CA1037029A - Water-soluble azoic dyestuffs derived from 4-4'-diaminobenzanilide - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
Sulphonated azoic dyestuffs of the formula:
(I) where A is:
, , ,or

Description

~37~Z9 q'he present invention relates to a new class of sul~
phonated azoic dyestu~fs which are well suited for the direct dyeing of cotton and other cellulosic fibers, such as flax, - regenerated cellulose fibers, hemp and jute; natural and æynthetlc polyamide ~ibers and blends thereof~ as ~lell as leather and other similar materials.
The invention provides a new class of water-soluble azoic dyestuffs having the ~ormula:

H~ - ~ N-N ~ CONH ~ N-N~A

COOH
wherein A i~: :

~=N ~ N2 ' :
H03S sa 3H

, ' ' .

N=N ~ SO~H

~2N
,.~
~3 - - Cu ' ~ N=~ - ~ , or :.~ HO S03H
''' '' ': ' '." ' . ,-. ~ ' . ~ : , `', '3 ~ ' . ~ '-, ' ~ ' .

~C~3~7029 ~ N~ ~ N-N ~ N=~ I~N ~ l-~-CO

S03H H2 ~ 1~2 ~ COOH
OH ~ N

~he~e direct dye~tuffs ha~e characteristics similar to those of the conventlonal direct dye~tuffs of the benzidine series, but the process for preparing them does not i~volve a~y toxicologi¢al risksO A¢tually, benzidine and its derivatives, ~ -which are used in preparing ¢onventional dyestuffs having c`haracteristics which are similar to those according to the invention, are dangerous substances, i.e.g they are carcinogenic and, conse~uently, the use and preparation thereof are extremely harmful to personnel handling them.
~he direct dyestuffs of the invention may be prepared accoxding to methods known in the art.
These dyestuffs dge cellulosic fibers, aæotized fibers and leather in dar~ shades ranging from green to brown.
Dyeing o~ ~ibers with the dyestuffs of the invention is carried out using the same methods as are used~with conventional direct benzidinic dyestuffs, i.e., at a te~perature generally rangl~g between 50 and loooa., in ~ aqueous bath containi~g ~itable amounts~ eOgO from 0,01% ~ to 2-3% g or according to ~he u~er~s exigence, o~ dyestu~f and from 5 to 20~o ~with respect .
to the ~iber weight) of anhydrous ~a2S04 or of NaCl.
he following examples are 8i~en to illustrate the invention, all parts being understood as parts by weight unless ~;!
otherwise indicated.

-2- ~ ~
~"'-~,-EXAMP~ 37029 19.6 parts of sulphanilic acid suspended in 170 parts of water~ 16.7 parts o~ 20 Bé HCl~ and 100 part~ o~ ice were diazotized at 0C. by pouring thereinto7 over a period of 20-30 minutes9 7t8 parts of ~aN02 as a 20~o solut~on (parts/volu-me). The mixture wa~ stirred ~or 2 hours and the exces~
nitrous acid was removed using sulphamic acid. The diazotiza~
tion mass was poured, o~er a pexiod of 15 minutes, onto a ~olu-tion of 12.2 parts of m.toluylenediamine in 200 part~ of water, ~0 100 parts o~ ice and 22 parts of 20 ~é HCl.
`~ ~he pH value of the mixture was brought to 5.5 6 by dxopping in o~er a period of 1 houx, a solution o~ 2007 g. of NaHC03 in 200 parts of water, and stirring was continued o~er-night. The n~xt morning, it was heated to 40~45C., and 140 parts of an aqueous solution of 10~ Na2C03 (parts/weight~ were admixed there-to, the resulting pH value being 9-9.5. Once solu-tion was completed, it was oooled to 10~. with ice and a diaæo-monoazoio mass, separately prepared by coupling 474~-diamino benzanilide with salicylio acid~ as hereinafter described, ~s ad~ixed thereto. The temperature was 10C. and the pH ~alue about 8. The reaction mixture was stirred overnight~ ~nd the next morning it was heated to about 70C, aoidi~ied with 28 part~ of 20 Bé HCl and salted with ~00 parts of rock salt.
The product was filterod under vacuum and washed with a lO~o ~ ~ -brine solution. I-t was then sgueezed dry. The product thus ;~
obtained7 a~ter being dried at 7Q-80C. ~or 24 hours, dyes cellulose fibers in ~ellowish-brown shades. -~he abore-mentioned diazo-monoazoic mass was prepared as follows.
2?.7 parts of 4-4~-diaminobensanilide, suspended in 100 parts of water and 52 parts of 20 Bé hydroohloric acid axe te~raazotized, after cooling with 100 parts of ice, by dropping

