CA1064914A - Monoazo and disazo colorants - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Water-insoluble azo dyestuffs of the Formula I:

Description

~649~

This invention relates to novel basic azo dye-stuffs and to the acid addition salt forms thereof.
U.S. Patent 2,761,868 discloses green and blue basic dyestuffs of the phthalocyanine series bearing from one to eight aminomethyl groups. German Patent 82,626 discloses basic azo dyestuffs obtained by diazotization of p-aminobenzylamine and coupling of the diazonium compound with beta-naphthol and resorcinol.
The present invention relates to certain water-insoluble azo dyestuffs of the formula ~ A~ ~ n FORMULA I
useEul for aoloring nakural ~ibers, s~nthetic fib~r-forming material and cellulosic materials as well as in the manu-acture of paper, varnishes, inks, coatings and plastics and to th~ acid addition salt forms of the dyestuff.
One can prepare the water-insoluble azo dyestuffs of Formula I by cliazotizing an appropriate 2-R-3-Rl-4-R2-5-R3-aniline and coupling the resulting diazonium salt with a coupling component from which the azoic coupling

-2-radical represented by A in Formula I is derived.
In particular, this invention relates to novel water-insoluble azo dyestuffs, and water-soluble acid-addi-tion salts thereof, of the formula N=l~ p,2 FORMULA I
wherein: n is an integer whose value is one or two; R is hydrogen, lower-alkyl, lower-alkoxy or halogen; R2 is hydro-gen, lower alkyl, lower-alkoxy, halogen, aminomethyl or 2-aminoethyl with the proviso that A is other than ~ -naphthol when R2 is aminomethyl or 2-aminoethyl; Rl and R3 are the same or different and are each hydrogen, lower-alkyl, lower-alkoxy, halogen or aminomethyl with the proviso that a~
least one of Rl and R3 is aminomethyl when R2 is other than aminomethyl or 2-aminoethyl; A is an azoic coupling radical ; which when n is one has the formula Q Q QH
OH ~ Ql Q \ r ~ ~ ~ G~f CONH _ ~ , ~ \ ~/ -CH3 , IA Q2 Q2 I~

OH ~ OH
or ~ ONH _ - IC ID

-3-and, when n is two, has the formula --~N~ --CE~ or ~ ~

in which Q, Ql and Q2 are the same or different and are each hydrogen, lower-alkyl, lower-alkoxy, nitro or halogen; and Q3 is hydrogen, lower-alkyl, lower-alkoxy or halogen.
One particular class of compounds of Formula I ~re those wherein n is one and A is an azoic coupling radical having the formula X ~CON}I

in which Qj Ql and Q2 each have the same respective meanings indicated in relation to Formula I. Preferred compounds within the ambit o~ this particular embodiment are o~ the ~ormula R Rl ' ~ 3 dNOC OH R

FORMULA II

1~16~9~9~
wherein Q, Ql, Q2, R, Rl, R2 and R3 each have the same re-spective meanings given in relation to Formula I.
Further particular embodiments deal with novel monoazo chemical compounds having the formulas:

R Rl N J~ 2 FORMULA III

~=N~R2 FORMULA IV
Q ~H R~r___~,R

~ NE~-C-~ ~ R2 j ::~ H3 R and : FORMULA VI

"
.

.

1~!69~4 N = N = _ ~o_, 3 , R~

= Q3 FORMULA VII
in which Q, Ql, ~2, Q3, R, Rl, R2 and R3 each have the same respective meanings given in Formula I.
The compounds of Formula I can be prepared by diazotizing an amine of the formula R~ Rl H2N~/ \~R2 :,, ' ' ~
R VIII
and coupling approximately n molecular proportions of the diazonium ~alt with one molecular proportion of a aoupling component ~rom which the azoic coupling radical ~ ls derived, in which A, n, ~, Rl,. R2 and R3 have ~he ~ame signlficance as in Formula I.
A particular embodiment of the above process com-prises diazotizing an amine of the formula VIII above and coupling approximately one molecular proportion of the coupl-ing component of the formula 3LOG491~4 ~CONH~

;~2 to yield an azo dyestuff having the structure shown in Formula II and in which Q, Ql, Q~, R, Rl, R2 and R3 have the s~me respective meanings indicated in relation to Formula II. Another particular process comprises diazotizing an amine of the Formula VIII above and coupling approximately one molecular proportion of the diazonium salt with one molecular proportion of the coupling component o~ the formula ~ NH-C-CH2-C-CH~

: 10 to yield an azo dyestuff having the structure shown in Formula VI and in which Q3, R, Rl, R2 and R3 have the same re~pective meanings indicated in relation to Formula VI.
A~ used throughout, the term "halogen" in~ludes bxomine, chlorine, ~luorine and i.odine.
As used herein, the term "lower-alkyl" is a satu-rated straight- or branched-chain aliphatic radical of from one to three carbon atoms represented, ~or example, by methyl, ethyl, propyl and isopropyl~
Similarly, the term "lower-alkoxy" includes straight- or branched-chain aliphatic groups attached to the oxygen atom. Included, for example, in this term are methoxy, ethoxy, propoxy and i~opropoxy.
The new dyestuffs of this invention are the water-insoluble basic azo compounds obtained by coupling the appro-priate diazotized mono aminomethylated-, mono-aminoethylated-or bis(aminomethylated)-aniline with the appropriate coupling component, and the water-soluble acid-addition ~alt for~s o~
said basic azo compounds.
The az~ic coupling radical3 represented by A are derived from coupling components which are generally known in the dyestuff art. The coupling components used herein are essentially o~ two types. One type is compri~ed of carbocyclic : or heterocyclic aromatic compounds bearing a hydroxyl group which compounds are capable of coupling in a position vialnal to said hydroxyl group, for example, the arylamides of 2-hydroxy-3-naphthoic acid and 1-aryl-3-methyl-5-hydroxy-pyrazoles.
The second ~ype of coupling component useful in this invention compri~es compounds containing in an open carbon chain an enolizable ketomethylene group o the formula o -~-CH2-, ~or example, thc arylamides o~ acetoaceti~ acid.
Many o~ the aoupling components u~e~ul in ~h~s lnvention are designated in the prior art by a Naph~hol AS ~e~ignation.
Where applicable, this designation will be used together with the chemical name.
2S ~he novel basic azo dyestu~fs of the invention pro-vide ~hades ranging ~rom yellow through orange and red to blue-scarlet which in the free-base form have valuable pro-per~ies as water-insoluble pigments, and in the acid-addi-tion salt form a~ water-soluble direct dyes, useful in the dyeing art for coloring natural fibers, synthetic fiber-form-ing materials and cellulosic materials such as threads, sheets, fibers, filaments, textile fabrics and the like, as well as in the manuacture of paper, varnishes, inks, coat-ings and plastics.
The water-insoluble pigments and the water-soluble acid-addition salts thereof of this invention are charac-terized by good light-~astness. The pigments in the form of their water-soluble acid-addition salt form are use~ul as dyes for dyeing operations and in the water-insoluble free-base form as pigments for printing operations on woven and non-woven substrates made from natural fibers, such as wool, cellulose or linen, those made from semi-synthetic ibers, such as regenerated cellulose as represented by rayon or viscose, or those made from synthetic fibers, such as poly-; addikion, polycondensation or polymerization compounds. Such dyeings or printings can be carried out in accordance with the usual dyeing and printing processes. The water-insoluble pigments can also be added to spinning solutions prior to polycondensation or polymerization.
~ he water-insoluble basic azo pigments of this invention are al90 suitable fox sur~ace coloring or printing paper and cardboard as well as for colorin~ paper pulps.
Moreover, they are useful for incorporation into lac~uers and films of various constitution, for example, those made rom aellulose acetate, cellulose propionate, polyvinyl chloride, polyethylene, polypropylene, polyamides, polyesters of alkyd resins. In addition the subject compounds are suit-able for coloring natural or synthetic resins, for example, acrylic resins, epoxy resins, polyester resins, vinyl resins, _g polystyrene resins, or alkyd resins.
The basic azo dyestufs of this invention are readily converted to water-soluble dyes by treatment with an aqueous solution containing a stoichiometric amount of an inorganic mineral acid selected from the group consisting of hydrochloric, nitric and phosphoric acids or with an organic acid selected from the group consisting of acetic, glycolic, formic, lactic and methanesulfonic acids. The acid-addition - salt forms can be isolated from the aqueous solution in which they are ~ormed by techniques well known in the art, for exarnple, by salting out, precipitation ox concentration by evaporation. However, the water-so}uble dyes thus formed are readily utilized in the form of aqueous solutions for many of their applications, particularly for dyeing cellulose.
Accordingly, it 1s particularly preferred to retain the dyes in a concentrated aqueous solution of the type regularly employed in the paper industry for dyeing paper products.
The water-soluble acid-addition salt form of the subject basic a20 dyestufs are especially valuable dyes for imparting various shades of a stable red, scarlet, orange or yellow color to cotton and to paper, both sized and unsi~ed.
For use in the paper trade, the dyes of this invention have 9everal out~tanding advalltages. ~heir high degree of water-solubility makes them particularly ~uitable for the prepara-tion of liquid dye concentrates which are preferred in thepaper industry. The subject dyes are also less prone to "bleed" when paper impreganated therewith is wet and placed in contact with moist white paper. This is a particularly desirable property for dyes designed for coloring paper to be used in facial tissues, napkins and the like wherein it .

