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Патент USA US3100771

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United States Patent O?lice
Patented Aug. 13, 1963
l
,
2
reacting a 2-(R-azo)rnonazine-N~'oxide, as above de?ned
3,100,766
with a salt of a metal having an atomic number greater
METALLIZED AZO DYES FROM 2-AMlN0
than 23 and less than 30.
PYRIDINE-l-OXIDE
The metallization reaction is preferably conducted by
Charles E. Lewis, Somerville, N.J., assignor to American
Cyanamid Company,‘ New York, N.Y., a corporation 5 heating the N-oxide with lirom about 0.5 to about 2 moles
of Maine
No Drawing. Filed May 19, 1961, Ser. No. 111,134
3 Claims- (CL “(F-146)
of the metal salt in an organic solvent such as dimethyl
form-amide, formamide, pyridine, aniline or an alcohol.
Reaction temperatures are from about 75-150° C. pref
. invention
.
.
_
This
relates to new metallized
azo > com-
erabl y =w'thin
the range
t
l
[of about 90° to about l140° C.
Metallization Will 0 to substantial com letion in a eriod
Pounds which are ‘{Seful as ,dyestu?s, ‘especially for ?bers 10 of less than aboutg3 or 4 hours. Afterpmetallizatioiii, the
such as wool and silk; the linear polyamides, e.g., nylon;
metal ‘complex is Team-1y separated from the reaction
mixture by drowning in water and ?ltration of the result
ing precipitate.
and the Pmtemaceous ?bers PTePared ‘from natural PTO‘
teins as disclosed in Man-Man Textile Encyclopedia (pp.
109411).’
.
.
Meta1hZ,at1°u 9f ‘imam 3,2?‘ dyestuffs for the PHI-PO56
15
Among the metal salts useful for the purpose of this
invention may be mentioned salts of inorganic acids such
‘of l’ncreasmg the" hght Stab?lty has been_known- Van"
as sulfuric, nitric and hydrochloric acids; and salts of
tous attempts have been made to utilize this principle for
increasing the stability of dyestuffs from azopyridine-N-
organic acids Suoh ‘as formic, acetic and lactic acids_
Among the N_oxides useful {01. the purposes 01; this in_
oxides and azoquinoline-N-oxides. However, such N- 20 ven?‘on ac’re.
oxides did not lend themselves to successful metalliza-
(1) 2_(2:hydroxy _ 5 _ Y _ phenylazol) _pyIidine_N_
“911' Thus" metal complexes could not befmled ?f’m
‘oxides such as the derivatives wherein Y is hydrogen or
either 2-(p-dlmethylannnophenylazo)-pyr1dme~N-ox1de,
methyl.
4—(4-hydroxy-1-naphthylazo)pyridine-Dioxide or 4-(4(2) 2_(2_hydroXy-5,6,7 or 8-Z-1-napl1thy1aZ0) - Pyri
hyd'IQXy'LnaPhthyhZQ -q_111'11°11¥1e-N-°X1d°-_
_
25 dine-N-oxides, wherein Z is a hydrogen, 6-su1famyl, 7
It 1s an ObJCCt of this mvention to provide metallized
chloro 01. 6dmethyl.
derivatives or arylazo monazine-N-oxides which are use-
(3) 2_(2_aml-no_’5,,6’7 m. slglmaphthylazo)_pyridine_
m1 m, ‘dyeing mtwgeilous ?ber?‘ .
_
.
,
N~0Xides wherein Z is hydrogen, 6-sulfo, 7-bromo or 5
It is a further object of this invention to provide n1methyl.
trogenons libers dyed with metallized derivatives of aryl- 30
(4) ’2_(2_hyd,mxy _ 5 _ Y _ phenylazo) _ quinolinc _ N_
azo‘monazme'N‘oxlfies of, th_e clas? helemafter desmb‘ed'
oxides such as the derivatives wherein Y is hydrogen or
In accorclllance with this mventgon 1t has 1.:l;1een2foung
that metals aving an atomic nunr er greater
methyL
an 3 an
(5) 2_(2_hydroXy_5’6,7 0r 8_Z_1_naphthy1am)_quino_
less than .30 (1'6" Cr’ Mn’ Fe’ (.JO’ N1 mid Cu) fol-“.1 com‘
l-ine-N-oxides wherein Z is hydrogen, 7-sulfamyl, 6-bromo
group
or S-methyl.
