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Патент USA US3099662

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United States Patent 0 "ice
3,099,652
Patented July 30, 1963
2
1
combined in the ratio of about one atom of metal to- two
molecules of the monoazo compound.
3,099,652
BENZOTHIAZQLEAZOPYRAZOLONE
The metallized
azo compounds are referred to herein as 1:2‘ metal com
plexes. The manner in which metallization can be car
DYE COMPGUNDS
James M. Straley, John G. Fisher, and Raymond C. 5 ried out is ‘fully described hereinafter.
Harris, Kingsport, Tenn, 'assignors to Eastman Kodak
Nickel chloride, nickel bromide, nickel sulfate, nickel
Company, Rochester, N.Y., a corporation of New
acetate, nickel formate, nickel thiocyanate [Ni(SCN)2],
cobaltous bromide, cobaltic chloride, cobaltous chloride,
cobaltous acetate, cobalt thiocyanate [Co(SCN)2], chro
mium trichloride, chromium tribromide, chromic sulfate,
chromic acetate and chromium thiocyanate [Or(SCN)3],
Jersey
No Drawing. Filed Dec. 7, 1959, Ser. No. 857,487
7 Claims. (Cl. 260-147)
This invention relates to certain metallized and non
metallized benzothiazoleazopyrazolone compounds and
for example, are illustrative of the metallizing agents
that can ‘be employed.
Both the non-metallized and the metallized azo com
15 pounds of our invention can be applied to polyacryloni
terials.
More particularly, the azo compounds of our invention
trile textile materials in the form of an aqueous disper
consist of the monoazo compounds having the formula:
sion. Coloration can also be aifected by incorporating
the non-metallized or metallized azo compounds into the
their application for the dyeing or coloring of acryloni
trile polymers, especially polyacrylonitrile textile ma
spinning dope, spinning the ?ber as usual and converting
20 the non-metallized azo compounds to their metallized
form if desired. Also the metallizing agent can be in
corporated in the spinning dope, the ?ber spun as usual
and then treated in a dyebath containing one or more of
|
the non~rnetallized azo compounds to form the metal
25 complex on the ?ber.
Y
wherein R represents an alkylene radical having 2 to 3
carbon atoms, R1 and R2 each represents an alkyl radical
having 1 to 4 carbon atoms and wherein
R1
The non-metallized monoaz-o compounds yield yellow
shades 'on polyacrylonitrile materials. The metallized
compounds yield fast yellow to orange shades on poly
acrylonitrile materials, such ‘as acrylic ?bers. The metal
30 lized dyeings have better fastness to washing than the
corresponding non~metallized dyeings and frequently have
improved tastness to light. Among. the acryilonitrile
polymers that can be dyed or colored with the non
metallized and metallized azo compounds of our inven
taken together represents a member selected from the
35 tion are those disclosed in Straley and Giles U.S. Patent
2,857,372, issued October 21, 1958.
group consisting of the morpholinyl and piperidy-l radi
2 - amino-6-[3-dimethylaminoethylthiobenzothiazole, 2
cals, X represents a member selected from the group con
amino-6-?-diethylaminoethylthiobenzothiazole, 2 - amino
sisting of an oxygen atom and the imino group, Y repre
sents a member selected from the group consisting of a 4.0 6-[3-di-n-propylaminoethylthiobenzothiazole, 2+arnino-6
hydrogen ‘atom the phenyl, chlorophenyl and tolyl radicals
?-di-n-butylaminoethylthiobenzothiazole, 2-amino-6-y-di
and Z represents a member selected ‘from the 1group con
me-thylaminopropylthiobenzothiazole, 2 - amino - 6 - 'y—di
ethylaminopropylthiobenzothiazole, 2 - amino-6-yedi-n
sisting of a methyl group, a low carbon carbalkoxy, the
propylaminopropylthiobenzothiazole, 2 - amino-G-y-di-m
phenyl radical and the amino group‘ and their metal com
plexes containing a metal selected vfrom the group con 45 butylaminopropylthiobenzothiazole, 2 - amino - 6-(,8-di
sisting of cobalt, nickel and chromium.
methylamino-u-methylethylthio)benzothiazole, 2-amino—
The non-metallized monoazo compounds of our in
vention are prepared by ldiazotizing a 2-aminobenzo
6-(5 ~ diethylaminowomethylethylthio)benzothiazole, 2
thiazole compound having .the ‘formula:
piperidylpropylthiobenzothiazole, 2 - amino-?-?-morpho
amino-6-,8-tpiperidyletthylthiobtenzothiazole, 2-arninIo-6-7
50
linylethylthiobenzothiazole and 2-amino-6-vemorpholinyl
propylthiobenzothiazole ‘are illustrative of the Z-amino
benzothiazole compounds used in the preparation of the
R1\
NH
/NRS—
mo compounds of our invention.
