DE1044311B - Process for the production of metallizable monoazo dyes and their heavy metal complex compounds - Google Patents

Description

NOTICE DEK APPLICATION AND ISSUE OF THE EDITORIAL: NOVEMBER 20, 1958

Method of manufacture

The invention relates to a process for the production of _{metalizable monoazo dyes} from metallizable monoazo dyes and their

Heavy metal complex compounds. and their heavy metal complex

It has been found that valuable metallizable compounds can be used

Monoazo dyes obtained if a benzene diazo 5 ^y

nium compound, which is in the o-position to the diazo cap

contains a hydroxyl group or a substituent which can be converted into a hydroxyl group and the rest still further, for example with halogen, alkyl, acylamino, sulfonic acid, alkylsulfonyl, sulfonic acid amide 1 ° and may preferably be substituted with a nitro group with a 4-methyl-1-oxybenzene compound coupling, which is substituted in the 2- and 5-position by an acylamino and a methyl group.

The new monoazo dyes give in the form of their 15
Heavy metal complex compounds real, red-brown,
brown to brown-purple colorations on natural or
synthetic polypeptide fibers, where the metallization during or after dyeing z. B. after the
Single bath chrome plating method or after the re-chrome plating ao
method and often more advantageous in substance before
Can carry out dyeing. For coloring natural
or synthetic polypeptide fibers such as wool, silk,
Super polyamide and super polyurethane fibers, made of weak ~
alkaline, neutral to slightly acidic liquor in real 25
red-brown, brown to brown-violet tones especially
those chromium and cobalt complex compounds which contain 2 unsulfonated dye molecules are suitable
contain bound to a heavy metal atom. One ver ~
expediently uses them in the form of their alkali salts,

for example in the form of the lithium, sodium, potassium or ammonium salts, in the presence of anion-active monoazo dyes from a 4-nitro-2-anuno-1-oxyben network and dispersants in neutral to weak zol compounds, which optionally only in 6-stelic acid Bath. treatment by halogen, an alkyl, an acylamino, a

For the preparation of the 35 alkylsulfonyl, sulfonic acid amide or sulfonic acid monoazo dyes obtainable according to the invention For example, the following group is suitable.

Diazo components: 4-nitro-2-amino-l-oxybenzene, 4-Ni The 4-methyl-l-oxy-

tro-6-methyl-2-amino-1-oxybenzene, 4-nitro-6-chloro-2-amibenzene azo components, which are in 2- and S-position no-1-oxybenzene, 4-nitro-2-amino-l-oxybenzene-6-sulfone- subsaured dimethyl by a methyl and an acylamino group or diethylamide, 4-nitro-6-methylsulfo- 40 are substituted, one of these two groups being the nyl- or 4-nitro-6-ethylsulfonyl- or 4-nitro-6-butyl- o- and the other the m-position with respect to the Hysulfonyl-2-amino-1-oxybenzene, ^ -Nitro-o-carbäthoxyami- droxylgruppe occupies are new. It is easy to obtain no-2-amino-1-oxybenzene, 6-nitro-4-methyl-2-amino-1-o:> cy- either by coupling 3,4-dimethyl-1-oxybenzene benzene, 6-nitro-4-tert.-butyl-2-amino-1-oxybenzene, 6-Ni with an aryldiazonium compound, reduction of the ertro-4-acetylamino-2-oxybenzene, 4-nitro-2-amino-1-meth- 45 containing monoazo dyes with isolation of 1-oxyoxybenzene, ö -nitro ^ -chloro ^ -amino-1-oxybenzene, 5-nitro-3,5-dimethyl-6-aminobenzene and acylation of the same 2-amino-l-oxybenzene, S-nitro ^ -chlor ^ -arnino-l-oxyben- or by mononitration of 2,4-dimethyl-l-aminozene, S-nitro ^ -methyl ^ -amino-1-oxybenzene, 4-chlorobenzene in concentrated sulfuric acid to 1-amino-2-amino-1-oxybenzene, 4,6-dichloro-2-amino-1-oxybenzene, 2,4-dimethyl-5-nitrobenzene, diazotization of amino-4-nitro-2-amino-1-oxybenzene-6-sulfonic acid, 6-nitro group with boiling of the diazonium group to 2-amino-1-oxybenzoI-4-sulfonic acid, 4-chloro-2-amino hydroxyl group, reduction of the nitro to the amino group

Applicant:
JR Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein and Dipl.-Chem. Dr. rer. nat. E. Assmann, patent attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland from February 23, 1955

Dr. Hans Ackermann, Riehen,

and Dr. Guido Schetty, Basel (Switzerland),

have been named as inventors

1 -oxybenzene-6-sulfonic acid, 6-chloro-4-methylsulfonyl-2-amino-1-oxybenzene.

