DE1644659C3 - Anthraquinone dyes, their production and their use - Google Patents

Description

-CH ₂ -, (CH ₂ ) ,. - (CH _:) ., -,
- (CH ₂ U-. HCH,), -.
-CH CH ₂ . CH ₂ -CH

CH ₃ CM,

or
-CH

CH,
Stands.

3. Anthraquinone dyes according to claim I of the formula _SQ]]

O NH-C ₂ H ₄ CO -N ■■ ·· ■ 'F /

! ' '

■■ "VV '\ R,

i B i [ !

O NH - <(H>

Before the rings B and E can be further substituted and R _{1 has} the meaning given in claim I.

4. Anthraquinone dyes according to Claim I of the formula

SO, H

O NH-CH-CH ₂ -CO-NK F. ^X
/ \ - "\ - ^y '\ CH, R, « o

O NH (H (H, CO N

CU, R ₁

in which the rings B and F are substituted

SO, H

can and R, which address in claim 1 |

Has meaning.
5. Anthraquinone dyes according to claims !.

the formula

SO ₁ H

O NH-CH CH, CON-, F "> ■ '■ ·., \ C" H, R,

O Nile, H>

wherein the rings B and E can be further substituted and R, the Be specified in claim 1 has meaning.

6. Process for the preparation of anthraquinone dyes of the formula 1, characterized in that a compound of the form)

A ₁

B!

O NH -alkylene -CO -N-R H

1 R,

O NH R,

in which R, the radical A ₁ or an optionally substituted alkyl or cycloalkyl radical, the ring B can be further substituted and R ₁ the | has the meaning given in claim 1, sulfonated.

7. Process for the preparation of anthraquinone dyes of the formula I. characterized that one has an anthraquinone compound of the form

O Y

\ Ä A.

t ^Y ΐ 1

ΎΥ

ο w

(III)

in which the ring B can be further substituted, "V denotes a substituent which can be exchanged for an amino group, and W denotes Y or a - NH - R ₂ group, or the leuco form of a compound of the formula III or a mixture of a compound of the Formula III or its leuco form with a compound of the formula

H, N - alkvlen - CO - N - R - Z

(IV)

wherein Z is a hydrogen atom or the sulfone

acid group means-'t. reacted, oxidized, if the compound of formula III was used in its leuco form, and sulfonated, if Z is a Wassei stoffatorn, where R ₁ and R have the meaning given in claim 1.

S. Use of the anthraquinone dyes hoi me! 1 according to claim 1 for dyeing wool. Silk, synthetic polyamide fibers, from Cellulose fiber !!, made of fibers made from regenerated cellulose and of leather

meaning and W for Y or for an NH R, -cir group, or the leuco form a connection; of formula III or a mixture au ·, a compound of the formula III and their Leuco form. with a compound of the formula

R ₁ (IV)

H, N alkslen CO N - R Z

The subject of the invention are anthraquinone acids and process for their preparation. They correspond to the formula

(") Ml alkylene CO N R S (), H

wherein Z is a hydrogen atom or the sulfonic acid group means, converts, oxidizes, if the compound of the formula IiI is used in its leuco form was, and sulfonated if Z is a hydrogen atom means.

The "alk \ len" resi is straight-chain, branched or substituted by a cyclohexyl or phenyl resi. Fr contains 1 to 12 carbon atoms and is preferably ■■ - ICH ₂ I ₁ , -. where η stands for a number from 1 to S and preferably for 1 to 6, / .. B.

CH

IClM,

I,),

O NH R,

wherein R is an optionally substituted arylene radical. R ₁ denotes hydrogen or an optionally substituted alkyl or cycloalkyl radical and R denotes the radical A or an optionally substituted alkyl or cycloalkyl radical, "alkylene" can optionally be substituted and the ring B can be substituted by nitrogen. One method is characterized in that there is a compound of the formula

I ₂ I ... - (CH ₂ ),

'Ί1 CH ₂
CIl.

ClI

cn ..,

.Here

CU

c ₂ iu

(CH ₂ ) ,,

CU ₂ CU

CH,

O NH -alkylene -CO N R H

A ₁

O NH -R.,

wherein R ₁ denotes the radical A ₁ or an optionally substituted alkyl or cycloalkyl radical, sulfonated.

The alkyl or alkoxy radical in each case contains 1 to 12 and preferably 1 to 6 carbon atoms.