2
R2
55
wherein R and R1 have the meaning previously assigned
to them and coupling the diazoniu-m compound obtained
with a pyrazolone compound having the formula:
I
Y
The [following examples illustrate the invention.
Example 1
2.8 grams of 2-arnino-6-B-diethylaminoethylthiobenzo
thiazole were dissolved in 14 cc. of 96% sulfuric acid and
24 cc. of water and diazotized by the addition of 0.72
60 gram of sodium nitrite in 5 cc. of 96% sulfuric acid, with
stirring, below 5° C. The reaction mixture was then
stirred tor two hours while maintaining the temperature
below 5° -C. after which it was slowly added to a solution
of 1.64 gram of 1~phenyl-3-methy1-5-pyrazolone in 50 cc.
65 of 2% aqueous sodium hydroxide while keeping the tem
perature below 10° C. by the addition of ice. The reac
The
wherein X, Y and Z are as de?ned herein'before.
non-metallized azo compounds can be metallized either
on ‘or o?c the materials they color. Metallization can be
tion mixture was allowed to stand for two hours without
further cooling and then made neutral to Congo red
paper by the addition of sodium carbonate. After
azo compound with a solution or ‘dispersion of the metal 70 neutralization, the reaction mixture was drowned in 1000
cc. of Water and the dye compound which precipitated
lizing agent. In the metallized azo compounds of our
was recovered by ?ltration, washed well with cold water
invention, the metal and the monoazo compound are
carried out, for example, by heating the non-metallized
3,099,652
3
it
and lair-dried. The dye compound thus ‘obtained :has the
formula:
15 cc. of 50% aqueous acetone were added over a period
of 15 minutes. Re?uxing was continued for three hours
after which the reaction mixture was poured into 400 cc.
of water and the temperature brought to 80° C. 10 grams
of sodium chloride were added, with stirring, and then
the reaction mixture was cooled to room temperature.
The metallized dye product, a 1:2 nickel complex in which
nickel and the monoazo compound of Example 1 are
combined in the ratio of about one atom of nickel to two
10 molecules of the monoazo ‘compound, which precipitated
was recovered by ?ltration, washed with a 2% aqueous
and dyes polyacrylonitrile ?bers yellow shades.
Example 2
sodium chloride solution and. air~dried. It colors poly
acrylonitrile textile materials yellow shades which have
good fastness to light, washing and gas.
15
A polyacrylonitrile textile fabric dyed yellow with a
1% dyeing (by weight ‘of pure dye) of the dye product of
Example 6
Example 1 was repeated using 1.64 gram of 1-phenyl-3
methyl-S-iminopyrazolone in place of l-phenyl-3-methyl
Example 1 was padded with a 3% aqueous solution of
5—pyrazolone. The dye compound obtained dyed poly
nickel thiocyanate under conditions such that a 60 to 20 acrylonitrile textile fabrics yellow shades. When it is
100% pick up, based on the weight of the fabric, was ob
metallized on the polyacrylonitrile ?ber, with nickel, co
tained. The polyacrylonitrile fabric was then aged in a
balt or chromium thiocyanate, for example, yellow shades
steam chest under 5 psi. pressure for 10 minutes after
fast to light, washing and gas are obtained. In each in
which it was scoured at 60° C. with soap and water,
stance a 1:2 metal complex is formed in situ on the poly
rinsed well with water and dried. A 1:2 metal complex 25 acrylonitrile fabric being dyed.
in which nickel and the monoazo compound of Example
1 are combined in the ratio of about one atom of nickel
to two molecules of the monoazo compound is formed
Example 7
ous solution of cobalt thiocyanate or chromium thiocya
converted to its nickel, cobalt or chromium form yellow
Example 1 was repeated using 2.66 grams of Z-amino
in situ Ion the polyacrylonitrile ‘fabric being dyed. The
6 - [3 - dimethylamino-a-methylethylthiobenzothiazole in
polyacrylonitrile fabric was dyed a yellow shade having 30 place of 2~amino-6-,8-diethylaminoethylthiobenzothiazole.
good fastness to light, washing and gas.
The dye compound obtained dyed polyacrylonitrile textile
When the above example is repeated using a 3 % aque
fabrics yellow shades. When the non-metallized dyeing is
mate in place of the nickel thiocyan-ate solution, the poly
shades having excellent fastness to light, gas and washing
acrylonitrile fabric is» likewise ldyed a yellow ‘shade having 35 are obtained. In each instance a 1:2 metal complex is
good fastness to light, washing and gas. The 1:2 cobalt
formed in situ on the polyacrylonitrile fabric being dyed.
complex and the 1:2 chromium complex, respectively, of
the monoazo compound of Example 1 are formed in situ
Example 8
on the polyacrylonitrile fabric being dyed.