can be foreseen that the colored paper, wetted with common household liquids such as water, soap solutions, milk, carbonated beverages and so forth, may come in contact with other surfaces, such as textiles~ paper and the like which should be protected from stain. Another advantageous property of these new water-soluble dyes for use in the paper trade is found in their high degree of color discharge when bleached with hypochlorite or "chlorine" bleach. Thi~
property of dyes is particularly desired by papermakers in order that dyed paper may be completely bleached prior to reprocessing. Still another advantageous property of the water-soluble dyestuffs of this invention is ound in their high resistance to a change of shade when used to color cellulosic materials, which have either previously been treated with or are treated subsequent to dyeings, with wet strength resin.
We have also found that the dyes of this invention have a high degree of substantivity for bleached fiber such as is used in most colored disposable paper products. More-over, they are absorbed by cellulosic fibers rom aqueoussolution a~ a very rapid rate. These properkies are advan-tageous to the paper industry, because it allows the dye to be added to the pulp just prior ko ormation o the sheet.
The novel dyestufEs of the invention are prepared by generally known methods, for example, by coupling the appropr.iate dlazotized mono-, ~is(aminomethyl)- or mono(2-aminoethyl)-substituted aniline with the appropriate coupling component in an aqueous medium. In preparation of the com-pounds of Formula I, the ratio of the quantity of diazonium compound to coupling component 1;; of course, dependent on 11~649~
the number o coupling sites available in the coupling com-ponent. Thus when a single coupling site is present, for example, in a 2-hydroxy-3-naph~hanilide, there is employed approximately one molecular proportion of the diazonium compound and when two coupling sites are available as, for example, in 4,4'-bi-acetoacet-o-~oluidide (Naphtol AS-G) there are employed approximately two molecular proportions of the diazonium compound. Since the reaction temperature has some effect on the shade of the resulting water-insoluble azo dyestu~fs, it is ordinarily desirable to maintain adequate control of the temperature of the reaction mixture in some predetermined manner. It is generally satisfactory to stir the reactants together at a temperature in the approximate range 0-15C., to effect only an incomplete coupling reac-tion and then to warm the mixture to a higher temperature, for instance in the approximate range 25-50C , preferably at 30-35C., to complete the coupling reaction and develop the dyestuff. The reaction is begun in an alkaline aqueous medium but the pH of the reaction mixture drops during the process to a final value of about 5Ø ~fter completion of the coupling reaction, khe water-insoluble basic azo dyestuffs can be lsolated ~rom the coupling mixture by filtra~ion. The compound9 thus obta~ned are readily converted to wa~er-soluble dyestufs by treatment in an aqueous medium with at least a stoichiometric quantity of an appropriate inorganic or organic acid as mentioned hereinbe~ore and the resultant dye can optionally be isolated or the aqueous solution in which it is formed can be adjusted to the desired concentration and used directly for dyeing operations.
The following compounds exemplify some of the azoic ' -~l~6~
coupling components useful for preparing the pigments of the invention.
3-Hydroxy-2-naphthanilide (Naphtol AS), 3-Hydroxy-2',$'-dimethoxy-2-naphthanilide (Naphtol (AS-BG), 3-Hydroxy-3'-nitro-2-naphthanilide (Naphtol AS-BS), 3-Hydroxy-2-naphtho-ortho-toluidide (Naphtol AS-D), 5'-Chloro-3-hydroxy-2',4'-dimethoxy-2-naphthanilide (Naphtol AS-ITR),

4'-Chloro-3-hydroxy-2',5'-dimethoxy-2-naphthanilide tNaphtol AS-LC), 3-Hydroxy-2'-methyl-2-naphth-para-anisidide (Naphtol AS--LT), 3-Hydroxy-2-naphtho-2,4-xylidide (Naphtol AS-MX), 3-Hydroxy-2-naphtho-ortho-anisidide (Naphtol AS-OL), 3-Hydroxy-2-naphtho-ortho-phenetidide ~Naphtol AS-PH), 3-Hydroxy-2-naphth-~ anisidide (Naphtol AS-RL), 3-Hydroxy-N-2-naphthyl-2-naphthamide (Naphtol AS-SW), 4'-Chloro-3-hydroxy-2-naphtho-ortho-toluidide (Naphtol AS-TR), 3'-Chloro-3-hydroxy-2-naphtho-ortho-toluidide (Naphtol AS-KB), 7-Bromo-3-hydroxy-2-naphtho-ortho-anisidide, 3'-Chloro-3-hydroxy-2-naphtho-ortho-anisidide (Naphtol AS~NEL), 3-Methyl-l-(~-tolyl)-5-hydroxypyrazole, 3-Methyl-1-~3-bromophenyl)-5-hydroxypyrazole, 3-Methyl-1-(4-iodophenyl)-5-hydroxypyrazole, 3-Methyl-l-(o-tolyl)-5-hydroxypyrazole, 3-Methyl-1-(4-chlorophenyl)-5-hydroxypyrazole, 3-Methyl-1-(2-ethoxy-5-nitrophenyl)-5-hydroxypyrazole, 3-Methyl-1 (2,4-dichlorophenyl)-5-hydroxypyrazole, 3-Methyl-1-(2,4-dinitrophenyl)-5-hydroxypyrazole, 4~4 3-Methyl~ 2-methyl-4-iodophenyl)-5-hydroxypyrazole, 3-Methyl-1-(2,5-dimethylphenyl)-5-hydroxypyrazole, 3-Methyl-1-(2,4,6-trichlorophenyl)-5-hydroxypyrazole, 3-Methyl-l-phenyl-5-hydroxypyrazole, 3-Methyl-1-(4-methoxyphenyl)-5-hydroxypyrazole, 3-Methyl-1-(4-ethoxyphenyl)-5-hydroxypyrazole, 3-Methyl-l-~4-propoxyphenyl)-5-hydroxypyrazole, 3-Methyl-l-(3-nitrophenyl)-5-hydroxypyrazole~
3-Me~hyl-l-(4-nitrophenyl)-5-hydroxypyrazole, : ~ 10 3-Methyl-1-(2-chlorophenyl)-5-hydroxypyrazole, : 4',4'''-Biacetoacetanilide, .:
4,4'-Bi-ortho-acetoacetotoluidide (Naphtol AS-G), 2',2" '-Diiodo-4',4''~-biacetoacetanilide, 2l~2l~-Dibromo-4l~4lll-biacetoacetanilide~
2',2'''-Dichloro-4',4 " '-biacetoacetanilide, 3',3"'-Diethoxy-4',4 " '-biacetoacetanilide, ; It will be obvious that those aryl moieties of the azoic coupling radicals represented by A in Formula I which are not shown bearing substituents represented by Q, Ql and Q2 can also be:substituted by groups, represented by Q, Ql ::~ : and Q2, ~or example, lower-alkyl, lower alkoxy and halogen.
The requisite diazotizable amines, which are : anilines bearing one or two aminome~hyl groups or one 2-amino-ethyl group on the ring are known alasses of compounds which are either~ commercially available or can be readily obtained by procedures well known in the prior art. For example/ an appropriate anilinu is interacted with approximately one molecular equivalent each o formaldehyde and phthalimide to obtain the corresponding phthalimidomethyl aniline which is : 30 then subjected to hydrolysis to obtain the desired mono-: -14-aminomethyl-substituted intermediate. The bis-aminomethyl-ated intermediates are similarly obtained by the interaction of an appropriate aniline with approximately two molecular equivalents each of formaldehyde and phthalimide to obtain the corresponding bis(phthalimidomethyl)aniline which is then hydrolyzed to obtain the desired bis(aminomethyl)aniline.
The ~ollowing compounds are exemplary of ring aminomethylated anilines useful in the practice of this invention.
3-Aminomethylaniline, 4-Methy~-3-aminomethylaniline, 2-Methoxy-3-aminomethylaniline, 4-Methoxy-3-aminomethylaniline, 2-Methyl~5-aminomethylaniline, 2,3-Dimethyl-5-aminomethylaniline, 2-Isopropyl-5-methyl-3-aminomethylaniline, 3-I~opropyl-2-methoxy-5-aminomethylaniline, 4,5-Dimethoxy-2-propyl-3-aminomethylaniline, 3-Bromo-5-aminomethylaniline,

