CA1182449A - Organic compounds - Google Patents

Abstract

Abstract of the Disclosure A compound of formula (I) in which R1 is hydrogen, chlorine, bromine or iodine;
R2 is hydrogen, chlorine or bromine;
R3 is -CO-R5; -COOR5; -COOCH2CH2OR5; or -SO2-R6;
where R5 is C1-4alkyl R6 is methyl or ethyl;
R4 is (C2-3)alkyl monosubstituted by cyano, or ?-chloroallyl.

Description

~z~
- 1 - Case 150-4604 I~tPROVEMENTS I~ OR REL.ATING TO ORGANIC COMPOUNDS

The invention relates to monoazo comp~unds particularly for the use as disperse dyes.
According to the invention there is provided a compound of formula I
R
NO2 ~ N= ~ / 4 (I~
CH -CH=CH-Cl ~2 NH-R3 2 in which R1 is hydrogen, chlorine, bromine or iodine R2 is hydrogen, chlorine or bromine;
R3 is -CO-R5~ -C0OR5; -COOCH2CH2OR5i -CO-t~OCH2CH ~2OR5 Qr -SO2-R6;
1D where R5 is Cl 4alkyl R6 iS methyl or ethyl;
R4 is (C2 3)alkyl monosubstituted by cyano, or ~-chloroallyl.
Preferably Rl is Rl where R~ is chlorine or bromine.
~5 Preferably R2 is hydrogen.
Preferably R3 is R3 wnere R3 is -CO~R6; -CO-OR6;
-CO0CH2CH2O-R6 or -SO2CH3, more preferably -CO R5; where the symbol R6 is defined above.
Preferably R4 is -CH2-CH2-CN.

- 2 - 150-4604 Preferred compounds of formula I are of fvrmula II
Rl NO ~ ~ ~ < CH2CH2CN
-R3 CH2-CH=CHCl where Rj and R3 are as deFined above.
More preferred compounds of formula I are the a and ~-modifications of the compound of formula III

NO2 ~ -N=N ~ / CH2CH2CN III
CH CH-CHCl N~COCH3 ?

where the a-modification has an X-ray diffraction spectra (Cu-~al-radiation) exhibiting lines at d-Yalues of 19.0 (weak, diffuse ) ; 15.5 (weak); 10.0 (very weak, diffuse); 8.5 (medium);
7.9 (medium); 3.4 (strong~diffuse) and 3 28 (weak, diffuse) A;
and where the ~-modification has an X-ray diffraction spectra (Cu-K~1-radiation) exhibiting lines at d-values of 16.0 (very weak); 8.4 (strong); 8.0 (weak);6.7 (m2dium~, 5.65 (medium);
5.10 (weak); 5.05 (weak); 4.25 (weak); 4.15 (weak); 4.02 (weak);

3.92 (weak); 3.86 (medium); 3.78 (weak)i 3.65 (medium); 3.58 (medium)j 3.51 (very strong); 3.39 ~very weak); 3.34 (weak); O
3.28 (weak); 3.22 (weak), 3.01 (very weak) and 2.74 (very weak)A.
The ~-modification is preferred to the a-modification of the compound of fsrmula III
The compounds of formula I may be prepared by diazotising a compound of formula IV

and then coupling it with a compound of formula V

~ ~ 4 V
NH-R3 CH2-CH=CHCl ~here the symbols R~ to Ra are defined above.
The amine of formula IY and the coupling compound of formula V are known or may be produced from known compounds according to known methods. Diazotisation and coupling may be carried out according to known methods.

The ~-modification of the compound of formula III may be formed directly after coupling by heating the ~modification (so formed on coupling) in an aqueous suspension at a pH above 3 ~preferably about 4) to a temperature above 65C (preferably 75-85C). AlternatiYely, the ~-modiFication may be formed from the ~-modification by recrystallisation in an organic medium (for example acetone or a lower alcohol such as ethanol).
When conversion of the ~-modification to the ~-modifi-cation is in an aqueous suspension it is desirable to performthe conversion in the presence of an anionic, cationic or non-ionic surfactant preferably a dispersing agent for example polyYinylsulphonate, dinaphthylmethane disulphonate, an alkali salt of lignin sulphonic acid or cellulose sulphite waste liquor.

