DE1927089A1 - Process for the preparation of disazo dyes - Google Patents

Description

CIB AAKTIE N GESE L L SCHAF T, BASEL (SCH WE IZ)

Case 6476 / E
Germany·

Additional patent to main patent no.

Registration P 1.643 283.O - Case 6087 / I + 2 / E

Process for the preparation of disazo dyes.

The main patent no. (Application P 1.643-283.0)

describes a process for the preparation of new disazo dyes of the formula

wherein R ₁ and R ₂ each have a hydrogen atom or substituted or unsubstituted alkyl groups which _{can be bonded to a ring with the radical. A or A p} in the ο-position to the _{coupling-directing nitrogen atoms, R 3} and R ^ alkylene groups which are the Nitrogen atoms and Z connect via preferably at least 2 carbon atoms, the groups -I

009848/1729

-NFL-RZ- or -NR-FL-Z a peri; .opyrazL. . it can form, A and A _p each a p-phenylene radical, D and Dp each the radical of an optionally quaternized diazo component, which preferably contains no heterocyclic rings and / or no quaternizable heteroatoms, and Z is a divalent bridge member preferably containing at least one heteroatom and without dye character which, if D, and / or Dp contains a heterocyclic group and / or a quaternizable heteroatom, is preferably (l) free of ether or CN bonds and / or (2) is not a divalent hydrocarbon radical, and which is in a training is characterized in that one bifunctional coupling components of the formula

HA ₁ -NR-RZR ^ -NR-AH

with the diazonium compounds of the diazo components D, -NHp and Dp-NH to form disazo compounds of the formula (1) and optionally quatßrnisiert the disazo dyes obtained on at least one of the radicals - D or D ₂ , if these contain quaternizable groups.

It has now been found that the disazo dyes, which can be alkylated, are particularly smooth and elegant obtained when the coupling is carried out with hydrazones of the diazo components or similar compounds.

009846/1729

The present invention therefore relates to a process cure preparation of the dyes of the formula (1), which is characterized in that one mole of a bifunctional coupling component of the formula

H -A _L -NR -RZ -R ^ -NR ₂ -A ₃ -

with two moles of a derivative of a diazo component in which the spatial arrangement of the nitrogen atoms of the azo group is present without it being a diazo compound acts in the usual sense, couples, and, if the diazo component can be quaternized, optionally simultaneously during the coupling or in a subsequent S '. ufe quaternized.

Derivatives of diazo components in which already the spatial arrangement of the nitrogen atoms is available, e.g. hydrazines or stable azo compounds, in which the azo bridge has a negative, organic, against coupling components bears interchangeable rest. Such azo compounds are e.g. the quaternary azo sulfones of the thiazole, Benzthiazole and quinoline series.

BATHROOM ORIGINAL - 3a -

Particularly suitable are the derivatives of heterocyclic amines, which couple in the presence of oxidizing agents, such as thiazole and imidazole derivatives, in which in the 2-position already the arrangement of the formula required for the azo bond

ι i

-C- • C,

C-N-

-N '

wherein X is an alkylimino group, an irinino group or preferably represents a sulfur atom and Y represents a hydrogen atom or an alkyl group. Connections of this kind

00934 6/1729

-v-

are in particular the hydrazones of imidazoles, benzimidazoles and especially thiazoles and benzothiazoles, which may optionally have alkylated nitrogen atoms, or the corresponding hydrazones, such as the methane, chloromethane, ethane (2-sulfuric acid esters), benzene, 4-toluene , 2,5-dichlorobenzene-, 2- or 3-nitrobenzenesulfonylhydrazones of heterocyclic (aromatic or partially hydrogenated) carbonyl compounds, e.g. the N-alkylbenzthiazolones- (2), N-alkyl-4,5 _J .6,7-tetrahydrobenzthiazolones- ( 2), N-alkyl-, N-aralkyl- and N-arylthiazolones- (2) and -pyridones- (4), N-alkylpyridones- (2), N-alkylquinolones- (2) and - (4), N -Alkyl-3,3-dimethylindolinone- (2), Ν, Ν'-dialkylbenzimidazolones, N-alkyl, 2,4-triazolone- (3), N-alkyl-l, 2,4-thiadiazolone- ( 3) and -l, 3i ^ -thiadiazolone- (2). These heterocyclic ring systems can also have "further fused rings" and also substituents such as halogen atoms, alkyl, alkoxy, aryl, mercapto, alkylsulfonyl, arylsulfonyl, carboxylic acid ester, nitro or optionally substituted amino, sulfonic acid amide or carboxamide groups wear.