5-Isopropyl-2-methyl-3-aminomethylaniline, 5-Ethyl-2-methyl-3-aminomethylaniline, 3,4-Diethyl-5-aminomethylaniline, 3-Methoxy-4-methyl-5-aminomethylaniline, 3-Chloro~4~i90propyl-5-aminomethylaniline, 2,3,4-Trimethyl-5-aminomethylaniline, 2-Chloro-4,5-dimethoxy-3-aminomethylaniline, 5 Chloro-2,4-diethoxy-3-aminomethylaniline, 4,5-Dimethoxy-2-~luoro-3-aminomethylaniline, 2-Chloro-4-methoxy-5-methyl-3-aminomethylaniline, 2,5-Dichloro-4-methoxy-3-aminomethylaniline, 4-(2-Aminoethyl)aniline, 1~64~
2-Methoxy-4-aminomethylaniline, 4-Aminomethylaniline, 2-Ch].oro-4-aminomethylaniline~
2-Ethoxy-4-aminomethylaniline, 5-Chloro-2-propyl-3-aminomethylaniline, 3, 5-Bis (aminomethyl)aniline, 4-Methyl-3,5-bis(aminomethyl)aniline, 4-Methoxy-3,5-bis(aminomethyl)aniline, 2-Methoxy-3,5-bis(aminomethyl)aniline, 2,4-Diethyl-3,5-bis(aminomethyl)aniline, 2-Iodo-3,5-bis(aminomethyl)aniline, 4-Fluoro-3,5-bis(aminomethyl)aniline, 2-Methoxy-4-methyl-3,5-bis~aminomethyl)aniline, 2,4-Diisopropyl-3,5-bis(aminomethyl)aniline, 4-~romo-2-methoxy-3,5-bi~(aminomethyl)aniline, and 2-Bromo-4-aminomethylaniline.
In the Eollowing examples, the term "parts" is in each instance used to indicate parts by weight and the rela-tionship of parts by weight to parts by volume is the same as : :, that of the kilogram to the liter.

To a solution oE 15.4 parts o~ 4-methoxy-3,5-bis(aminomethy1)aniline trihydroahloride in 250 par~ o water and 6 part~ o~ concentrated hydrochloric acid were added 200 parts o crushed ice. The amine was then diazo-tized at a temperature between 0-5C., by adding a solution o~ 4.2 parts of ~odium nitrite in 30 parts of water. The reaction mixture was stirred at less than 5C., for 30 minutes ater which the excess nitrate was removed by the gradual addition of sulfamic acid until nitrite ion could no longer :
: : ,,j,, ~6~

be detected by testing with starch-iodide paper. The cold solution was then made slightly alkaline to Congo Red paper by the addition o~ sodium acetate.
In a separate container, 14.7 parts of 3-hydroxy-2-naphth-o-anisidide (Naphtol AS OL) were mixed with 46.5 parts of 2-ethoxyethanol, 94 parts of warm water, 8 parts of 50 per cent aqueous solution of sodium hydroxide and .033 parts of nonylphenoxypoly(ethyleneoxy)ethanol ~Igepal~ 0-630).
The solution thus obtained was diluted with 310 parts of cold water and the cold diazonium solution obtained as described above was added in a thin stream to the diluted solution.
The reàction mixtuxe was stirred at 20-25C., until consump-tion of the diazonium salt was complete. Eleven parts o glacial acetic aaid were added to the resulting red mixture, which was heated to 50C. and iltered. The alear red filtrate wa~ made slightly alkaline to Brilliant Yellow paper by the addition of sodium carbonate whereupon a tacky red solid precipitated. The solid was collected and washed with water and dried in a vacuum oven to obtain chiefly the red dyestuff having the formula N -N ~ CH3 :: ~

~ ~0~9~

The visible absorption spectrum of an aqueous acetic acid solution of this dyestuff, containing 0.02 g. of dye per liter of solution showed maxima at 503 millimicrons, A=0.848 and at 525 millimicrons, A=0.820.
A concentrated dye solution was prepared by adding 20 parts of this dyestuff to a mixture of 11.4 parts of 70 per cent glycolic acid, 8 parts of 2-(ethoxyethoxy)ethanol and 34 parts of water at a temperature between 50 and 60C.
The mixture was stirred until solution was complete. Paper dyed with agueous dilutions of this concentrate had a scarlet shade and was found to be highly bleachable, in the bleach test described below. The dye was also found to bleed only slightly in the water-bleed test and in the soap-bleed test when tested in accord with the procedure described below.
Testing Procedures ~ The ~ollowing test procedures were employed to ; determine the resistance of the dyestuffs to bleed in moist paper, bleed from paper in the presence of soap and to bleach-, ing with hypochlorite bleach.
~ !
Water "Bleed" Test This procedure is a modification of the AATCC
Standard Test Method 15-1962, "Colorfastness to Perspiration".
~est pieces consisting o ~our plies, each one inch square, are cut from the dyed paper to be tesked. One or more dyed papers of known dye migration quality are included in the test series as standards.
The absorbent material consists of filter paper hav-ing a relatively smooth finish (Whatman #1, 4.25 cm. dia.
equivalent). In addition, smooth, flat, glass or clear plastic plates of adequate stiffness, measuring two inches . .

wide and three inches long, are required as separating plates.
A 1,000 gram weight serves as a dead weight loading.
Four filter paper absorbent pieces are used for each dyed paper test square, two for each side.
The migration test "sandwich" is constructed as follows. A separating plate is placed on a horizontal support and two pieces of the filter paper placed centrally on this plate with the smoother side up. The square dyed paper test pieces, held by tweezers, are immersed in tap water at room 10 ~ temperature for ~ive seconds, drained for five seconds and immediately centered on the filter paper. Immediately, two pieces of filter paper are centered on the test square and followed at once by another separating plate. This "sandwich" is pressed for a moment with the fingers, aEter which, without delay, a piece of filter paper is positioned on the top separating plate as before to receive a second test square of wetted dyed paper. The above procedure is then repeated as rapidly as possible and without interruption, stacking one "sandwich" on the other, until all dyed paper test pieces have been put under test.
As soon as a stack is completed, a 1,000 yram weight is centered on the top separating plate. ~he stack is allowed to ~tand at room temperature ~75F.) Eor Ei~teen minutes.
At the end of the migration period, the stack is disassembled and each dyed paper test square and its filter paper absorbents clipped to a supporting card. A separate card is used for each test s~uare. The dyed paper test squares and filter papers are air dried at room temperature for at least two hours (in the dark) before ranking. Relative ~;4~