You can also prepare the dyes of formula 1, if you have an anthraquinone compound of the formula

O W

where Y is an exchange for an amino group

■ * ° CH CU ₂ CH ₂

CH,

The arylene radical R stands mainly for a phenylene radical: it can also be a naphthylene or tetrahydronaphthylene radical. In addition to the sulfonic acid group, it can be substituted by further substituents, specifically by an optionally substituted sulfonic acid amide, alkyl or arylsulfonyl group. an optionally substituted alkyl or alkoxy radical having 1 to 12 and preferably 1 to 6 carbon atoms. The alkyl radicals can be halogen atoms. 7. B. chlorine or bromine, the hydroxyl or the cyano groups carry, z. B. chloromethyl. Chloroethyl. Hydroxymethyl. Hydroxyethyl or cyanoethyl: the arylene radical can also be replaced by halogen atoms, preferably chlorine. Bromine, but also by an optionally substituted amino group or by hydroxyl, phenyl. Phenoxy. Be substituted cyan or nitro.

R ₁ can stand for hydrogen, but can also mean an optionally substituted alkyl radical, for example a methyl, ethyl, propyl. Chloromethy! -. Chloroethyl, hydroxymethyl, hydroxyethyl. Cyanoethyl or benzyl radical; but it can also represent an optionally substituted cycloalkyl radical, preferably a cyclohexyl radical or an alkyl, ζ. Β. Mcthylcyclohcxylrest stand. R ₂ can

For the radical A or an optionally substituted alkyl or cycloalkyl radical, where the alkyl or cycloalkyl radical can have the same structure as the radical R ₁ .

The ring B can by halogen, such as chlorine or Bromine, or substituted by hydroxyl.

Y in the formula UI sees door one against one: Amino group exchangeable substituents. /. B for the hydroxyl or amino or alkoxy group having, for example, 1 to 4 and preferably 1 or 2 carbon atoms.

W stands for Y. but it can also be an NH R group mean.

Good dyes are obtained. if now a connection the formula

O NH - (\ H_. -CO- N 1

B i

IV)

O NH -, H

wherein the l'henyl radical I; can be further substituted, sulfonated.

Similar good dyes are obtained. if you can cn connection the formula

O NH CH -CH; CO N

CW, R _:

(M

O NH

or if you have a compound of the formula

O NH CH -CH, CO N

i I

■ \. · '\ ^Λ \ ^CH ' ^R i

B; ι

O NHCH-CH ₂ -CO-N

(VIII

CH.,

R,

sulfonated.

The sulfonation is advantageously carried out in sulfuric acid monohydrate or in 5 to 10 ° oleum or in chlorosulfonic acid at temperatures between 0 and 40 ° C., preferably between 20 and 25 ° C.

The reaction of a compound of the formula IV. When Z is a hydrogen atom, with a compound of formula III is advantageously carried out in an organic medium. F. a connection ι. 'Τ Formula IV or a mixture of compounds of Shape! IV can with a compound of the formula III (,, or their leuco derivative or with a mixture of compounds of the formula III or their I.eucoforms / ur reaction to be brought. The so obtained Reaction products are optionally oxidized and then sulfonated.

The IJmsei / ung a compound of the formula IV if / denotes the sulfonic acid group, or a: mixture of such compounds of the formula l \ with a compound of the formula Ii! or their I-cukoderi \ ai or a mixture of these Compounds or their leuco forms is usually carried out in an aqueous medium

As organic media in which a compound; of formula IV with a compound of formula 11 Can be implemented, may be mentioned, for example, higher molecular weight alcohols, such as butyl alcohol. Iso but \! alcohol. Amyl alcohol. Octyl alcohol. Dodecvl alcohol, etc. nitrobenzene. Chlorobenzene etc. or mixtures of such solvents, where you Reaction at temperatures from XO to 14 (J C. vor preferably at temperatures from KX) to 130 ° C can be carried out.

The new dyes are used for dyeing. Padding or printing on fibers of animal origin, ζ. Β from wolfe or silk, from synthetic polyamide lasers and leather, also cellulose fiber !! B. Cotton or linen, and made of fibers au; regenerated cellulose. e.g. viscose rayon. copper ravon or rayon, of mixtures and or structures from these fibers.

When dyeing. Padding or printing can mar the usually used mesh. F.galisier thickening and other textile or leather auxiliaries serve.

