Note: Descriptions are shown in the official language in which they were submitted.
l04sno2
';UMMARY OF TH~ INV~.NrION
Therc is a ~reat necd in the tra~e ror disperse
navy dyes for polyester having both good light- and sub-
llm~tlon fastness comblned with satisfactory application
propertles, such as buil~up and transfer. This lnvention
supplle~ a class of monoazo disperse dycs which are l~seful
for dye~n~ and ~rintin~ ~)olyester fiber~ in navy-bl~le
shades.
It is an object of this invention to provide
navy-blue monoazo disperse dyes. It is a further object
to provide dyes having good to excellent sublimation and
bulldup properties. It is a still further ob~ect to pro-
vlde disperse dyes having g~od light- and dry cleaning
fastness, good hydrolytie stability and good transfer
properties on polyester fibers. These and other objects
are fulfilled by the following invention, wherein the
inventor has provided a new class of monoazo dyes of
the formula: ~1
02N _ ~ _N=N ~ NH-R3-OR4
2 ~
wherein Rl is Br, Cl or CN; R2 is CN or N02; R3 is Cl 4
branched or straight-chain alkylene; R4 is cyclohexyl,
Cl 4 alkylcyclohexyl, benzyl, furfuryl, tetrahydro-
~ur~uryl or Cl 6 branched o-r straight-chain alkylene-R5;
R5 ls CN, OH~ -OCl_4alkyl~ -OR6, -OCOCl 4alkyl or -OCOR6;
~nd R6 is phenyl or phenyl substituted with 1-2 groups
selected from C1J Br, NO~, C1 4alkyl, OCl_4alkyl and CF3.
.
lO~gO02
I)l"rAILf`l) DE"CRIPrION
The rnonoazo navy ~yes of this inventlon can be
prepared by conventional diazotlzatlon and coupllng pro-
cedures wherein a primary aromatic amine of the formula
Rl
R2
whereln Rl and R2 are as deflned above, ls diazotlzed and
coupled to an aromatic amine of the formula
,~
<~\ : '
wherein R3 and R4 are as defined above. In the case
wherein R4 contains a readily hydrolyzable group, e.g.,
when R4 is Cl 6alkylene-OCOC1 4alkyl or Cl_6alkylene-
OCOR6, whereln R6 is as defined above, coupling of the
diazotized amine can also be made to an aromatic amine
of the formula
~ NH-R3-OCl ~alkylene-OH
,' <~/\, .
followed by acylation of the primary hydroxy group of the
re~ultant monoazo compound by conventional technlques with
an aliphatic or aromatic carboxylic acid chloride, bromide
or anhydride to yield the deslred dye.
The diazotization Or the primary aromatic amine
can be carried out at from ~ to 25C., preferably at
~0~90~2
20-25C., by the act1on of nitrosylsulfuric ~cid in
70_96% aqlleous sulfuric acid. Collpl~ng is carrled out
by dl~solvln~ the aroma~c amin~ coupler in an organic
or aqueous or~anic solv~nt system (such as a mixture of
methanol and water), cooling the resultant coupler solu-
tlon to 15C. or less and then slowly adding the diazo
solution to the cold couple r solution. After the coupling
is complete, the disDerse dye is precipitated by raising
the pH to about 1-3 wit~ a suitable salt or base, such
as sodium acetate or sodium hydroxide. The precipitated
monoazo dye is isolated by filtration. Examples of
diazotizable amines which are useful in the present inven-
tion are given in Table I.
In order that the invention may be comp]etely
understood, the preparation of the coupling components
employed in the preparation of the dyes of this invention
are given hereinafter. The coupling components are pre-
pared by known techniques, for example, by reacting a
N-hydroxyalkyl-l-naphthylamine with an epoxide such as
ethylene, propylene or butylene oxide, followed by
alkylation of the resultant N-hydroxyalkoxyalkyl-l-
naphthylamine with alkyl halides, alkyl sulfates, aralkyl
halides, etc. The aforementioned n-hydroxyalkyl-l-
naphthylamine can also be reacted with activated vinyl
compounds such as acry]onitrile to form the N-cyanoalkoxy-
al~yl-l-naphthylamine coupling components.