-3 '':

~ 37~2~
thereinto~ at o-5~a.5 a sol~ on ~3f ~4 parts o~ N~10~ in 60 parts of water. After stirring for 60 minutes, thé excess nitrous acid was removed using s~lphamic acid.
15 parts o~ salicylic acid were dissolved in 150 parts of H20 and 14.6 parts of 36 Bé NaOH. The resulting solution~
to which were added 5 par-ts of ~a2C03 as a 20~ solution (parts/
volume) and cooled to 0~20a. with 50 parts of ioe, was rapidly admixed within about 2 minutes to the tetrazo-mass. 15 parts of Na2C03 as a 20% solutio~ (parts/volume) were poured into the reaction mixture over a period of 1 hourD ~he temperature was kept at 0-2C. and -the pH value at about 9. ~inally~ the produot was stirred for 2 hours to complete the ¢oupling.
~XAMP~E 2 18~9 parts of 2-amino-phenol-4 sulphonic acid suspended in 150 parts o~ water and 10.5 parts of 20 ~é hydrochloric acid were cooled with 10Q parts of ice and wexe diazotized, at ~
0-5C. by dropping thereinto, over 30 minutes, a solution of ~ -;
7 parts o~ ~aN02 in 30 parts of H20. After stirring ~or 60 minutes, the excess nitrous acid waæ removed using sulphamic aoid.
11.6 parts o~ resor¢in were dissolved in 70 parts of water and 13~3 parts of 36 Bé NaOH. The diazoti~ation mass was poured over a 1 hour period onto the solution thus obtained, ~hile keeping the temperature at 0-5C. with 150 parts of ice and maintaining a p~ ~alue of about ~ with 26.5 parts of ~6 ~é NaOH. Stirxing wa carr~ed on for 1 hour to complete the --~` ~ coupling, whereupon a æolution o~ 26 parts of CuS04.5H20 in 80 parts of H20 at 70~C. was admdxed thereto. ~he~ 8 parts of ., ~ ~odium aoe~ate.3H20 were added to the mi~ture. ~he whole mass wa~ ke2t for 3 hours at 35-40C., the pH ~alue being 5-5.50 It ,:
wa~ the~ salted with 45 parts o~ rock salt. The resulting precipitate wa~ ~iltered undex ~acuum and sgueezed dry. The . . . ..

- 4 . .
,, .'~

~3~25~;
cake was treated with 150 parts o~ water at 400a . and ~olubi-lized by adding Q solution of 15 parts o~ Na2C03 in 70 parts o~ H20, at a pH of about 9~ ~ile keeping the temperature at 10~15~o~ the solution was poured onto a diazo-monoazoic mass, prepared separately by ¢oupling 474~- diaminoben2anilide with ealicylic acid, as described in Example 1. The reaction mix-ture was stirred overnight. ~he next morning it was heated to 60-70C. and slightly aoidified to Congo red with 20 Be hydro-chloric acid~ It was filtered under vacuum and the resulting cake was squeezed dr~.
The produot thus obtained, after being dried at 70-80C., ~s useful in dyeing oMd printing on ¢ellulosic fi~ers9 providing reddish brown shade~ exhibiting an excellent stability to mois-ture and lighto 13.8 parts of p-nitroaniline were suspended in 50 parts o~ H20 and 35 parts of 20 Be HCl. After addition o~ 100 parts o~ ice it was diazotized by rapidly pouxing thereinto a 20% ~i ~olution (part~/volume) of 7 g. of ~a~02 `at a temperature of : :
?oC. Stirring was conducted for 30 minutes1 A solution of :~
39 parts of H acid in 150 parts o~ H20 and 14.6 parts of 36 . B~ NaOH was poured o~er 45 minutes at 0-5Co onto the clari~ied diazo solution, the pH value being 0.8-1.1. It was stlrred :
o~ernight and the whole wa9 poured onto a diazo-monoazoic mass ~eparately prepared by coupling 4,4'-diaminobenzanilide with salicylic acid, as described in Example 1. Thereafter, 50 parts o~ ice were added and the pH value waa brought to 805-9 with 16 parts of Na2C03 dissolved i~ 70 parts of H20. It was stirred overnightO The next morning after it was heated to 70~. and f~ltered under ~acuum. ~he cake wàs squeezed out and then dried at 80-90Co . ~he re~ulting product dye~ ¢ellulosic and polyamide . .

