DE2120877A1 - Azo compounds that are sparingly soluble in water, their production and use - Google Patents

Description

Azo compounds that are sparingly soluble in water, their production and use.

The invention relates to compounds of the ^ -nitro-E'-alkoxyacylamino- ² ! · ¹ -dialkylamino-l, l'-azobenzene series which are free of sulfonic acid groups and which are excellent as disperse dyes, for dyeing fibers or threads or materials made therefrom made of fully or semi-synthetic, hydrophobic, high-molecular organic substances. The dyeings obtained are notable, in particular, for their fastness to sublimation, their good drawability and color strength

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characterized by their light and wet fastness.

The new dyes correspond to the formula

wherein R is chlorine, bromine, cyano, nitro or optionally substituted alkylsulfonyl or phenylsulfonyl,

R _{2 is} hydrogen, chlorine or bromine,

R, hydrogen, chlorine, bromine or acylamino, but where at least one of the substituents Rp or R is hydrogen,

R ₁ , hydrogen or optionally substituted alkyl or alkoxy,

Rp. And Rg * independently of one another, if necessary Chlorine, bromine, cyano, hydroxy, alkoxy, chloroalkoxy, bromoalkoxy, cyanoalkoxy, optionally Alkylcarbonyloxy bearing substituents,

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Benzoyloxy, alkoxycarbonyl, phenoxycarbonyl, alkoxycarbonylcxy or phenoxycarbonyloxy as substituent-bearing alkyl, R ₇ optionally substituent-bearing alkyl, X is a group of the formula -CO-, -COO- or -SOp-

and

η mean 2, J or 4,
however, the molecule is free of sulfonic acid groups.

All of the alkyl, alkylene and alkoxy groups mentioned generally contain 1, 2, 3 or 4 carbon atoms. Preferred substituents on the alkyl or. Alkoxy groups are, for example, halogen atoms, in particular chlorine or eromatic atoms, hydroxyl or cyano groups.

The phenyl radicals mentioned (also the phenyl nucleus of the benzojl radical) can, for example, have chlorine, bromine, cyano, nitro, acyl, alkyl or alkoxy as substituents.

Preferred acyl groups correspond to the formula R-X- or or R'-Z- therein

R is a hydrocarbon radical bearing the substituents listed above and / or He-

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may contain teroatome, preferably one

Alkyl or. Phenyl radical, Y is a radical -0-C0- or -SOg-, R ^{1 is} a hydrogen atom in or R, Z is a radical -CO-, -NR ¹¹ CO- or -NR "S0 ₂ - and R" is a hydrogen atom or R .

The new compounds of the formula (I) are prepared by diazotizing an amine of the formula

(II)

R ₃ R ₂

and coupling the resulting diazonium compound with a compound of the formula

^XR 6

(in).

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Part of the compounds of formula (I), namely the the formula

j -I alkylene-O-Rp

N = K- / Vn " ^ö (IV),

γ- / ^ Alyklen-R ^ R ₂ NH-X- (CH ₂ ) _n -0R _?

wherein Rg is alkylcarbonyl, alkoxycarbonyl, benzoyl or Phenoxycarbonyl

and Rg cyano, alkoxycarbonyl, phenoxycarbonyl, alkylcarbonyloxy, Alkoxycarbonyloxy, benzoyloxy or phenoxycarbonyloxy can also mean by acylation of an azo compound of the formula

| ^R 1 | ^R 4

rA / —I alkylene-OH N- () -N = N- (Vn '' (V)

V- / V- ^{7 X} alkylene-R ₁₀

NH-X- (CH ₂ ) _n -0R _?

wherein R _1n alkoxycarbonyl, phenyloxycarbonyl, cyano or

Hydroxyl means with an acid of the formula

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B ₈ -OH (VI),

wherein R _{o is} alkylcarbonyl, alkoxycarbonyl, benzoyl or ο

Phenoxycarbonyl means, or a functional derivative of such an acid

getting produced. Suitable functional derivatives

^ψ are, for example, the anhydrides or halides, especially the chlorides of these acids.

The diazotization and the coupling are carried out according to general methods, some of which have been known for over 100 years.