Alternatively, the coupling components can be
synthesized by the well-known B~cherer reaction, which
lnvolves the reversible replacement of a hydroxy group
of a naphthol derivative by an amino group in the presence
-- 4 --
~04900Z
of aqu~o~s sulfite, bisulrite or sulfurous acid (e.g.
S2 + H20) (Or~anic ~eactions, Vol. I, Chapter 5,
1942J P. 105). Reaction of l-naphthol with 1 to 2
equlvalcnts Or a prlmar~ allphatlc amine of the formula
H2N-R3-OR4, whereln R~ and R4 are as defined above, in
the presence of aqueous sulfite or bisulfite at 120-150C.
provides excellent yieJds (75-90%) of high purity (~ 90~)
product having the formula
~ NH-R3-OR4
<~ .
The latter process, thus, provides a high yield route
for obtainin~ the desired coupling components which does
not involve using l-naphthylamine as starting material.
This is a particularly desirable feature since 1-
naphthylamine has recently been added to the growing list
of industrial carcino~enic materials.
The aforementioned primary aliphatic amines,
H2N-R3-OR4, can be readily prepared by reaction of the
appropriate alcohol R4-OH, wherein R4 is as previously
defined, with acrylonitrile, methacrylonitrile or
crotononitrile followed by catalytic reduction of the
cyano group. Alcohols, R4-OH, operable in the above
process include, among others, cyclohexanol, methylcyclo-
hexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol,
benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol,
1-methox~-2-propanol, 2-propoxyethanol and 1-propoxy-2-
propanol. Examples Or coupling components prepared by
the aforementioned procedures and havin~ utility in the
present invention are ~ive~ in Table II.
In the case where the coup~ing component has
the formula:
~, , . . _
10490~:
<~ NH-R3-OC1 6alkylene-OH
~>
as descrlbed herelnbefore, the resulting monoazo dye
derlved therefrom can be acylated with an acld hallde
or anhydride ln the presence of an organlc or lnorganlc
acld acceptor, such as pyridlne, trlmethylamlne or
potasslum carbonate, ln a sultable organic solvent to
yleld the de~lred acylated dye. Polar nonhydroxylic
solvents, such as dimethylformamlde, dlmethylacetamlde,
dlmethylsulfoxide and dlethyleneglycol-dlmethylether,
are useful ln the acylatlon. Pyrldine i8 particularly
useful in the acylation ln that it acts as both reaction
solvent and acid-blndlng agent Temperatures of from 0
to 25C. are operable in the acylation, the preferred
range belng from 10 to 15C, Examples oi acylatlng
agents hav~ng utlllty ln thls invention are given in
Table III.
