CH634089A5 - WATER-SOLUBLE MONOAZOIC DYES. - Google Patents

Description

The present invention refers to a new class of water-insoluble monoazoic dyes deriving from 6 - hydroxy-2-pyridones, to their preparation process.

More particularly, the invention relates to the monoazocolourants included in the general formula:

0 0

the II

X-C-H CO-C 5 2

ch.

®-N = NXT

the

©

10

where is it:

X means OR3 or NHR3, NR3R4 (with R3, R4 possibly forming a ring having from 5 to 6 carbon atoms), NHR5,

15 Ri = H, alkyl having from 1 to 5 carbon atoms or (CH2) 2OH, (CH2) 3OR3,

R2 = CN, COOR3, CONHR3, CONRsR4 (with R3, R4 possibly forming a N with 5 or 6 carbon atoms),

20 R3, R4 = alkyls having from 1 to 5 carbon atoms, Rs = cycloalkyl with 5 or 6 carbon atoms.

They are prepared, as illustrated below, by reaction of an intermediate (II) with a halogen derivative (III):

25

ch.

HO ~ -N = N- R2

hdAI ^ O

(II)

30

35

the

Alg-CH2-CO-X Alg = CI, Br

(III)

This reaction was unexpected due to the fact that normally in nucleophilic reactions an OH of the phenolic type is more reactive than a COOH group. [See. J.O. Edwards -40 Journal of Amer. Chem. Society, 76, 1540 (1954)].

According to the invention, intermediates (II) and (III) are reacted in the presence of an acidity acceptor (e.g. K2C03 or CHjCOONa) in a protic or aprotic solvent (e.g. water, tert-butanol, DMF, N -methyl-pyrrolidone, 45 N, N-diethylaniline, nitrobenzene, sulfolane), or mixtures of these solvents, at temperatures that can vary from ambient to boiling of the solvent, depending on the mobility of the halogen atom of (III ), possibly also under pressure, in the presence of an alkaline iodide, or 50 of an alkaline iodide + a quaternary ammonium base or salt (e.g. benzyltrimethylammonium hydroxide, tetrabutylammonium iodide).

The acidity acceptor can be omitted if an alkaline salt of (II) is used.

55 The products (III) that can be used for the invention are, for example, the following:

- methyl chloroacetate C1CH2C00CH3

- ethyl bromoacetate Br CH2COOC2H5

- butyl chloroacetate ClCH2COO (CH2) 3CH3

60 - neopentyl chloroacetate ClCH2COOCH2C (CH3) 3

- chloroacetic acid diethylamide ClCH2CON (C2H5) 2

- cyclohexylamide of chloroacetic acid

ClCH2CONHC6H11

- piperidinoamide of chloroacetic acid 65 C1CH2CONC5H10.

The preferred concentration of (II) in the reaction medium can vary from 15 to 70%. The dye (I) is isolated at the end of the reaction by filtration by operating in water for

3

634089

dilution with water the solvent is with this miscible or by steam distillation after any neutralization of alkalinity (e.g. with H3P04) if the solvent is insoluble in water.

The dye is finally filtered and washed.

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

Any purifications from the unreacted intermediate (II) can be carried out by crystallization from suitable solvents (eg DMF) or by treatment with weak alkalis.

The intermediates (II) are obtained according to conventional techniques by diazo-copulation between aminobeno-zoic acids and 6-hydroxy-4-methyl-2-pyridones replaced in position 3 and nitrogen respectively with the groups R2 and Rj indicated above.

The diazotable bases used for the preparation of (II) are:

- anthranilic acid

- m-aminobenzoic acid

- p-aminobenzoic acid.

The couplers used for the preparation of (II) are prepared through well-known condensations, for example between H3CCOCH2COO-alkyl compounds, RXNH2 and RjCHjCOO-alkyl compounds (see for Rj = CH3, R2 = CN Guareschi, Zentralblatt 1907 I 875) or between H3COOCH2COO-alkyl compounds and RjCHjCONH-Rj compounds.

By way of example, some of the 6 - hydroxy-4-methyl-2-pyridones usable for the invention are reported:

- 3-cyan

- l-methyl-3-cyan

- l-ethyl-3-cyan

- l-butyl-3-cyan

- l- (beta-idrcssietil) -3-cyan

- l- (Y-methoxypropyl) -3-cyan

- l-ethyl-3-carboethoxy

- l-ethyl-3- (N, N-diethylcarbamoil)

- l-methyl-3- (piperidinylcarbomoyl).

The dyes of the present invention are particularly suitable for dyeing and printing synthetic fibers, in particular polyester fibers.

Applied according to the usual dyeing methods (e.g. from aqueous magno under pressure at 130 ° C), and printing (e.g. with the well-known Thermosol method) they give these materials intense and bright yellow-green dyes and prints which they have excellent fastness properties, especially in light and sublimation.

The dyes are also very suitable for the realization of corrosion effects both white and colored, with the "alkaline reserve" method (treatment of the foular fabric given with alkaline pastes based on Na2C03 or NaHC03, possibly added with alkali-resistant dyes, suitable for making certain designs and steaming).