The coupling components of the formula (III) are prepared by methods known per se, for example by one is an amine of the formula

NH ₂

-0-R "is reacted with an acid of formula HOOC (CH ₂₎ at temperatures between about 150 ° and 200 ⁰ C with elimination of water, reducing the nitro group and the radicals R _c and Rz is introduced by condensation or addition. 109848/1716

Preferred compounds of the formula (I) correspond to the formula

¹⁵ (VII),

^R i6

NHC0 (CH ₂ ) _m -0R ₁₇

where R "hydrogen, chlorine or bromine, R-, chlorine, bromine, cyano, nitro, methylsulfonyl,

Phenylsulfonyl, or toluylsulfonyl, R-_, hydrogen, chlorine, bromine or alkylcarbonylamino with 1-2 carbon atoms in the alkyl radical, which can have chlorine or bromine as a substituent, but one of the substituents Rp or R _{1 is} hydrogen, R ₁ J, Hydrogen, methoxy or ethoxy, R ₁ C and Rig, independently of one another alkyl with 1-4 carbon atoms, which can carry hydroxy, cyano, methoxy, ethoxy, acetoxy, propionyloxy, butyryloxy, eenzoyloxy, methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy or aethoxycarbonyloxy as substituents, R ₁₇ methyl, ethyl or propyl and

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m are 2 or 3.

The processing of the new compounds of the formula (I) into coloring preparations is carried out in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the possibly in a vacuum or preparations dried by spraying, after adding more or less water, dye in so-called long or short liquor, pad or print.

The dyes pull out of aqueous suspension excellently on textile material made of fully synthetic or semi-synthetic, hydrophobic, high molecular organic Fabrics on. They are particularly suitable for dyeing or printing textile material made of linear, aromatic polyesters, as well as cellulose-2 1/2 acetate, Cellulose triacetate and synthetic polyamides. They can also be used to color polyolefins. Man colors or prints according to known methods, e.g. that in French patent specification No. 1,445,371 described procedure.

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The dyeings obtained have good all-round fastness properties; to be emphasized are the lightfastness, the thermosetting, Fastness to sublimation and pleating, they are excellent water-fast, e.g. water-, seawater-, wash- and sweat-proof, solvent-proof, especially dry-cleaning-proof, lubricant, rub, over-dyeing, ozone, smoke and chlorine law; they are extremely resistant to the effects of the various permanent « pressing process and the so-called "soil release" equipment. The etchability, the resistance to reduction (when dyeing with wool) and the reserve of wool and Cotton are good.

Compared to the night comparable, from the French Patent Specification No. 1382654 and I382655 known The new dyes have better fastness to sublimation. The invention therefore serves inter alia the purpose of creating new, better dyes for the fully or semisynthetic ones that are coming onto the market in ever greater numbers To deliver materials, with particular attention to the suitability for the use of modern, More efficient dyeing processes (continuous dyeing processes, high-temperature dyeing processes) pay attention

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was laid.

In the following example, the parts are parts by weight and the temperatures are given in degrees Celsius.

example 1

7 parts of sodium nitrite are added to 155 parts of concentrated sulfuric acid at temperatures up to a maximum of 70.degree then at 15 °, 24.2 parts of 2-amino-3-bromo-5-nitro-benzonitrile. The mixture is stirred at 15 to 20 ° for 2 hours. The diazonium salt solution thus obtained is then with a Solution of 2 parts of urea and 25 parts of 1-N, N-diethylamino-3- (3'-niethoxypropionyl) anilide combined in 100 parts of glacial acetic acid. After adding 500 parts of ice water the mixture is stirred for a further 2 hours, the precipitated dye is filtered off and washed acid-free with water and dried. It dyes polyester fiber material strongly in brilliant blue shades with very good fastness properties.

The table below shows further dyes of the formula (I) prepared analogously to the above example.

