonate in 4-00 parts of water for food gaia * "" ". The resulting dye mostly fails. When dried, it represents a darkly colored substance which is dissolved in water and a dilute sodium carbonate solution with ruby red and in conc. Sulfuric acid with a blue color dissolves, and wool from acid baths dissolves a bluish red color Tones colors.

This dye can be converted into the complex chromium compound without separation. For this purpose the Kupplungsgemisoh obtained according to the above specifications is diluted water with 200 parts and loj & sulfuric acid to the weak mineral acid reaction added "After adding a 5.7 parts of containing Cr amount Ghromsulfat / Cr ₀ (SO ₁₎ -" rhitzt the reaction mixture in the leaded stirred autoclave to 120-125 and stir for 15 hours at this temperature. The resulting chromium compound is largely precipitated. After allowing it to cool to room temperature, it is filtered off and dried. In this state it is a dark-colored substance, which dissolves in water with blue, in dilute alkali hydroxide solutions with ruby red and in concentrated sulfuric acid with a dirty violet color, and wool from sulfuric acid bath in real * very uniform, pure reddish-tinged blue tones, which show practically the same color shade in artificial light as in daylight.

A chromium-containing dye with similar properties is obtained if, instead of 18.8 parts, 2.5 ~ bijaetiioxy-1-amino-4-chlorobenzene is used starting from 15 * 3 parts of 2 ^ 5-Dimefchoxy-laminober.sol and otherwise according to the above information moves.

3.5 * 3 parts 2, 5-2imethoxy-l - & minobenzol be in the customary manner in the presence of 47 parts of 38 ^ sulfuric acid with 7 parts of sodium nitrite; diazotized. The filtered solution of the diazo compound w4 # d / is added with thorough stirring to a solution, cooled to 10, of 31 parts of 1-oxynaphthalene-3j8-disulfonic acid and 4-0 parts of anhydrous sodium carbonate in 400 parts of water The largest part of 7 ^E ^ is dried and represents a dark red substance which dissolves in dilute sodium carbonate solution with red and in concentrated sulfuric acid with blue color and dyes wool from acid baths in red shades.

This dye can advantageously be converted into the complex chromium compound without prior drying. For this purpose, the dye paste obtained according to the above information is stirred with 1000 parts of hot water and IQ ^ ige sulfuric acid is added until the mineral acid reaction is very weak. After adding an amount of basic chromium sulfate (CrOH-SO4) containing 5 * 7 parts of Gr, the reaction mixture is heated to 115-125 ° in the leaded stirred autoclave and stirred for 15 hours at this temperature. Most of the chromium compound formed falls out. The separation can be completed by adding sodium chloride. The dye is filtered off after cooling to room temperature. When dry, it is a dark-colored substance ₅ which, in dilute sodium carbonate solution, is concentrated in red-blue and in

tared Schxiefelic acid dissolves with violet-red color and wool from sulfuric acid bath dyes in real "very even blue tones, soft in artificial light practically the same hue here in daylight".

A chromium-containing dye with similar properties is obtained if, instead of 15.3 parts of 2,5-dimethoxy-1-aminobenzene, 18 _? 8 parts of 2,5-diethoxy-4-chloro-lciTiinobensol starts out and <3 otherwise proceed according to the above information.

19.8 parts of 2,5-dimethoxy-4-nitro-1-aniinobenzene are diazotized with 7 parts of sodium nitrite in a customary manner in the presence of 115 parts of 30% hydrochloric acid. The filtered solution of the Diazoverbir.äung with thorough stirring to a solution, cooled to 10, of 23 parts of 2 ~ 0A "ynaphtha3in- ⁱ l -sulfonic acid and 100 parts of anhydrous sodium carbonate in 800 parts of water. The resulting dye falls off

/ uji ^ jtfird abtil ^ riext ^ /

The largest part of 7 "" He "" is dried and represents a dark red substance that dissolves in a dilute sodium carbonate solution ee-MHOter and in concentrated sulfuric acid with blue

Color dissolves and waves from sour baäe colors in red tones.

This dye can? beneficial oh ^ e previous

to be converted into the complex chromium compound » Zv, this is the purpose of the above. The dye paste obtained is mixed with 10000 parts of hot water and mixed

Sulfuric acid was added until the reaction was weakly mineral acid. After the addition of an amount of chromium sulfate / "crpfsOw" 7 containing 5 * 7 parts of Cr, the reaction mixture was heated to 120-125 ° in the leaded stirred autoclave and stirred at this temperature for 20 hours. The chromium compound formed was largely precipitated The filter residue is heated to 60 ° with 200 parts of cold water and 15 parts of 3Q sodium hydroxide solution, the chromium-containing dye Irs solution being released. The filtered dye solution The complex chromium compound can be deposited by adding sodium chloride and neutralizing it with dilute hydrochloric acid. When dry, the dye is a dark-colored substance which dissolves in dilute sodium carbonate solution with a dull, violet-blue color and in concentrated sulfuric acid with a gray-blue color Wool from sulfuric acid bath in real, very uniform in a rich gray-blue tones.

A chromium-containing dye with similar coloring properties is obtained if, instead of the 2-Qxynaphfchalin- "· "Sulphonic acid the same amount of 2-0jcyns.phthalin-6-sulphonic acid, the chromation in the autoclave for 25 hours

30 and otherwise ver

moves. The dye obtained in this way is a dark powder which, in dilute sodium carbonate solution, turns into a blue one

and dissolved in concentrated sulfuric acid with a burgundy color

and wool from sawdust!

Claims (1)

Process for the production of chromium-containing monoazo color & tofre _P characterized in that one is based on monoazo dyes of the general formula O = A ₁ HO 0-A ₀ in which R _{1 is} a sulfur-free aromatic radical of the benzene series, in which the subscribers -W = N -, - -O ⁰ A ₁ and -O-Ag are in 1.2.5 "position to one another, A ^ and A _p each have one Alkyl radical, preferably a metal radical each and R "denotes a naphthalene radical which contains one or preferably two sulfonic acid groups and which is in 2-5 position to the azo group and in 1-position to the hydroxyl group or preferably in!" Position to the αo group and in 2-position is bonded to the hydroxyl group, under conditions in which a cleavage of the radical A ₁ takes place j, cn romabgebe η de means let act. ^cy WJUUUUUUUf MA B 1 1 (Äsats 1 nni Z) 2 (J & s & fcB 1 rna 2} 4 (AbMfta 1 anft 2} SIt
10O feil «i Wed