DE2122975A1 - Basic dyes, their manufacture and use - Google Patents

Description

Basic dyes, their manufacture and use

The present invention relates to basic dyes of formula I.

-R

(D

where X is an oxygen or sulfur atom, R is an aliphatic, araliphatic, aromatic or heterocyclic radical nit a grouping of the formula

- N I

where R ^ and Rp are hydrogen, an alkyl, aralkyl or cycloalkyl radical, R, hydrogen, an alkyl, araikyl, cycloalkyl or alkoxy radical or an amino group and II with R ^ and / or Έ. ^ and / or S , can form a heterocyclic ring, R ^, R ₁ -, Rg and Hn are hydrogen or nonionic sweeteners and A® is an anion

209849/1117

Dyes of the formula II are of particular interest

^ N - Alk - N / I. CO R.

(ID

in which R. -H ", X- and A® have the meaning given above and Alk is a straight or branched chain, optionally means substituted alkylene radical with up to 6 carbon atoms.

The dyes can be prepared in such a way that dyes of the formula III

- R

(III)

where X and ¹ R ₁ , - R "have the meaning given above and R is an aliphatic, araliphatic, aromatic or heterocyclic radical which contains a primary, secondary or tertiary amino group, treated with an inorganic or organic acid or with quaternizing agents.

209849/1117

Examples of inorganic or organic acids are hydrohalic acids, sulfuric acid, phosphoric acid, Formic acid, acetic acid, propionic acid, lactic acid or glycolic acid can be considered.

Quaternizing agents are alkyl halides, aralkyl halides, Haloacetamides, ß-halopropionitriles, halohydrins, Alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or organic sulfonic acids, halogenamines or hydroxylamine-O-sulfonic acid into consideration.

The quaternization is expediently carried out in an inert organic solvent, for example in a hydrocarbon, Chlorinated carbon or nitrocarbons, such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride, such as dimethylformamide, N-methylacetamide or acetic anhydride, in dimethyl sulfoxide or in a ketone such as acetone or methyl ethyl ketone. Instead of an organic solvent, an excess of the Alkylating agent can be used. The quaternization is carried out at an elevated temperature, optionally with the addition of acid-binding agents, such as magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and optionally under pressure. The most favorable conditions in each case can easily be determined through a preliminary test. Possibly the quaternization can also be carried out in water.

The dyes of the formula III used as starting compounds can be prepared by known methods such as, for example in German Offenlegungsschrift 1 569 761, 1 569 755, 1 569 737 and in the German explanatory document 1,297,259.

209849/1117

2122S75

As aliphatic ^ radicals R are straight-chain or branched, optionally further substituted alkylene radicals with 1 to 6 carbon atoms, as araliphatic ^ radicals, for example, the benzyl or hienethyl radical, as aromatic radicals in particular those of the benzene series. Suitable heterocyclic radicals are 5- or 6-membered nitrogen-containing radicals, for example the pyridine, pyrazole, imidazole, triazole, oxazole, thiazole, thiadiazole or pyrimidine series and their benzo compounds j '.. *. ". .. \ '.. the newly · s dyes contain a quaternary nitrogen atom in the form of the salts of primary, secondary or tertiary amines. in particular, however, they contain trialkylammonium in which the alkyl groups may be straight or branched and are optionally substituted and preferably 1-6 C -Atoms have, ΙΤ, ΙΤ-dialkyl-F-aryl or -aralkylammoniumgruppen, in which the aryl radicals are preferably radicals of the benzene series, which can be further substituted ^ ammonium groups in which the ammonium nitrogen atom is bestiiteil of a hetero ring, such as in the case of Pyridinium radical, that is to say a cyclammonium group, represents ^ N-alkyl-li-cyclamino groups, such as N-alkyl-morpholino or -piperidino groups, as well as others, tetravalent substituted Residues containing nitrogen such as 1,1 ~ N-dialkylhydrazinium or Ν, Ν-dialkyl-N-oxide groups.

The new dyes can also contain any nonionic substituents as substituents R 1, R ₁ , R 1 and R 1, for example halogen atoms, alkyl, alkoxy, carbalkoxy, carboxy, alkylsulfonyl, carbamyl, sulfamyl, amino -, trifluoromethyl, acyl or acylamino groups.

- 5 -209849/1117

The new dyes contain an inorganic anion A or organic ion, preferably the remainder of a strong acid, for example sulfuric acid or its half-ester, an arylsulfonic acid or a hydrohalic acid. These anions introduced according to the method can also be replaced by anions of other acids, for example phosphoric acid, Acetic acid, oxalic acid, lactic acid or tartaric acid can be replaced. The dyes can also be in the form of their double salts obtained with zinc or cadmium halides.