The hydrazones used as starting materials can be either alkylated or partially alkylated (e.g. in the case of the N-alkylimidazoles) or in non-alkylated form will.

The 2-hydrazino derivatives may be mentioned as starting compounds from

009846/1729

Benzthiazole, 6-methoxybenzthiazole, 6-methylbenzothiazole, 6-cyanobenzothiazole, 6-acetylaminobenzothiazole, 7-methylbenzothiazole,

6-ethoxybenzothiazole, 6-nitrobenzthiazole, thiazole,

3i4-diphenylthiazole, 3i ⁱ l - dimethylthiazole, 3,4- (1 ', 2'-naphtho) -thiazole,

3,4- (2 ', l'-naphtho) -thiazole _J ~ ■

3,3-dimethylindolenine, 5-chloro-3,3-dimethylindolenine, 5-bromo-3i 3-dimethylindolenine, 6-methoxy-3,3-dimethylindolenine, 5-methoxy-3J3-dimethylindolenine _J 6-acetylamino-3 * 3 -dimethylindolenine, 5-benzoylamino-3,3-dimethylindolenine, 5-nitro-3,3-dimethylindolenine and the compounds of the formulas

00 9846/1729

CIL

■ = H-NH-SO.

H, CN> = Ν-ΝΗ SO ₀

-C CH, ί \ / 3

I. V

Il
CC

Xi = N-

^C 6 ^H 5

98 4 8/1729

H-O-C 3

CH,

The coupling with simultaneous quaternization can be carried out using the model of a monoazo dye as follows " represent:

R ₁

C = N-NH ₀ + H-dVN " ²

CH ₃

Examples of dehydrating or oxidizing agents are atmospheric oxygen, hydrogen peroxide, hypo-. chlorites, persulfates, perborates, iron (IIl) -, copper (III) -, mercury (II) -, lead (IV) or cerium (IV) salts and hexacyanoferrate (III) to be mentioned, if necessary, oxygen carriers, e.g. heavy metals and their salts, can also be used can also be used.

The hydrazones can be prepared by known methods [R.Riemschneider and S.Georgi, MONTHS FOR CHEMISTRY, Volume 91, 623 (1960); S. Hünig et al, Angewandte Chemie Volume JO, 215 (1958); Volume ^J4,818 (1962); Volume 80, 343 (1966); Chimia, Volume 1 ^ _x 133 (I96I); H.Baumann and H.Dehnert, Chimia, Volume 1 ^, I63 (I96I)].

009846 / 172S

The hydrazine derivatives of negatively substituted benzenes are also suitable.

The coupling components mentioned in the main and additional applications mentioned above, compounds containing acyl groups or ester groups are preferably used. Also in terms of application For the quaternized connections that have arisen, what is said in the above-mentioned main and additional registrations applies.

• In the following examples, unless otherwise specified, the parts mean parts by weight, the Percentages by weight and temperatures are given in degrees Celsius.

Example Ir

19 parts of 3-methyl-benzthiazolon-2-h7 / drazon are concentrated in 3OO parts by volume of water and 10 parts by volume. hydrochloric acid stirred. A solution of 22 parts of di- [ß- (N-ethyl-N-m-tolyl) -amino] -ethyl adipate is then added in 200 parts by volume of methanol and 20 parts by volume of conc. Hydrochloric acid too. 200 parts by volume of a 35% iron (III) chloride solution are added at room temperature and the solution blunted by adding sodium acetate solution. After the coupling is complete, the dye, if necessary, salt out, filter off and dry in vacuo

A product of the formula is obtained
Cl "

\ j H.-O-CO-CH ^ -CH; CH ₃ ⁴

which colors polyacrylonitrile in blue tones.