degrees of dye migration, as compared to that from standard samples, are determined by visual ratings, in daylight, of the intensity of dye stain on the filter paper surfaces which had been in contact with the test square.
Soap Bleed Test This procedure utilizes the same method employed in the Water Bleed Test described above, except that the dyed paper test squares are immersed in a 0.5 per cent tap water solution of white soap flakes (a mixture of 80 per cent sodium soap and 20 per cent potassium soap produced from 70 per cent tallow and 30 per cent coconut oil glyceride blend; "Ivory" brand, Procter and Gamble Co.) at 120F., instead of water alone.
Bleach Test This procedure compares the degree to which the color of dyed papers would be discharged in a waste paper recovery operation employing hypochlorite bleach.
; A preliminary estimate of bleachabiLity is obtained by placing a drop of hypochlorite bleach, containing 2.5 per cent available chlorine; on the dyed paper and allowing it to dry at room temperature. From this tes~, both rate and degree of bleaching are estimated.
A more aacurate ~es~, approximating paper mill procedur~, is performed by de~ibering three gram~ o~ dyed paper in 150 ml. of distilled water using a kitchen blender.
The defibered pulp slurry is placed in a jar and hypochlorite is added to the extent desired, usually 2.5 per cent avail-able chlorine based on the weight of the dry fiber. The slurry consisting of pulp and hypochlorite is adjusted to pH 9 with dilute sulfuric acid or dilute aqueous solution of sodium hydroxide and placed in a water bath to maintain the interval in the temperature range o~ 115F. to 125F. ~fter the test is started, the jar is loosely capped. At five minute intervals, the cap is tightened and the jar inverted twice to circulate the liquor. The cap is loosened between inversion~. After twenty minutes, the pH is checked and, if higher than 7.5, is adjusted thereto. The test is then con-tinued for an additional twenty minutes (with five minutes between inversions). The terminal pH is generally found to be 6.0-6.5. An excess of sodium thiosulfate i5 added as an antichlor, mixed ~or five minutes and the s}urry is diluted to a concentration of approximately 0.3 per cent of iber.
Sheets are then prepared at pH 7 without a washing step.
Finally, this sheet is pressed and dried in a paper dryer.
Control dyeings at specific levels can then be made to ac-curately determine the loss of strength of color on bleaching.

Following the procedure described in Example 1 ; ~ above, 7.58 parts of 2-methoxy-5-aminomethylaniline in a solution of 137 parts of water and 12 parts o~ conoentrated hydrochloric acid were diazotized with 3.5 parts o~ s~dium nitrite at 0C. In a separate container 9.2 partR of 4,4'-bi-acetoacet-o-toluidide ~Naphtol AS-G) were mixed with 15.7 parts of isopropanol, 95 parts of water and 5.3 parts of 50 per cent aqueous solution of sodium hydroxide. A
solution re~ulted which was then added in a thin stream to the cold diazonium solution. The reaction mixture was stir-red at room temperature until there was ns diazonium salt remaining. The solid product, whi~h resulted, was collected by ~iltration and dried in a vacuum oven. There was thus :

i49~
obtained a yellow dyestuff having the formula ~ ~ ~-CH3 ~ 2NH2 _ ~ ~:H- - H-N=N _ ~

O-C~3 2 The visible absorption spectrum of an aqueous acetic acid solution of this dyestuff, containing 0.02 g.
of the dye per liter of solution showed a maximum at 402 millimicrons, A=0.99.
A dye solution was prepared by thoroughly mixing one part of this dyestuff with one part of acetic acid and diluting the resultant paste o~ the acetic acid addition salt to a volume of one liter with water. Paper dyed with this solution had a yellow shade and was found to be highly bleachable and showed no bleed in the water-bleed test and in the soap-bleed test.

Following the procedure described in Example 1 above, 15.4 parts of 2-methoxy-3,5-bis(aminomethyl~aniline trihydrochlorlde in a solution o 250 parts water and 6 parts o concentrated hydrochloric acid were diazotized with 3.5 parts o~ sodium nitrite at 0C. In a qeparate container, 5.8 parts of 6-amino-1-naphthol-3-sulfonic acid were dissolv-ed in a solution of 100 parts of water and 7.9 parts of 50 per cent aqueous solution of sodium hydroxide. The solution was added in a thin stream to the cold diazonium solution.
The reaction mixture was allowed to warm to 30C. and stirring was continued until there was no diazonium salt remaining.

~22-~649~4 qlhe resulting dark solu~ion was made slightly alkaline to Brilliant Yellow paper and 100 parts of sodi-~ chloride were added to precipitate the product. The separated solid was collected by filtration and dried in a vacuum oven to obtain chiefly a brown dyestuff having the formula N=N CH

¢ ~ CH2NH2 C~2NE1 The visible absorption spectrum of an aqueous acetic acid solution of this dyestuf, containing .02 g. of the dye per liter of solution showed a maximum at 475 milli-microns, A-. 72.
A dye solution was prepared by thoroughly mixing one part of this dyestuff with two parts of ten per cent aqueous acetic acid and diluting the mixture to a volume of one liter with water. Paper dyed with this solution had a brown shade and was found to be highly bleachable. The dye was ound to bleed only sligh,tly in the water-bleed test and in the soap-bleed tes~.

Following the procedure described in Example 1 above, 15.4 parts o 2-methoxy-3,5-bis(aminomethyl)aniline trihydroahloride in a solution of 250 parts of water and 6 parts of concentrated hydrochloric acid were diazotized with 3.5 parts of sodium nitrite at 0C. In a separate container, nine parts of 4,4'-bi-acetoacet-o-toluidide (Naphtol AS-G) were mixed with 15 parts of isopropanol, 90 parts of water and 5.3 parts of 50 per cent aqueous solution of sodium hydroxide. A solution resulted which was then added in a thin stream to the cold diazonium solution. The reaction mixture was stirred at a temperature in the range of 10-15C.
for one hour and was then warmed to 30C. Stirring at 30C.
was continued until the consumption of the diazonium salt was complete. The slurry was made slightly alkaline to Brilliant Yellow paper and the yellow product was collected by filtration, washed with water and dried in a vacuum oven to obtain chiefly a yellow dyestuff having the formula ~NH~ CH-N--N~ ¦

The visible absorption spectrum of an aqueous acetic acid solution of this dyestuff, containing 0.02 g.
of the dye per liter of solution showed a maximum at 387 millimicrons, A=l. 324.
A concentrated dye dispersion was prepared by add-ing 18.5 parts o~ this dyestuff -to a mixture of 20 parts of acetic acid and 74 parts o~ water at 60C. The mixture was 20 heated at 90C. for one hour then cooled. Paper dyed with aqueous dilutions o this dye dispersion had a greenish yellow shade and was found to be highly bleachable. The dye was ~ound to have no bleed in the water-bleed test and in the soap-bleed test.

~6~

Following the procedure described in Example 1 above, 15.4 parts of 4-methoxy-3,5-bis(aminomethyl)aniline trihydrochloride in a solution of 250 parts water and 6 parts of concentrated hydrochloric acid were diazotized with 4.2 parts of sodium nitrite at 0C. In a separate container, nine parts of 4,4'-bi-acetoacet-o-toluidide (Naphtol AS-G) were mixed with 15 parts of methanol, 90 parts of water and 5.3 parts of 50 per cent aqueous solution of sodium hydrox-ide. A solution resulted which was then added in a thinstream to the cold diazonium solution obtained as described above. The reaction mixture was stirred between 10 and 15C., for one hour and then was warmed to 30C. Stirring at 30C., was continued until consumption o the diazonium salt was complete. The slurry which resulted was made slightly alkaline to Brilliant Yellow paper by the addition of sodium carbonate and the product was collected by iltration and washed with water. The product was dried in a vacuum oven to obtain chiefly a yellow dyestuff having the formula _ ~ H~ E-N=

The visible absorption spectrum of an aqueous acetic acid ~olution of this dyestu~ containing 0.02 g. of the dye per liter o solution showed a maximum at 384 milli-microns, A=1.394.
A concentrated dye solution was prepared by adding seven parts of this dyestuff to a mixture of 3.5 parts o ~649~4 acetic acid and 24 parts of water at a temperature between 70 and 80C. The mixture was stirred until the solution was compleke. Paper dyed with aqueous dilutions of this dye concentrate had a greenish yellow shade and was found to be highly bleachable. The dye was found to bleed only slightly in the water-bleed and in the soap-bleed test.
A concentrated dye solution was also prepared by mixing 115 parts of a dyestuff paste containing approximate-ly 7 parts of this dyestuff and 108 parts of water with 10.2 parts of a 70 per cent aqueous methanesulfonic acid solution and 60 parts of water. The resulting mixture was heated to approximately 60C., cooled to ambient temperature and the insolubles removed by filtration. The filtrate showed a maximum in the visible absorption spectrum at 385 milli-microns.
~ he ollowing Table lists further Examples of addi-tional azo dyestuffs of this invention prepared by diazotiz-ing the amines shown in the second column of the table and coupling the resulting diazo compounds with the coupling components shown in the third column of the table following procedures similar to those desaribed in Examples 1-5 above.
The indicated shades are obtained when aqueous ~olutions of the a¢id-addition salt ~orms of the dyestu~5 are used or dyeing cellulose.