The new dyes are suitable for dyeing or printing from tannin cellulose fibers, silk, leather or fully synthetic fibers such as acetate silk or anionic modified fibers, for example from acidic groups, such as - sulfonic acid groups, containing or by acidic groups, such as sulfonic acid, sulfimide, carboxyl and / or phosphonic acid groups, modified polyacrylonitrile or polyvinylidenecyanide, through carboxyl and / or sulfonic acid groups modified polyesters such as polyethylene terephthalate, polycyclohexanedimethylene terephthalate, heterogeneous polyesters made from terephthalic acid, isophthalic acid and ethylene glycol or made from terephthalic acid, sulfo-isophthalic acid and ethylene glycol, also copolyether ester fibers from p-oxybenzoic acid, terephthalic acid and ethylene glycol, or polyamides modified by sulfonic acid groups, such as polyhexamethylene adipate, polycaprolactam or poly-w-amino-undecanoic acid.

The dyeings available on these fibers are usually very brilliant and strongly colored and generally have good colors Lightfastness and good ITassfastness, for example good washing, Full, over-dyeing, carbonizing, chlorine and perspiration fastness,

0 9 8 4 9/1117

as well as good decatur, steam, ironing, rubbing and solvent fastness properties. The dyes are generally largely insensitive to a change in the pH of the dyebath and can therefore be used in both weakly acidic and strongly acidic baths. They are also stable at temperatures above 100 ^° C., as used in high-temperature dyeing. Wool is completely reserved by the dyes under normal dyeing conditions.

The dyeing is carried out in such a way that the textile material is treated in neutral or acidic, preferably in acetic or mineral acid, baths, if appropriate in the presence of auxiliaries, and the dyeings thus obtained are completed in the customary manner. In general, the reaction goes into the dyeing bath at about 40 - 60 ⁰ C and dyed at the boil. If necessary, dyeing can also be carried out under pressure above 100 °.

For printing on textile material, the dyes are used together with the usual thickeners and if necessary, printing aids and fixes the Dyes in the usual way by steaming.

The dyeing can also be done in an organic solvent, for example in an aliphatic chlorinated hydrocarbon in the presence of amines, amides, amine oxides or Ammonium compounds and optionally emulsifiers are carried out.

-7 -209849/1 1 17

To prepare the aqueous dye baths and printing pastes, the dyes can be used in the form of powders, which may contain adjusting agents such as inorganic salts, dextrin and optionally other additives. However, it is more advantageous to use concentrated aqueous solutions of the dyes that are easier to handle and contain about 20 to 60 % dye, one or more lower aliphatic ^ carboxylic acids, such as formic acid, acetic acid, propionic acid or lactic acid, and optionally other additives such as water-soluble polyhydric alcohols Ethers or esters, polyethers, aliphatic ^ carboxamides, lactams, lactones, nitriles, dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or urea and water.

Used to prepare the dye baths that only contain organic solvents, such as chlorinated hydrocarbons one advantageous concentrated solutions containing the dye as a free base or as a salt of a monobasic, organic Contain acid, chlorinated hydrocarbons, organic acids and polar organic solvents.

The following examples serve to illustrate the invention.

209849/1117

example 1

A mixture of 16 parts by weight of 10-McthO3cybenzo [kl] xanthene-3,4-dicarboxylic anhydride, 6 parts by weight of ^ -dimethylaminopropylamine and 250 parts by volume of ethyl alcohol is refluxed for 8 hours and then cooled to 0 °. the deposited crystals are filtered off with suction, washed with a little ethyl alcohol and dried at 60 °. You get 18 parts by weight of dye of the formula

A mixture of 10 parts by weight of dye, 0.1 part by weight of magnesium oxide, 3 parts by volume of dimethyl sulfate and 150 parts by volume of water is heated to 60-65 ° for 3 hours. After adding a further 150 parts by volume of water, the mixture is filtered at, the filtrate is cooled to 10 °, the quaternary dye is separated off by adding 50 parts by volume of 5N hydrochloric acid and 10 parts by volume of zinc chloride liquor, and is filtered off with suction and at 60 of the formula

dried. 15 parts by weight of dye are obtained

CH ₇ ι 3

- N-CH ₀ CH ₀ CH ₀ N-CH

CO CH,

ZnCl _x '3

which is yellow in color in water and diluted acids solves.

209849/1 1

10 parts by weight of dye are in the heat in one Mixture of 15 parts by weight of glacial acetic acid and 25 parts by volume Dissolved water and then filtered. A solution is obtained that does not change after several weeks of storage shows.