The corrosion effects are superior to those achievable with dispersed dyes known and selected for this application derived from the 6-hydroxy-2-pyridones, for example those described in the Italian patent 866 676 of formula:

(cVn * 1

a-n = n -

wherein A can be (Cj-C ^ -OOC alkyl

5 Equally superior are the strengths to sublimation.

For the above applications, the dyes, in the dry or paste state, are ground in the presence of suitable dispersing agents, such as, for example, sodium lignosulfonate, up to a particle size of 0.5 -1 u and applied on the fibers according to the aforementioned techniques, for example from an aqueous bath for exhaustion, or for foularding, eventual printing of the reserve, steaming.

The invention will now be more precisely illustrated with 15 the following examples.

In the examples the parts are expressed by weight, unless otherwise indicated.

20

25

30

Example 1

A mixture of 11 p. of intermediate II (p-COOH; R1 = CH3; R2 = CN), 5 p. of K2C03 an., 0.6 p. of KI and 30 p. in vol. of dimethylformamide is heated to 70 ° C. 4.5 p. Are added to this temperature. of ethyl chloroacetate.

The mixture is heated for 1 h at 90 ° C, is left to cool to room temperature, is poured into acidulated water, stirred, filtered, washed.

After drying 13 p. Are obtained. of the formula dye:

ch3

h5c2o-c-h2od

35

-c- <5) _N = K VjX

cn

0

THE

ch.

40 Example 2

A mixture of 18.7 p. of intermediate II (p-COOH; R1 = CH3; R2 = CN), 10 p. of K2C03 an., 1.3 p. of KI, 2 p. in vol. of 40% solution in Triton B methanol (benzyltrimethylammonium hydroxide), 14.4 p. in you. of chlorine-45 ethyl acetate and 100 p. in you. of nitrobenzene is heated 3 h under stirring at 120-160 ° C.

After neutralization with H3P04 and distillation of the solvent in a stream of steam, the dye of Example 1 is obtained with good yields.

50

Example 3

A mixture of 9.4 p. of intermediate II (p-COOH; Rj = CH3; R2 = CN), 5 p. of K2C03 an., 0.65 p. by KI, 20 p. in vol. DMF and 5.5 p. of N, N-diethylchloroacetamide is heated for 1 h at 90 ° C under stirring. The mass is poured into acidulated water, filtered and the solid washed.

The formula dye is obtained with good yields:

60

0 or (H5C2) 2N-C-CH20-C- ^ O) -N = N-ij

65

634089

4

Example 4

To a mixture of 15 p. of sodium salt of (II) (p-COOH, R1 = CHS; R2 = CN), 0.3 p. of K2C03 an., 0.9 p. of KI, 1,8 p. of tetrabutylammonium iodide and 50 p. in you. of nitrobenzene are added under stirring at 90 ° C 5.4 p. in you. of ethyl chloroacetate. The temperature is then raised to 130 ° C. After 1 hour at this temperature the chromatography of the raw reaction mass reveals the transformation to the dye of Example 1.

Example 5

To a mixture of 9.3 p. of sodium salt of II (p-COOH, R1 = CH3, R2 = CN), 4.2 p. of K2C03, 0.7 p. by KI, 10 8 p. of tetrabutylammonium iodide and 100 p. of water are added under stirring at 70 ° C 7 p. in you. of ethyl chlorine-acetate. The temperature is then raised to 90 ° C. After filtration and treatment of the reaction raw product with boiling water, 10.3 p. Are obtained. of the dye of example 1.

Dye Example (1)

Tone on PE

n. 8

n. 9

n. 10

i n. 11

15

n. 12

R1 = n-C4H9, R2 = CN, X = OC2H5 yellow-

substitution on phenyl = para greenish

R1 = n-C4HB, R2 = CN, X = OC2H5 yellow-

substitution on phenyl = greenish vegetable garden rx = n-c2h4oh, r2 = cn, x = oc2h6

substitution on phenyl = para

R1 = (CH2) 3OCH3, R2 = CN, X = OCH2 (CH3) 3 substitution on the phenyl = para

R1 = CH3, R2 = CN, X = OC2H5 substitution on the phenyl = meta yellow-greenish yellow-greenish yellow-greenish n. 15

n. 17

Example 6 (application) 20 n. 13

In a pressure dyeing machine, 100 g of polyester fabric, previously purified, are treated for 10-15 minutes in 2 liters of n. 14

50 ° C containing 2g / l of ammonium sulphate and 1 g / 1 of Emul-son ELU (non-ionogenic surfactant, Montedison product). 25

1 g of dye, prepared according to Example 1, is added and micro-microfinated at 20% liquid by means of ethylene glycol, water, Saltetra SS (formaldehyde condensate, m- and p-cresol and Schäffer acid). The bath is brought to pH 5.5 L with formic acid, heated to 20 ° C in 20-30 minutes, 30 then the temperature is slowly increased to 130 ° C and maintained at this temperature for 60 ml. nuti. At the end of dyeing, it is cooled to 80-85 ° C, the bath is discharged, rinsed and an alkaline reducing treatment is carried out for 20 minutes at 80 ° C with a bath containing 2 ml / 1 of NaOH 35 at 36 ° Bé, 2 g / 1 of 85% Na2S204 and 0.5 g / 1 of DIAPAL CW® (non-ionogenic detergent).