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Tabel

O CD OO

E.g.
No. ^R l ^R 2 H R ₄ ^R 5 -C ₂ H ₅ -C ₂ H ₅ do ^R 6 "τ - η X Nuance on
polyester 2 Br -CN H H - CHgCHgOCOCH ^ -CHgCHgCN do C ₂ H ₅ CH ₃ 2 -CO- blue 3 Cl H H H do -CH ₂ CHgOCOCgH ₅ CHgCHgOCOCH do 2 do do 4th -CN H H H -CHgCHgCN do do C ₂ H ₅ 2 do ruby VJl -CN H H H do -CHgCHgOCH, do do 2 do do 6th -SogCH, H Ή H -C ₂ H ₅ do CH ₃ 2 do Red 7th -NOg BT H H -C ₂ H ₅ do 2 do violet 8th ok do H OCgH ₅ -CHgCHgOH do '
t 2 do blue 9 10 do H do .CHgCH ₂ OCOCgH ₅ do 2 do do 10 ok do H do do do 3 do do 11 ok 31 Cl do CHgCHgCN do 2 do do 12th ok H -NHCOCH ₃ H "C ₂ H ₅ do Oil do do 13th ok H. -NHCOCH ₂ CH ₂ H do do Ol ' do reddish
blue 14th ok H Cl H do do 2 do do

ISJ O 00

' ^R l
t ^R 2 ^R 5 H ^R 5 -C ₂ H ₅ ^R 6 ^R 7 η X Nuance on
polyester E.g
No -CN Br H -OC ₂ H, -CH ₂ CH ₂ OCOCH ₃ -C ₂ H ₅ -CH (CHj) ₂ 2 -CO- blue 15th Cl H do do -CHgCHgOCOCH ₃ -CH ₃ 2 do do 16 I ₃ -O-SQ do H do do do do 2 do do ο ¹ ^ do Cl H do do do -CH (CH _{; 5} ) ₂ 2 do do P. 18 do Cl H do do do -C ₂ H ₅ 2 do, do ™ 19 do do H -OH -CH ₂ CH ₂ CN do do. 2 do do Ij 20 • NOg Br H do do -CgH ₅ do 2 -COO- do ^OT 21 do Br H H
-OCH ₃ -CH ₂ CH ₂ COOCH ₃ do do 2 -SO ₂ - do 22nd do
do H
Br -NOCOCH ₀ CH,
Br
H -OC ₂ H ₅ -CH ₂ CH ₂ COOCgH do do
do CU CU -CO-
do reddish
blue
do 25th
24 do Cl H do
do -CH ₂ CH ₂ OC ₂ H ₅ .-C ₂ H ₅ do 2 do do 25th do
do Br
Br H
H -CHgCHgOCHgCH.
-CH ₂ CH ₂ CN do
do CU CU do
do do
do 26th
27

Example no

Shade on polyester

28

29

-NO

31

do do do

Br

Br Br Br

H H H

do do do

-CH ₂ CH ₂ CH ₂ CH ₃

CH ₂ CH ₂ OCOOCH
CH ₂ CH ₂ OCOOC ₂ H ₅

-CH ₂ CH ₂ COOC

-C ₂ H

₂ H ₅

-CH ₂ CH ₂ CN

-θΗ _Λ θΗ _Λ οσοοσ _Λ Η,

₂ CH ₂

-CH

do do do

2 2 2

-CO-}

do do

do

reddish blue

do do do

Application example

7 parts of the dye prepared according to Example 1 are mixed with 4 parts of dinaphthylmethandisulionsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill for 48 hours ground to a fine powder.

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained is poured through a sieve was added to a dyebath containing 2 parts of sodium lauryl sulfate in 4000 parts of water. The liquor ratio is 1:40.

100 parts of cleaned polyester fabric are now added to the bath at 40-50 °, and 20 parts of a chlorinated one are added Benzene emulsifies in water, slowly heats the bath to 100 ° and stains for 1-2 hours at 95-100 °. The blue dyed fabric is washed, soaped, washed again and dried. The level, strong coloring is excellent light, overdyeing, washing, water, sea water, welding, subliming, smoke gas, thermosetting, pleating and permanent press-proof.

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Claims (1)

