DE156477C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

- M 156477 CLASS 226.

When trying to condense Alizarin with b-amidophenol, the reaction Triphendioxyazin ^ ^ i8 is the only 10-grasp product - won ^ 2 Oi, so that one must assume that the Alizarin here only acts as an oxidizing agent. On the other hand, it has been possible, by condensation of o-amidophenols with alizarins hydroxylated or amidated in the 4-position, respectively. whose

ίο to represent sulfonic acids well characterized anthraquinone derivatives that contain an oxazine ring. The presence of such is evident from the insolubility of the dyes containing no sulfo groups in dilute alkalis and is further confirmed by the analysis of the condensation product of purpurine and o-amidophenol, which resulted in numbers _{that match the formula C 20} H _n NO _1.

Accordingly, the following two constitutional formulas could be assigned to this connection:

I.

or

OH

II.

OH

of which the former is more likely because this body generally has the Has properties which in "Example V of the patent 141575 for the formula I corresponding Oxidation product of i-anilido-2 · 4-dioxyanthraquinone are given.

Example I: 13 kg purpurin be heated for several hours under pressure to 140 ⁰ with 8 kg o-amidophenol, 13 kg of boric acid and 60 1 of alcohol. After cooling, the contents of the pressure vessel are filtered off and the residue is extracted with cold pyridine. The oxazine remains undissolved and can be obtained in purple needles by recrystallization from pyridine.

The body is insoluble in water and in the usual inert solvents extremely difficult to dissolve; in hot pyridine it dissolves with blue, in hot glacial acetic acid with a reddish blue color. The solution in concentrated sulfuric acid is green-blue. In the body is insoluble in watery alkalis; by adding caustic soda to the alcoholic Suspension becomes the sodium salt soluble in hot alcohol with a pure blue color educated. The sulfonic acid obtained by treating the body with sulfonating agents colors unheated wool in beautiful blue-violet tones.

The same procedure is followed when using 4-amidoalizarin.

Example II: 18 kg of purpurin sulfonic acid (acid potassium salt), shown according to the information of the patent 84774, with 8 kg of o-amidophenol, 13 kg of boric acid and 60 1 Water for several hours in the enamelled

Pressure vessel heated ^{to 140 0.} The deposited product is filtered off after cooling and freed from unchanged purpurin sulfonic acid by leaching with hot, dilute soda solution. For further purification, it can be dissolved in water and precipitated from the aqueous solution with a little common salt.

The dye represented in this way dissolves difficultly in cold water, more easily in hot water with blue color. The aqueous solution is precipitated with soda or caustic soda. the Solution in concentrated sulfuric acid is green. On unheated and chrome-stained You get beautiful blue tones from wool.

The heteronuclear purpurin sulfonic acids behave analogously to the above purpurin sulfonic acids, which are obtained by using the o-methoxyanthraquinone sulfonic acids described in patent 145188 respectively the α-oxyanthraquinone sulfonic acids formed therefrom by cleavage sulfonated to oxyanthraquinone trisulfonic acids and these are then heated in aqueous solution with lime under pressure.

Instead of o-amidophenol, its substitution products or homologues, e.g. B. the o-amido-p-cresol (CH ₃ : NH ₂ : OH = 1: 3 .: 4) can be used.

Oxazine.

Oxazine from: Solution in: Pyridine Glacial acetic acid more focused
H ₂ SO, 2 percent
smoking
sulfuric acid Purpurin + o-amidophenol blue blue ■ blue green blue green Purpurin + - amidocresol
(CH _S : NH.,: OH = 1: 3: 4) blue blue blue green blue green 4-amido-alizarin + o-amidophenol blue blue red-violet in the through
falling, blue im
striking light green.

The distinctive features of some of the dyes in this range are as follows Tables indicated:

Oxazine sulfonic acids.

Oxazine from:

Solution in:

Water more concentrated

Coloring on wool

Coloring on

chromed

Wool

Purpurin + o-amidophenol sulfurized

blue reddish green-blue

violet

Purpurin + amidocresol sulfurized

blue reddish green-blue

violet

4-amidoalizarine + o-amidophenol
sulphurized

blue, red-violet in the diaphanous, blue in the
striking light

blue

green

green

blue

Purpurinsulfonic acid 4-o-amidophenol

blue green

blue

green.

Claims (1)

Patent claim:
Process for the preparation of oxazine derivatives of the anthraquinone series, consisting in that one is hydroxy in the 4-position. lated or amidated alizarines condensed with o-amidophenols.