5 ecm of the resulting solution are stirred into 6 liters of water and 1 g of crystalline sodium acetate and 10 g of calcined sodium sulfate are added to the dyebath. Then one proceeds with 100 g of washed yarn from polyacrylonitrile at 60 ⁰ C in the dyebath, the temperature is raised slowly to 100 ⁰ C, and dyeing is 1 Ütunde at boiling temperature. Then allowed to cool slowly to about ^ 0 ⁰ G , rinsed and dried. A brilliant greenish yellow coloration with very good light and wet fastness properties is obtained. On acid-modified polyamide and polyester fibers, brilliant greenish yellow colorations with good light and wet fastness properties are also obtained.

Example 2

A mixture of 30 parts by weight of benzo [kl] thioxanthene-3,4-dicarboxylic anhydride and 150 parts by volume of 2-aminopyridine is heated to 180 - 190 ° for 5 hours, cooled to 80 °, rapidly mixed with 150 parts by volume of methyl alcohol and Stirred at 40 ° for 15 minutes. The deposited crystals are filtered off with suction, washed with methyl alcohol and stored at 60 ° dried. 34 parts by weight of dye of the formula are obtained

209849/1117

A mixture of 10 parts by volume of dye, 10 parts by volume of dimethyl sulfate and 30 parts by volume of dimethylformamide is heated to 1.50-155 ° for 4 hours, cooled to 60 ° and mixed with 50 parts by volume of ethyl alcohol. The departed one Dye of the formula

- 5th

is suctioned off, washed with a little ethyl alcohol and dried.

The dye dissolves in water and dilute acetic acid with a yellow color and yields to polyacrylonitrile and acidic modified polyester fibers golden yellow dyeings with good light and wet fastness properties.

209849/1 1 17

The table below contains further dyes of the formula I according to the invention and the shades of the dyeings on polyacrylonitrile, acid modified polyester and acid modified polyamide fibers.

X R

hue

Ni CD CO OO * ~ CO

O NO ₂ H 10-ΟΗ, Ο Η

OHH 10-CH, 0H

l ^ GH,)

CH-

ZnCl;

reddish yellow

brilliant yellow

O HH 10-CH, 0H

CH

ZnCl,

brilliant yellow

HH 10-CH _x OH

CH ₂ CH ₂ CH ₂ NHO
OH,

ZnCl ^

brilliant yellow

- 12

hue

OHH .10-CH _x OH

HH 10-CH, 0H

OHH 10-CH _z 0 K

0 H. H H

HHH

OHH 10-CH, 0H

CH.

H N.

ρ *

CH

J,

H -OH ₂ CH ₂ K (CH ₅ ),

CH

2
ZnCl,

brilliant yellow

brilliant yellow

brilliant yellow

brilliant yellow brilliant yellow brilliant yellow

- 13 - p

XR ₄ Rc R ₆

hue

HHH

■ ^Ai 3

ZnCl ,, ® ⁶ brilliant yellow

OHH

OH H iO-CHzO H

OH H ^- H

CH

CH-, 5

Θ
2. ι 2

ZnCl

brilliant yellow brilliant yellow

brilliant yellow

OHHH

HHH

CH

2
ZnCl,

brilliant yellow

brilliant yellow

^ / ftf -

E ₇

hue

OHHH

H -CH ₂ CH ₂ CH ₂ M (CH,) ₂ Cl® brilliant

OHH

CH ^ COO

brilliant yellow

ro ο co oo

H . H H

, Θ

brilliant yellow

HHE

-CH ₂ CH ₂ CH ₂ M ₇

CHjCOO® brilliant yellow

H H H

Cl ¹ =

brilliant yellow

CH

HHH

, CH ₂ N (CH ,;
2

Cl®

brilliant yellow

—A N) N)

Χ> fit fS X> iH X) rH rH rH 0) rH O) 0) (D CD O Ü O -P Ul CQ Φ Q) ί, -P -P CtS ö Pm cö CtS rH rH rH iH •H •H X) Q

OJ KN

OJ

OJ OJ

OJ LiN • KN \ o

OJ

6th

OJ

OJ

W. -O

O CQ K

ro »

to, W O

B 6

KN

CO

CM

LfN

-CM O

ω ο

OJ

W. O O I. I. O O ν V

KN

KN

O O O KN

OJ ΙΛ

I— < Hi

CM O

OJ W O

OJ

CU

KN

O CS3

CM

CM LTN

O ^ CM

O CM

KN g OO

209849/1117

C5

O Pi tsi

CVI

CO

KN

• Ü

209849/1 1

Pt O -P

CU

β)

ho

• Η

-P

οι, α

4> Η

ο α>

CVJ

If

tr »

