DE127245C - - Google Patents

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PATENT OFFICE.

PATENT LETTERING

M 127245 CLASS 22 β.

FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in ELBERFELD. Process for the preparation of basic stains.

Addendum to patent 121837 of July 21, 1900.

Patented in the German Empire on February 12, 1901. Longest duration: July 20, 1915.

In the patent specification 121837 it is shown that very valuable red to violet basic dyes can be obtained by one either unalkylated or alkylated amidoketones of the p-diamidobenzophenone type respectively the corresponding thioketones or auramines are condensed with α-methylindole, or by p-diamidobenzhydrol respectively. its alkyl derivatives condensed with a-methylindole and the leuco bases thus obtainable are oxidized to the dyes.

It has now been found further. that, in addition to α-methylindole (Pr ₂ - methylindole), α-phenylindole or in the benzene nucleus in the para position to the carbon imide alkylated or Halogen-substituted derivatives of α-methylindole and α-phenylindole are capable of providing valuable basic dyes by the process protected by the main patent. The following indole derivatives have proven to be particularly suitable according to previous experiments:

B ₃ Pr ₂ -dimethylindole.
Mp. 114 to 115 ° C.

CH,

CH

C-CH ₃

Ann. 239, p. 227.

Pr ₂ -phenylindole. M.p. 186 ^° C. CH

C ₆ H ₅

Ann. 236, p. 133.

-Bg-chloro-Pr ^ methylindole. Fp. I ₉ ⁰ C. "

Bj-methyl-Prj-phenylindole. Mp. 213 ⁰ C.

CH.

YY-

CH

C- C _n H ₅ NH /

.Bg-Chlor-Prjj-Phenylindole.

Mp. 196 ⁰ C. Cl ^ CH

YY

CC ₆ H ₅

The representation of the B
indols happens completely analogously to that of E. Fischer, Ann. 236, p. 126 for the a-methylindole (methyl ketol) described method. Instead of the hydrazone made from phenylhydrazine and acetone, the hydrazone made from p-chlorophenylhydrazine, which is obtained by known processes, and acetone are to be used. The cold aqueous solution of ι MoL. hydrochloric acid ρ - chlorophenylhydrazine and 1 mol. acetone mixed with acetic acid sodium and shaken vigorously. The hydrazone very soon separates out in solid form. After filtering off and pressing, the mass obtained in this way is fused with zinc chloride under exactly the same conditions and processed further as described for the preparation of methyl _{ketol. The β 3} -chloro-Pr ₂ -Methylindole is volatile with water vapors and possesses after recrystallization, from warm ligroin the melting point iig ° C. It crystallizes in flat crystals. _{For the preparation of the Pr 2} -phenylindole substituted by methyl or chlorine in the benzene nucleus in the para position to the carbon imide, the same applies to the Pr ₂ -phenylindole itself. 236, p, 133. The hydrazones to be used from p-tolyl- respectively. p-Chlorophenylhydrazine and acetophenone are also easily formed in the manner described above and separate after prolonged shaking! in solid form.

Both substituted phenylindoles are with

. Water vapors are difficult to escape and are best made from Acetoia-Ligroin or Chloroform-Ligroin umkrystall'isireji. The crystallization is only completed when standing for a long time.

B _z - methyl - Pr ₂ - phenylindole shows the melting point 21 ° C 3, JSG-Chloro-P ^ -Phenylindol the melting point of 196 ⁰ C. Both form slightly yellowish krystalJinische powder.

The characteristics of the dyes obtainable by the present process should be emphasized, i.e. the. Derivatives of those indole bodies which, in addition to being substituted _{by methyl in the Pr 2} position, are also alkyl or halogen-substituted in the benzene nucleus ^; , in which the nuances differ only slightly from the corresponding products derived from Pr ₂ -methylindole (ct-methylindole). On the other hand, the dyes obtained from Pr ₂ -phenylindole and from its derivatives alkylated or halogen-substituted in the benzene nucleus show a marked shift in shade towards blue. Uiradl in comparison) with the corresponding bodies, '-Methylindole a more difficult solubility in water. E.g. the dye obtainable from p-diamidobenzophenone and Pr ₂ -phenylindole is not red, but violet. , The product resulting from MicM.er's ketone and Pr _{2 -phenylindole is}

Spoken blue and difficult in cold water, easily soluble in hot water and in fuel.