- 4 - 150-4604 The compounds of formula I are useful as disperse dyes particularly in dyeing, padding or printing processes of fibres, threads or substrates derived from synthetic or semi-synthetic hydrophobic high molecular weight organic material. Preferred substrates are linear, aromatic polyesters, cellulose 21/2 acetate, cellulose triacetate and synthetic polyamides. The substrates may be in loose fibre, yarn or fabric for~.
Dyeing, printing or padding may be carried out according to known methods, for example as described in British Patent 1,114,433 The compounds of formula I can be prepared as dyeing preparations. Such preparations are known and may be prepared for example by grinding the dyestuff in the presence of dis-persing agents and/or filling agents after which the preparation may be dried by vacuum or dried by atomisation and then on the addition of water dyed, printed or padded in a short or long aqueous dyebath.
The compounds of formula I have good fastness properties.
In particular they have good light fastness, thermofixation-, sublimation-,pleating-fastness, wet-fastness(such as water-9 sea-water-, wash- and sweat-fastnesses),fastness to solvents, (particularly to dry-cleaning solvents),fastness to softening agents, fastness to rubbing, fastness to over-dyeing, fastness to o~one, fastness to gas fumes, fastness to corrosion, reduction fastness (when dyeing with wool),reserve on wool or cotton and fastness to chlorine properties. The compound of ~ormula I are extr~mely useful in various permanent press processes and in "Soil Release" textile finish processes.
The ~-modification of the compound formula III also sho~ls 3~ good stability and is particularly useful for dyeing at tempera-tures over 70Ca especially for cross spool dyeing (where the

- 5 - 150-4604 dyeing liquor is passed through the spool). It is important in cross spool dyeing not ito form large crystals that asglomerate on the outer surfaces of the substrates being dyed but to Form a fine dispersion (circa 1,~ in ;ize) of the dyestuff in solution in dyeing conditions.

The invention will now be illustrated by the following Examples in ~Ihich all percentages and parts are by weight and all temperatures are in C.

- 6 - 150-46D4 a) 34.5 Parts of 2-chloro-4-nitroaniline, 88 parts of concen-trated hydrochloric acid and 25~ parts of wa-ter are stirred together for 12 hours after which 40 parts of ice are added and over a period of 40 minutes 13.~ parts of sodium nitri-te in 50 parts of water are added to l;he mixture at 0 to 2. The mixture is stirred for a further 2 hours whilst cooling to keep the temperature between 0 and 5 and then the so-formed dia-~onium salt solution is filtered to remove any residual solids.
A solution of 55.5 parts of l-(N-~-cyanoethyl-N- ~-chloroallyl)-amino ~3-acetylamino-benzene in lO0 parts of glacial acetic acid and 200 parts of 30 % hydrochloric acid at 0 to 5 is added dropwise over 45 minutes whilst stirring and cooling (by the addition of ice) to the above formed diazonium salt solution.

b) At the end of coupling the dyestuff suspension is adjusted topH 4 with approximately 400 parts of a 30 G sodium hydroxide solution, whereby the temperature rises to 40-45, after which the dyestuff suspension is hea~ed to 80-~5 by introducing steam directly into the solution and this temperature is held for ~5 minutes whilst stirring. The ~-modification so formed is then filtered off, washed neutral with water and dried.

c~ Instead of treating the suspension as in part b) above the dyestuff may be filtered after coupling, washed neutral with water~ dried and then recrystallised from ethanol or acetone.
In this ~ay the ~-modification is formed having a A max in dimethylformamide of 515 nm and is a red shade~
d) The coupling component 1-(N-~-cyanoethyl-N- ~-chloroallyl)-amino- 3-acetylamino-benzene may be prepared by reacting 40.6 parts of l-(N-~-cyanoethyl)amino, 3-acetylamino benzene in 50 parts of water with lO parts of magnesium oxide, 27 parts of 92 ~ l,3-dichloropropane (cis, trans) and stirring the mixture for 24 hours at 80C. After stirring it is cooled

- 7 - 15~-4604 and 200 parts of water are added and the reaction prGduct is extracted with chloroform.