Those obtainable according to the invention are particularly valuable

and acylation thereof.

The acyl residues of the acylamino group of the azo component are preferably residues of lower fatty acids

«09 679/302

into consideration, for example the acetyl, propionyl, chloroacetyl, Methoxyacetyl, / I-bromopropionyl radical, furthermore Residues of lower alkyl sulfonic acids and aryl sulfonic acids, for example the methylsulfonyl, chloromethylsulfonyl, Ethylsulfonyl and toluenesulfonyl radicals, as well as radicals of the Carbonic acid monoesters with lower alcohols, for example carbomethoxy, carbethoxy, carbomethoxyethoxy, the carbäthGxyäthoxyest. The azo components used according to the invention show relatively good coupling power, so that the yield of the azo coupling is mostly technical is satisfactory to very good. The azo coupling is carried out in an alkaline medium, often advantageously in the presence of magnesium oxide ,. Calcium hydroxide and / or water-soluble tertiary nitrogen bases, such as pyridine, Triethylamine, methyl or ethyl diethanolamine, triethanolamine.

The metallization of the monoazo dyes obtainable according to the invention in substance by treatment with chromium- or cobalt-releasing agents is expediently carried out in an aqueous solution or suspension in the heat, open or under pressure, with alkali metalicylchromates for chromium plating and cobalt salts for cobalt plating with an alkaline reaction of the agent be used. The metallization of unsulfonated o-Alkoxyazofarbstoffen by the hydroxyl group is carried out by replacing the alkoxy useful in organic solution at elevated temperatures, for example at 120 to 160 ⁰ C, in formamide or alkylene glycol having Chromisalzen through. In the process according to the invention, uniform monoazo dyes according to the invention or their mixtures with one another or with other unsulfonated ο, ο'-dioxy or o-carbonoxy-o'-oxyazo dyes can be subjected to metallization.

The alkali salts of the particularly valuable, consisting of 2 unsulfonated dye molecules and a heavy metal atom existing chromium and cobalt complex compounds obtainable according to the invention are mostly in the presence of anion-active wetting and dispersing agents in hot water clear and sufficiently soluble to make neutral to be able to be colored to weakly acidic liquor. They dye wool and super polyamide or urethane fibers each according to the composition and the complex bound heavy metal in brown-violet, deep brown to brown-red Shades that are characterized by good to very good lightfastness.

In comparison with the o, o'-dioxyazo dye of the composition 6-methyl-4-nitro-2-amino-1-oxybenzene - »- 2-acetylamino-4-methyl-1-oxybenzene known from US Pat. No. 2229 200 The ο, ο'-dioxyazo dye obtainable according to the invention and having the composition 4-nitro-2-amino-l-oxybenzene - »- 2-acetylamino-4,5-dimethyl-l-oxybenzene gives a chromed wool dyeing of better lightfastness and evening color and in comparison with the cobalt complex compound known from French patent 1,073,728 of the ο, ο'-dioxyazo dye of the composition 4-nitro-2-amino-1-oxybenzene ■ * - 2-acetylamino-4-methyl-1-oxybenzene gives the cobalt complex compound obtainable according to the invention of the ο, ο'-dioxyazo dye of the composition 4-nitro-2-amino-1-oxybenzene - »- 2-acetylamino-4,5-dimethyl-1-oxybenzene a wool dye with a better evening color.

The following examples serve to illustrate the subject matter of the invention in greater detail. In it mean the parts, unless otherwise noted, are parts by weight, and the temperatures are in degrees Celsius specified. Where parts by volume are expressly mentioned, they are in the same proportion to the parts by weight how liters to kilograms.

