DE1927309A1 - Process for the preparation of anthraquinone dyes - Google Patents

Description

concerning: . ₁₉₂₇ 309 Process for the production of anthraainone dyes

The priority of registration in Great Britain from 5/30/68

is used

The invention relates to a method for producing Anthraquinone dyes.

According to the invention, a method for producing Anthraquinone dyes of the formula:

wherein X represents a hydroagr or amino group, R represents Hydrogen atom or an optionally substituted hydrocarbon

Represents a group of substances, R is a substituted or unsubstituted hydrocarbon = * represents a hydrogen or heterocyclic radical or R and R together with the nitrogen atom N is a 5- or 6glled ° form ring nitrogen-containing heterocyclic ring, and the rings A and B may contain substituents, suggested that consists in an anthraquinone compound of the formula:

Formula I.

O in reaction with an amine of the formula:

009837/2068 -2-

HN

"V

is brought, whereby Y represents a chlorine or bromine atom

12th
and B, R, X ₁ A and B have the meanings given above.

The method according to the invention can expediently be implemented in that the reactants together in an organic liquid, which may optionally be an excess of the amine, preferably at between 20 ° C and the Boiling point of the organic liquid lying temperature in the presence of an acid-binding agent, which may be a excess of the amine may be, be stirred. The so The dye obtained can then be isolated in a manner known per se, e.g. by adding water to the reaction mixture with subsequent acidification with hydrochloric acid and Filtering off the precipitated dye. At the through » Execution of the method are preferably 2 to 10 Hol Aain per hol anthraquinone compound used. The reaction time is not critical as it has been found that the reaction comes to a conclusion after a period of 1 to 20 hours.

In the context of the invention, the terms "never alkyl" and "lower alkoxy" mean alkyl or alkoxy radicals having 1 to 4 carbon atoms.

The hydrocarbons ra, which may be substituted by R and R ^ radicals are preferably substituted or unsubstituted alkyl, in particular lower alkyl radicals, cycloalkyl radicals and, if appropriate,

009837/2068 - 3 -

K)

19273C9 - 5 -

substituted aryl, especially monocyclic, Axgrl radicals. Ala certain examples of such radicals can be given as follows mention: lower alkyl radicals, such as s.B. Methyl-, JCthy 1-, n-Propyl and n-Butgrl radicals, Bydrocxy lower alkyl radicals, like s.B. β-hydroxyethyl, β- or Y- ^ hydroxypropyl and B, Y-dihydroxypropyl radicals, cyano-lower alkyl radicals, e.g. ß-Cyanoäthylradikal ·, aryl-lower alkyl radicals, as s.B. Bensyl and ß-phenylethyl radicals, lower alkoxy-lower alkyl radicals, such as s.B. p- (methoxy- or xthoxy) ethyl- and ß- or Y (Wethoxy or Xthoxy) propyl radicals, C? Ycloalkyl radicals, like i.B. the Qyolohtxylradikal, and optionally substituted monooyoliaohe Ixgrlradikalische, as b.B. Phenyl, tolyl, chlorophenyl, Methoxyphenyl, nitrophenyl, carbomethoxyphenyl and Bordroocyathoxyphenyl radicals.

The optionally substituted heterocyclic ones represented by Br

3Ar · Badicals are torsionally / substituted 5- or 6-membered heterocyclic radicals such as B. 2- and ^ -pyridyl- and 2- and 4-quinolyl radicals.

Piperidine, horpholine, and piperatin ring systems can be mentioned as examples of the five- or six-membered nitrogen-containing bsteroeyolic bings composed of h \ B ^{2 and the nitrogen atom.}

As examples of the substituents in hangings A and B can contain the following chlorine, Bromine, Vitro, Cyano, Aatlno, Bydroxy, lower alkyl such as Methyl, blederalkoocy such as methoxy, anilino and substituted Anilino such as chloroanilino, bromanilino, bltroanilino, carboaqr-

009837/2068 - ^ -

BATH ORIGINAL

19273C9

substituted anilino, ßulfoanilino, toluidine, anisidlno and 2,4,6-tri-methylanilino, sulfonic acid, sulfonamido and N1 Derivatives thereof such as sulfo-N-methylamido and sulfo-N, N-diithylamido, acylamino such as acetylamino and benzoylamino, mercapto and substituted mercapto such as methyl mercapto and phenylthio. If necessary, the Hing A with a group of the formula:

/ ^R -CH ₀ If in one of the ß-positions of the ring and old one

^V 2 R ²

group X be substituted in the neighboring α-position «

When carrying out the process according to the invention, a molecular proportion of the amine per -CHgY group of the anthraquinone should be compound of the formula I can be used. However, it is also possible to use amines with two primary or secondary amino groups, each of which can condense with a »CHgY group use, whereby the products obtained then contain two anthraquinone cores, which have a remainder of the formula:

-CH ₀ N - Έ? - KCH ₀ -

R ² R ² -

are connected to one another, where R * is a divalent hydrocarbon radical, in particular an optionally substituted one

Represents phenylene or alkylene radical or R ^ together with the two -N-R groups form a heterocyclic ring.

• 2
the two -NR groups a 6güedrigen nitrogen-containing

All examples of the amines used in the invention Methods that can be used can be the following

009837/2068 - 5 -

BATH ORIGINAL

19273G9 - 5 -

Mention: methylamine, ethylmain, n-propylamine, dimethylamine, diethylamine, N-methyl-M ^ äthylamine, ß- ^ droxyäthylamin, ß-Qyanoäthylamin, di (p <-hydro3gritbyl) amine, ß-Methoayäthylamin, ß-Ä ^ hoarypropylamin, Bemsylarain, Pheßy lathy larain, Cyclohexylamin, Ethylenediamine _t Trimethylendiamisii, l ^ li-Dimethylethylenediaain, a-'Phenylenediamine, p-Ri © nylandiaain _s piperazine, aniline, m ^ phenylenediamine, p-Pheaylendlamine, Piperlinθ thy! aniline, toluidine, inisidine, Y-msthosypropylamine, morpholine \ md piperidine.

The additions to formula I can be produced by treating the corresponding hydroxymethyl compounds fertilize with a chlorinating or brominating agent, the droopethyl compounds in turn according to the processes described and claimed in British patent specification 1,152,244 can be produced. The following can be mentioned as specific examples of such anthraquinone compounds: 1- (Amino ~ or Hördroxy -) - 2 ° (chloromethyl- or -bromomethyl) anthraquinone, 1,5 ^ diaffiino ~ 2,6 »di (chloromethyl) <= anthraquinone, 1 ~ amino ~ 2-chloromethy 1 ~ 4 ~ {chlor-, «= brom ~, -anilino-, = p« "toluidino => (, -p ~ sulfoanilino«, -siethossyahilino-, -> p- = toluolsul < - "fonamido =, -pheayIthio ^, -mesidino", -ehloranilino "," hydroxy =, "acetylaaino = or -sulfo) anthraquinone, i-AjaiKO-2-chloromethyl = 5 ~ (ehlor" or "ßulfo) anthracliinoa, ij ^ DihydiOSQr - ^^ 2 »(ij. ^L -.hydro3syphenyl) -6-chloromethylanthraquinone and 2, (chloromethyl) -i, 8-dihyaro3iy anthraquinone.

Many of those produced by the method of the invention Anthraquinone dyes are new compounds, certain of which

009837/2068 -6-

BAD ORSGSNAL

Classes are:
1). The dyes of the formula j

19273C3

in which A, X, H and H have the meanings given above and the benzene ring T is optionally substituted by chlorine, bromine, methyl, methoxy or sulfonic acid.

2). The dyes of the formula:

CHJJ.

0 SE '

where A, X, R and R have the meanings given above and R an optionally substituted alkyl, phenyl or a heterocyclic one Is radical.

3). The dyes of the formula:

HHCOR-

009837/2068

- 6a -

ÖAD ORIGINAL

wherein A, R ¹ and R have the meanings given above and R ^ elnggf. substituted lower alkyl or phenyl radical.

The anthraquinone dyes produced according to the invention, the Containing sulfo groups are suitable as acid dyes for the dyeing of full, silk and synthetic polyamide fabrics according to the conventional methods sum Application of water soluble dye to such fabrics. The dyeings obtained in this way have excellent fastness in the samples that are customary for such textile fabrics be performed.

Preferably contain the according to the invention Process produced anthraquinone dyes do not have sulfo groups, so that these dyes are insoluble in water. Such dyes are suitable for coloring synthetic fabrics, 2.B, cellulose acetate and Cellulose triacetate textile fabrics, polyamide text list of fen, e.g. textile fabrics made of poly hexamethylene adipamid, polyacrylonitrile ^ textiles and preferably

009837/2068

19273C3

aromatic polyester textile fabrics: see B. Textilstoff en aus Polyethylene terephthalate = Solehe Textilstoffο can change the shape of threads, gems?., fabrics or Gs% rirL-ir? to have". Desired-·* If necessary, the textile fabric can be different Textilstoff en, ζ, B. under formation s.'r ^^ mixture of polyester fabrics and cellulose * - or full "textile fabric be.

