CA1045122A

CA1045122A - Diazo compounds

Info

Publication number: CA1045122A
Application number: CA255,394A
Authority: CA
Inventors: Antonino Condo; Sisto S. Papa
Original assignee: Aziende Colori Nazionali Affini ACNA SpA
Current assignee: Aziende Colori Nazionali Affini ACNA SpA
Priority date: 1975-06-25
Filing date: 1976-06-22
Publication date: 1978-12-26
Also published as: ES449157A1; FR2315523A1; FR2315523B1; NL7606704A; BE843448A; GB1543243A; DE2628470A1; IT1039386B; CH628076A5; JPS524535A

Abstract

ABSTRACT OF THE DISCLOSURE
Novel organic tetrazo compounds are set forth, which contain up to 3 sulphonic groups, and are useful as acid dyes for natural and synthetic polyamidic fibres, such as wool, silk, superpolyamides and superpolyurethanes. The compounds have the general formual ( I ) wherein:
X = -H, -CH3, -OCH3, -Cl, -SO3M, or -NO2;
Z = -H, or -CH3;
Y = -H, or -SO3M;
R = a lower alkyl having from 1 to 4 carbon atoms, or -CH2CH2-SO3M, when Y is hydrogen; and M = -H -Na, -K or -NH4.
The SO3M group takes the position 6 or 7.

Description

. ~;0451~Z
THE PRESENT INVENTION concerns a new group of organic tetrazo compounds of the general formula~

~3--N=!~ ~N=~N~ ~ ( I ) ', ...
wherein:
. X = -H, -CH~;, -OCH3, -Cl, -S03M, or -N2i :
. Z = -H, or-CH; i ~
3 .: .
y = -H, or-S03M;
R = a lower alkyl havir.g frorr. 1 to 4 carbon atoms, or -CH2CH2-SO~
when Y is hydrogen; and .. .
M = -El, -Na , -K or -NH4 . -The S03M group takes the position 6 or 7. ,:
. . . - .
... ...
: . .
These new tetrazo compounds, containing upto three sulphonic groups, find application as acid dyes for natural and synthetic ; ~ -~polyanlidlc fibres, such as wool, silk, superpolyamides and super- ..
polyurethanes.
:- .
~--, 15 . ~ Tetrazo dyes for natural and synthetic polyamidic fibres which are of a broadly similar structure are already availa-ble, for ~ :
i nstance9 the dye of the fornmula: . .
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~045~Z :
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~-~=N ~ ~_ / 2 5 . , >~ / ~CII ~ (II) 503Na ~

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Also known (see U.S. Patent No. 3,580,901) are tetrazo dyes having structures corresponding to the general formula: ;

~ .

N=N-~ -C~

, wherein: . `
R1: = -H~ -CH3~ -OCH3, or chlorine;
~R2 = -H, or-cH3;
: R3 = lower alkyl radical having from 1 to 4 carbon atoms; and ~, :
~: M = -H , _Na , -K , or -NH4 .

Dyes of general formula (I) on nitrogenous fibres generate shades varying from red to violet, and exhibit a good .
behaviour in relation to, for exàmple, general fastnesses, affinity ::
and equalization, being at least the equal of those of the dyes of :
- ::
: : ~
~: ;: : ' ~ 3~ . : :
:: . .

; ~ : . .
:
:~ :
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:., , ~()45~2 formulae (II) or (III). In comparison with both these latter groups of dyes, they offer the determining and fundamental advantage of not needing the use of alphanaphthylamine which, because of its toxicological characteristics, requires pa~ticular care and precautions.
', .

On the contrary, it has been found that the aminonaph-thalenesulphonic acids used in the preparation of the dyes of general formula (I), in accordance with the present invention, do not show the above mentioned toxic characteristics.
. .
Particularly useful results in the dyeing of nitrogenous fibres, irom the point of view both of intensity and of affinity of the ~ ;
dyes prepared, have been obtained with dyes of the general formulao ~

" .