Table I
Examples of Amlnes Useful ln the
Present Invention
2-chloro-4,6-dlnltroanlline
2-bromo-4,6-dlnitroanlline
2-chloro-6-cyano-4-nitroaniline
2-bromo-6-cyano-4-nitroaniline
2,6-dicyano-4-nitroanlline
2-cyano-4,6-dlnitroaniline
~04900Z
Table II
Examples of Couplers Useful in the
Pres en' Invention
_
~O~ NH-R3-OR4
~\
\~/ R
- ( CH2 ) 3 - C2H40 CH3
- ( CH2 ) 3 - -CH( CH3 ) CH20CH3
- ( C~I2 ) 3 - -CH( CH3 ) CH20C3H7 -n
-( CH2)3- _~
- ( CH2 ) 3 - -CH2 ~
3 ~~\
-CH2CH( CH3 ) CH2~ \~/
- ( CH2 ) 3 - -CH2--
- ( CH2 ) 3 - -CH2 -C ~H
-C2H4 - -C2H4CN
- ( CH2 ) 3 - -C2H4CN
-cH2cH( CH3 ) CH2 - -C 2H4CN
-CH2CH( CH3 ) - -C2H4CN
2 4 -C2H40H
-CH2CH( C2H5) - -C2H4cN
-CH2CH2CH(CH3)- C2H40C2H5
-( CH2 ) 3 - -C2H40C4Hg -n
-CH2CH2CH(CH3) - --~--C(CH3)3
-CH2CH(CH3)CH2- -CH2CH(OC2H5)CH3
C~H5
-CH2CH2CH( CH3) - ~>
10490(~2
Table ~ Contlnue~)
R R4
-(C~2)3- -CH2CH(OCH3)CH2CH3
-(CH2)3- C2H40C6H5
2 4 -C2H40coH4-(4 )~2
-C2H4- -C2H40C~34-(4')CH3
-(CH2)3- -C2H40C~H4-(4')Br
-C2H4- -C2H4oc6H3-(2l)OCH3~(5l)CH3
Table III
Examples of Acylating r.gents Useful in
. the Pre~ent Invention
.
acetic anhydride
n-butyric anhydride
propionic anhydride
benzoic anhydride
acetyl chloride
acetyl bromide
benzoyl bromide
benzoyl chloride
2-bromobenzoyl chloride
4-bromobenzoyl chloride
p-anisoyl chloride
p-tert.-butylbenzoyl chloride
propionyl chloride
butyryl chloride
isobutyryl chloride
o-chlorobenzoyl chloride
m-chlorobenzoyl chloride
p-chlorobenzoyl chloride
2,4-dichlorobenzoyl chloride
3,4-dichlorobenzoyl chloride
1049()0Z
Table ~II (Continued)
3,5-dimethcxybenzoyl chloride
3,5-dinitrobenzoyl chloride
m-nlt-robenzoyl chloride
p-nltrobenzoyl chloride
o-toluoyl chloride
m-toluoyl chloride
p-toluoyl chloride
m-trifluoromethylbenzoyl chloride
The crude dyestuffs are conveniently converted
into a commercially usable form by mixing the crude dye
(e.g., ten parts on a 100% basis) with a~out 2.5 parts
Or a lignin sulfonate dispersant and water in a colloid
or sandmi~l Milling is continued unt~l a fine, stable,
aqueous dispersion or paste is obtained wlth dye particle
size reduced to approximately one micron.
The inventlon dyestufrs have excellent affinity
and buildup properties on polyester textile materials,
thus enabling deep navy-blue shades to be obtained. The
resultlng colorations Æenerally have ~ood fastness to
llght, to wet treatments and in particular to dry heat
treatments such as those carried out at high temperature
during pleating operations.
The inventioil dyes can be app~'ied to polyester
riber by an aqueous procedure, preferably under pressure,
or by padding polyester ribers with an aqueous dispersion
of said dyes followed by dry heat (e.g., Thermosol)
~ixation. Both dyeing procedures are wideiy used in
the trade. The present invention also encompasses
polyester fibers dyed or printed with an invention dye.
_ 9 _
104900~
In the foll~win~ examples, all parts ar~ eiven
by wel~ht. ~xamples 21 an~ 24 are intended to lllustrate
aqueous arld Thermosol dyeln~ procedures, respectively.
EXAMPLE 1
a) A mixture of 144 parts of l-naphthol, 100
parts of water, 210 parts Or diglycolamine (H2NC2H40C2H40H)
and 12.8 parts of sulfur dioxide was heated at 135 + 5C.
for 20 hours. Aqueous sodium hydroxide was added in an
amount sufficient to form the water-soluble sodium salt
of any unreacted l-naphthol and the resulting mixture
heated at 50-60C. for 1 hour. The crude product was
extracted with benzene, and the benzene extract water-
washed. Upon removal of the benzene, 190.5 parts (77.5%
yield) of N-(~-hydroxyethoxyethyl)-l-naphthylamine were
obtained, which had a purity of 93.8%.