EXAMPLES 2 to 12 Further compounds of formllla I

~1 R
N ~ N=N ~
r CH CH=CHGl in which the symbols Rl to R4 are ~iven in the Table below and where the nuances shown in the Table are on polyester material, the dyestuffs being applied to polyester material according to known methods) may be prepared in a similar manner to Example la) followed by pouring the mixture into 500 parts of water, filtering~ washing in non-acidic water and then drying.
TABLE

. Example Rl Rz - R3 ¦ R4 ¦ shade ¦
_ _ _ _ j 2 Cl H -COC2H5 -CH2CH2CN red 516 3 Br H -COCH3 do. do. 517 4 H H do. do. scarlet 495 Cl Cl -C-c~2c~i2c2H5 doO red 517 6 Cl H -COCH3 -CH2CH=CHCl do. 521 7 Cl H -CO~cH2)3cH3 ~ -C~2CH2CN do. 516

8 Cl H -COOCH3 do. do. 51i

9 Cl H COO(CI-I ~ CH do. do. 513 lD Cl H COOCH2CH2OC2H5 do. do. 511 11 Cl H S2CH3 do. do. 508 12 Cl H . -CH2CH=CHCi do. 514 ~z~

- 8 - 150-~04 Application Example a) An ultra disperse dyeing preparation is produced by sand grinding the ~-modification of the dyestuFf of Example 1 ~formed according to Example lb) or 1c)] in the presence of a lignin sulphonate dispersing agent followed by atomisation to give particles of average size l ~ or less and a coupage ratio of 3:10.
b) 6 Parts of the ultra disperse preparation of a) above are dispersed in 1000 parts of water and then introduced into a dyeing autoclave having a circulating liquor of 13,000 parts water and a buffer solution of 30 parts ammonium sulphate and 0.3 parts of formic acid at 60. A precleaned and pressed cross spool (~000 parts of P.E. yarn on a plastic spool) is introduced into the autoclave, which is then closed and the liquor is heated over 35 minutes from 60 to 130. After 15 minutes at 130 the liquor is cooled to 80, the bath emptied and the spool ~horoughly washed with cold water. The spool is then spin-dried and then further dried in a drying machine. A pure, level red dyeing having a deep shade is produced, substantially free of undesired deposits with extremely ~ood ~et- and rub-fastnesses. The backwater of the dyeing is practically colourless and no traces of deposits are found in the dyeing apparatus which can immediately be used for the next dyeing.

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS

1. A compound of formula I
(I) in which R1 is hydrogen, chlorine, bromine or iodine;
R2 is hydrogen, chlorine or bromine;
R3 is -CO-R5; -COOR5; -COOCH2CH2OR5; or -SO2-R6;
where R5 is C1-4alkyl R6 is methyl or ethyl;
R4 is (C2-3)alkyl monosubstituted by cyano, or ?-chloroallyl.

2. A compound according to Claim 1, in which R1 is R'1 where R'1 is chlorine or bromine.

3. A compound according to Claim 1, in which R2 is hydrogen.

4. A compound according to Claim 13 in which R3 is R'3 where R'3 is -CO-R6; -COOR6; -COOCH2CH2O-R6 or SO2CH3 where R6 is as defined in Claim 1.

5. A compound according to Claim 1, in which R4 is -CH2-CH2CN.

6. A compound according to Claim 1 of the formula III

III

7. The .beta.-modification of the compound of Claim 6, where the .beta.-modification has an X-ray diffraction spectra (Cu-K.alpha.1-radiation) exhibiting lines at d-values of 16.0 (very weak); 8.4 (strong); 8.0 (weak);6.7 (medium); 5.65 (medium);
5.10 (weak); 5.05 (weak); 4.25 (weak); 4.15 (weak); 4.02 (weak);
3.92 (weak); 3.86 (medium); 3.78 (weak); 3.65 (medium); 3.58 (medium); 3.51 (very strong); 3.39 (very weak); 3.34 (weak);
3.28 (weak); 3.22 (weak); 3.01 (very weak) and 2.74 (very weak) .ANG..

8. A process for preparing a compound of formula I
comprising diazotising a compound of formula IV
IV
and then coupling it with a compound of formula V
V

where the symbols R1 to R4 are defined in Claim 1.

9. A substrate when dyed with a compound according to Claim 1.