l~G4914 Ex-ample Diazotized Coupling No ~mine Com~onent Shade

6 4-methyl-3-amino- 4,4'-bi-ortho-aceto- Greenish-methylaniline acetotoluidlde Yellow (Naphkol AS-G)

7 do 5'-chloro-3-hydroxy- Red 2',4'-dimethoxy-2-naphthanilide (Naphtol AS-ITR)

8 do 3-methyl-1-(p-tolyl)- Reddish-5-hydroxypyrazole Yellow

9 do 3'-chloro-3 hydroxy- Red 2-naphtho-ortho-anisidide ~Naphtol : AS-NEL) do 4',4'''-biacetoacet- Yellow anilide 11 4-methoxy-3-amino- 3-hydroxy-2-naphtho- Red methylaniline ortho-anisidide ~Naphtol AS-OL) 12 do 2',2" '-dichloro- Greenish-4',4'1'-biacetoacet- Yellow anilide 13 do 3-methyl-1-(p-tolyl)- Reddish-5-hydroxypyrazole Yellow 14 do 4'-chloro-3-hydroxy- Red 2',5'-dimethoxy-2-naphthanilide (Naph-... 30 tol AS-LC) 154-methyl-3,5-bis- 3-hydroxy-2-naphtho Red ~aminomethyl)- ortho-ani~idide aniline ~ tol AS OL) 16 do 2',2" '-diqhloro-4 Greeni~h-4',4 " '-biaceto- Yellow acetanilide 17 do 3-methyl-1-(~- Reddish-tolyl)-5-hydroxy- Yellow pyrazole 18 do ~ 4'-chloro-3-hydroxy- Scarlet 2',5'-dimethoxy-2-naphthanilide (Naph-tol AS-LC) 19 do 4',4'''-biacetoacek- Greenish-anilide . Yellow 1~6~
Ex-ample Diazotized Coupling No Amine comPonent Shade 4-methoxy-3,5-bis- 3-hydroxy-3'-nitro- Red (aminomethyl)aniline 2-naphthanilide (Naphtol AS-BS) 21 do 3-hydroxy-2-naphth- Scarlet anilide (Naphtol AS) 22 do 3-hydroxy-N-2-naph- Scarlet thyl-2-naphthamide (Naphtol AS-SW) 23 do 3'-chloro-3-hydroxy- Scarlet 2-naphtho-ortho-anisidide (Naphtol AS-NEL) 24 do 5'-chloro-3-hydroxy- Bluish-: 2',4'-dimethoxy-2~ Red naphthanilide (Naph-tol AS-I~R) do 3-methyl-l-phenyl- Reddi~h-5-hydroxypyrazole Yellow 26 2-methoxy-2,5-bis- 3-hydroxy-2-naphth- Scarlet ~aminomethyl)anil- anilide (Naphtol AS) ine 27 ~ do 3-hydroxy-2-naphtho- Scarlet ortho-anisidide - : (Naphtol AS-QL) ., , ~ 28 ~ do 3-hydroxy-2-naphtho- Scarlet : : ~ara-anisidide . ~p-htol ~S-RL~
29 do 3'-chloro-3-hydroxy- Scarlet 2-napht~o-ortho-ani~idide ~ tol AS-NEL) do 3-hydroxy-3'-nitro- Red 2-naphthanilide (Naphtol AS-BS) 31 do 2-naphthol Orange : 32 do 3-methyl-l-(~-tolyl)- Yellow 5-hydroxypyrazole 33 3-aminomethylaniline 3-hydroxy-2-naphth- Scarlet anilide (Naphtol AS) -2~-~' ~ - ` ;
G4~
Ex-ample Diazotized Coupling No. Amine Component Shade 34do 3'-chloro-3-hydroxy- Scarlet 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 35do 2',2'''-dibromo- Yellow 4',4'''-biacetoacet-anilide lO 36do 4'-chloro-3-hydroxy- Red 2-naphtho-ortho-tolu-idide (Naphtol AS-TR) 37do 4',4'''-biacetoacet- Yellow anilide 15 38do 3-methyl-1-(4-methoxy- Reddish-phenyl)-5-hydroxy- Yellow . pyrazole 39 2-methoxy-3-amino- 3'-chloro-3-hydroxy- Red methylaniline 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 40do 3-hydroxy-2'-methyl- Red 2-naphth-para-anis-idide (Naphtol AS-LT) ~ldo 3',3" '-diethoxy- Yellow 4',4'''-biacetoacet-anilide 42do 7-bromo-3-hydroxy-2- Red naphtho-ortho-anis-idide 30 43do 4',4' " -biacetoace~- ~ellow anilide 44do 3-methyl-1-~4-e~hox~- ~eddish-phenyl)-5-hydroxy- Yellow pyrazole 2-methyl-5-amino- 2',2''l-diiodo- Yellow methylaniline 4',4'''-biacetoacet-anilide 46 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 47 do 3-hydroxy-2',5'-di- Bluish-methoxy-2-naphth- Red anilide (Naphtol AS-BG) Ex-ample Diazotized Coupling No. Am ne _ Component Shade 48 do 2',2'''-dichloro- Greenish-4',4'''-biacetoacet- Yellow anilide 49 do 3-methyl-1-(4-pro- Reddish poxyphenyl)-5- Yellow hydroxypyrazole 2,3-dimethyl-5- 3'-chloro-3-hydroxy- Red aminomethylanil-~ 2-naphtho-ortho-ine toluidide (Naphtol AS-KB) 51 do 3-hydroxy-3'-nitro- Bluish-2-naphthanilide Red (Naphtol AS-BS) 52 do 5'-chloro-3-hydroxy- Bluish-2',4'-dimethoxy-2- Red naphthanilide ~Naph-tol AS-ITR) 53 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 54 do 4',4' "-biacetoacet- Yellow anilide do 3-methyl-1-(3-nitro- Reddish-phenyl)-5-hydroxy- Yellow pyrazole 56 2-isopropyl-5- 3-hydroxy-2-naphtho- Red methyl-3-amino- ortho-toluidide methylaniline (Naphtol AS-D) 57 do 4,4'-bi-ortho-acet.o- Yellow acetotoluidide (Naph-tol AS-G) 58 do 3',3 "'-diethoxy- Reddish-4',4'''-biacetoacet- Yellow anilide 59 do 3-methyl-1-(~-tolyl)- Reddish 5-hydroxypyrazole Yellow 3-isopropyl-2-meth- 3-hydroxy-2-naphtho- Red oxy-5-aminomethyl- 2,4-xylidide (Naph-aniline tol AS-MX) 61 do 2',2'''-dichloro- Yellow 4',4'''-biacetoacet-anilide ~1~6~4 Ex-ample Diazotized Coupling No Amine Component Shade 62 do 5'-chloro-3-hydroxy- Bluish-2',4'-dimethoxy-2- Red naphthanilide (Naph-tol AS-ITR) 63 do 7-bromo-3-hydroxy- Red 2-naphtho-ortho-anisidide 64 do 3~methyl-1-(4-nitro~ Reddish-: phenyl)-5-hydroxy- Yellow pyrazole 4,5-dimethoxy-2- 3-hydroxy-2-naphtho- Red propyl-3-amino- ortho-phenetidide methylaniline (Naphtol AS-PH) 66 do 2',2'''-dibromo Yellow 4',4'''-biacetoacet-~: anilide 67 do 3-hydroxy-N-2-naph- Bluish-thyl-2-naphkhamide Red (Naphthol AS-SW) : 68 do 4'-chloro-3-hydroxy- Red 2-naphtho-ortho-tolu-idide (Naphtol AS-~R) 69 do 4',4' " -b.iacetoacet- ~ellow anilide do 3-methyl-1-(2-chloro- Reddish-~: : phenyl)-5-hydroxy- Yellow ~:30 ~ pyrazole : :
: 71 3-bromo-5-amino- 3~hydroxy-2-naphth- Red methylaniline Para-anisidide htol AS-R~) 72 do 4'-chloro-3-hydroxy- Blui~h-2',5'-dimekhoxy-2- Red naphthanilide (Naph-tol AS-LC) 73 do 3-hydroxy-N-2-naph- Bluish-thyI-2-naphthamide Red ~Naphtol AS-SW) 74 do 3'-chloro-3-hydroxy- Red 2-naphtho-orkho-anis-idide (Naphtol AS-NEL) ~ ~ ' .~ .