4.52
grams
of
the
dye
of Example 7 were added in
40
Example 3
small portions to 5.4 grams of CrCl3-6H2O in 50 cc.
'of ethylene glycol at 140° C. The reaction mixture was
stirred at 140° C. for 1 hour longer, cooled to 80° C. ‘and
then poured into 110 cc. of a 20% aqueous NaCl solu
tion. The reaction mixture was ?ltered and the solid
2.93 grams of 2-amino-6-'y-diethylaminopropylthioben
zothiazole were diazotized ‘and the diazonium compound
obtained was ‘coupled with 0.98 gram of S-methyl-S-py
razolone. Diazotiza-tion, coupling and recovery of the dye
collected on the ?lter was sucked as dry as possible and
compound formed were carried out in accordance with
the procedure set forth in Example 1. The dye com
the ?ltrate made basic with 10% NH4OH. The 112
chromium complex :of the dye of Example 7 Which pre
pound obtained dyed polyacrylonitrile yellow shades.
cipitated was recovered by ?ltration, washed with a dilute
_ When the dye compound of this example is applied to
a polyacrylonitrile textile fabric and converted to its 50 aqueous sodium chloride solution and air-dried. It yields
‘orange shades on polyacrylonitr-ile textile mate-rials made
nickel, cobalt or chromium complex, yellow shades which
of Verel or Orlon 42 acrylic ?bers which have good fast
are fast to light, washing and gas are obtained. ‘In each
ness, for example, to light, gas and washing.
instance a 1:2 metal complex is formed in situ ‘on the
polyacrylonitrile fabric being dyed.
Example 4
55
Example 9
2.95 grams of 2-amino-618-morpholinylethylthiobenzo
2.93 grams of 2-amino-6-?-piperidylethylthiobenzothi
azole were diazotized and coupled with 1.56 gram of 3
thiazole were diazotized and the diazonium compound
obtained was coupled with 0.98 gram of S-methyl-S-pyraz
carbethoxy-S-pyrazolone. Diazotization, coupling and
olone. Diazotization, coupling and recovery of the dye
recovery of the dye compound formed were carried out 60 compound formed were carried out in accordance with
in accordance with the procedure set forth in Example 1.
the procedure set forth in Example 1. The dye com
The dye compound obtained dyes poly-acryllonitrile tex- v pound iolbtained dyed polyacrylonitrile yellow shades. In
tile fabrics yellow shades. In each instance a 1:2 metal
each instance a 1:2 metal complex is formed in situ on
complex is formed in situ on the polyacrylonitrile fabric
the polyacrylonitrile fabric being dyed.
being dyed.
65
When the dye compound of this example is applied
When the dye compound of this example is applied to
a polyacrylonitrile textile fabric and converted to its
to a polyacrylonitrile textile fabric and converted to its
nickel, cobalt or chromium complex, yellow shades which
nickel, cobalt or chromium complex, yellow shades which
are fast to light, washing and gas are obtained.
The following tabulation further illustrates the azo com
70 pounds of our invention and sets‘ forth (1) the colors
are fast to light, washing and gas are obtained.
Example 5
the non-metallized azo compounds yield on polyacryloni
trile textile fabrics made of Verel or Orlon 42 acrylic ?ber
and (2) the colors obtained when the nonametallized dye
aqueous ammonium hydroxide were re?uxed together
ings are metallized with nickel thiocyanate to obtain the
and a solution of 0.7 gram of Ni(OOCCI-I3)2-4H2O in 75 1:2 nickel complex in situ on the polyacrylonitrile textile
One gram of the non-metallized monoazo ‘dye com
pound of Example 1, 15 cc. of acetone and 2 cc. of 28%
3,099'5652
5
ture was-allowed to stand overnight. The reactionprod
not which precipitatedwas.recoveredby ?ltration, washed
lized dyeing and “Final” refers to the metallized dyeing.
with cold water and lair-dried.
Color
2-Am1'nobcnzothiazole
'
Original
69..4 vgrams of 2-amino~
6- 'y - dimethylaminopropylthiobenzothiazole having the
Coupler
Compound
6
tinned for one hour further after. which. the reaction'mix
material being dyed; “Original” refers to the non-metal
formula:
_
Final
S
G-?-dimethylamino-
l-phenyl-3-methyl-
ethylthio.
5-pyraz0ione.
?-y-dimethylamino-
.____do _________ __
propylthio.
?w-diethylaminopropylthio.
_____do _______________ _. ___do___-_
Do.
3-methyl-5-pyrazol0ne. ___do____.
Do.
d-y-di-n-propylaminopropylthio.
G-B-di-n-butylaminoethylthio.