X ~t d , S03M '~ ' wherein:
.
X,Z and M have the meanings already defined for general formula (I) and - -~
R1 is a lower alkyl radical having from 1 to 4 carbon atoms.

The dyes of general formula (I) are prepared by diazotizing , aniline or a derivative, such as toluidine, anisidine or chloro-aniline, and by subsequent coupling with the chosen 1-amino-naphthalene~6(or7)-; .., . -: ~ :

:

, ~ .
...

SlZZ
sulphonic acid, to give the intermediate aminoazo-compound (V) ' ~N=N ~NH2 =y~ ' :'~' ~, X

l . 3 - ~. ~

and finally by coupling the product (V), after diazotisation, with the .
chosen, variously substituted benzyl-(R)-aniline (VI).
.' ~ ~:
The preparation of thls end coupling componexlt of the general fQrmula:
,. . .
R

CllZ -<~2 (V~

' ': '' ' . wherem Z,Y and R have the~meanings specified for general formula (I), may be carried out by known methods, that is, by benzylation and, as required, ~ by sulphonation of the chosen -N(R)-aniline and the ~, ~: N-(R)-toluidine (see "Fundamèntal Processes of Dye Chemistry" by ~ ~Fierz-David & Bangley, ed. 1949, by Interscience Publishers Inc., New York, pages 134- - 137) .

The dyes m accordance with the invention~may be applied :: ~ 5- :
:: : :

. .

:: :

~04~i~2~
to nitrogenous fibres by conventional dyeing processes in an acid or neutral bath, if desired in the presence of auxiliary substances with e. g. a retarding and equali~ing action.
.:
The following examples illustrate how the invention may be carried into effect. The parts and percentages are expressed by weight, unless otherwise specified. Whiere appropriate, relative proportions are indicated as mols.

EXAMP~E 1 9.3 parts of aniline (0.1 mols) were dissolved in 25 parts by volume of hydrochloric acid at 20 Bé in 100 parts of ice9 and then diazotiséd at 0C with 6~9 parts of sodium nitrite as a 20~o solution.
. ' ' . ~:
Separately there was prepared a solution of 22 parts (0.1 mols) oi Cleve acids 1.6 and 1.7 (consisting of 40% OI
1.6-aminonaphthalenesulphonic acid and of 60% of 1.7-aminonaph-thalenesulphonic acid) in 250 parts of water and 9 parts by volume of caustic soda at 36 Bé, to which were then added 25 parts of sodium acetate crystals. Into this solution, cooled down to 0 - 5 C~ there was ~dripped over a period of 10 minutes the solution of diazo aniline, following which the reaction rnass was kept stirred over^night. There-~ upon the mass was made alkaline with 25 parts by volume of a 36 Bé
caustic soda solution. After this there were added 8.1 parts of sodium ~ ~ nitrite as a 20% solution and ice in a quantity sufficient to bring the ;~ ~ temperature to 0 - 5 C. Finally there were quickly added 50 parts by volume of a 20 Bé hydrochloric acid.

6~
. . . . .
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. .
: . :.
:: , . .
~ .. .
. .

. . .

~a4~z~ ~
The diazotation of the monoazo product was accomplished at between 0 and 5C in four hours.

