DE2017967A1 - Water-insoluble monoazo dyes and process for their preparation - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Biyerwerk Patent department * K / bU

H, April 1970

Water-insoluble monoazo dyes and process for their preparation.

The present invention relates to new * valuable, sulfo group-free monoazo dyes of the general formula

OH

R -oc ^ ^v c-nh- / a Vn = N

R ₂

in which

R _{1 stands} for an alkyl radical,

Ro denotes an amino group -NR ¹ R ", in which R ¹ and R" independently represent hydrogen, alkyl, phenylalkyl or phenyl,

R ~ represents an alkyl or phenyl radical and the nucleus A further

Can carry nonionic substituents, as well as their production and use. ,

Suitable alkyl radicals R 1 and R ^ are those with 1 to 4 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl radicals. They can be substituted, for example by hydroxyl, methoxy or ethoxy groups. Le A12987

'* ■ _ ■. · "■■ '.' ■ BAD ORIGINAL

10-9844 / 1494

Suitable alkyl radicals R 'and R "are, for example, ^{alkyl groups with 1-4 C atoms optionally substituted by"' 1} hydroxyl, chlorine, cyano or alkoxy, such as methyl, ethyl, η- and i-propyl, η-, ir and t -Butyl, chloroethyl, cyanathyl, methoxyethyl, hydroxyethyl, hydroxypropyl and others

A suitable phenylalkyl radical R «is the benzyl radical, the may optionally be substituted, for example, by chlorine or methoxy.

The phenyl radicals in R ₂ or the phenyl radicals R- can be substituted by chlorine, bromine, alkyl or alkoxy radicals each having 1-4 carbon atoms.

Suitable nonionic substituents in core A are in substituents commonly used in dye chemistry, such as fluorine, chlorine, bromine, nitro, cyano, carbarnoyl, alkyl, alkoxy carbonyl Alkoxy, hydroxyalkoxy and alkylsulfonyl, alkylcarbonylamino, where alkyl and alkoxy are those. Remainders with .1 * 4 carbon atoms are to be understood.

The new dyes (I) can according to various ver. drive to be made.

One method is that you go in any order successively 1 equivalent of a cyanuric halide with

a) about 1 equivalent of an alcohol RiOH

b) about 1 equivalent of an amine RpH and

c) about 1 equivalent of an aminoazo dye of the formula

BATH ORIGINAL

Le A 12 987 - 2 -

1Ü984WU9

where R ,, Rp, R, and A have the meaning given above, in the presence of acid-binding agents.

It is particularly advantageous if the cyanuric halide is mixed with the reactants mentioned in the order a) c) b) to implement. .

Another process for the preparation of the dyes (I) is characterized in that amines of the general formula

^ AV NH ₂ - III

in which R ,, Rp and A have the meaning given above,
diazotized and with phenols of the formula

IV

in which R, has the meaning given above, clutch.

Cyanuric chloride is preferably used as the cyanuric halide.

Suitable alcohols R ₁ OH are, for example:

Methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, t-butyl alcohol, ethylene glycol, 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol.

Le A 12 987 _ V_

10.9 84

Suitable amines R ₃ H (or HlJR ¹ R ") are, for example:

Methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine.

Dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, Di-n-butylamine, di-i-butylamine, di-t-butylamine, 2-aminoethanol, 2-amino-chloroethane, 2-methoxy-ethylamine, 3-aminopropanol- (l), l-amino-propanol- (2), 5-amino-l-methoxypropane, N-methylethanolamine, N-ethylethanolamine, diethanolamine, Dipropanolamine, N-methyl-2-methoxyethylamine, N-methyl-2-cyanoethylamine, Benzylamine, 4-chlorobenzylamine, aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 4-fluoroaniline, 2-toluidine, 2-anisidine.

Coupling components IV are:

4-methyl-phenol, 4-ethyl-phenol, 4-n-propyl-phenol, 4-i-propylphenol, 4-n-butyl-phenol, 4-i-butyl-phenol, 4-t-butyl-phenol, 4- (2'-hydroxyethyl) phenol, 4-hydroxydiphenyl.

Suitable acid-binding agents are e.g. alkali hydrogen carbonates, Alkali carbonates and alkali acetates.

The water-insoluble new dyes of the general formula I obtained according to the process are suitable for dyeing and dyeing Printing of fully synthetic fibers, e.g. those made of polyamides, cellulose esters and aromatic polyesters, in particular those made of polyethylene glycol terephthalate.