The dyes can be made from acidic or new neutral medium at temperatures from 70 to 100 ° C preferably at boiling temperature, colored. You hey sit on these substrates a good build ability and equalize excellent.

The dyeings or prints obtained are above excellent, between red-tinged and green-tinged blue brilliance and have very good lightfastness, especially on WoIK and synthetic polyamides Salvation. They dye streaky nylon with a distinctive character net: also the wet fastness properties, such as washing. WaIk-W ater-. Sea water, sweat and soda boiling resistant licit, as well as the rubbing and dry cleaning fastness are good.

As synthetic polyamide fibers, for. B. Regarding: The condensation products of 1.6-Hcxa !!! ethylenediamine with adipic acid or sebacic acid the polymerization products of / -Caprolactarr or the polycondensation products of ■. -amino undeean acid and mixed condensation products /. B. from l.o-Hexamcthylcndiamine, adipic acid . -Caprolactam.

Some of the compounds of the formula II can from the corresponding l-amino-4-alkyl or 4-cy clohexyl-aminoanthraquinone by addition of unsaturated aliphatic carboxylic acids or theirs functional derivatives, such as acid nitriles or acid amides, e.g. B. Acry'säurc, methacrylic acid. Croton acid or by condensation with halogenated aliphatic carboxylic acids or their lactones z. B. halobutyric acid. Halopropionic acid. Haloienvaleric or I lalogenisovaleric acid. Halo gencaproic acid. 1 lalogenoenanthic acid. Butv rolac'.or Valerolactone or caprolactone. to h / w. with de 1- \ minogruppc and they lead to known ones! Methods are produced in the acrylamide compound.

Other compounds of formula 11 can be prepared by reacting 1,4-dihydroxyanthraehinone with the corresponding amino acids, e.g. B. with aminoacetic acid. ί- or / ί-aminopropionic acid c. (i-aminobutyric acid. κ-aminoisobutyric acid. aminovaleric acid. / .. II. < i-aminovaleric acid or aminocaproic acid, and converted into the arylamide compounds by known methods.

Some of the compounds of formula 11 can be seen produce when you have a compound of the formula

O NII,

(VlI

C) NH

by known methods with a haloacetic acid and the resulting carboxymethylaminoanthraehinone or its functional acid derivative with an arylamine of the formula

N R H

(IXI

implements.

US Pat. No. 32 47 229 discloses the use of the dye of the formula

SO, H

O NH -CH -CH ₁ -CH ₂ -;

CH, - CH

CH,

O NH - CH - CH, - CH,

CH ₃
CH, - CH

CH,

SO ₃ H

registered according to the details of the French patent 14 70 597. One gives S parts of what is weak Add oleum and stir for 5 hours at 18 to 20. The The reaction product is poured into 150 parts of water and 50 parts of Fis, filtered and the residue with a 10% aqueous sodium chloride solution. He gets up to one with lithium carbonate kneaded constant pH value of 7.5 and dried at 100 °. The dye dyes synthetic polyamide fibers from a weakly acidic bath in bright blue tones. The dyeing is wet fast and has an excellent quality Lightfastness. Striped material is colored regardless.

Example 2

In 50 parts of sulfuric acid monohydrate at 12 up to 16 '6.7 parts of 1,4-di- (2'-carbophenylamido) -älhylamino-anthraquinone, manufactured according to the details of the French patent 13 90 833, registered. 4 parts of 25% strength oleum are added and the mixture is stirred at 20 ° to 25 ° for 5 hours.

The Rcaklionsprodukt is poured onto 200 parts of ice and 100 parts of water, filtered and the residue washed with a 20% aqueous sodium chloride solution. It is then kneaded with sodium carbonate and dries at 100 ". The dye dyes wool and synthetic polyamide fibers from weakly acidic Bathroom in lively reddish blue tones. The dyeings on synthetic polyamide fibers are particularly wetfast and extremely lightfast. Strong nuances can be achieved and streaky Material is colored regardless.

Staining example

A dyebath is prepared from 4000 parts of water. 4 parts of ammonium sulfate and 4 parts of the dye of Example 1 and heat it to 40 '. At this temperature, 100 parts of fabric are used synthetic polyamide fibers. The bath is heated to boiling temperature in the course of 30 minutes and colors for 60 minutes. After 30 minutes the evaporated water is replaced and 2 parts glacial acetic acid admitted. After dyeing, the fabric is rinsed with cold water and dried.

