CH644620A5 - MONOAZOIC DYES INSOLUBLE IN WATER AND THEIR PREPARATION PROCEDURE. - Google Patents

Description

The present invention relates to a series of monoazoic dyes insoluble in water and free of water-solubilizing groups, to their synthesis, as well as to the preparation of the relative intermediates.

More specifically, the present invention relates to the synthesis of new monoazoic dyes having the following general formula:

1,5-dihydroxy-naphthalma with an alkoxy CrC4 alkylene-C, -C3 amine.

In general, the dyes of general formula (I) are in the state of high purity, since no purification is necessary.

The monoazoic dyes of the present invention are particularly suitable for the dyeing and printing of synthetic polymeric materials such as, for example, polyesters, polyamides, polyacrylonitrile and cellulose esters under any form.

Applied according to the usual dyeing methods, for example from an aqueous bath under pressure at 130 ° C or by fulardage-vaporization or by fulardage and heating with dry air (Thermosol), or by printing they give on these i5 materials dyes and prints of a reddish blue to green blue tone, intense and bright and showing good affinity as well as good fastness to light, washing and sublimation.

For the excellent stability shown when the pH of the dye bath varies, the monoazoic dyes of general formula 20 (they are particularly suitable for dyeing polyester at high temperature.

There are known azo dyes of shades ranging from reddish blue to greenish blue with a structure similar to that of the dyes of the present invention, for example those described in the patents:

- Pat. Ger. 659 147 and 658 124, wherein the 6-chloro- or 6-bromo-2,4-dinitroaniline are diazotized and copulated respectively on:

nh (ch2) n or

(THE)

where is it:

Y = H; CI; Br

X = H; CI; Br; alkyl CrC4; alkoxy CrC4; Cn; CF3; N02;

S02 alkyl CrC4; COO alkyl Cj-C ,,

n = 2; 3

R = CrC4 alkyl

NHCH "-

CH -CH2OH

OH

O) -NHCH -

40

The dyes of general formula (I) are prepared according to known techniques, by diazotizing an amine of general formula in an acid medium:

X 45

CH - CU OCH

I b o

OH

V - (öVN ";

Y

(Ii)

US Pat. U.S. 2 434 150 wherein 2-alkylsulfonyl-4-nitro - anilines are diazotized and copulated on:

O) - NHCH -CH-CH OH '2. 2

I - (O

OH

and copulating, in an aqueous medium, preferably at pH = 4 5, the diazo thus obtained with the general formula coupler

I HAVE

NH (CH) OR 2 n

(III)

US Pat. Ger. 639 727 wherein 2-amino benzothiazoles are diazotized and copulated on:

O / -NH alkylene-OH

where is it:

X, Y n and R have the previously defined meanings.

The new intermediates of general formula (III) are obtained under the conditions of the Bucherer reaction, according to the procedure described in the examples, by reacting the

HO- / O (Ro y

Other blue-colored azo dyes are also known, deriving for example from 2-amino-5-nitrothiazoles or from substituted 2-aminobenzothiazoles diazotized and copulated on N, N - substituted dialkyl-anilines such as:

644 620

4

O> -N (c2H40H)

ch.

n (W2

or dyes derived from 6-bromo- or 6-chlorine 2,4-di-nitro aniline diazotized and copulated on N, N-dialkylanilines substituted as: och o> - n (c2h4ococh ^)

3 2

/

nhcoch,

All these dyes, however, have the defect of being unstable to changes in pH during dyeing, or of degrading during dyeing itself, when they do not even have low light fastness values.

The Applicant has now surprisingly found that the dyes of the general formula (I) obtained in the present invention show, compared to the known ones, improved general fastness and in particular to light and sublimation, and notable improvement in the dyeing properties, and in particular a high stability to changes in the pH of the dye bath: there are practically no substantial differences in tone between dyes conducted at pH between 7 and 3.

For the aforementioned applications, the dyes in the dry or paste state are ground in the presence of suitable dispersing agents, such as, for example, sodium Iigninsulphonate, up to a particle size of 0.5 - l {i, and applied on the fibers according to the techniques mentioned above.

The following examples illustrate, without limiting them, the characteristics of the invention. Unless otherwise specified, the term "parts" must be understood as expressed in weight units.