If the hydrazones indicated in column I are coupled with the coupling components indicated in column II, so one obtains dyes, which polyacrylonitrile in the in Color column TII given tones.

BATH ORIGINAL

ü u Ji 8 ■ »ß -T. ■

II

CO

C = Ii-NH,

blue

r /

Nj ₀ H ₁₁ -O-CO-CH,

On-

C ₀ H ^ -CN

On

C _O H.-CN _Γ / 2

Nj ₂ HO-CC

009846 / $ 172

4Ϊ

CH.

^: 10

i ii

• s ·

C = NNH _0/2

CH.

H CO

C = NH-SO "C _C H _C

2 6

fS

Nl = IiNH ₂

C ₂ H ₅

"T 7- ~

II

C ₀ H ₁ -

j / 2 5

N ₀ H ₇₁ -O-CO-C ₀ H

2 4

^1/2 5

C ₀ H ₁

C _O H _C t / 2 5

OCOCH ₂ -

C ₀ H.CN

i ₂ H occ

C ₀ H, CN

₂ H oco—

009846/1729

blue

blue-violet

blue

1927Q89

N.
\

C = NNH

H "C CH" ί 5 N _0/3

¹³ ! • C = NNHSO ^ H ₁

CH,

II

OK

C ₀ H.CN ^{2 4}

-H .

blue

blue- j purple

violet violet

Example 2.

3.4 parts of the compound of the formula N

CH
6 5

[Y

0 _o S ^/ ^ ^s
2

C-NHNH

and 2 parts of the coupling component of the formula

₀ H, GN NCH.C ^{2 4 4}

v / earth presented in 50 parts by volume of glacial acetic acid. In addition you give one Trace of iron (II) sulfate and 3 parts by volume are added dropwise with stirring 35 ^ iges HO to. After the coupling is complete, the dye is with V / ater precipitated, filtered off, washed well with V / ater and dried in vacuo. A product of the formula is obtained

.H_
6 5

which dyes polyester with a red shade.

If the hydrazones indicated in column I are coupled with the coupling components indicated in column II, then one obtains dyes ^ which polyester fibers in the in Color column III indicated colors.

II

ο., κ ·

C-NHNH-30

IL

CAL.

■ If

CH-

ruby

I blush ig red

i \ x \

COCIL.

C,

C-IiKIiH

, S.

i /

Q— ΙΙΙϊ2ϊΗ3Ο,

NHC -H ₁ .

00 9 8

N;

^ h.

46/1729

BATH

ruby

blue- j tinged i Red ;

-NHNH,

HC S

Il I

C-NHNH,

Q ^ C-NHNH ₂

III

Red

bluish red

Red

0098A6 / 1729

Example "5.
0.95 parts of the quarfare azosulfone of the formula

OH _n

+ N

BF,

and 0, ^ 9 parts of. Coupling component of the formula

C ₀ H.CN

^{2 4}

are refluxed for some time in 60 parts by volume of acetone. By adding sodium chloride solution, the resulting Dye precipitated, filtered off and dried in vacuo. A product of the formula is obtained

r =

Cl "

+ N

H ₅ C ₂

'C-N = N-

-W

₂ H ₄ 0C0-C

which colors polyacrylonitrile in blue tones.

If the hydrazones indicated in column I are coupled with the coupling components indicated in column II, dyes are obtained which acrylic fibers in the in column III . color specified tones.

6/1729

J *

! 3 ί

CIL

BP ₁

⁾ 2 ^C 6 ^H 4 ^CH 3

F ^ N = N-SO ₀ C, -H. CH,

1+ d D 4 y

° 2 ^E 5 BP. "

fN = NS0 _o C _c + 2 6

^C 2 ^H 5 BP

II

III

C ₀ ILCN

^4th

blue

Ο, Η. CN

Il
C.

