Note: Descriptions are shown in the official language in which they were submitted.
~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 ~ ~
IE 2 HO3 IF NH2
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
--4--
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
OH R3
FORMULA IV
Q ~H R~r___~,R
-CH3
~ NE~-C-~ ~ R2 j
::~ H3 R and
: FORMULA VI
"
.
.
1~!69~4
N = N = _
~o_, 3 , R~
= Q3
NH 2
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
-6-
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,
--7--
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
-8-
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
--10--
.
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
-12-
' -
~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,
-13-
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-
L4
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,
-15-
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.
EXAMPLE 1
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
-16-
:
: : ,,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
CH2NH2
N -N ~ CH3
H CH2NH2
:: ~
OCH3
-17-
~ ~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
-18-
. .
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
--19--
~;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
-20-
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.
EXAMPLE 2
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
-21-
:
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.
EXAMPLE 3
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
NH2
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~.
EXAMPLE 4
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)
-23-
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~ ¦
H3 H2NH2
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.
--24--
~6~
EXAMPLE 5
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
_
CH3 CH2NH2
~ H~ E-N=
CH2NH2
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
-25-
~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.
-26-
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
-27-
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)
-29-
L4
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
-30-
~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)
-31-
~ ~ '
.~ .
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)
-32-
-
~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
-33-
:
~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
-34-
~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
-35-
.
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)
-36-
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)
-37-
;
~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
EXAMPLE 164
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-
--38--
~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.
EXAMPLE 165
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-
-39-
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--\
2NH2
=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~
-40-
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.
EXAMPLE 166
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
-41-
~4~14L
2 4~2
H
OCH3
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.
-42-
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
--44--
~.~