OH

example 1
OH

V-N =

NO ₉

- NH-COCH,

CH

CH,

Chromium complex compound

15.4 parts of 4-nitro-2-amino-1-oxybenzene are diazotized as usual. The excess acid is truncated with sodium bicarbonate and the suspension of the yellow diazoxide in a solution, cooled to 5 °, of 18.8 parts of 2-acetylamino-4,5-dimethyl-1-oxybenzene, ISO parts of water, 4.2 parts of sodium hydroxide and 12 Parts poured anhydrous sodium carbonate. It adds so much pyridine added that a 20 ° / ₀ strength solution, and stirred at 0 to 5 ° until the end of pigment formation. The coupling mixture is then admixed with hydrochloric acid until the Congo acid reaction occurs and the dye which has separated out is filtered off. To clean it, it is suspended in hot water and converted into the sodium salt with sodium carbonate. By adding sodium chloride, this is completely separated out and filtered off. It dyes wool in real brown shades using the single-bath chrome plating method.

The moist dye is suspended in 600 parts of hot water and refluxed with 120 parts of a solution of sodium chromium salicylic acid, corresponding to 3.1 parts of chromium, until the starting dye has disappeared. The chromium-containing dye is completely separated out by adding sodium chloride and filtered off. It is soluble in hot water and dyes wool from neutral to weakly acidic baths in very real brown tones.
. In a dyebath which contains 2 parts of this dye and 3 parts of ammonium acetate in 4000 parts of water, 100 parts of wool are placed at 40 °, heated to boiling for 30 minutes and kept at this temperature until the liquor is practically exhausted, which is the case after about half an hour. The wool, dyed in level brown tones, is rinsed and dried.

The dyes of Examples 2 and 3 below and those mentioned in the table can also be used in the same way to be colored.

Similar dyes are obtained if 18.9 parts of 6-chloro-4-nitro-2-amino-1-oxybenzene are used instead of 4-nitro-2-amino-1-oxybenzene or 16.8 parts of 6-methyl-4-nitro-2-amino-1-oxybenzene are used.

OH

Example 2

OH

V-N = N

NO ₉

CH

COCH ₃
Chromium complex compound

15.4 parts of 4-nitro-2-amino-1-oxybenzene are how usually diazotized. The slurry of the diazoxide neutralized with sodium bicarbonate is dissolved in a solution of 18.8 parts of S-acetylamino ^ .i-dimethyl-l-oxybenzene,

i U44 S 1 I.

4.2 parts of sodium hydroxide and 12 parts of anhydrous sodium carbonate are poured into 150 parts of water. After adding as much pyridine, that a 30 ° / ₀ solution disfigured is stirred at 0 to 5 ° .to the termination of dye formation. It is acidified with hydrochloric acid until the reaction is Congo-acidic, the precipitated dye is filtered off and purified by converting it into the sodium salt. He dyes wool in real brown shades using the single-bath chrome plating method.

The moist dye is dissolved in 600 parts of hot water with 120 parts of a solution of chromsalicylic acid Sodium, corresponding to 3.1 parts of chromium, under reflux cooling until the metallization reaction has ended heated. The chromium-containing dye is completely separated out by adding sodium chloride and filtered off. It is soluble in hot water and dyes wool from a weakly acidic bath in real brown shades.

Example 3
OH OH

38.2 parts of the sodium salt of the diazotized according to the information in Example 2! 4-nitro-2-amino-1-oxybenzene and 20.5 parts of S-carbomethoxyamino ^^ - dimethyl-1-oxybenzene available metal-free dye are suspended in 600 parts of water and with 60 parts of a cobalt acetate solution, corresponding to 3.54 parts of cobalt, heated to 80 to 90 ° for 1 hour. The metallization mix is then made alkaline to phenolphthalein with sodium carbonate and after stirring for 2 hours

ίο at 80 to 90 ° the dye completely through sodium chloride deposited and filtered off. It is soluble in hot water and dyes wool from a weakly acidic bath in red-brown tones of excellent lightfastness. The table below contains more examples of heavy metal containing monoazo dyes according to the invention, which are prepared according to the methods described in Examples 1 to 3 above.

Example 4

OH OH

, -N = N- / V-CH.

