DE2120877C3 - Monoazo compounds sparingly soluble in water, process for their preparation and their use - Google Patents

Description

Ri chlorine, bromine, cyano, nitro, methylsulfo-

nyl, phenylsulfonyl or toluylsulfonyl, R ₂ hydrogen, chlorine or bromine,

R ₃ hydrogen, chlorine, bromine or alkylcar

bonylamino with 1 or 2 carbon atoms in the alkyl radical, which can have chlorine or bromine as a substituent, but at least one of the substituents R ₂ and R _{3 is} hydrogen, R _{4 is} hydrogen, methoxy or ethoxy,

Rs and R6 are independent of each other. Alkyl with 1-4 Carbon atoms, the hydroxyl, cyano, methoxy, ethoxy, acetoxy, propionyloxy, butyryloxy, benzoyloxy, methoxycarbonyl, Ethoxycarbonyl, methoxycarbonyloxy or ethoxycarbonyloxy can carry as substituents, R7 alkyl with 1-4 carbon atoms,

X -CO -, - CO-O- or -SO ₂ - and

η 2 or 3

2. Process for the preparation of the azo compounds of the formula according to Claim 1, characterized characterized in that an amine of the general formula

O, N

diazotized and with a compound of the general formula

NH-X- (CH ₂ I ₁₁ -OR ₇

couples, in which formulas Ri, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , X and / 7 have the meanings given in claim 1.

3. Use of the azo dyes of the formula according to claim 1 as disperse dyes for Dyeing, padding or printing of fibers or threads or materials made therefrom fully or semi-synthetic, hydrophobic, high molecular weight organic substances.

O, N

N = N

(D

NHX (CH ₂ I.

Ri chlorine, bromine, cyano, nitro, methylsulfonyl.

Phenylsulfonyl or toluylsulfonyl,

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

R ₃ hydrogen, chlorine, bromine or alkyl carbon

nylamino with 1 or 2 carbon atoms in the alkyl radical, the substituent being chlorine or can carry bromine, however

at least one of the substituents R ₂ and R _{3 is} hydrogen,

R ₄ hydrogen, methoxy or ethoxy,

R5 and Re independently of one another, alkyl with I -4
Γι carbon atoms, the hydroxyl, cyano,

Methoxy, ethoxy, acetoxy, propionyloxy, butyryloxy, benzoyloxy, methoxycarbonyl, Ethoxycarbonyl, methoxycarbonyloxy or ethoxycarbonyloxy as substituents tra-4i) gen can

R7 alkyl with 1-4 carbon atoms,

X -CO -, - CO-O-or-SO ₂ - and

π 2 or 3

4> are.

The process for the preparation of the new compounds is characterized in that an amine is used general formula

Ri

O, N

NH,

(M)

diazotized and with a compound of the general formula

¹ ^ R,

O> -

R «,

Nil X- (CH ₂ ) ,, OR ₇

coupling, in which formulas Ri, R ₂ , R3, R ₄ , R5, Rb, R7,
and n have the meanings given above.

The diazotization and the coupling are generally known after more than 100 years Methods carried out

The coupling components are produced by methods known per se, e.g. B. by a Amine of the formula

10

15th

20th

with an acid of the formula

HOOC (CH ₂ ) ,, - OR ₇

is reacted at temperatures between about 150 ° and 200 ° C with elimination of water, the nitro group is reduced and the radicals Rs and Rt are introduced by condensation or addition.

The processing of the new compounds of formula 1 to dye preparations takes place in a general manner known way, e.g. B. by grinding in the presence of dispersants and / or fillers. With the possibly Preparations dried in a vacuum or by atomization can, after the addition of more or less water, dye, pad or print in a so-called long or short liquor.

The dyes are excellent on textile material made of fully synthetic materials from aqueous suspension or semi-synthetic, hydrophobic, high molecular weight organic substances. They are particularly suitable for dyeing or printing textile material made of linear, aromatic polyesters, as well as cellulose-2 '/ 2-acetate, Cellulose triacetate and synthetic polyamides. They can also be used to color polyolefins. One dyes or prints according to known, z. B. that in French patent 14 45371 described procedure.

Compared to the next comparable, from French patents 13 82 654 and 14 28 383 known dyes have the dyes according to the invention, colored on cellulose triatetate material, Dyeings with better heat setting and dry cleaning fastness.