Such fabrics can be dyed with the water-insoluble anthraquinone dyes of the invention by immersing the fabric in a dye bath consisting of an aqueous dispersion of one or more of the dyes and preferably a low-ionic, cationic and / or anionic surfactant «= Holds, after which the dyebath is heated to a suitable temperature for a corresponding time. In the case of cellulose acetate secondary fabrics, the dyeing process is preferably carried out at a temperature between 60 and 85 ° C .; with cellulose triacetate - = - or polyamide text! If open, the dyeing is preferably carried out at a temperature between 95 and 00 ° G; at erGisatlachen polyester · --- fabrics characterizing the dyeing either toi oißer swisehen 90 and 100 ° C lying temperature preferably in the presence of a carrier such as diphenyl or t -ky & roxydiphenyl performed or to see at Creamer ^ zwj i20 UCD 120 ° 0 lying Temperature can be effected under atmospheric pressure.

You can also proceed in such a way that the present *!

0f98 37 / y0 6

^. V A- - Of «8 37 /? 0? 8 ^ _d . ,. _Jf V ^

BATH ORIGINAL

- «, .. 1927303

ea mentioned anthraquinone dye on the fabric is applied using a padding or printing process, according to which the textile substance is heated to temperatures of up to Heated 23O ° C c & he is treated with steam. In such Process includes the aqueous dispersion of the anthraquinones dye preferably a thickener such as tragacanth, Gum arabic or Hatrlwoaiginat.

At the end of the dyeing process, the fabric is dyed preferably rinsed with water or "very old" soapy water treated before it is finally dried. For aromatic polyester fabrics, the dyed fabric is preferably treated with an alkaline aqueous sodium hydrosulfite solution subjected before it is treated with soapy water to remove loosely tied dye from the surface Remove the textile.

The anthraquinone dyes according to the invention have outstanding «» Excellent affinity and build-up capacity with regard to synthetic textile fabrics, especially aromatic polyester fabrics, so that deep color tones can be achieved. The resulting colorations have excellent resistance to Light, wet treatments and especially dry heat treatments, such as those used for pleating at high temperatures be performed"

If desired, the dyes according to the invention can be used bala application on dia eynthe-fc. see fertilizers in ind *? ^ with amle-fu 3 liaperuua ^ ar

009837 / 208fl

in British patents 8C6 271, 835 819, 840 905, 847 175, 855 396, 852 493 * 859 899, 8S5 528, 872 204, 894 012, 903 656, 909 845, 910 5C6, 913 856, 919 424, 944 513, 944 722, 953 887, 959 816, 960 235, 961 4i2, 976 213, 993 162 and 998 858 can be used.

The invention is illustrated below with the aid of examples explained in more detail, with all quantities given by weight related are:

example 1

A mixture of 3.62 parts of 1-amino-2-chloxiaethyl "4-anilinoanthraquinone vai <& 10 parts of aniline was stirred for 3.5 hours at 20 ⁰ C. The mixture is poured into water, acidified with hydrochloric acid, and the precipitated 1 - = - aaiino-2- * (aailinomethyl) = 4 = -aniXinoaathraehinone is filtered off, washed with water and dried. The yield is 72%.

With an aqueous dispersion of the dye thus obtained can Pelyest © r ~ textile fabrics in deep blue colors © mangen » be dyed with excellent fastness.

If the starting material is the corresponding Mesgs from 1 broaunethyl-4-anilinoaathrachinoi-i used, «o you get the same dye as the product.

from 5 _? ^ 2 Seiisa 1: -Jia.il '.. ϋ-2 = »οΜο: Ώ33tis liiaoÄ imä 10 · 1ί-5 ± 1-ί. · Ε ^ -Tolnidiii wild 1 B 009837/2083 ^ io«

.. 0AD ORIGINAL

19273G3

rc -

stirred at 60 ° O. After reddening the dye as in

Example 1 gives 1 ~ Aaino ~ 2 = (o ~ methyJ.anillnometh5rl) ^ f ^ anilinoanthraquinone in a yield of 88%.