^C 2 ^H

CH. I ₄ -OCOC ₂ H ₄ -

violet blue

009846/172

Claims (1)

Claims. . 1. Process for the preparation of dyes of the formula 1 ₂ where R, and R _{p are} each a hydrogen atom or alkyl groups, which can each be connected to a ring with the beat A. or A in o-3position to the coupling-directing Si-iakstoffatomen, R .. and R ^ alkylene groups, which the Nitrogen atoms and Z via vc-r: -; u ^ sweise at least 2 carbon atoms connect, the groups -NR, -R -.- ZR ₄ -N -NR, -R- -Z- or -NRp-R ₄ -Z - Can form a ferhydropyrazine radical, A ^ and A ₀ each a p-phenylene _{radical, D 1} and D. each the radical of an optionally quaternized diazo component * which preferably contains no heterocyclic rings and / or no quaternizable heteroatoms and Z preferably contains at least one heteroatom divalent bridge link without dye character which, if D and / or D _{0 is} a heterocyclic group and / or a 1 <- contains quaternizable heteroatom, preferably (1) free of ether or C-N bonds and / or (2) is not divalent Hydrocarbon residue is, thereby 0 0 9 8 A. 6. / 1 7 2 9 BAD ORlGINM. characterized in that one bifunctional coupling components of the formula with two moles of a derivative of a diazo component in which the spatial arrangement of the nitrogen atoms of the azo group is present without it being a diazo compound in the usual sense, couples and, if the diazo component can be quaternized, if appropriate simultaneously during the coupling or in a subsequent one Quaternized level. 2. The method according to claim 1, characterized in that that one starts from hydrazones, which are the diazonium compounds of the diazo components in the arrangement correspond to the nitrogen atoms. 3. The method according to claim 2, characterized in that one of the NHp group is unsubstitu.ten Runs out of hydrazones. 4. The method according to claim 2, characterized in that substituted on the NHp group Runs out of hydrazones. 5. Process according to claim k, characterized in that sulfonylhydrazones are used as the starting material. 009846/1729 9 * 6. 'The method according to claim 2, characterized in that coupling is carried out in the presence of oxidizing agents » 7. The method according to claim 1, characterized in that couplable compounds are used _s the one radical of the formula R'-Bh- (CH = CH) - ^ C = N-JF contain, where R ^! an alkyl, cycloalkyl, "aralkyl or aryl radical, n. one of the numbers 0 to 1, X 'a divalent atom or a divalent one to form an unsaturated heterocyclic one 5- or 6-membered ring capable group mean" δ. Process according to claims 2 and 7 * characterized in that that one uses diazo components that have a Atom skeleton of the formula contain-, where X is an imino = or alkylimino group or preferably represents a sulfur atom and Y represents a hydrogen atom or an alkyl group. 009846/1729 _BAD ORlGiNM- «■■■■" .. 9 · The method according to claims 7 and 8, characterized thereby draws that hydrazones of imidazoles or thiazoles or their benz derivatives are used « 10. The method according to claims 1, 7 and 8, characterized characterized in that stable azo compounds are used, in. which the Aezo Bridge has a negative * organic, against Coupling components replaceable rest carries * 11. The method according to claim 10, characterized 'characterized' that one quaternary © azosulfones from heterocyclic Slide components used. 12. The method according _{spoke Ii 5,} characterized in that sian qv.artäre «zosulfone der Thiaaol-, Benzthl £: .aol-GäerCIiinolinlinie" iferw 13. The method according to claims 1 Ms 12., characterized in that "that, one acyl group-containing © used coupling components _o 14. The method according to claim I ¹ I-, characterized in that-one uses coupling components containing ester groups «, 15. The method according to claim 13 *, characterized in that that one uses coupling components. In which the rest of Z contains at least one acyl group, preferably at least one ester group. 009846/1729 ORKSNAL INSPECTED