The dyeings on synthetic polyester and polyamide fibers are characterized by excellent light, wet and sublimation fastness properties.

In the following examples, parts mean parts by weight.

Le A 12 987 - 4 -

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Example 1; . "

In a mixture of 95 "5 ml of methyl alcohol and 18.9 parts of sodium hydrogen carbonate 20.5 parts of cyanuric chloride are added at 8 ⁰ C and stirred for 5 this suspension at 8-10 ⁰ C. Subsequently, this mixture is 62 parts of water was added and the solution of 22.7 parts of ^4-amino-2> -hydroxy-5 * -pethyl-l, .l ^ -azdbenzoi added in 82 ml of acetone and 82 ml of methyl alcohol. After stirring for one hour at 25 * 30 °, 15 parts of ethanoramine are added, the mixture is heated to the boil (65 °), heated to reflux and then methanol and acetone are distilled off. The dyestuff of the formula which has crystallized out in good yield

H ₃ COC ^ C-HN -q v- N = N

NH-CH ₂ -CH ₂ -OH

Is sucked off and washed out thoroughly with water. Of the . Wet dye is comminuted in the usual way together with a dispersing agent. After suitable drying, a readily dispersible dye powder "If the procedure is as indicated above, but instead of the aminoazo dyestuff used equivalent amounts of ^{4-amino-2-ohlor-2>} -hydroxy-5 ^f -raethyl-l, l ^t azobenzene or 4 -Amlno-2-methyl-hydroxy-5'-methyl-l, l ^r -azobenzene used, valuable yellow disperse dyes are also obtained.

In the table below there are other valuable disperse dyes described, which can be prepared by the above process. They correspond to the composition

Le A12987

- 5 -109844/1494

N = N

wherein. -R _{2 stands} for the radical -N of an amine.

R ^m and R, are, in the entDie meaning of R _1, R ^1, R "
appropriately designated columns of the table are reproduced »The last column shows the color shades of the dyeings on synthetic polyamide and polyester fibers.

Le A12987

1 0 98 4 W ed

■ /

R, It * H" CII ₃ R " ¹ hue -CH ₃ -II -CII ₃ CH ₃ 2-01 yellow -CII ₃ -H -C ₂ H ₅ CH ₃ 2-CH, Il -CH ₃ -II -C ₃ H ₇ (η) CII ₃ H Il -CH ₃ : -H -C ₃ IL (ISo) CII ₃ H Il -CH ₃ ; -H -C ₄ IT ₉ Cn) CH ₃ H Il -CH ₃ j -H -C ₄ H ₈ (iso) CH ₃ H Il -CH ₃ j -H -CH ₂ -CH ₂ -CH ₂ -OH CH ₃ H Il -CH ₃ -H -CH ₂ -CH ₂ -CH ₃ ti Il OH CH ₃ -CH ₃ -H -CH ₂ -CH ₂ -Cl CH ₃ H Il -CH ₃ -H -CIl, - / ^ λ CH ₃ H Il -CtI ₃ -H CH ₃ 3-0CH, i " -CH ₃ -H ■ - © ■ H Il Cl CII ₃ -CH ₃ -H -CH ₂ -CH ₂ -0-CH ₃ - CH ₃ H Il -CH ₃ -CH ₃ -CH ₃ CH ₃ H ti -CH ₃ -CH ₃ -CH ₂ -CH ₂ -OH CH ₃ ; H yellow -CH ₃ -CH ₃ -CH ₂ -Cn ₂ -CH ₂ -OH CH ₃ H η -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CHa H Il OH CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -O-CII ₃ CH ₃ H Il -CH ₃ -CH ₃ -CH ₂ -CH ₂ -Cl CH ₃ H Il -cn ₃ -CH ₃ -Cl ₂ -CH ₂ -CN CH ₃ H Il -CH ₃ -C ₂ H ₅ -C ₂ H ₅ CH ₃ H Il -CH ₃ -C ₃ H ₇ (Ii) -C ₃ H ₇ (Ii) CH ₃ H Il -CH ₃ -C ₃ H ₇ (Ii) -C ₃ H ₇ (ISO) CH ₃ H Il -CH ₃ -C ₄ H ₉ (Ii) -C ₄ H ₉ (η) CH ₃ H Il -CH ₃ -C ₄ H _e (iso) -C ₄ H ₉ (IsO) H η