Separately there was prepared a solution of 29.1 parts o~ N-ethyl-N-(benzyl m-sulphonic acid)-aniline (0.1 mols) in 200 parts of water and 20 parts byvolume of a ~6 Be caustic soda, to which was then added 25 parts of sodium acetate crystals. This solution, after cooling down to 5C, was rapidly dripped into the bis-diazo product, leaving the reaction to complete itself overnight. In the morning the product was salified with 130 parts of rock salt and then ,;
filtered under vacuum, washing with brine.
~
The resulting pad was thoroughly pressed and then dried in an oven at 60C. There was obtained a dark power which, as an acid, slightly acid or neutral aqueous solution, dyes nylon and wool with a Bordeau red tinge, with good fastness to light and stability to laundering.
'.''~..
Operahng as ~ described in example 1, but using the ' reactants listed in the table below, there were obtained dyes which on polyamlde fibres exhibited analogously good applicational characteristics.
~he shades are given in column 4.
.
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, ~ ~ ~ ' . .. '' ' - I
. , '-~ 7 ~
:~
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z T A B L E .- . .
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Example Initial amine 1st Coupling 2nd Coupling Tonality on No. Component Component Polyamide _ . _ . .... __ . .. _ ~ :

Cl ~ NH2 ~ I bluish .

2 ~ Bordeau ~ ~ ~

S03Na ~1 , .~
. , . _ ~ ,' ' . :"'.. ~ ':' . ,. ~_ ,, :, .,,:
\~ bluish S~ NH2 ~ ~ Bordeau . ~ ~:

. SO3Na : : S03Na ~ ~ ~
. .,.~,,~; , -.. ~.:.

O3Na~ ~:

o~deau . . .
. ::
..
8-- .:

, .: .

~,. ",.. i,.
~',` .

9 3 parts (0.1 mols3 of aniline were dissolved in 25 parts byvolume of a 20 Bé hydrochloric acid in 100 parts of ice, and then diazotized at 0C with 6. 9 parts of a 205~ solution of sodium nitrite.

., .
Separately? a solution was prepared of 22.3 parts of 1-amino-6-naphthalene-sulphonic acid in 250 parts of water and 9 parts by volume oi 36 Bé caustic soda, to which were added 25 parts of sodium acetate. To this solution, externally cooled down to 0 - 5C, the aniline diazo solution was added dropwise over a period of 10 minutes and the mixture was then kept stirred for 2 hours, until completion of the reaction.

The reaction mass was then made alkaline with 25 parts by volume of :~6 Bé caustic soda, treated with 8.1 parts of sodium ;
nitrite as a 20% solution, cooled down to 0 - 5C with ice and then charged quickly with 50 parts by volume of 20 Bé hydrochloric acid.
The diazotation of the monoazo product was completed in 4 hours at o _ 5C.
''-- To the bisdiazo compound thus preparèd there were directly added 22.6 parts of N-ethyl-N-benzyl-m-toluidine followed slowly, batchwise, with 75 parts of crystalline sodium acetaté. The reaction was then left to go to completion overnight, keeping the mixture stirred and at room temperature.
,~

. . _ g _ ~ ' . . .

~ . . ~ . .

~o~ z Next mormng the reaction mixture was filtered under - vacuum, washed, and the resulting filter calse, well pressed out, was dried at 70C. In this way a dark powder was obtained that, in an acid or neutral bath, dyes nylon and wool with a bluish Bordeau tinge with good fastness to light and stability to laundering.
. .

9.3 parts (0.1 mols) of aniline were dissolved in 25 parts by volume of 20 Bé hydrochloric acid in 100 parts of ice and then diazotized at 0C with 6.9 parts of sodium nitrite as a 20% solution.
, ,. ~ .
Separately there was prepared a solution of 22.3 parts of 1-amino-6-naphthalene-sulphonic acid in 250 parts of water and 9 parts ~y volume of a 36 Bé caustic soda, to which were then added i 25 parts of crystalline sodium acetate.
;~ ' ' ' .,:
Into this solution, cooled down to 0 - 5C~ was dripped over a period of 10 minutes the diazo aniline solution which was then ; . , .
left, stirred, for 2 hours to complete the reaction. ~-` ~ Thereupon the solution was made alkaline with 25 parts by volume of a 36 Bé caustic soda and to it were then added 8.1 parts of sodium nitrlte as a 20% solution. The whole was then cooled down ;; 20 to 0 - 5C with ice and then quickly charged with 50 parts by volume ,. ..
~- of 20 Bé hydrochloric acid. The diazotization of the monoaæo ; ~ product was completed in 4 hours at 0 - 5C.
." . ~ . : .
.; .
... :
.-;,. - ~: .