Example 1

1.52 parts of 2-methyl-4-nitro-aniline are heat treated with 4.0 parts by volume of HCl d = 1.18 and 30 parts by volume of water. After cooling the solution to 5 - 10 ° C, 0.69 p are slowly added. of sodium nitrite in 10 p. by volume of water.

The diazo solution is then clarified and poured, at 5-10 ° C, on a solution of 2.31 parts of the coupler:

(Ò) -NH (ck2,3och3

I have "

in 20 parts by volume of acetic acid and 50 parts by volume of water.

During copulation the pH = 4 5 is maintained by adding sodium acetate crystals.

After stirring for 30 minutes, the precipitate is washed with water and dried.

3.8 parts of the dye are obtained:

CM.

which dyes synthetic fibers, in particular polyester fibers, in a reddish, intense and bright navy blue tone, with good fastness to light, humidb and sublimation: excellent is also the stability of the dye when the pH value changes. 3 to the value 7.

The coupler used in the described example is summarized as follows.

2.0 parts of 3-methoxy-propylamine are treated with 27.4 parts by volume of NaHSOs d = 1.309 and 100 parts in I volume of water. The solution is left to stir for 10 minutes at room temperature, then 20.3 parts of 1,5-dihydroxy-naphthalene and 14.7 p are loaded. of 3-methoxy-propylamine, the temperature is raised to 106 ° C and kept at this value for 27 hours. At the end, the solution is cooled to the temperature is 20 ° C and s brought to pH = 14 with sodium hydrate d = 1.18. The mixture is left under stirring for 1 hour, then filtered by separating the 1,5-bis (3-methoxy-propylamino) -naphthaline.

The filtrate is acidified with HCl d = 1.09 at pM = 1, treated with carboraffin and left to stir for about 1 hour; m is then filtered to eliminate the unreacted 1,5-dihydroxy-naphtha-Iine.

The filtrate is again treated with NaOH d = 1.18 up to pH = 7: there is the precipitation of I- (3-methoxy-pro-pilamino) -5-hydroxynaphthaline, first in the form of 25 dense oil and then as a crystalline solid which is separated by filtration. After washing and drying the cake, 17.7 parts (yield 58.8%) of product having m.p. = 78-80QC and the following elementary analysis:

calculated% C 72.73 H 7.36 N 6.06 3rd found% C 72.15 H 7.29 N 6.03

Example 2

1.38 parts of p-nitro-aniline are dissolved in 4.0 parts by volume of HCl d = 1.18 and 20 p. by volume of water. 35 The mixture is diazoted to 5-10 ° C by slowly loading a solution of 0.69 parts of sodium nitrite in 10 parts by volume of water.

The solution of the diazo, after clarification, is poured at 5-10 ° C on a solution of 2.31 parts of the coupler of Example 1 in 20 parts by volume of acetic acid and 50 parts by volume of water.

Proceeding as described in Example 1, 3.65 parts of the dye are recovered:

45

02n- (0) -n = n - (o \ nh (ch) 3och

I HAVE

OR

I know that it dyes the fibers shown in a very reddish navy blue tone with good general fastness and excellent pH stability.

Example 3

2,17 parts of 2-bromo-4-nitro-aniine are diazotized 55 and copulated on 2.31 parts of the coupler of Example 1, according to the modalities reported in Example 1.

4.4 parts of the dye are obtained:

Br

° 2N ~ \ 0V N = N -

nh (ch2) 3och3

which dyes the fibers shown in a very greenish blue tone with good general fastness and excellent pH stability.

5

644620

Example 4

1.73 parts of 2-chIoro-4-nitro-aniIina are diazotized and copulated on 2.31 parts of coupler of Example 1 according to the methods reported in Example 1.

3.9 parts of the dye are obtained:

-ac »3

° 2N "\ 0) ~ N = N- ^ 0 / -NH (CH2) 3OC2H5

ho- / o

° 2N "(0) - N = N" (û V NH (CH2) 30CH3

™ <o)

which dyes the fibers shown in a dark greenish blue tone d: good general fastness and excellent pH stability.

Example 5

1.68 parts of 2-methoxy-4-nitro-aniline are diazotized according to the methods reported in example 1 and copulated on 2.17 parts of the coupler:

nh (ch2) 2och3

in 20 parts by volume of acetic acid and 50 parts by volume of water.