9~4 Ex-ample Diazotized Coupling No. Amlne Component Shade do 3-methyl-1-(3-bromo- Reddish-phenyl)-5-hydroxy- Yellow pyrazole 76 5-isopropyl-2- 4'-chloro-3-hydroxy- Red methyl-3-amino- 2-naphtho-ortho-tolu-methylaniline idide (Naphtol AS-TR) 77 do 2',2'''-diiodo- Reddish-4',4'''-biacetoacet- Yellow anilide 78 do 3-methyl-1-(p-tolyl)- Reddish 5-hydroxypyrazole Yellow 79 do 4,4'-bi-ortho-aceto- Yellow acetotoluidide (Naph-tol AS-G) 5-ethyl-2-methyl- 3-hydroxy-2-naphtho- Red 3-aminomethylanil- 2,4-xylidide (Naph-ine tol AS-MX) 81 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide 82 do 2',2'''-dibromo- Yellow 4',4'''-biacetoacet-anilide 83 do 3',3' " -diethoxy- Yellow 4',4" '-biacetoacet-anilide 84 do 3-methyl-1-(4-iodo- Orange phenyl)-5-hydroxy-pyrazole 3,4-diethyl-5-amino- 3-methyl-1-~-tolyl)- Reddish-me~hylaniline 5-hydroxypyrazole Yellow 86 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) : 87 do 2',2' " -dichloro- Greenish-4',4 " '-biacetoacet- Yellow anilide 88 do 3-hydroxy-2',5'-di- Bluish-methoxy-2-naphth- Red anilide (Naphtol AS-BG) -~649~

Ex-ampleDiazotized Coupling No. Amine Component Shade 893-methoxy-4-methyl- 3-hydroxy-2-naphth- Red 5-aminomethylaniline anilide (Naphtol AS) do 7-bromo-3-hydroxy-2- Red naphtho-ortho-anis-idide 91 do 2',2'''-diiodo- Reddish-4',4'''-biacetoacet- Yellow anilide 92 do 3-methyl-1-~p- Reddish-tolyl)-5-hydroxy- yellow pyrazole 933-chloro-4-iso- 3-hydroxy-3'-nitro- Bluish-propyl-5-amino- 2-naphthanilide Red methylaniline ~Naphtol AS-BS) 94 do 5'-chloro-3-hydroxy- Bluish 2',4'-dimethoxy-2- Red naphthanilide (Naph-tol AS-ITR) do 7-bromo-3-hydroxy- Red 2-naphtho-ortho-anisidide 96 do 2',2 " '-dibromo- Yellow 4',4" '-biaceto-:~ acetanilide : 97 do 3-methyl-l-(o- Reddish-tolyl)-5-hydroxy- Yellow pyrazole 982,3,4-trimethyl-5- 3-hydroxy-2-naphtho- Red aminomethylaniline ortho-toluidide rNaphtol AS-D) 99 do 3'-ahloro-3-hydroxy- Red 2-naphtho-ortho-ani~-idide (Naphtol AS-NEL) lO0 do 4,4'-di-ortho-aceto- Yellow acetotoluidide (Naphtol AS-G~
lOl do 3-methyl-l-(~-tolyl)- Reddish-5-hydroxypyrazole Yellow 102 do 4',4'''-biaceto- Yellow a~etanilide :

~4gl~ ' Ex-ample Dia~otized Coupling No~ Amine Component Shade 103 2-chloro-4,5-di- 3-hydroxy-2-naphth- Red methoxy-3-amino- para-anisidide methylaniline (Naphtol AS-RL) 104 do 7-bromo-3-hydroxy-2- sluish naphtho-ortho-anis- Red idide 105 do 3'-chloro-3-hydroxy~ Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 106 do 3-methyl-1-(4-chloro- Reddish-phenyl)-5-hydroxy- Yellow : 15 pyrazole 107 5-chloro-2,4-di- 3-hydroxy-2'-methyl- Red ethoxy-3-amino 2-naphth-para-anis-methylaniline idide (Naphtol AS-LT) 108 do 2',2'''-dichloro- Yellow 4',4'''-biacetoacet-. anilide 109 do 3',3" '-diethoxy- Yellow 4',4'''-biacetoacet-anilide 110 do 3-methyl-1-(~-tolyl)- Reddish-: 5-hydroxypyrazole Yellow 111 4,5-dimethoxy-2- 3-hydroxy-2-naphtho- Red fluoro-3-amino- ortho-phenetidide methylanilide ~Naphtol AS-PH) 112 do 3-hydroxy-2-naphth- Red anilide ~Naphtol AS) 113 do 2',2" '-dibromo- Reddish-4',4'''-biacetoaaet- Yellow anilide 114 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 115 do 3-methyl-1-(2-ethoxy- Reddish-5-nitrophenyl)-5- Yellow hydroxypyrazole 116 2-chloro-4-methoxy- 3-hydroxy-2-napnth- Red 5-methyl-3-amino anilide (Naphtol AS) methylaniline ~11364~

Ex-ample Diazoti~ed Coupling No. Amine Component Shade 117 do 3-hydroxy-2-naphtho- Red ortho-phenetidide (Naphtol AS-PH) 118 do 3-methyl-1-(p-tolyl)- Reddish-5.-hydroxypyrazole Yellow 119 do 5'-chloro-3-hydroxy- Red 2',4'-dimethoxy-2-naphthanilide (Naphtol AS-ITR) 120 do 4',4'''-biacetoacet- Yellow anilide 121 2,5-dichloro-4- 7-bromo-3-hydroxy-2- Red methoxy-3-amino- naphtho-ortho-anis-methylaniline idide 122 do 3',3'''-diethoxy- Yellow 4',4' " -biacetoacet-anilide 123 do 4,4'-bi-ortho-aceto- Reddi~h-acetotoluidide Yellow - ~Naphtol AS-G) 124 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 125 do 3-methyl-1-(2,4-di- Yellow chlorophenyl)-5-hydroxypyrazole 126 5-chloro-2-propyl- 4'-chloro-3-hydroxy- Bluish 3-aminomethylanil- 2',5'-dime~hoxy-2- Red ine naphthanilide (Naph-tol AS-LC) 127 do 3 methyl~ tol~1)- Reddish-5-hydroxypyrazole Yellow 128 do 2',2'''-dichloro- Yellow 4',4" '-biaceto-acetanilide 129 do 3-hydroxy-2-naphtho- Red ortho-anisidide (Naphtol AS-OL) : 130 3,5-bis(aminomethyl)- 3-methyl-1-(p-tolyl~- Reddish- aniline 5-hydroxypyraæole Yellow .