Le A12987

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R » 8th 201796 / -CH ₃ H hue Ri -CH ₂ -Cl ₂ -OI R "R, R" -CH ₃ H yellow -CH ₃ -CH ₃ J-CH ₂ -CH ₂ -OH -CH ₃ H Il, -C ₂ H ₅ -H -CH ₃ -CH ₃ H Il -Ci-H ₅ CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ ' H Il ■ -C ₂ H ₅ -H -CH ₂ -CH ₂ -0-CII ₃ -CH ₃ H ti -C ₃ II ₇ (Ii) -CH ₃ -C ₂ H ₅ -CH ₃ H ^: Il -C ₃ H ₇ (Ii) -C2 H ₅ -CH ₂ -CH ₂ -OH -CH ₃ H Il -C ₃ H ₇ (Ii) -H
• -C ₂ H ₅ -CH ₃ H Il -C ₃ H ₇ (IsO) -CH ₃ -C ₂ H ₅ -CH ₃ H Il -C ₃ H ₇ (ISO) -H -CH ₂ -CH ₂ -OH -CH ₃ H ti -C ₄ H ₉ (Ii) -CaH ₅ -CH ₃ -CH ₃ H Il -C ₄ H ₈ (η) -H -C ₂ H ₅ -CH ₃ H Il -C ₄ H ₉ (Ii) -CH ₃ -CH ₂ -CH ₃ -0-CH ₃ -CH ₃ H Il -Cli ₂ -CH ₂ -OH -CH ₃ -CH ₃ -CH ₃ H Il -CH ₂ -CH ₂ -OH -CK, -CH ₂ -CH ₂ -0-Cn _a -CH ₃ H It -CH ₂ -Cl, -0-CH ₃ -H -CH ₃ -CH ₃ H It -CH ₂ -CB ₂ -0-CH ₃ -CH ₃ -CH ₂ -CH ₂ -OH -CaH ₈ H Il -CH _2. -CH ₂ -0-CH ₃ -CH ₃ -CH ₂ -CH ₂ -CN -C ₂ H ₈ H I. -CH ₃ -H -CH ₃ . -C ₂ H ₅ H η -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₂ -OH -C (CH ₃ ) a H It -CH ₃ -CH ₃ -CH ₂ -CH ₂ -OH -C (CHa) ₃ H Il -CH ₃ -CH ₃ -CH ₃ -C (CH ₃ ) ₃ . H It - CH ₅ -CK, -CH ₂ -CH ₂ -OH. -C (CH ₃ ) a H H -C ₃ H ₇ (ISO) -H -CH ₃ H Red-
0 + -CH ₂ -CH ₂ -0-CH ₃ -H -CH ₃ H Bk *
yellow -CH ₃
Ν ». -H -CH ₂ -CH ₂ -OH H I. -C ₈ K ₁ <η) -CH ₃ -CH ₃ -CH ₈ -CH ₂ -OH H I.
■ -CH ₃ -CII ₂ -OH -CH, -CH ₃ -CH ₃ -CHa -OH H yellow -CK, - - -H -CH ₃ -CH ₄ -CHg -OH H N -C ₈ H ₈ -H
* -CH ₃ Il -CK ₂ -CH ₂ -0-CH ₃ -C ₃ H ₈ rf »
Le A12987 8th -

109844/1494

Example 2 .

Ιβ.Ό parts of methoxy-dichloro-s-triazine are dissolved in 50 ml of acetone and poured onto 100 parts of ice-water. 9.2 parts of aniline are added to this fine suspension and held at 10 ° Adjust the pH of the mixture to 6-6.5 by adding soda solution. When the pH value doesn't change anymore, the solution is given of 22.7 parts of ^ -amino ^ '- hydroxy-S'-methyl-l / l'-azobenzene in 100 ml of acetone and 8.4 parts of sodium bicarbonate to and boils under reflux until the diazotizable aminoazo dye disappeared. After the acetone has been distilled off, the dye becomes of the formula: ·.

suctioned off and recrystallized from butanol or glycol monomethyl ether. After adjustment with a dispersant This dye dyes fibers and fabrics made of polyamides in yellow tones with very good wet and light fastness.

Example j?