Proceeding as described in Example 1, 3.75 parts of the dye are obtained:

0CH3

° 2n- (o \ - n = n - (o) - nh (ch2) 2och3

which dyes the fibers shown in blue green tone with good general fastness and excellent pH stability.

The coupler was synthesized in a similar way to that described in Example 1.

Example 7

1.83 parts of 2,4-dinitro-aniline are tested according to the methods reported in example 6 and copulated on 2,59 parts of the coupler:

-nh (ch) oc h 2 3 3 7

or I have 20 parts by volume of acetic acid and 40 parts by volume 25 of water.

By proceeding in a similar way to that described in Example 6, 4.35 parts of the dye no.

nh (ch2) 30c3h7

which dyes the fibers shown in blue green tone with good general fastness and excellent pH stability.

The coupler was synthesized with a process similar to that described in Example 1.

which dyes the fibers shown in a reddish navy blue tone with good general fastness and excellent pH stability. The coupler was synthesized with a process similar to that described in Example 1.

Example 6

2,16 parts of the 2-methylsulfones I-4-nitroaniline are added, at 0 - 5 ° C and in the time of 1 hour, to a solution consisting of 0,69 parts of sodium nitrite in 20 parts by volume of H2S04 d = 1 , 84.

After further stirring for 30 minutes, the diazo solution is poured at 5-10 ° C on a solution of 2.45 parts of the coupler:

nh (ch2) 3oc2h5

in 15 parts by volume of acetic acid and 40 parts by volume of water. During copulation the pH = 4- ^ 5 is maintained by adding sodium acetate crystals.

After 1 h of stirring, the precipitate is filtered and washed with water. By drying the cake, 4.4 parts of the dye are obtained

Example 8

A solution of 1.63 parts of 2-cyan-4-nitroaniline in 20 parts of acetic acid, 4 parts of propionic acid and 2 parts by volume of water is cooled to 5 - 10 ° C, then they are loaded slowly 10 parts by volume of Nitrosylsulphoric acid IN.

After about 1 h of further stirring at 5 - 10 ° C, the diazo solution is slowly poured onto a solution of 2.73 parts of the coupler:

50

Tnh (ch2) 3oc4h9

I have 20 parts by volume of acetic acid and 40 parts by volume of water. Proceeding in a similar way to that described in Example 6, 4.2 parts of the dye are obtained: 60 cn

° N- (0> - N = N - <OV NiI (CH2) 30C4H-

I have-/

OR

which dyes the fibers shown in blue green tone with good general fastness and excellent pH stability.

644620

6

The coupler was synthesized with a process similar to that described in Example 1.

Example 9

To a solution consisting of 1.96 parts of the methyl ester of 2-amino-5-nitro-benzoic acid in 10 parts by volume of H2SO4 d = 1.84 and cooled to 0 - 5 ° C is added over time. 1 hour a solution of 0.69 parts of sodium nitrite in 10 parts by volume of H2S04 d = 1.84.

After further stirring for 1 hour, the diazo solution is poured at 5-10 ° C on a solution of 2.31 parts of the coupler:

- nh (ch2) 2oc2h5

I have 20 parts by volume of acetic acid and 50 parts by volume of water.

Proceeding in a similar way to that described in Example 6, 4.1 parts of the dye are obtained:

COOCH ^

°, N = N

HO J. or which dyes the fibers shown in blue green tone with good general fastness and excellent stability to pH.

The coupler was synthesized with a process similar to that described in Example 1.

Example 12

2.06 parts of 2-trifluoro-methyl-4-nitroaniline are diazotized and copulated on 2.31 parts of the coupler of Example 1 according to the methods reported in Example 1.

4.25 parts of the dye are obtained:

nh (ch2) 30ch3

i5 which dyes the fibers shown in a greenish blue tone with good general fastness and excellent pH stability.

Example 13

0.6 parts of the dye of Example 1, previously microcrossed, are added to a dye bath at 40 ° C containing 100 parts of polyester yarn.

The pH is brought to 5 with acetic acid then, operating with a 1: 15 bath ratio, the bath is slowly heated to 130 135 ° C and dyed at this temperature for 1 hour. 25 The bath is cooled, the bath is discharged and the normal reducing alkaline cleaning treatment is carried out on the dyed material. An intense and brilliant reddish navy blue dye is obtained with good fastness to light, wetness and sublimation, and with excellent stability as the pH of the tin varies from value 7 to value 3: the tone remains practically unchanged from pH 7 to pH 3.