i49~
i Ex-ample Diazotized Coupling No Amine Component Shade 131 do 3-hydroxy-2',5'-di- Red methoxy-2-naphth-anilide (Naphtol AS-BG) 132 do 3'-chloro-3-hydroxy- Scarlet 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 133 do 2',2'''-diiodo- Yellow 4',4'''-biaceto-acetanilide 134 2,4-diethyl-3,5-bis~ 3'-chloro-3-hydroxy- Scarlet (aminomethyl)aniline 2-naphtho-ortho-anisidide (Naphtol AS-NEL) 135 . do 5'-chloro-3-hydroxy- Red 2',4'-dimethoxy-2-naphthanilide ~Naph-tol AS-lTR) 136 do 3-hydroxy-3'-nitro- Red 2-naphthanilide (Naphtol AS-BS) 137 do 3'-chloro-3-hydroxy- Scarlet 2-naphtho-ortho-toluidide tNaphtol AS-KB) 138 do 4',4'''-biacetoacet- Greeni~h-anilide Yellow 139 do 3-methyl-1-(2,4-di- Orange nitrophenyl)-5-hydroxypyrazole 140 2-iodo-3,5-bis- 3-methyl-1-~- Reddish-~aminomethyl)- tolyl)-5-hydroxy- Yellow aniline pyrazole 141 do . 3',3" '-diethoxy- Yellow 4',4" '-biacetoacet-anilide 142 do 4,4'-bi-ortho-aceto- Greenish-acetotoluidide ~Naph- Yellow tol AS-G) 143 do 4'-chloro-3-hydroxy- Bluish-2',5'-dimethoxy-2- Red naphthanilide ~Naph-tol AS-LC) 1064g~4 Ex-ample Diazotized Coupling No. Amine Component Shade __. _ _ 144 4-1uoro-3,5-bis- 2'2'''-dichloro- Greenish-(aminomethyl)anil- 4',4'''-biacetoacet- Yellow ine anilide 145 do 3-hydroxy-2-naphtho- Scarlet 2,4-xylidide ~Naph-tol AS-MX) 146 do 3-hydroxy-2-naphtho- Red ortho-anisidide (Naphtol AS-OL) 147 do 5'-chloro-3-hydroxy- Red 2',4'-dimethoxy-2-naphthanilide (Naph-tol AS-ITR) 148 do 3-methyl-1-(2- Reddish-methyl-4-iodophenyl)- Yellow 5-hydroxypyrazole 149 2-methoxy-4-methyl- 4'-chloro-3-hydroxy- Scarlet 3,5-bis~aminomethyl)- 2-naphtho-ortho-tolu-aniline idide (Naphtol AS-TR) 150 do 3-hydroxy-N-2-naph- Red thyl-2-naphthamide (Naphtol AS-SW) : 151 do 2',2'''-dibromo Yellow 4',4' " -biacetoacet-anilide 152 do 3-hydroxy-2-naphtho- Scarlet ortho-phenetidide ~Naphtol AS-PH) 153 do 3-methyl-1-~2,5- Reddish-meth~lphenyl)~5- ~ellow hydroxypyrazole 154 2,4-diisopropyl- 3'-chloro-3-hydroxy- 5carlet 3,5-bis~amino- 2-naphtho-ortho-anis-methyl)aniline idide ~Naphtol AS-NEL) 155 do 4'-chloro-3-hydroxy- Red 2',5'-dimethoxy-2-naphthanilide (Naph-tol AS-LC) 156 do 3-hydroxy-2-naphth- Scarlet para-anisidide (Naphtol AS-RL) ;

~al 6~

Ex--ampleDiazotized Coupling No. _ Amine Com~onent Shade 157 do 3-methyl~ p-tolyl)- Reddish-5-hydroxypyrazole Yellow 158 do 4',4'''-biacetoacet- Greenish-anilide Yellow 159 4-bromo-2-methoxy- 7-bromo-3-hydroxy- Red 3,5-bis(aminometh- 2-naphtho-ortho-yl)aniline anisidide 160 do 3-hydroxy-2-naphth- Scarlet anilide (Naphtol AS) 161 do 2',2" '-diiodo- Yellow 4',4'''-biacetoacet-anilide - 162 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anis-idide (Naphtol AS-NEL) 163 do 3-methyl-1-(2,4,6- Yellow trichlorophenyl)-5-hydroxypyrazole Following the procedure described in Example 1 above, 4.3 parts o~ 4-aminomethylaniline dihydrochloride in a solution o~ 100 parts of water and 2.4 parts of concentrat-ed hydrochloric acid were diazotized with l.S parts of sodium nitrite dissolved in 12 parts o~ water at 0-5~C. In a separate container, 5.9 parts o~ 3-hydroxy-2-naphth-o-anisidide tNaphtol ~S-OL) was mixed wlth 38 parts o hot water, 18.6 parts of ethoxyethanol, 2 drops o nonylphenoxy-poly(ethyleneoxy)ethano} (Igepal~ C0-630) and 3.1 parts of 5~ per cent aqueous sodium hydroxide. To the solution thus obtained, there was added in a thin stream the cold diazonium solution prepared as described above. The reaction mixture was stirred at ambient temperature until the consumption of the diazonium salt was complete. The slurry was made slight-~4~

ly alkaline to Brilliant Yellow test paper and the red product which separated was collected by ~iltration, washed with 200 parts of a one per cent aqueous sodium chloride solution and dried in a vacuum oven to obtain a red dyestuff having the formula =N _ ~ 2 2 H _ ~ H

~OCH3 The visible absorption spectrum of a solution con-sisting o 0.02 g. o the dyestuff dissolved in 200 ml. o dimethylformamide diluted to one liter with an aqueous solu-tion o one per cent Igepal~ C0-630 and containing 3 drops of glacial acetic acid showed a maximum at 500 millimicrons, A=0.8656.
A concentrated dye solution was prepared by dis-solving one part of the dyestu in 200 ml. o dimethyl-formamide and 3 drops o glacial acetic acid and then dilutiny this solution to a total volume of one liter with water. Paper dyed wlth this 901utlon had a yellow-scarlet shade and was ound to be highly bleachable. The dye was found to bleed only slightly in the water-bleed test.

Following the procedure described in Example 1 above, 4.3 parts o 3-aminomethylaniline dihydrochloride in a solution of 100 parts of water and 2.4 parts of concen-i49~

trated hydrochloric acid were diazotized with 1.5 parts of sodium nitrite at 0 to 5C. In a separate container 5.9 parts of 3-hydroxy-2-naphth-o-anisidide (Naphtol AS-OL) were dissolved in a solution of 38 parts hot water, 18.6 parts of ethoxyethanol, 2 drops of nonylphenoxypoly(ethyleneoxy)ethanol (Igepal~ C0-630) and 3.1 parts of 50 per cent aqueous sodium hydroxide. To the resulting solution there was then added in a thin stream the cold diazonium solution prepared as describ-ed above. The reaction mixture was stirred at room tempera-ture until the consumption of the diazonium salt was com-plete. The resulting solution was made slightly alkaline to Brilliant Yellow test paper by the addition o approximately 2.3 parts of concentrated aqueous ammonia and the solid which separated was collected by filtration, washed with 200 parts of one per cent aqueous sodium chloride solution and dried in a vacuum oven to obtain a red dyestuff having the formula fi--\

=N

NH _ ~ OH

~OCH3 The visible absorption spectrum of an aqueous acetic acid solution of this dyestuff, containing 0.02 g. o~

the dye per liter of solution showed a maximum at 498 milli-microns, A-0.756.
A dye solution was prepared by dissolving 1.0 g. of this dyestuff in 200 ml. of dimethylformamide and 3 drops o~

glacial acetic acid and then diluting the solution to a volume of one liter wikh water. Paper dyed with this solu-tion had a yellow-scarlet shade and was found to be highly bleachable. The dye was found to bleed only slightly in the water-bleed test.

Following the procedure described in Example 1 above, 2.72 parts of 4-(2-aminoethyl)aniline in a mixture of 100 parts of water, 7.14 parts of concentrated hydrochloric acid and 80 parts of crushed ice were diazotized at 0-5C., with 1.5 parts of sodium nitrite disso}ved in 12 parts of water. In a separate container 5.9 parts of 3-hydroxy-2-naphth-o-anisidide (Naphtol AS-OL) were mixed with 18,6 parts o~ 2-ethoxyethanol, 38 parts of hot water and 3.1 part~ of 50 per cent aqueous sodium hydroxide. To the resulting 901u-tion was then added in a thin stream the cold diazonium solution prepared as described above. The reaction mixture was stirred at ambient temperature until no diazonium salt remained. The resulting solution was made slightly alkaline to Brilliant Yellow paper by the addition of aqueous ammonia and the ~olid product which resulted was collected by filtra-tion and dried in a vacuum oven. There was thus obtained a red dyestu~ having the ~ormula ~4~14L

2 4~2 H

The visible absorption spectrum of an aqueous acetic acid solution of this dyestuff, con~aining 0.02 g. of the dye per liter of solution showed a maximum at 504 milli-microns, A~0.8176.
A dye solution was prepared by thoroughly mixing one part of this dyestuff with five parts of 10 per cent acetic acid and diluting the resultant paste of the acetic acid addition salt to a volume of one liter with water.
Paper dyed with this solution had a yellow-scarlet shade and was found to be highly bleachable. The dye was ~ound to bleed only slightly in the water-bleed and in the soap-; ~ bleed test.
The following table lists further Examples of addi-tional azo dyestuffs of this invention prepared by diazotiz-ing the amines shown in the second column of the table and coupling the resul~ing diazo compounds with the coupling components shown in the third column of the table following procedures similar to those described in Examples 1-5 above.
The indicated ~hades are obtained when aqueous solutions of the acid-addition salt forms of the dyestuffs are used for dyeing cellulose.