plexes Wlllll 2-(R-az0)~monaz1ne-N-ox1des wherein the 35 or 5_methy1. and
monazineradical has less than three six-membered rings
(6) 2 _ (iamhw _ 5,6,7 .01- 8.Z-1_naP11thylazo)-qnino
(‘3'43" Pyndyl and qumolyl) and R ‘S a Tadlcal of the
line-N-oxides wherein Z is a hydrogen, 6-sulfo, 7-bromo
‘
011
'
Where the desired N-oxide starting material is not
'Q
40 known, it may be prepared by diazotizing Z-amino-py-ri
dine-N-oxide or Z-amino-qu-inoline-N-oxide, as the case
may be, coupling with the coupling agent corresponding
I
Y
to the “R” radical shown on the azo linkage of the start
OH
45 ing material. Diazotization, coupling agents, coupling
l____
conditions useful for this purpose are conventional in the
art.
The metallized azo dyes of the present invention have
af?nity for wool, silk, linear p’olyamide and arti?cial pro
50 teinaceous ?bers, which they dye level, deep reddish
Z
shades. They are generally applied by the so called
“neutral” dyeing method which employs ammonium ace
tate or acetic acid in small amounts to give the dyeing
and
NlHi
bath a weakly acidic pH. They exhaust well and give
|__
‘ 55 level shades.
Q
The following examples are presented to more fully
illustrate the present invention. Parts are by Weight un
less otherwise noted.
Z
60
wherein Y is hydrogen or lower alkyl; and Z is hydro-
gen, sulfamyl, sulfo, halo (e.g. chloro, bromo and iodo),
and alkyl (e.g., lower alkyl such as methyl, ethyl and
Example 1
(A)
OH
I
propyl), which complexes dye nitrogenous ?bers level,
Ill
deep shades when applied by conventional neutral dyeing 65
0
methods.
‘
The metallized dyes of this invention are prepared by
/_N=N_
I
‘
80mg,
3,100,766
.3
-
4
11.0 parts of 2~arninopyridine-1-oxide are dissolved in
until uniform, ?ltered, Washed with cold Water and dried
160 parts of 7.5% hydrochloric acid and cooled to 0° C.
at 50° C. It is then recrystallized from 50% ethanol.
6.9 parts of sodium nitrite dissolved in 13.4 parts of Water
(B) Copperization of: the prodzwts of part A.—-1.32
are added all at once and stirred at 0° C. for 15 min. until
parts of the product of part A, 1.0 part of cupric acetate
diazotization is complete. (An orange ‘color develops.) 5 monohydrate‘slurried in 25 parts by volume of formamide
23.7 parts of real 2-naphthol-6-sulfonamide are disare heated three hours at 90-100° C. The Whole is then
l
r
r
l
' ‘i?
" “ “ll
Wolltl llllllltd With'an?tualvolumcotwatcr and ?ltered.
5
3,100,766
sulfo, halo and lower alkyl; vand vthe metal has an atomic
number greater than 23 and less ‘than 30.
2. The chromium complex of 2-(2-hydr0Xy-5-sulfamyl
l-naphthylazo ) épyridine-N-oxide.
‘3. The copper complex of 2-(2-l1yd11oXy-1-naphthyl
azo) ~pyridine-N-ox-icle.
6
2,903,324
2,929,809
2,957,862
Hirsbrunner __________ -_ Sept. 8, 1959
Menzi et ,al ___________ __ Mar. 22, 1960
Riat et a1. ____________ __ Oct. 25, 1960
2,987,368
Bene ________________ __ June 6, 1961
OTHER REFERENCES
Cheng et al.: “Analytical Chemistry,” vol. 27, N0. 5,
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,827,680
Tisza et ‘a1. __________ __ Oct. 13, 1931
May 1955, pp. 782-785, (Available ‘in Div. 59.)
'
Colonna et al.: “Gazz. Chim. Ital.” vol. 85, November
01955, pp. 1508-1518. ‘(Available in Scienti?c; Li
brary. )
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