NO ₉

NH

CO

CH,

OCH ₃
Cobalt complex compound

No. Diazo component Azo component Me Shade on wool 1 4-nitro-2-amino-1-oxybenzene 2-carbomethoxyamino-4,5-dimen-
ethyl 1-oxybenzene Cr Brown 2 the same 2-acetylamino-4,5-dimethyl-
1-oxybenzene Co Brown 3 the same S-propionylamino ^^ - dimethyl-
1-oxybenzene Co Red-brown 4th 4-nitro-6-chloro-2-amino-l-oxy-
benzene S-acetylamino ^. ^ Dimethyl-
1-oxybenzene Cr Brown 5 4-nitro-6-methyl-2-amino-1-oxy-
benzene the same Cr Brown 6th o-nitro ^ -chlor ^ -amino-l-oxy-
benzene the same Cr Brown purple 7th 4-chloro-2-amino-1-oxybenzene the same Cr Brown purple 8th the same S-carbomethoxyamino ^^ - dime-
ethyl 1-oxybenzene Co Reddish brown
violet 9 5-nitro-2-amino-1-oxy benzene S-acetylamino ^^ dimethyl-
1-oxybenzene Cr Gray purple 10 4-nitro-2-amino-1-oxybenzene 2-propionylamino-4,5-dimethyl-
1-oxybenzene Cr Brown 11 the same S-carbethoxyamino ^^ dimethyl-
1-oxybenzene Cr Brown 12th 4-nitro-6-methyl-2-amino-1-oxy-
benzene the same Co Red-brown 13th 4-nitro-2-amino-1-oxybenzene S-carbomethoxyamino ^^ dime-
ethyl 1-oxybenzene Cr Brown 14th o-acetylamino ^ nitro ^ -amino-
1-oxybenzene S-acetylamino ^^ dimethyl-
1-oxybenzene after-
chromed Brown 15th the same 2-acetylamino-4,5-dimethyl-
1-oxybenzene after-
chromed Brown

23.4 parts of 4-nitro-2-amino-1-oxybenzene-6-sulfonic acid are suspended in 200 parts of water with the addition of 15 parts of 30% strength hydrochloric acid and at 0 to 5 ° with 16.6 parts by volume of a 33.3 ° / ₀ igen sodium nitrite solution diazotized. The clear diazo solution is neutralized with sodium bicarbonate and at 0 to 5 ° in a solution of 18.8 parts of 5-acetyl-2,4-d: methyl-1-oxybenzene, 4.2 parts of sodium hydroxide and 12 parts of anhydrous sodium carbonate in 150 parts Poured water. 100 parts by volume of pyridine are added and the mixture is stirred at 0 ° to 5 ° until the formation of the dye has ended. It is then acidified with hydrochloric acid until the reaction is Congo-acidic, the precipitated dye is filtered off and dissolved in hot water by adding sodium carbonate. The sodium salt of the dye is precipitated with sodium chloride, filtered off and dried. It is a dark brown powder that is used to dye wool, for example, as follows:

In a dyebath containing 1.5 parts of the dye, 10 parts of Glauber's salt and 3 parts of 40% acetic acid in 3000 parts of water, 100 parts of wool are added at 40 to 50 °, brought to a boil and boiled for ¹ Z ₂ hours with the addition of 1 part sulfuric acid. Then 0.8 parts of potassium chromate are added and the mixture is boiled for a further 40 minutes. A very real brown coloration is obtained.

A dye with very similar properties is obtained when using the azo component in the above example 18.8 parts of 2-acetylamino-4,5-dimethyl-1-oxybenzene were used.

Claims (4)

Patent claims: 1. Process for the production of metallizable monoazo dyes and their heavy metal complex 30th compounds, characterized in that a benzene diazonium compound which is in the o-position to Diazo group contains a hydroxyl group or a substituent convertible into a hydroxyl group and can be further substituted, couples with such a 4-methyl-1-oxybenzene compound, which in the 2- and 5-positions still have a methyl and contains an acylamino group, whereupon the dye obtained in substance or on the fiber, optionally with conversion of substituents in the o-position to the azo group into the hydroxyl group converted into chromium or cobalt complex compounds. 2. The method according to claim 1, characterized by the use of a mononitrated benzene diazonium compound, which contains a hydroxyl group in o-position to the diazo group and can be further substituted. 3. The method according to claim 1 and 2, characterized by the use of a 4-nitro-2-diazo-1-oxybenzene compound, which can be further substituted. 4. The method according to claim 1, 2 and 3, characterized by the use of a diazo component, which does not contain any carboxyl or sulfonic acid groups. Considered publications: French Patent No. 1,073,728;
U.S. Patent No. 2,229,200. When the registration was announced, 2 staining tables were laid out. SOS'67SßOZ 11.58.