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 ° and 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 l-N, N-diethylam'no-3- (3'-methoxypropinonyl) anilide in 100 parts of glacial acetic acid combined. After adding 500 parts of ice water, the mixture is stirred for a further 2 hours precipitated dye is filtered off, washed acid-free with water and dried. He dyes polyester fiber material strongly colored in brilliant blue tones, with very good fastness properties.

The following table contains further dyes of the formula 1 prepared analogously to Example 1 above specified.

Ji 3

P -S -S

JH öJ2 = Jä

ι ι ι ι ι ι ι ι ι ι ι ι ι

ocoooooooooo ο

uuuuuuuuuuuu u

I I I 1 I I i I I I I I I

Ol Ci Ol

UUUUUUUUUÜÜÜ U

I I I I I I I I! I I I I

XU
OO

TO

X desg desg desg X X X desg X X X X U U U U U (J
I. U
I. ü
! X X X X Γ * U
I. U
I. U
I. U U
I.

DODO the same Z ü , 0COC the same 8th X
U X
U X
η U X
U X X X
U
I. ^: HD- ¹ HD I? (j υ
υ ι ι
X) II ^r HD (J X ΐ ^x , ΐ
UUOU
IIII X X £ U U U

XXXXXX

I χ χ χ

X X

U U

O O

U U

X X

Y. Z

xxxxxxxxxxu

I I

cqXXXXcqcqcqcq

XXX

Y. 7. 7. c O OOOOOCC

UUU i7> V. YY YYY Y Y.

IuIIIIIIfII! I.

continuation R; R .. H H R, R ₁ , Rt Il X Nuance on 1 UI K) Example R ₁ H -OC; H ₅ Polyesler K) No. Br H -OC ₂ H ₅ -C ₂ H, -C ₂ H, -CH (CHj) ₂ 2 —CO- blue 0 I? -CN Cl H H -OC ₂ H ₅ -CH ₂ CH ₂ OCOCHj -CH ₂ CH ₂ OCOCH, -CH, 2 -CO- blue CO 16 H ₅ C-SO ₂ - Cl H H -OC ₂ H the same the same -CH, 2 —CO- blue "^ IV CH, - (O> SO ₂ -
V Cl H -OC ₂ H ₅ the same the same -CHfCHj) ₂ 2 —CO- blue 18 the same. Cl H H - OCH, the same the same -QH, 2 —CO- blue 19 the same. ' Cl H H - OCH, the same the same -C ₂ H ₅ 2 —CO- blue 20 the same Br H H H -CH ₂ CH ₂ CN -QH, -QH, 2 - COO- blue 21 -NO; Br H H the same the same -QH, 2 -SO ₂ - blue 22 -NO, H -NOCOCH ₂ CH ₂ - ■ OCH, -C ₂ H, -C ₂ H, C2H5 2 —CO- reddish
blue 23 -NO ₂ Br H "OC ₂ H ₅ reddish
blue Br H -CH ₂ CH ₂ COOCH, -CH, -QH, 2 —CO- reddish
blue 24 - NO ₂ Cl H -OC; H ₅ -CH ₂ CH ₂ COOC ₂ H ₅ -C ₂ H, -QH, 2 —CO- 25 -NO; H -OC ₂ H ₅ reddish
blue Br H CH ₂ CH ₂ OC ₂ H ₅ -CH ₂ CH ₂ OCH ₂ CH, -QH, 2 —CO- reddish 26 -NO ₂ Br H -OC ₂ H ₅ -CH ₂ CH ₂ CH, -CH ₂ CH ₂ CN -QH, 2 —CO- blue 27 -NO; H -OC ₂ H ₅ reddish
blue Br Cl -OC ₂ H, -CH ₂ CH ₂ CH ₂ CH, -CH ₂ CH ₂ COOC ₂ H, -C ₂ H, 2 —CO- reddish
blue 2S-NO; Br Cl -OC ₂ H ₅ - CH ₂ CH ₂ OCOOCH, -CH ₂ CH ₂ CN -QH. - -CO- reddish
blue 29 -NO; Br CH ₂ CH ₂ OCOOC ₂ H ₅ -CH ₂ CH ₂ OCOOC ₂ H, C2 Hj 2 -CO- reddish 30 -NO; Br H -CH ₂ CH ₂ OCOCH, -CH, -C ₂ H ₅ τ -CO- blr.U 31 -NO ₂ H pink red H H -C ₂ H, -C ₂ H. -C ₂ H, η —COO- pink 32 cl H H -C ₂ H, -C ₂ H ₅ -QH, 2 - COO- pink 33 Br H H -CH, -CH, -QH, -i - COO- pink 34 cl H H -CH ₂ CH ₂ CH ₂ CH, -CH ₂ CH ₂ CH ₂ CH, -C ₂ H, 2 —COO- pink 35 cl H H - CH ₂ CH ₂ CH, -CH ₂ CH ₂ CH, -C ₂ H, 2 —COO- pink 36 cl H H the same the same Ι.Π, 2 —COO- ios red 37 Br H H -CH, -CH, -CH, 2 —COO- pink 38 Cl H -C ₂ H, -C ₂ H, -QH, 2 - COO- pink 39 Cl H -C ₂ H ₅ -C ₂ H ₅ -CH, - COO- 40 CI