OJ

8 8 "

OJ

CQ

ta -ι » 2122975 approx CO ο ff ¹ " φ Q) Λ ω to ω
• Η fcO I α> • Η α> ! d °° ω
• π υ to
• Γ « ο ο ^Η , Cj • rl • Η ♦ Η ι O ■ Ρ O 4 » • Η (4th • Η Ul, Q CO tO 43 4> +> Η 5S- CQ, Q Η + » W P O O 0> H 4> Η ω ο 43Η HO bOO O O O O) HO H cij

rf O

OJ

tsl

OJ

HO

tS5

OJ

OJ

tr

HO

CQ.

CQ

KN W. C3 W. O OJ O OJ W. πΓ ü ο
OJ W. w ⁰¹ O ο O I. OJ I. W. ο I.

CQ

209849/1117

pi
O -P

\ Thu

ITN

W (0 W

H O faO ti HO

• H + *

■ PH

ο α)

H a>

CO

CM

CO

CQ

CQ

fcD

Φ ■ 3- Φ O O CQ O KN O KN

i-l O

CM

CM

CM O

co

CQ KN

CM

bO

O KN IfN Ό VN O W. IfN KN CM
ο b • 3 · CM
O
ν- / © a
<Μ CM CM CM CM CM O O O 8 _w O O CU CM CM CM W. W. W. W. O O ο ο ο O I. I. ι I. i I. rH rH O O I. W. W. I. O H * "* ι KN KN H KN r ~ t W. O
CO W. 8th O
O O O I. pH

CQ

2122S75 ¹

2098A9 / 1117

Claims (6)

2122S75 claims 1) Basic dyes of the formula NO wherein X e - in oxygen or sulfur atom, R is an aliphatic, araliphatic, aromatic or heterocyclic radical with a group of the formula where Rj and Ro are hydrogen, an alkyl, aralkyl or cycloalkyl radical, R, hydrogen, an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group and N with R-, and / or R ~ and / or R, can form a heterocyclic ring, R ₂ , R ₁ -, R, - and R "hydrogen or nonionic substituents and A." is an anion. 2) Basic dyes of the formula R / ¹ V Alk - H - wherein X is an oxygen or sulfur atom, R, and R _{2 is} hydrogen, an alkyl, aralkyl or cycloalkyl radical, R ^ is hydrogen, an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group, R ^, R ₁ -, R ^ and R ₁ -, hydrogen or nonionic substituents, Alk is a straight-chain or branched, optionally substituted alkylene radical with up to 6 carbon atoms and kP is an anion. 2 0 9 8 4 9/1117 - 20 - 3) Process for the preparation of "\ 'on basic dyes of the formula Ii-R »Θ where X "is an oxygen or sulfur atom, R is an aliphatic, araliphatic, aromatic or heterocyclic rent with a grouping of the formula where R- and Rp are hydrogen, an Alley 1, aralkyl or cycloalkyl radical, R, hydrogen, an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group and K with R-, and / or Rp and / or R ₇ can form a heterocyclic ring, R,., R ₁ -, Rc and Rr _{7 are} hydrogen or nonionic Substituents and A denote an anion, characterized in that that one dyes of the formula -R where X and R. - R ₁ - have the meaning given above and "R" denotes an aliphatic, araliphatic, aromatic or heterocyclic radical which contains a primary, secondary or tertiary amino group with an "inorganic""" or organic Acid or treated with quaternizing agents. - 21 - 209 849/11 17. BATH ORIGINAL 4-) Process for the preparation of basic dyes of the formula - Alk - H "ι ^E 3 wherein X is an oxygen or sulfur atom, R-, and Rp is hydrogen, an alkyl, aralkyl or cycloalkyl radical, R ^ is hydrogen, an alkyl, aralkyl, cycloalkyl or alkoxy radical
or an amino group, R ₂ , R ^, Rg and R ₁ -; Hydrogen or
nonionic subditüenten, Alk is a straight-chain or branched, optionally substituted alkylene radical with up to rs 6 carbon atoms and A is an anion, characterized in that that one dyes of the formula wherein X and R ^ - R ₁ -, has the meaning given above and R is a straight-chain or branched, optionally substituted alkylene radical with up to 6 carbon atoms, which contains a primary, secondary or tertiary amino group, with an inorganic or organic acid or with quaternizing agents treated. 5) Use of the dyestuff according to claim 1 for dyeing
synthetic textile material. 6) Use of the dyestuff according to claim 2 for coloring
synthetic textile material. 209849/1117