22.7 parts of 4-amino-2'-hydroxy-5 ¹ -methyl-1,1 ¹ -azobenzene are reacted in a fine aqueous suspension in the presence of 9 parts of sodium acetate with 18.4 parts of cyanuric chloride at 5 °. The reaction can be followed very well by the disappearance of the diazo.table aminoazo dye. After the reaction has ended, 9.2 parts of a 50% strength aqueous ethylamine solution are added and a pH of 8.5 is maintained at 50 ° with dilute sodium hydroxide solution. The reaction has ended after 1 hour, as can be seen from this that the pH is no longer increasing

Le A 12 987 .. - 9 -

109844/1494

IQ

changes. To replace the last chlorine atom, 50 parts of methyl alcohol are added and kept under constant flow Adding soda solution cooked until the resulting solution reacts weakly alkaline. After cooling to room temperature, the yellow dye of the formula obtained is filtered off

N = N

NH-C ₂ H ₅

and cleans it by recrystallizing it from n-butanol. Of the The dye obtained in this way dyes polyester fibers and fabrics in lightfast, sublimationfast and wetfast yellow colorations.

Example 4

24.6 parts of 2- (4'-aminophenyl) -amino ^ -methoxy-o-methylamino-striazine (made from methoxy-dichloro-s-triazine by reaction with methylamine and N-Ac e ty 1-p-pheny lend iair.in with subsequent saponification of the acetylamino group) are dissolved in 200 parts of 5 ^ hydrochloric acid and mixed with 7 parts of sodium nitrite diazotized at 0.5 °. The resulting diazonium salt solution is filtered and with thorough stirring at 5 ° in a Solution of 10.8 parts of 4-methylphenol, 28 parts of sodium carbonate, Run in 10 parts of sodium hydroxide and 300 parts of water let go »When the coupling is finished, filter the fancy yellow dye of the formula

Le A12987

N = N

NH-CH.

- 10 -

BATH ORIGINAL

1098 44/1494

and recrystallizes it / for purification from n-butanol. This On polyamide and polyester, dye provides yellow colorations with very good light, wet and sublimation roughness.

Dyeing process for Polyestex fans

A dispersed dye prepared according to Examples 1-4 made into a paste in 10-15 times the amount of water at 40-45 ° is added at this temperature to a dye liquor, which is mixed with acetic acid is set to a P "value of 4.5-5 and im Liter 2g of an anionic condensation product of aromatic sulfonic acids, 5g of a self-emulsifying one that acts as a carrier aromatic carboxylic acid ester and Ig monosodium dihydrogen phosphate contains.

This is added to this liquor (liquor ratio 1:40 - 1:30) pre-cleaned polyester material, increases the temperature to 80-85 ° in the course of 15-20 minutes and remains in this Temperature range another 20 minutes, then you bring the Float gradually to boil, after a boiling time of 1-1 1/2 The dyeing process is finished hours. After that it gets hot once and then rinsed cold. Clear yellow colorations of very good light, sublimation and wet fastness are obtained,

Dyeing process for polyamide fibers

A heated bath to 40 ° (Flottenverhältnia 1:40 to 1:30) is charged with the following additions: l-2g / l of an anionic Kondensationeproduktes aromatic sulfonic acids or l-2g / l of non-ionic polyglycol ether derivatives, are one Thereafter _t e inen according to Example 1 - 4 prepared, dispersed dye and draws in the pre-cleaned polyamide material. In the course of% 0-60 minutes, »increases the liquor temperature to the boiling point and holds at this temperature for about 60 minutes. It is then rinsed and dried. A clear yellow coloration of very good dryness, sublimation and wetness is obtained.

Le A 12 987 - ¹³ -

109844 / U94 ■ '· - .. ^BA0

Claims (1)