Claims 1. Azo compounds of the formula which are sparingly soluble in water wherein R is chlorine, bromine, cyano, nitro or optionally substituted alkylsulfonyl or Phenylsul- ^(fonyl, R _{2 is} hydrogen, chlorine or bromine, R, hydrogen, chlorine, bromine or acylamino, but where at least one of the substituents R ₂ or R is hydrogen, R ^ hydrogen or optionally substituted Alkyl or alkoxy, R_ and Rg, independently of one another, optionally Chlorine, bromine, cyano, hydroxy, alkoxy, chloroalkoxy, bromoalkoxy, cyanoalkoxy, optionally Alkylcarbonyloxy bearing substituents, 109848/1716 Benzoyloxy, alkoxycarbonyl, phenoxycarbonyl, Alkyl bearing alkoxycarbonyloxy or phenoxycarbonyloxy as substituents, R_ optionally substituent-bearing alkyl, X is a group of the formula -CO-, -COO- or - . and η mean 2, 3 or 4,
however, the molecule is free of sulfonic acid groups. 2. Azo compounds according to claim 1, of the formula NHC0 (CH ₂ ) _m -0R ₁₇ wherein R _{2 is} hydrogen, chlorine or bromine, R ^ _{1 is} chlorine, bromine, cyano, nitro, methylsulfonyl, phenylsulfonyl, or toluylsulfonyl, hydrogen, chlorine, bromine or alkylcarbonylamino having 1-2 carbon atoms in the Alkylyrest which can carry as substituents chlorine or bromine, but one of the substituents R ₂ or R ₁ - means hydrogen, 109848/1716 Ru hydrogen, methoxy or ethoxy, R ₁ ^ and R, g, independently of one another, alkyl with 1-4 carbon atoms, which can carry hydroxy, cyano, metnoxy, ethoxy, acetoxy, propionyloxy, butyryloxy, eenzoyloxy, methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy or ethoxycarbonyloxy as substituents, R._ methyl, ethyl or propyl and m are 2 or 5. Process for the preparation of azo compounds of the formula which are sparingly soluble in water ^R l S wherein R _{1 is} chlorine, bromine, cyano, nitro or optionally substituted alkylsulfonyl or phenylsulfonyl,
Rp hydrogen, chlorine or bromine, 109848/1716 R._ hydrogen, chlorine, bromine or acylamino, where, however, at least one of the substituents Rp or R_ is hydrogen, R ^ hydrogen or optionally substituted alkyl or alkoxy, R, - and R ^, independently of one another, optionally Chlorine, bromine, gyan, hydroxy, alkoxy, chloroalkoxy, bromoalkoxy, cyanoalkoxy, optionally Alkylearbonyloxy, benzoyloxy, alkoxycarbonyl, phenoxycarbonyl bearing substituents, Alkoxycarbonyloxy or phenoxycarbonyloxy as substituent-bearing alkyl, R optionally substituent-bearing alkyl, X is a group of the formula -CO-, -COO- or -SOp- and η mean 2, 3 or 4, However, the molecule of sulfonic acid is free, is characterized in that an amine of the formula (II) alazotized and with a compound of formula 109848/1716 (in) NH-X- (CHg) _n -ORr
clutch. 4. Process for the preparation of azo compounds of the formula R ₂ B ₄ > —I / —I alkylene-0-R _n OpN- / Vn = N- / Vh ' ^ö (iv), ^d > - / \ - / ^ alkylene-R ₉ R, R ₀ '
^ NH-X- (CH ₂ ) _n -OR ₇ wherein R., Rg, R, R ^, R ", X and η are those in the foregoing Claim mentioned meanings have Ro alkylcarbonyl, alkoxycarbonyl, bonzoyl or Phenoxycarbonyl and Rq Cya.1, alkoxycarbonylalkyl, phenoxycarbonylalkyl, Alkylcarbonyloxy, alkoxycarbonyl oxy, Benzoyloxy or phenoxycarbonyloxy, characterized in that one is an azo compound the formula ■ Γ / 1 0 9 8 A 8/1 7 1 6 ^R l ^ 4
>—I> —I alkylene-OH 0 _ρ Ν- (VN = N- / VN ^ (V), ^ /  Np / ^ alkylene-R ₁₀ R ₂ NH-X- (CH ₂ ) _n -0R ₇ wherein R _{10 is} alkoxycarbonyl, phenoxycarbonyl, cyano or Hydroxyl means
with an acid of the formula R ₈ -OH (VI) or a functional derivative of such an acid condensed. 5 · Process for dyeing or printing fibers or
Threads or materials made from them made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances with a dye of the formula
(I) according to claim 1. 6. The materials dyed or printed according to claim 5. 109848/1716 7 · Use of the dyestuff according to claim 1 for Dye or. Printing of fibers or thread or materials made from them from solid or semi-synthetic, hydrophobic ,, high molecular weight organic Fabrics. 1098A8 / 1716