-5~

1~37Q;~9 fibers bluish green wi-th an excellent stability to moisture and light.
~XAMP~E 4 20.4 parts o~ 4,4'-diaminobenzanilide, suspended in 45 parts of H20 and 52 par-ts of 20 Bé HFl, after cooling with 200 parts of ice, were tetraazotized by dropping therein-to at 0-50a. a solu-tion of 12~5 parts of Na~02 in 50 parts of H20.
It was stirred 1 hour at a p~ of 1-1.5. The exoes~ nitrous acid was removed using sulphamio acid.
13.5 parts of salicyll¢ acid were dissol~ed in 180 parts o~ H20 and 6~5 part~i of ~a2C03, the pH value being 7~5. After addition of 100 part~ of ice, the whole was poured, in the form o~ a flne streiam, onto the tetraazotization mass. The pH value was brought to 9-9~5 by means of 29 parts of Na2C03~ Stirring was carried on for 3 hours at 0-5Co and a solution consisti~g of 17.2 parts of 1-naphthylamino-6- or -7 sulphonic acid dis-solved in 270 parts of H20 at 40C. a2ld 9.3 parts of 36 Bé
NaOH and cooled with 100 parts of ice was admixed thereto. It was stirred overnight. ~he next morning, the pH was brought to 2.5 with 42 parts of 20 Bé HCl; after stirring for 15 minu-tes the pH value was then raised to 8.5 with 22.5 parts of 36 ~;~
Bé NaOH to complete the coupling. ~he mas3 was mixed with 200 parts of ioe~ 60 parts o~ 60 ~é H2~04 and was diazotized by gradually i~troducing a solution of 11.5 parts of NaN02 in 50 parts of H20. ~tirring ~as carried ~n until the next day, whereupon the exoess nitrous acid was removed using sulphamic acid. A su~pension, prepared as herei~after described was admdxed thereto:
16.3 parts of m.phenylenediamine were dissolved in ~30 parts of water and brought to a pH of 5-5.5 with a 20 Bé HCl.
~70 parts of ice and 702 parts o~ sodium nitrite were added;
~ ~ùbsequently9 oYer 3 hours, 26.1 parts of 20 ~ HCl, diluted ~ --.~....................... . .~

-6-' ~

~ 0 ~7 ~ %9 with 26.~ parts of H20, were introducedO ~he mixture was slightly aoid -to Congo red. Stirring was carried on at room temperature until the next day.
The mass was salted with 135 parts rock salt; the precipitated dyestuf~ was filtered under vacuum and squeezed dryO ~he cake was suspended in 400 parts of H20 at 90~C. It was then homogenized and cooled with 300 parts of iceO
~ he ooupling mass was brought to a pH of 7.5 with 120 parts of 36 Bé NaOH and was kept under stirring until the next day~ It was heated to 700a~ and salted with 90 parts of rock salt. It was ~iltered under vacuum and accurately ~ æquee~ed dryO It wa~ then dxied at 80Co The dyestu~ thus obtained dyes cellulosic ~ibers with brown hues and good stability characteri~ticæO
Variations can, of course, be made without departing from the spirit and scope of the in~ention.

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Claims

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

1. Sulphonated azoic dyestuffs of the formula:

(I) wherein A is:
, , , or