If you dye wool according to the same method, you get a dye with similarly good properties.

like this.

Example 3

known for dyeing polyamide fibers.

It is surprising that the dyes of the formula I,

also dyed on polyamide fibers, have an improved build-up capacity.

In the following examples, the parts mean

Parts by weight, percentages percentages by weight, and temperatures are given in degrees Celsius.

example 1

In 75 parts of sulfuric acid monohydrate at 14 to 18 ° 11.7 parts of l- (2'-carbophenylamido) ethylamino-4-cyclohexylamino-anthraquinone, 1 η 80 parts of sulfuric acid monohydrate are produced at 15 up to 20 "12 parts of 1- (2'-carbopheny] amido) -a-methylethyl-amino-4-cyclohexylaminoanthraquinone registered. 8 parts of weak oleum are added and the mixture is stirred at 20 ° for 3 hours. The mass is set to 150 Poured parts of water and 50 parts of ice, filtered and the residue with a 5% aqueous sodium chloride solution washed. It is made with lithium hydroxide up to a constant pH of 7.5 to 8 kneaded and dried. The dye dyes wool and synthetic polyamide fibers from weakly acidic Bathroom in vivid blue tones.

The dyeings are wetfast and have a high lightfastness on wool and a very high lightfastness.

609 630/47

9

is based on synthetic polyamide. Synthetic polyamide material with streaks is dyed evenly.

Example4 ^ §

In 200 parts of normal butanol, Zimmer- - = J = · = ==

temperature 16 parts of 1,4-dihydroxvanthraquinone and - ξ Ξ5 5 5

8 parts of the same compound in the leuco form a Sj = ^ *. r. j-.

carried. ; _; :; "= ■ = ■ =

4 parts of 3-amino- ίο = ΐΐ ~ ~ ^ are added to this mixture

3-methyl-propionic acid phenylamide to and under one. ' ~, -1 ¥ ¥ 2

The mass is heated to 100 to 1010 in a nitrogen atmosphere. After 4 hours of reaction, the stream of nitrogen ceases replaced by a stream of air to oxidize the leuco components.

The precipitated dye is sucked off. then washed with methyl alcohol and water and dried.

15 parts of the dye thus obtained. 1,4-di- [1 -methyl -2 '- (Phynylamtnocarbonyl) -äthyliimino] -anlhraquinone. are at 1 5 to 20 in SO parts Schwcfelsjuremonohydrat registered. 14 parts of weak oleum are added and the mixture is stirred at 20 for 3 hours until 25. The reaction mass is poured into 150 parts of water and 50 parts of ice. filtered and washed the back 2s stood with a 10% aqueous sodium chloride solution. The obtained dye is made with sodium bicarbonate kneaded to a constant pH value of 7.5 to 8 and then dried. The dye dyes wool and synthetic polyamide fibers

weak acid bath in vivid and clear blue - ^ ^

Tones. The coloring is wet fast and has a high ~; "

Lightfastness. Striped material is colored regardless.

The amine used can be obtained by known methods, e.g. B. by reductive amino? S lysis of acetoacetylanilide or by hydrogenation of the corresponding 3-aminocrotonic acid phylanilide.

Example 40 = T - - -

If you replace the 40 parts of the amine in Example 4 _

by 45 parts of 3 · amino- 3 -methyl-propionic acid- ^

| 2 -methoxyhphenylamid and proceeds otherwise.

according to the information given there, 45 is obtained;

1,4-Di- [I'-methyl-2 '- (2 "-methoxyphenylaminocarbo- ^.

nyl-ethylaminoi-anthraquinone. F> ~

The sulphonation of this dye is carried out as in the ^w

Game 1 performed. . _v

The dyeings obtained on wool are also 50. . ,

lightfast like the dye in Example 4 and have ^ ί;

very good wet fastness properties.

The following table shows the structure of other dyes which can be obtained according to the information in Examples 1 to 5 . They correspond to the formula έ 'a? * r ~ *

NH-alkylene-CO-N -R-SO ₃ H | 'V * f * f

R ₁

¹ E.