Irt their other properties, e.g. B. in behavior against. Acids and alkalis, in the ability to be reproduced with table salt from mineral acid solutions, etc., the dyes are in every respect similar to those described in patent specification 121837.
. The process for the preparation of the new dyes is completely analogous to that of the main patent.

The following examples serve to explain the procedure:

Example 1.
P-diamidobenzophenone dye

and B ₃ - Pr ₂ -D ime thy lind al,
2.1 kg of p-diamidobenzophenone and 1.5 kg of i $ ₃ -Pr ₂ -dimethylindole of the formula:

-CH

C-CH,

we; rd, eu in, 2> o kg S> prit dissolved in the heat, 5 kg concentrate hydrochloric acid was added and heated on the water bath until almost boiling. The solution gradually turns purple-red, the condensation process is approx. Finished 3 hours. Half of the fuel is then distilled off and the liquid in stirred in with ice and table salt, mixed water. The precipitated dye is filtered off, with. little, k. saline water washed out · ,, vacuumed and dried at approx. 40 to 50 ". Egg? represents a brownish red Powder, which, in water, easily dissolves with rather color, and tannic cotton, Dyes silk and wool in vivid red tones.

Example 2.
F a, r b>s; t. ο ff from Au π am in G and Β _Ά , -

ChI <D> r- Pr ₂ - M et hy Ii α d ο Γ.
r 5 kg reines- Äuramin G and ^'8: 3 kg B ₃ - chloro-Pr ₂ ^-Methyß: ndol · the formula ^1:

CH

C-CH ₃

are with 65 kg 30 proc. Hydrochloric acid ge
and ι to 21 stands · heated on the water bath. The browned solution is then poured into ice water mixed with a little sodium chloride solution while stirring. The dye which precipitates out in dark flakes is filtered off, pressed and. dried at 80 to 90 ^0. He dyes tannic cotton, silk and wool red, violet.

Example 3.

Dye from tetraethyldiamidothiobenzophenone and Pr ₂ -phenylindole.

3.4 kg of tetraethyldiamidothiobenzophenone and 2.1 kg of Pr ₂ -phenylindole of the formula:

CH,

are finely ground and left with 20 kg of fuel and 8 kg of concentrated hydrochloric acid for 24 hours Water bath digests until all the ketone has disappeared. Escapes during the reaction slowly hydrogen sulfide. When the finished melt is poured into ice water, the greater part of it separates into cold water Water-poorly soluble dye in the form of dark blue flakes. The rest can be precipitated with a little common salt. The filtered, washed out with saline water, Pressed and dried dye is a dark powder, which dissolves in water with a magnificent, blue color and tannied cotton, silk and wool dyed blue in the neutral bath. Analog dyes arise from the phenylindoles which are alkyl- or halogen-substituted in the benzene nucleus.

The thioketone can be replaced by equivalent amounts of the oxygen ketone with the advantage that the condensation process is then completed more quickly.

Example 4.

Dye from tetramethyldiamidobenzhydrol and jB ₃ -Pr ₂ -dim ethylin dol.

ι. Representation of the leuco base.
2.7 kg of tetramethyldiamidobenzhydrol are combined with 1.45 kg of JJ ₃ -Pr ₂ -dimethylindole of the formula:

Dissolved in ι ο kg of fuel while warming and, after cooling, gradually concentrated with 4 kg Hydrochloric acid (30 pct.) Added. The condensation takes place very quickly. After soaking in water, the leuco compound becomes precipitated with sodium acetate, filtered off and dried.

2. Oxidation of the leuco compound.
4 kg of the leuco base are dissolved in 7.5 kg of concentrated hydrochloric acid and 50 liters of hot water, 5 kg of table salt are added and, with stirring, so much of a ferric chloride solution is gradually added dropwise until the dye, which separates out as a metallic, crystalline powder, no longer multiplies and the filtrate of a sample is only slightly purple in color when iron chloride is added. After cooling, it is filtered off and the dye is purified by dissolving it in water containing hydrochloric acid and salting it out with common salt. The dye forms a metallic, green, shimmering powder which is easily soluble in hot water and dyes tannic cotton, silk, and wool vividly violet. The colorations are more reddish than those of the dye described in patent specification 121837 made of tetraethyldiamidobenzhydrol and methyl ketol.

Claims (1)

Patent claim:
Modification of the process of patent 121837, consisting in that instead of the a-methylindole, a-phenylindole or in the benzene nucleus in the para position to the carbon imide is alkylated or. Halogen-substituted derivatives of a-methylindole and a-phenylindole are used.