By operating in a similar way to that described in the previous examples, the following monoazoic dyes of the general formula (I) are obtained:

Example 10

2,18 parts of 2,4-dinitro-6-chloroanaline are diazotized according to the modalities shown in example 9 and copulated on 2.31 parts of the coupler of example 1 according to the modalities reported in example 1.

4.35 parts of the dye are obtained:

° 2N- \ O

N = N -

_ nh (ch2) 3och3

which dyes the fibers shown in a very green blue tone with good general fastness and excellent pH stability.

Example 11

2.62 parts of 2,4-dinitro-6-bromo-aniline are diazotized and copulated on 2,17 parts of the coupler of Example 5 according to the procedure described in Example 9.

4.8 parts of the dye are obtained:

N0_

M- / Q V N = N - (O HlKCMj OCH3

60

Br HO - / Q

which dyes the fibers shown in a very green blue tone with good general fastness and excellent pH stability.

14

15

16

17

18

19

20

21

22

23

24

25

7

644 620

X

Y

n

R

Color tone on polyester fiber so2c2h5

h

3

ch3

Green blue no2

h

3

ch3

Blue green cn h

3

ch3

Green blue

Br h

2

ch3

Greenish blue ch3

h

2

C2H5

Reddish navy blue och3

h

2

CJH,

Reddish navy blue no2

Cl

2

C4H9

Very green blue no2

Br

2

ch3

Very green blue

CI

Cl

3

C4H9

Green blue

Br

Br

3

C3H7

Blue green cn

Br

3

C2H5

Very green blue cf3

h

3

C3H,

Greenish blue

Claims (2)

644 620 CLAIMS 1. Mono-azo dyes of general formula (I): X ° 2N - (0VN = N "<0V NH (CH2) n ° R V— (<i) I have in O where: Y = H; CI; Br X = H; Cl; Br; alkyl CrC4; alkoxyl Cr'C4; Cn; CF3; N02; S02 alkyl CrC4; COO alkyl Cj-Cj n = 2; 3 R = alkyl Cl-C4 2. Monozo dyes according to claim 1, characterized in that Y = H, e X = CH3, Br, CI, OCHa, CF3 3. Monoazoic dyes according to claim 1, characterized in that R = CH3 and n = 3. The dye according to claim 1: 10. The dye according to claim 1: o2n- nh (ch2) 3oc3h? The dye according to claim 1: 02n_ <fov n = n ~ (o \ nh (ch2) 30c4hs HOV O cn i5 12. The dye according to claim 1: ° 2n- (0 ^ "n = n - ^ ovnh (ch2) 2 ° c2h5 cooch, or n-2 The dye according to claim 1 ° 2n "(2)" n = n "(or m- * 0 nh (ch2) 3och3 The dye according to claim 1: 0 n- nh (ch) och, 2 2 or < The dye according to claim 1: n = n 0 n- 2 TNH (CH2) 30CH3 8. The dye according to claim 1: ° 2n- {0) 'n = n- (ovnh (ch2) 2och3 'h0_ / och \ u 3 The dye according to claim 1: V-CcTy- N = N - (^ V NH (CH2) 30C2H5 I know ch höa o 2 3 13. The dye according to claim 1: no? 02n- (q) _ n = n - (c nh (ch2) 3c? Ch3 i have o 30 14. The dye according to claim 1: no. ° 2n- (or n = n - <> -nh (ch2) 30ch3 Br 15. The dye according to claim 1: 02n- nh (c112) 30ch3 16. Preparation process for monoazoic dyes of general formula (I) characterized in that the diazonium salt is copulated with an amine of general formula: ^ °, n- (or v nh: on the new compound of general formula: (Ii) I have - \ nh (ch) or 2 n (hi 65 in an aqueous medium at pH = 4 + 5, where: Y = H; CI; Br X = H; CI; Br; C1-C4 alkyl; alkoxyl Cx-C4; CN; CF3; Noz; S02 alkyl CrC4; COO alkyl CrC4 3 644 620 n = 2; 3 R = C ^ C alkyl ,, 17. Intermediate compound products of general formula: - NH (CH) OR 2 no (Ih) where is it: n = 2; 3 R = CrC4 alkyl as means for carrying out the process according to claim 16.