Rinse thoroughly and dry.

The dye thus obtained, yellow-green in tone, has high intensity, excellent fastness to light, wetness and thermal treatments.

Example 7 (application) n. 18

25 p. of the microfine liquid of example 6 are mixed with 100 p. of Lamitex LIO® (thickener based on sodium alginate), 2 p. of sodium chlorate, 2 p. of 45

citric acid and 745 p. of water. The liquid thus obtained is used to foulard a polyester fabric.

After drying at 80-90 ° the fabric is printed with a white corrosion paste containing 90 p. of sodium dicarbonate, 66 p. of polyethylene glycol, 33 p. of glycerin, 400 p. of Lamitex LIO®, 210 p. of water and 200 p. of an emulsion containing 80% mineral spirits, 6% Diphasol EV® emulsifier (based on a long chain condensate of ethylene oxide with a branched alcohol C16-C18) and 14% of water.

It is then vaporized at 170 ° for 8-10 minutes. After washing and reducing cleaning with 4 g / 1 NaOH and 2 g / 1 hydrosulphite at 70-80 ° C, a bright yellow dye of intensity of about 1/1 E.C.E. is obtained, perfectly white in the areas subject to corrosion. 60

The same observation on corrodibility can be made using 50 p. of the microfine liquid. In this case the tincture has an intensity of about 2/1 E.C.E.

The dyes show good fastness to sublimation and wet washing and excellent fastness to light. 63

The following table provides a list of dyes (I)

obtained according to the method of the invention and the tone on text. 123 polyester fabric.

R ^ CH ,, R2 = CN, X = OC2H5 substitution on the phenyl = vegetable garden n. 19

50

55 no. 20

n. 21

n. 22

ri ch3, r'2 cooc2h5,

x = OC2H5

substitution on phenyl = para

R1 = CH3, R2 = CON (C2H5) 2, substitution on phenyl = para yellow-greenish yellow-greenish yellow-greenish

C2H5

R1 = CH3, R2 = CN, X = -NC ^ yellow-

C4H9 greenish substitution on phenyl = meta

ça

R1 = CH3, R2 = CN, X = -NC substitution on the phenyl = yellow para-

Greenish C4H9

R1 = CH3, R2 = CN, X = HN- yellow-

greenish h '

substitution para ri = ch3, r2 = cn, X = N ^ H) gi v — t VP

greenish-yellow replacement para

Ri = ch3, r2 = with (c2h5) 2, X = n (c2hs) 2 substitution para

Rx = CH3, r2 = cn, x = nhc2h5

substitution para r, = chs, R2 = CN, x = nhc4h9 substitution meta r ^ cä, r2 = cn, x = nhc4h9 substitution para yellow-greenish yellow-greenish yellow-greenish yellow-greenish

5

634089

n. 24 Ri = CH3, R2 = C0NHC2H5,

x- / i>

green-yellow meta replacement n. 25

n. 26

Ri-CHa, R2 = C0N;

(D

X = OC4H9 replacement for r ^ ch »r2 = cooc2h5,

x = nhc4h9

meta replacement greenish-yellow greenish-yellow v

Claims (3)

634089 2. Process for the preparation of dyes of general formula (I), characterized in that it is reacted in a protic or aprotic solvent, or in a mixture of these solvents, in the presence of an alkaline iodide or an alkaline iodide + a base or a quaternary ammonium salt, the alkaline salt of an intermediate (II): HOOC (II) R (where Rj and R2 have the meanings indicated in claim 1), i.e. the same intermediate (II) + an accept of acidity, with a compound of the general formula (III): Alg-CH2COX (Ih) where Alg = CI, Br and X = OR3 or NHR3, NR3R4 (with R3, R4 possibly forming a C5-C6 ring), NHR5; R3, R4, R5 have the meanings indicated in claim 1. 2 CLAIMS 1. Water-insoluble monoazoic yellow dyes meeting the general formula: Q 0 X-LH CO-C 2 CH. ^ ■ :: u a) R where is it: X means ORs or NHR3, NR3R4 (with R3, R4 possibly forming a ring having from 5 to 6 carbon atoms), NHRS, Rj = H, alkyl having from 1 to 5 carbon atoms or (CH2) 2OH, (CH2) 30R3, R2 = CN, COORs, conhr3, CONR3R4 (with R3, R4 possibly forming a N with 5 or 6 carbon atoms), Rs, R4 = alkyls having from 1 to 5 carbon atoms, R5 = cycloalkyl with 5 or 6 carbon atoms. 3. Process according to the preceding claim, characterized in that the solvent or the mixture of solvents used in the reaction are selected from the group consisting of water, tert-butanol, dimethyl-formamide, N-methyl-pyrroli-done, N, N- diethyl-aniline, nitrobenzene and sulfolane.