Pa t entans prüehe / ν 1) Sulphonic acid group-free azo dyes of the formula R 1 in which R _{1 stands} for an alkyl radical, R ₂ denotes an amino group -NR ¹ R "in which R ¹ and R" independently of one another represent hydrogen, alkyl, phenylalkyl or phenyl ', · R-x represents an alkyl or phenyl radical and the nucleus A further can carry nonionic substituents. 2.) Sulphonic acid group-free azo dyes of the formula -NH-C B VN = N OH in which X, for an optionally by hydroxyl, methoxy-ode, r Ethoxy-substituted alkyl radical with 1-4 C atoms, X ₂ denotes an amino group -NX ¹ X ¹¹ , vjorin X ¹ and X ^M independently of one another represent hydrogen, optionally substituted by chlorine, hydroxyl, methoxy or cyano groups alkyl radicals with 1-4 C atoms, optionally by Le'A 12 987 - 12 - 1098ΑΛ / 1494 BATH ORIGINAL 2017987 Benzyl radicals substituted with chlorine or methoxy or _ optionally substituted by chlorine, bromine, alkyl or alkoxy groups each having 1 - 4 carbon atoms Phenyir residues are * X ^ is an alkyl radical X, or optionally pheny radicals substituted by chlorine / bromine, alkyl or alkoxy groups each having 1-4 carbon atoms, and the nucleus B by fluorine, chlorine, bromine, nitro, cyano, carbamoyl, alkyl, alkoxycarbonyl, alkoxy , Hydroxyalkoxy and alky! Sulfonyl, alkylcarbonylamino, whereby alkyl and alkoxy are to be understood as meaning those radicals with 1 - 4 carbon atoms,
can be substituted. "" - 3) Sulphonic acid group-free azo dyes of the formula Y "' in which Y, for methyl, ethyl, propyl, butyl, methoxyethyl or Hydroxyethyl stands, Y ₂ denotes the radical -τΝΥ'Υ ", in which Y ¹ and Y" independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, cyanoethyl, chloroethyl, phenyl, chlorophenyl or benzyl, yn » _{for r} Hydrogen, chlorine, methyl and methoxy, Y, represents methyl, ethyl, propyl, butyl or phenyl. 4) Sulphonic acid group-free azo dye of the formula )H ^ BATH ORIGINAL Le A 12 987 -_ 5) Sulphonic acid group-free azo dye of the formula OH i_C "0-c> ci: h - (/ V- k = -ij ₀ RF 6) Sulphonic acid group-free azo dye of the formula -IiN -V V Ii = N-, N (CH, -) ₂ CH-, 7) Sulphonic acid group-free azo dye of the formula V \ - N * N NH-CH ₂ -CH ₂ -OH CH, 8) Sulphonic acid group-free azo dye of the formula OH -O-C ^ C-HN - / V- N = N- N-CH ₂ -CH ₂ -OH
5 CH, 9) Sulphonic acid group-free azo dye of the formula )H N-CH ₂ -CH ₂ -OH H ₃ CC-CH ₃ CH CC CH ₃ Le A12987 - 14 - ORIGINAL 1Ö984A / V4 ■■■■ ... : fS 10) Process for the production of sulfonic acid groups-free Azo dyes of the formula OH R ₁ -0-C ^ C-NH- / Λ VN = N - ^ 1 ι ι \ / I R ₂ in much sooner R _{1 stands} for an alkylreat, R ₂ denotes an arcino group -KR ¹ R ", Korin K ¹ and R" independently represent hydrogen, alkyl, phenylalkyl or phenyl, R, an alkyl or phenyl radical and the nucleus A further can carry non-ionic substituents, dadui-ch marked that one can be in any order successively 1 equivalent of a cyanuric halide with a) about 1 equivalent of an alcohol R. b) about 1 equivalent of an aniine R ₀ H and c) about 1 equivalent of an aminoazo dye of the formula where R- ,, R ₂ * Rx and A have the meaning above-r:; r.anrite, in the presence of acid-binding agents. 11) Process for the preparation of sulfonic acid group-free azo dyes of the formula r ₁ -oc ^ ^Tn c-nh- / a Vn = H R ₂ BATHROOM ORIGINAL Le A 12 987 - 15 - 109844/1494 in which Rj stands for an alkyl radical, R "2 is an aromatic group -NR ¹ R", where R 'and R "are independently hydrogen, alkyl, phenylalkyl' or phenyl, TU represents an alkyl or phenyl radical and the nucleus A further Can carry nonionic substituents, characterized in that amines of the general formula Rn c ¹ Ä R ₂ in which R- ,, Rp and A the obsn ^ onated meaning own, diazotized and with phenols of the formal in which R-, has the meaning given above , couples. 12) Use of the monoazo dyes of claims 1-8 for Dyeing and printing of synthetic fiber materials. 15) With the dyes of claims 1-8 dyed or printed synthetic fiber materials, Le A 12 98? "- 16 - 10984 ^ / 1494