• SI «

-R ₃

wherein "alkylene", B. R, R ₁ and R _{3 are} those in the table ■. _Λ · have given meanings. 'ta

11th 12th

υ "

ΕΛ C / 3 .E J =

continuation

'■' ξ

at
game
No. Position of
Substituents
in ring B »Ulkylen« R. / X 17th - C ₂ H ₄ - . · '' V ' 18th - C ₂ H ₄

19th

20 -

21 -

22nd

23 -

CH,

C ₂ H ₄ -

-C ₂ H ₄ -

C ₂ H ₄

CH, - CH ₂ - CH -

CH, -CH ₃ -CH

C ₂ H,

-CH ₃ -C ₂ H ₅

- CHXTKOII

-CH, -CH,

Color shade on synthetic polyamide or wool

reddish blue

reddish blue

reddish blue

reddish blue

red stitch blue

neutral blue

reddish blue

24

-CH ₁

neutral blue

O U

ο - _

υ ¹

18th

i "

continuation

Example of the game SubstiUienlen No. in the RiriL! B.

»•; ttk v

CH,

38 5.8-dihydroxy -CH ₂ -CH-

--CH ₂ - CH SO ₁ H

CO-NH- /

NiMiHr the Vurhmw on

smiiIicIiscIk'iii IVh.iiiml uiIl-i wool

münlilau

5-hydroxy -C ₂ H ₄

CII, (II. CO - NII

üninstidiiulilaii

- CH- CH ₂ CH ₃

CH-CH ₂ CH,

- (CH ₂ )., - (CH ₂ I ₅

-CH-CH,

C!

SO, H

SO ₁ I.

CiI C \\ _: CO NH

CII, (.,

CH,

CH, S (J ₁ H

CH - ■ CO Nl-I --- -OCH,

Neuiniles Ulan

neutral blue

reddish blue

OCH,

Continuation University:

at Position older "AMcylcH" cn, game Subscribers No in the gutter B 45 -CH- CU, CH 46 ClI,

CH CHy-CH,

-C ₂ H ₄ -

Cl

Il

H>

CII C (J NII CII, CH ₁

H ,

FSrhtmp ntif s \ nlhi'lisL'hem I'olvaiiiicl

oiler W'nllc

neutral blue

Hhiu

nculiak's blue

blue

-C ₂ H ₄ - - H

CH, CH-CH ₂ - -.

CH, -CH-CIl ₂ - H ₁ CO-

CH ₁

OCH, H

CII, -CH- CW ₂

CH, CO N -

SO ₁ H

CH ₁

CH CH- (O NII

OCH,

SO ₁ II

blue

neutral blue

blue

OCH,

continuation

Example of the game substituent no. In ring B

»Tilkylen«

54 55 56 57 58 59 -

CH ₃ ι

-CH-CH ₂ -H ₃ CO-X X-OCH ₃ H

CH, Ό CH-CH ₂ - L. CH, O CH- L. C ₂ H ₅ Vx CH-CH ₂ - ι C ₁ H ₇ J χ ^
Vx CH-CH ₂ - V CH, \. A. CH- X _x CH ₃ / \ CH-CH ₂ - CH ₃ Hc C CH-CH, -

Br

CH- CH, - CO- NII -

H ₁ CO Br

Nuance of Fiirbunu on n> niheliM-'hem P ^ l \ .itiiul or wool

iirünstichiecs BIa

H ₃ OS OCH,

-CH, -CH ₁ -CO — NH- ''

-SO ₁ Heir-tinged blue

- CH-CO -NH

C ₂ H ₅ -CH-CH ₁ -CO-NH

C ₃ H. - CH - CH ₁ - CO - NH

CH,

SO ₃ H

__ SO ₃ H

SO ₃ H

^CHi ^ ¹¹ - '__ SO ₃ H

CH-CO —NX '">

reddish blue

neutral blue

neutraics blue

reddish blue

neutral blue

neutral blue

25th

ο — υ

—Υ ο

i ■ »■ § ■;

582]

Claims (2)

Patent claims: 1. Anthraquinone dyes of the formula O NH alkylene -ι "O -N R. SO _S H i ί / \,
BI -Λ. Λ R. ν / ' ^N j
'τ (D O NH R-. wherein R is an optionally substituted arylene radical. R ₁ denotes hydrogen or an optionally substituted alkyl or cycloalkyl _{radical and R 2} denotes the radical A or an optionally substituted alkyl or cycloalkyl radical, "alkylene" can optionally be substituted and the ring B can be further substituted, where R. R ₁ . R ₂ , “alkylene” and any substituents present on ring B have the meanings given in the description. 2. Anthraquinone dyes according to Claim 1. characterized in that in the form! I "alkylene" for