b) 2-Chloro-4,6-dinitroaniline (32.5 parts)
was added in several portions to a stirred solution of
50.2 parts of nltrosylsulfuric acid (38~ active ingredient)
and 90 parts of 73~ sulfuric acid at ?0-25C., and the
mixture stirred for 3 hours. Excess nitrosylsulfuric
acid was destroyed with urea. The diazo solution was
then added dropwise to a c~ld (0 + 5C.) aqueous methanol
solutlon of 34.6 parts of N-(B-hydroxyethoxyethyl)-l-
naphthylamine. The resulting reddish-brown slurry was
stirred at 0 + 5C. for 0.5 hour, and the pH ad~usted
to approximately 2 by the dropwise addition of aqueous
sodium hydroxide. The precipitated dye was collected
by ~iltration, washed acid-free with water and dried to
give 60.5 parts (88% yield) of product. Recrystalllza-
tion from isopropanol-dimethylformamide provided an
- 10 --
~04!~00Z
analytlcally pure sample, m p 192-193C, having an
absorptivlty (a ~ of ~2 llters g lcm 1 at a wave-
length (~ max ) of 612 rn~. The dye was of this fornula:
~Cl N~C2N40C2~40
EXAMPI,E 2
Trimethylamine (30.4 parts~ was added to a
cold (10-15C ) solutlon of 93.5 parts of the monoazo
dye obtained in b~ above in 238 parts of dimethylform-
amide. Acetic anhydride (41 parts~ was added dropwise
over 15 minutes at 10-15C. The resultlng mixture was
stirred for llhour at 10-15C. The pH of the mixture
was then ad~usted to 5,5 by the dropwise addition of
hydrochloric acid The reaction mixture was then heated
to 80-85C, water was added, and the mixture was allowed
to cool slowly to 25C. The precipitated solids were
i801ated by filtration and recrystallized from isopropanol-
dimethylformamide to give 94.5 parts (93,5~¢ yield~ of
bronze-colored solid, m p 133-135C., having an
max, ~ f 85 liters g ~lcm -1
20 length (j3 max ~ f 612 m~l. The dye was of the formula:
Cl
NHC2H4 OC2H4 OCOCH3
N2 ~
EXAMPLE 3
Benzoyl chloride (5,34 parts~ was added drop-
wise to a cold (0-10C~ solution of 16 1 parts of the
lO~!~OOZ
monoazo ~ye obtalned in Example l(b) above in 100 parts
or pyridine. The resulting solution was stirred at
10-20C. for 5 hours. The dye was then precipitated by
the dropwise addition of ~ater. The resultant solids
were lsolated by filtration and recrystallized from
isopropanol-dimethylformamide to give 17 parts of product,
m.p. 183-186C., having an absorptivity (a a ) Or 70
liters g.~lcm.~l at a wavelength (~ max ) f 617 m~.
The dye was of thls formula:
Cl
O~N- ~ -N=~ NHc2H4oc2H4ococ6H5
2 ~ ~
EXAMPLE 4
2-Chloro-4,6-dinitroaniline was dlazotized as
described in Example 1, part (b) above and coupled to
an N~ cyanoethoxyethyl)-l-naphthylamine coupling
component, thus provlding a monoazo dye, m.p. 190-192C.,
havln~ ar~ absorptivity (a ) of 88 liters g. lcm.
at a wavelength (~ max ) f 608 m~. The dye was of this
formula:
~Cl
02N- ~ N--N- ~ -NHC2H40c2H4cN
N02
EXAMPLES 5-22
The dyes shown in Table 4 were prepared by
procedures similar to those described in Examples l to
4. The R groups refer to the R groups of the aforesaid
formula.
- 12 -
a~
. ~,
~ ~.