With an aqueous dispersion of this dye you can Polyester textile fabric in deep blue shades » be dyed with excellent authenticity.

Example 3

A mixture eus 3 "62 parts of i <~ amino-2-chloromethyl ~ 4 -" - anilino ^ anthraquinones 5 parts of p-anisidine and 10 parts of dioxane is stirred for 60 hours at ⁰ C. Isolation according to Example 1 gives 1-amino-> 2- (p-methoxjaDilinomethjl) -4- "anilinoantlira ·» quinone in a yield of 78%. With this dye, polyester fabrics can be dyed in green-blue shades of excellent fastness.

Example 4

When Example 1 is repeated, 10 parts of Y «methoxypropyl ~ amine used instead of 10 parts aniline, where 1 -amino-2 - »(Y-. methoxypropylaminomethyl) - ^ »- anilinoanthraquinone in 84 # -iger Yield is obtained. With this dye herds polyester fabrics dyed from an aqueous dispersion in bright blue shades of excellent fastness.

The table below are more examples of the dyes prepared according to the invention can be found in each of the dyes indicated in the 2nd and 3rd columns by the reaction Anthraehinone compounds or amines with one another as in Example 3 ^ but under the Eeaktionsbedingungen according to the

00 9837/2068 - 11 ~ "

19273C9

^. Column of the table. The 5th gap © the Table iot the Jeweilig® Zwff.airjioJieetsimi 'des Farbotoffe au take, from the 6th column die Fe <ebtonimg angitst « di © when coloring polyether textile fabrics with the Dye will cool down »

et- ■ «

009837/2068 ' _el « _IClAL

gAD ORIGINAL

■ - '(- ■ - ■' • ■ «Τ

Amia

Reactions asit -temp.

product

toaisag

idiao) anthr & chlaoa

<= · Ai3.il isoanfcferaehinoa

dto.

dto.

aathraehinoa

■ i i

12th

15th

y3 anthraehinone

(b © asthiasol-2 * -ylthio) « aathraquinone

IS

, yy _t 7 m © tbyl) anthraquinone

18th

propelamin

idia

a & ilia

dto.

dto.

18th

18th

18th

Y-methoxy »18 propylamia

α-butylamine 12

0.25 60

BIa ^- U

1-Aaiaö-2-i ISf-

Sf-C

arai & GM © thy1) -4-aniline © =
aatferaehiaea

anthraekinoi.

aozast ^ l I- = 4 = (p <= t © l "& i & ia © Xoaaiaido) eata? A © feia @ a

1 »Ämiao» 2 = Cdi <= (li <= »m © thyi) affii <= aom © thyl) -4 = aail ί aoaat tea = chiaoa

Blue ^ Hau Or aage

Hot . Hot V *

blue

% y C

me t hjl ) aathraskiaoä

■ butjlamla © - yellow

• methoaypropyl «= bot

amiaomet 2 -yltaio)

1,8-dihydro2iy-2,
amiaomethyl) joathraehiaoa

CO O CO

yellow

E.g. Anthraquinone conversion

Response time temp.

product

Color = tint

2- (4 · hydroxyphenyl) «-6-chloroiv methylanthraquinone

1 ~ amino = 2-chloromethyl ~ anthraquinone

n «butylamine

Horpholin

1,5 »Dihydro3iy - ^, 8-dianiino ~ blue 2- (4 '«-hydroxyphenyl) -6- (n = buty laminomethyl)» anthraquinone

1-Jtoino "= 2 - (& - morpholino- orange methyl) anthraquinone

Claims (2)

Claims Process for the production of anthraquinone dyes der Formula: 0 X ¹ wherein X represents a hydroxy or amino group, R represents Represents a hydrogen atom or an optionally substituted / hydrocarbon group, R represents an optionally substituted hydrocarbon or heterocyclic radical or R and R together with the nitrogen atom N form a 5 "or 6-membered nitrogen-containing heterocyclic ring, and rings A and B may contain substituents thereby characterized in that an anti-quinone compound of the formula: in reaction with an amine of the formula: HH is brought, where Y represents a chlorine or bromine atom and A, B, R ^ and R and X have the above meanings. 009837/2068 2. Anthraquinone dyes of the formula: wherein A ₁ B ₁ E, H and Z have the meanings given in claim 1, characterized in that they were prepared by the process according to claim 1. PAlENtANWXLTl H FIMCKi D1H.-W .KiOHt LlTAMOl 009837/2068 ORIGINAL INSPECTED