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.. ,', . . .
i`,' ~
."
, ', 104S~22 ,... :.
The so-prepared solution of bisdiazo compound was then poured into a solution of ~0.8 parts c~ N-benzyl-N-beta-...
sulphoethyl-m-toluidine in 250 parts of water, maintaining the pH
at 4- 5 by the simultaneous addition of 36 Bé NaOH.

After having left the stirred solution overnight (at room tempexature), it was filtered under vacuum, washed with a solution of rock salt and finally dried. The product was a water-soluble powder which, in an acid or neutral bath, dyes wool and nylon with a Bordeau red tinge showing a good fastness to light and stability to laundering.

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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Tetrazo compounds of the general formula ( I ) wherein:
X = -H, -CH3, -OCH3, -Cl, -SO3M, or -NO2;
Z = -H, or -CH3;
Y = -H, or -SO3M;
R = a lower alkyl having from 1 to 4 carbon atoms, or -CH2CH2-SO3M, when Y is hydrogen;
M = -H, -Na, -K or -NH4;
and wherein SO3M group takes the position 6 or 7.

2. Tetrazo compounds according to claim 1, having the general formula (IV) wherein:
X,Z and M have the meanings given in claim 1 and R is a lower alkyl radical having from 1 to 4 carbon atoms.

3. Tetrazo compounds according to claim 2, wherein X is hydrogen, M is sodium and R is ethyl.

4. Tetrazo compounds according to claim 2 wherein SO3M
on the naphthalene nucleus is at the 6 or 7 position, X is hydrogen, M is sodium, Z is hydrogen, R is ethyl and SO3M on the benzene nucleus is at the meta position.

5. Tetrazo compounds according to claim 2 wherein SO3M
on the naphthalene nucleus is at the 6 or 7 postion, X is chlorine at the para position, M is sodium, Z is hydrogen, R is ethyl and SO3M on the benzene nucleus is at the meta position.

6. Tetrazo compounds according to claim 2 wherein SO3M
on the naphthalene nucleus is at the 6 or 7 position, X is -SO3M at the meta position, M is sodium, Z is hydrogen, R is ethyl and SO3M on the benzene nucleus is at the meta position.

7. Tetrazo compounds according to claim 2 wherein SO3M
on the naphthalene mucleus is at the 6 position, X is hydrogen, M is sodium, Z is hydrogen, R is ethyl and SO3M on the benzene nucleus is at the meta position.

8. Tetrazo compounds according to claim 2 wherein X is -CH2 at the para position, SO3M on the naphthalene nucleus is at the 6 position, Z is hydrogen, M is sodium, R is ethyl and SO3M on the benzene nucleus is at the meta position.

9. Tetrazo compounds according to claim 1 wherein X is hydrogen, SO3M on the naphthalene nucleus is at the 6 position, M is sodium, R is ethyl and Y is hydrogen and Z is methyl at the meta position with respect to the tertiary amine group.

10. Tetrazo compounds according to claim 1 wherein X is hydrogen, SO3M on the naphthalene nucleus is at the 6 position, M is sodium, Y is hydrogen, R is -CH2CH2SO3M and Z is methyl at the meta position with respect to the tertiary amine group

11. A process for the preparation of tetrazo compounds according to claim 1, claim 2 or claim 3, in which an amino-azo compound of general formula (V):

wherein X and M have the meanings given in claim 1, is diazot-ized, and the bis-diazo compound so obtained is condensed with a coupling component of general formula (VI):

(VI) wherein Z, Y and R have the meanings given in claim 1.

12. A process of dyeing nitrogenous fibres, using as acid dyestuff a tetrazo compound according to claim 1, claim 2 and claim 3.