DE947013C - Process for the production of basic methine dyes - Google Patents

Description

(WiGBl. P. 175)

ISSUED AUGUST 9, 1956

F 323 ¹ J IVb 122 e

(Ges. Of 15.7.1951)

There are already dyes known that by condensation of heterocyclic ω- aldehydes - that is, compounds that contain an aldehyde radical in the 2-position to the nitrogen atom of the hetero ring - arise with bodies which in a ring a

- C - N grouping

Rhodanine or its N-alkyl,

how

contain

N-alkylene, N-aralkyl or N-aryl substitution products. These dyes are water-insoluble products, which is why their use is natural much more difficult.

It has been found that valuable water-soluble dyes can be obtained by using these Starting materials for example with haloalkylates, e.g. B. iodine alkyl or alkyl sulfates condensed. The resulting New dyes therefore have the valuable property of water solubility, as they do this Dye class not previously exhibited. These dyes can now also be used to make wool and silk color well. In addition, there is a color shift towards the long-wave part of the spectrum the starting body.

The dyes used as the starting material have the following general composition: "

5 C \ /

II C = CH-CH = O

C / I C = S

W W \

Herein, R ₁ denotes alkyl, R ₂ denotes H, alkyl, alkylene,

Aralkyl, aryl, X 0, S, Se, C ( ^CHs , - CH = CH-, ^6s

■ - ^ CH ₃

A and B aryl, alkyl or H or H ₂ or A and B together form a benzene nucleus, which in turn can be substituted.

These dyes are compared with those in cyanine dye chemistry common quaternizing agents such as alkyl halides or alkyl sulfates by heating condensed to dyes of the following composition:

bA, '

Egg 1 +

C = CH-CH = C

I Ό = CC "- S - R ₁

Herein Z means any acid residue, e.g. B. such as - Cl, - Br, - I, - SO ₄ , - Cl O ₄ , - alkyl · SO ₄ , p-toluenesulfonate. The other reference symbols mean the same as above.

Here, the quaternized dyes obtained can, if necessary, by that in cyanine dye chemistry customary methods of salination can be modified.

Example ι. _go

The dye from i 3, s-trimethylindoline-co-aldehyde and N-Äthylrhodanin, the orange is, is reacted with an excess of dimethyl sulfate ¹ J heated for ₂ hour at 120 °; the color changes more to red. The resulting dye is washed with ether alcohol and appears in shiny green crystals. Solution color in water / methanol red. Absorption maximum at 535 ταμ.

CS-CH ₃

CB.S0,

Example 2 -

The dye from 1, 3, 3-trimethyl-5-methoxymdoline-co-aldehyde and rhodanine

H ₃ CO "-I

CH ₃ CH ₃

= CH-CH = C

O = C

C = S

CH ₃

is heated with an excess of dimethyl sulfate io minutes at 130 ^0th The resulting dye is purple-tinged red. Absorption maximum
in methanol 545 ταμ. 65

CH ₃ CH ₃

HXO-

-C ^

CH ₃ , S,

= CH-CH = C

O = C C ^- -S-CH,

CH ₃ SO

₃ SO ₄

Example 3 20 The dye from i-ethylbenzobiazole-co-aldehyde and N-ethylrhodanine

C = CH-CH = C C = S

NC ₂ H ₅

C ₂ H ₅

is reacted with 1,2 mole of diethyl ¹ Z heated for ₂ hour at 130 ^0th The resulting dye has a carmine-red color on tannin cotton
on:

/ C = CH-CH = C

O = C

C ₂ H ₅

C ₂ H ₅ CHSO *

⁵⁰ Example 4

The dye from i-ethylthiazolin-oj-aldehyde and | Heated dye formation. The resulting dye 115

N-Ethylrhodanine is treated with dimethyl sulfate up to | is yellow. Absorption maximum 482 ΐημ:

H ₂ C

H ₂ CC —S —CH,

C = CH-CH = C

S C ₂ H ₅

C ₂ H ₅

Example 5 "
Analogously to Example 4, a dye of the following composition is obtained with phenylrhodanine:

r s.

H ₂ C

CH ₃

Absorption maximum 490 τημ.

C = CH-CH = C

H ₉ C

C-S-CH,

CH ₃ SO ₄ -

Example 6

From i-ethyl-benzselenazoline-CD-aldehyde and. Allylrhodanin is a dye with the following compounds setting received: ■ <-. 80

Ί-Se /

^ C = CH-CH =: C

JN I CS-CH ₃

I O = C

(Allyl).

CHoSO,

Absorption maximum 545 ηιμ.

Example 7

35 95

From i-ethyl-i, 2-dihydrochinoh ^ i-2-methine-a) -aldehyde and allykhodanine a dye becomes the following

Composition obtained:

C - S - CH,

CH ₃ SO

₃ SO ₄

Absorption maximum 555 ταμ.

Claims (1)

Claim ·. - Process for the preparation of basic methine dyes, characterized in that the condensation products of heterocyclic ω-aldehydes with compounds which have a reactive CH ₂ group and also an S in a ring: - C - N - grouping contain ', as in particular with rhodanine and
whose -N-alkyl, N-aralkyl or N-aryl substitution products, ■ reacts with the quaternizing agents customary in cyanine dye chemistry, such as 115 alkyl halides or alkyl sulfates. Considered publications:
British Patent No. 438 420. 1 609574 8.56