0 ,1 c~ 0 ~ ~ 0 ~ a~ 0
_
K ~ U~ L~
~ -- ~D ~O~O ~ ~O ~O ~O ~O ~ ~O ~O
~ P:
oc~l VC~ I
~1~ a~ O o
P:~ ^ ~ _ ~ ~ U~ O O
~t V ~ ~ ~ ~ p:: Z ~
i~; P; J ~ ~ v~ --r ~ ~ ) O O
~ _ ~ C~
,, v~`J v v ~ ' v V ~g V~ VN V~ V~
~ l l l ~ I I I I I I
E~
I, , , , , , , m,
_
N ~ N C~.l V CU ~ :~
~ p N tq m ~q
~3 V V ~ V ~3 V P:~ ~ CU N
-- -- -- -- -- --~ -- V -- V ~
C~ N CU C\J C~J CU C~J N CU C~J
C~J O O O O O O O O O O O
~;Z Z 5C S; Z IZ; Si; Z ~ iZ Z
~; I V V C~ V V V V
O ¦ o ~I N
Z 11~ ~O ~ 0 ) ~ 'I ~I ~ ~I ~I '
--13-
~049002 _ ,4
-
~ 6 u~
~1
X-~ ~n ~1 ~ ~ ~D U~
E; 6
.~
~ 1~
^
5: ~: ~ O ~
~; V ~ C~ `-- C~ C~ V
~ o~ o~,. ~ 3 ~
~ ~ C~ C~C~
,,
~ , . . .
E~ ~1
CU
~ æ z o o o z; o
P; C~ C~ Z Z Z C~ :Z
.-: . ,
æ z
~; ~ m c~ ~ m c~
0 c~ o
104900Z
F~' MPT,E ?~ A~UEOUS~RE:SSURE ) DYI~ING PROCEDIJR~
_. _
Five grams of commercially available "Dacron"*
5)~ polyester fabric were put into an autoclave containin~:
an aqueous dye paste (15i' active ingredient) containlng
the d~ of Example 1 . . . . . . . . . . . 0.1 gram
"Avitone"* T sodium hydrocarbon sulfonate (10~
solution) . . . . . . . . . . . . . . . . . 1.0 ml.
"Merpol" HCS long-chain alcohol-ethylene oxide
adduct (lO~o solution) . . . . . . . . . . . 0.5 ml.0 ethylenediaminetetraacetic acid sodium salt (1~
solution) . . . . . . . . . . . . . . . . 1.25 ml.
butyl benzoate carrier (10~ emulsion) . . . . . 1.5 ml.
water .................................. to 75 ml.
acetic acid . . . . . . . . . . . . . to ad~ust the pH to 5.5.
The temperature was raised to 265F. for 1 hour to effect
dyeing. The dyed fabric was rinsed in water and then
dried. It exhibited a navy shade of good fastness to
light and excellent fastness to sublimation.
EXAMPrE 24- THERMOSOL PROCEDURE
"Dacron" polyester fabric was immersed for
flfteen minutes at 82 C. in an aqueous bath containing
1~ of a commercially available ether-alcohol sulfate
surface-active agent (detergent) and l~o of tetrasodium
pyrophosphate. The fabric was rinsed in cold water,
dried and then padded at 50-60~ pickup, based on the dry
fabric weight, in a dye bath containing:
an aqueous dye paste (155~ active ingredient)
containing the dye of Example 2 . . . . . 50 grams
purified natural gum thickener . . . . . . . . 20 grams
water . . . . . . . . . . . . . . . . . . . to 1 liter.
* denotes trade mark
-15-
-` 104900Z
'l`he pa(ldc(3 material was passed through an infrared pre-
dr~er, then ~Icate~ to arl~ held at 2l3C. for 90 seconds.
The fabr:ic was rinsed in water at 27C., scoured for 5
minutes at ~3C. in water containing 1~ of a commercially
available ether-alcohol sulfate detergent, rinsed in
water at 27C., and dried. The polyester fabric was
d~ed to an attractive navy shade having excellent fastness
to sublimation.
*
16 -