continuation

E.g. R, No. 41 Cl 42 Cl 43 Cl 44 -SO ₂ CH ₁ 45 -NO ₂ 46 -NO ₂ 47 -NO ₂ 48 Cl 49 Cl 50 -NO ₂ 51 Cl 52 Br 53 Cl 54 -SO ₂ C ₆ H ₅ 55 -SO ₂ CH ₅ 56 Cl 57 -NO ₂ 58 Cl 59 Br 60 Cl

H Cl H Cl H Cl Cl H Cl H Il H H H Cl H Cl H Br H H H H H H H H H H Cl H H H H H H H H H H

H H H H H H H H H Il H H H H H H H H H H

R ₅

-CH ₂ CH ₂ CH,

-CH ₂ CH ₂ CH ₂ CH, -CH, -C ₂ H ₅

-C ₂ H,

-CjH ₅ -C ₂ H ₅

-C ₂ H ₅ -QH ₅ -C ₂ H ₅ -C ₂ H ₅ -QH ₅

-CH ₂ CH ₂ CH, -C ₂ H, C ₂ H ₅ -C ₂ H, -QH ₅ -C ₂ H ₅ -L ₂ H ₅ -C ₂ H,

R "

CH ₂ CH ₂ CH,

CH ₂ CH ₂ CH ₂ CH,

CH,

C ₂ H ₅

QH ₅

C ₂ H ₅

C ₂ H,

C ₂ H ₅

C ₂ H ₅

CiH5

QH ₅

C ₂ H,

CH ₂ CH ₂ CH,

C ₂ H,

QH ₅

C ₂ H ₅

QH ₅

QH ₅

C ₂ H ₅

C ₂ H,

R- M. X Nuance on Pol \ ester -CH, T - COO- pink -QH, -) —Coo— pink -QH ₅ T - COO- pink -QH, T —Coo— violet -QH, -i —Coo— violet -QH ₅ "> —Coo— violet -QH, -) —Coo— violet -QH ₅ 1 —Coo— violet -CH, -> —Coo— violet -QH ₅ -> —Coo— violet -CH, ■) —Coo— pink -CH, ■> —Coo- pink -CH, 1 —Coo— pink -CH ₃ *) —Coo— violet -QH ₅ τ —Coo— violet -CH ₂ CH ₂ CH, -1 —Coo— violet the same -> —Coo— violet —CH (CH,) ₂ -) —Coo— ro'.arot -CH ₂ CH ₁ CH ₂ CH, -> —Coo— pink -CH ₂ CH (CH ₁ I ₂ T —Coo— pink

OO

Application example

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

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained through a sieve a 2 parts sodium lauryl sulfate in 4000

Parts of the dyebath containing water were added. The liquor ratio is 1:40.

100 parts of cleaned polyester fabric are then 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 colors at 95-100 ° for 1-2 hours. The blue colored fabric is washed, soaped, washed again and dried. The level, strong color Coloring is excellent light, overdyeing, washing, water, sea water, sweat, subliming, smoke gas, thermosetting, pleating and permanent press-proof.

Claims (1)

Patent claims: 1. The monoazo compounds of the general formula NH-X— (CH ₂ ) "- O — R ₇ The invention relates to compounds of the 4-nitro-2'-alkoxyacyiamino-4'-dialkylamino-l, l'-azobenzene series which are free of sulfonic acid groups and which are excellent as disperse dyes, suitable for dyeing fibers or threads or materials made from them made from fully or semi-synthetic, hydrophobic, high-molecular organic substances. The dyeings obtained are distinguished in particular by their fastness to sublimation, their good drawability and color strength, but also by their light and wet fastness properties. The new dyes correspond to the general formula