6~9~

Ex-ample Diazotized Coupling No. Amine Component Shade 167 3-methoxy-4-amino- 3-hydroxy-2 naphtho- Red methylaniline ortho-anisidide (Naphtol AS-OL) 168 do 2',2"'-dichloro- Yellow 4',4'''-biaceto-acetanilide 169 do 3-methyl~ p-tolyl)- Reddish-5-hydroxypyrazole Yellow 170 do 4'-chloro-3-hydroxy- Red 2',5'-dimethoxy-2-naphthanilide (Naph-tol AS-LC) 171 4-(2-aminoethyl)- 2',2" '-dichloro- Greenish-aniline 4',4'''-biaceto- Yellow acetanilide 172 do 3-methyl-1-(p-tolyl)- Yellow 5-hydroxypyrazole 173 do 4'-chloro-3-hydroxy- Scarlet 2'~5'-dimethoxy-2-naphthanilide (Naph-tol AS-LC) 174 do 4',4" '-biacetoacet- Greenish-anilide Yellow 175 3-bromo-4-amino- 4,4'-bi-ortho-aaeto- Greenish-methylaniline acetotoluidide Yellow (Naphtol AS-G) 176 do 5'-chloro-3-hydroxy- Red 2',4'-dimethoxy-2-naphthanilide . (Naphtol AS-ITR) 177 do 3-methyl-1-(~-tolyl)- Yellow 5-hydroxypyrazole 178 do 3'-chloro-3-hydroxy- Scarlet 2-naphtho-ortho-anisidide (Naphtol AS-NEL) 179 4-aminomethyl- 3-hydroxy-2-naphtho- Scarlet aniline ortho-toluidide (Naphtol AS-D) 180 do 4,4'-bi-ortho-aceto- Greenish-acetotoluidide (Naph- Yellow tol AS-G) . -43-~L~ E;4~

Ex-ample Diazotized Coupling No. Amine C_ml~onent Shade 181 do 3-methyl-1-(p-tolyl)- Yellow 5-hydroxypyrazole 182 3-chloro-4-amino- 4'-chloro-3-hydroxy- Scarlet methylaniline 2-naphtho-ortho-toluidide (Naphtol AS--TR) 183 do 2',2'''-diodo- Yellow 4',4'''-biaceto-acetanilide 184 do 3-methyl-1-(p-tolyl)- Yellow 5-hydroxypyrazole 185 do 4,4'-bi-ortho-aceto- Yellow acekotoluidide (Naph-tol AS-G) 186 3-ethoxy-4-amino- 3-hydroxy-2-naphtho- Red methylaniline 2,4-xylidide (Naph-tol AS-MX) 187 do 3'-chloro-3-hydroxy- Red 2-naphtho-ortho-anisidide 188 do 2',2' "-dibromo- Yellow 4',4'''-biacetoacet-~: ~ anilide 189 do 3',3" '-diethoxy- Yellow 4',4" '-biacetoacet-anilide ~.~

Claims (31)

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

1. A compound of the formula wherein:
n is an integer whose value is one or two;
R is hydrogen, lower-alkyl, lower-alkoxy or halogen;
R2 is hydrogen, lower-alkyl, lower-alkoxy, halogen, aminomethyl or 2-aminoethyl with the proviso that A is other than .beta.-naphthol when R2 is aminomethyl or 2-aminoethyl;
R1 and R3 are the same or different and are each hydrogen, lower-alkyl, lower-alkoxy, halogen or aminomethyl with the proviso that at least one of R1 and R3 is aminomethyl when R2 is other than aminomethyl or 2-aminoethyl;
A is an azoic coupling radical which when n is one is selected from the class having the formulas , and and when n is two is selected from the class having the formulas and in which Q, Q1 and Q2 are the same or different and are each hydrogen, lower-alkyl, lower-alkoxy, nitro or halogen, and Q3 is hydrogen, lower-alkyl, lower-alkoxy or halogen; and the acid addition salts thereof.

2. A compound according to claim 1, wherein n is one having the formula in which Q, Q1, Q2, R, R1, R2 and R3 each have the same respective meanings given in claim 1.

3. The compound according to claim 2, wherein Q, Q1, Q2 and R2 are each hydrogen; R is methoxy; and R1 and R3 are each aminomethyl,

4. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2 and R2 are each hydrogen; R is methoxy; and R1 and R3 are each aminomethyl.

5. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2 and R2 are each hydrogen; R2 is methoxy; and R1 and R2 are each aminomethyl.

6. The compound according to claim 2, wherein Q1 is 4-methoxy; Q, Q2 and R2 are each hydrogen; R is methoxy and R1 and R3 are each aminomethyl.

7, The compound according to claim 2, wherein Q is 2-methoxy; Q1 is 3-chloro; Q2 and R2 are each hydrogen; R is methoxy; and R1 and R3 are each aminomethyl.

8. The compound according to claim 2, wherein Q, Q2 and R2 are each hydrogen; Q1 is 3-nitro; R is methoxy; and R1 and R3 are each aminomethyl.

9. The compound according to claim 2, wherein Q, Q2 and R are each hydrogen; Q1 is 3-nitro: R2 is methoxy; and R1 and R3 are each aminomethyl.

10. The compound according to claim 2, wherein Q1 is 4-methoxy; Q, Q2 and R are each hydrogen; R2 is methoxy; and R1 and R3 are each aminomethyl.

11. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2, R and R1 are each hydrogen;
R2 is methoxy: and R3 is aminomethyl.

12. The compound according to claim 2, wherein Q, Q1, Q2 and R are each hydrogen; R2 is methoxy; and R1 and R3 are each aminomethyl.

13. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2 and R are each hydrogen; R2 is methyl; and R1 and R3 are each aminomethyl.

14. The compound according to claim 2, wherein Q is 2-methoxy; Q2 is 5-chloro: Q1 and R are each hydrogen; R2 is methoxy; and R1 and R3 are each amino-methyl.

15. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2, R, R1 and R3 are each hydrogen;
and R2 is 2-aminoethyl.

16. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2, R, R1 and R3 are each hydrogen;
and R2 is aminomethyl.

17. The compound according to claim 2, wherein Q is 2-methoxy; Q1, Q2, R, R2 and R3 are each hydrogen;
and R1 is aminomethyl.

18. A compound according to claim 1, wherein n is one having the formula in which R, R1, R2 and R3 each have the same respective meanings given in claim 1.

19. The compound according to claim 18, wherein R is hydrogen; R2 is methoxy; and R1 and R3 are each aminomethyl.

20. A compound according to claim 1, wherein n is one having the formula in which R, R1, R2 and R3 each have the same respective meanings given in claim 1.

21. The compound according to claim 20, wherein R is methoxy; R2 is hydrogen; and R1 and R3 are each aminomethyl.

22. A compound according to claim 1, wherein n is one having the formula in which Q, Q1, Q2, R, R1, R2 and R3 each have the same respective meanings given in claim 1.

23. The compound according to claim 22, wherein Q1 is 4-methyl; R is methoxy; Q, Q2 and R2 are each hydrogen; and R1 and R3 are each aminomethyl.

24. A compound according to claim 1, wherein n is two having the formula in which Q3, R, R1, R2 and R3 each have the same respective meanings given in claim 1.

25. The compound according to claim 24, wherein Q3 is methyl; R is methoxy; R1 and R2 are each hydrogen; and R3 is aminomethyl.

26. The compound according to claim 24, wherein Q3 is methyl; R is methoxy; R2 is hydrogen; and R1 and R3 are each aminomethyl.

27. The compound according to claim 24, wherein Q3 is methyl; R is hydrogen; R1 and R3 are each aminomethyl;
and R2 is methoxy.

28. The compound according to claim 24, wherein Q3 and R2 are each methyl; R and R3 are each hydrogen;
and R1 is aminomethyl.

29. A compound according to claim 1, wherein n is two having the formula in which R, R1, R2 and R3 each have the same respective meanings given in claim 1.

30. The compound according to claim 29, wherein R
is methoxy; R2 is hydrogen; and R1 and R3 are each aminomethyl.

31. The process for preparing the compound according to claim 1, which comprises diazotizing an amine of the formula and coupling approximately n molecular proportions of the resulting diazonium salt with one molecular proportion of a coupling component from which an azoic coupling radical A is derived, wherein n, R
and A each have the same respective meanings indicated in claim 1.