G-B-dimethylsrninoethylthio.
Do _________________ ..
G-B-morpholinyl'ethylthio.
?-y-morpholinyl-
I
1,3-d1phenyl-5-pyrazclone.
1-m-chl0r0phenyi-5pyrazolone.
l-p-methylphenyl-Zimethyl-?-pyraz
olone.
3-phenyl-5-pyraz0lone.
1'-phenyl-3-'methyi-5-
.__do_____
Do.
r__do_____
~__do__.__
D0.
Do.
___do.__,_
Do.
Do.
Do.
o-v-piperidyl-propylthio._ .____do _______________ ._ ___do_____
Do.
pyrazolone.
?-?-piperidyl-ethylthim.__ 1~phenyl-3'-methyl-5'
iminopyrazoione.
?-?-dimethylamino3-methy1-5-iminoethylthio.
pyrazolone.
Do _________________ _.
3-pheny1-5-iminopy-
10
/ \
___do_____
.__do_____
Do.
Do.
___do___._
Do.
razolone.
C
I \N/
and melting at 1-l3".5—1l6°‘ C. were thus obtained.
Example 11
15
Example 10 was repeated using 57.8 grams of 2+diethyl
aminoethyl' chloride hydrochloride in place‘of 'y-dimethyl
aminopropyl chloride hydrochloride.
___do.____
___do___._
propylthio.
romimomomoms-
yellow__ yellow.
71 grams oi 2
amino~6r-?rdiethylaminoethylthiobenzothiazole melting at
92-94?" C. were obtained.
20
Example 12
Example 10 was; repeated using 52.8 grams of 2-di
25
methylarninoethyl.chloride’ hydrochloride in place'of 'wdi
methylaminopropyl chloride hydrochloride. 2-amino-6-?
dimet‘hylaminoethylthiobenzothiazole melting at 110-112°
C. was obtained.
Example 13
Metallization can also be eilected with a suitable cobalt
or chromium metallizing agent, especially cobalt thio
cyanate and chromium thiocyanate, to form the 1:2 cobalt
The general procedureset forth in Example 10 was fol
lowed using ?-dimethylamino-a-methylethyl chloride hy
and 1:2 chromium complexes of the non-metallized azo
drochloride in‘ place of 'y-dimethylaminopropyl chloride
compounds disclosed in the tabulation just given. As pre
hydrochloride.
viously noted metallization can be effected either on or
oil the ?ber.
2 -. amino - 6 e?-dimethylamino-aemethyl
ethylthiobenzothiazole was obtained as a gummy solid.
Example 14
The 2-arn'rnobenzothiazole compounds used in preparing
the azo compounds of our invention can be prepared by 35
reacting the hydrochloride salt form of a compound hav
ing the formula:
The general procedure set forth in Example 10} was
followed using ;8—piperidylethyl chloride hydrochloride in
place of 'y-dimethylami-nopropyl chloride hydrochloride.
Z-annno-6-13-piperidylethylthiobenzothiazole having the
R1
formula:
R
wherein R, R1, R2 and
H2O
N
45
R:
N
was obtained as a solid melting lat 78—81° C.
(taken together) have the meaning previously assigned to
Example 15
them and Y represents a chlorine or bromine ‘atom with
'
2-amino~G-mercaptobenzothiazole or its alkali metal salts.
The general procedure set forth in Example 1'0 was fol
The non-salt form of the compounds having the formula 50 lowed using ?-rnorpholinylethyl chloride hydrochloride in
just given can be employed but inasmuch as these com
place of 'y-dimethylaminopropyl chloride hydrochloride.
pounds are more easily prepared in their salt form, such
Z-amino-6-?-rnorpholinylethylthiobenzothiazole was ob
as the hydrochloride salt form, the use of the hydro
tained as. a solid melting at 71-73 ° C.
chloride salt form is shown in the examples illustrating
Example 16
the preparation of the 2-aminobenzothiazole intermediate 55
The general procedure set forth in Example 10 was
compounds.
‘followed using 'y-diethylarninopropyl chloride hydrochlo
ride in place of y-dimethylaminopropyl chloride hydro
The Z-aminobenzothiazole compounds are new com
pounds. They are described and claimed in copending
Straley and Fisher US. application Serial No. 2,869, ?led
January 18, 1960‘, now abandoned.
chloride. 2 - amino-6-y-diethylaminopropylthiohenzothia
zole was obtained as a solid melting at 812—84° C.
2-amino-6-mercaptobenzothiazole is a known com
pound. It can be prepared by reacting 2-amino-6-thio
cyanobenzothiazole with sodium sul?de. As shown here
inafter the 2-amino-6-mercaptobenzothiazole thus formed
can *be used, in \situ, without being separately isolated.
Example 10
68.4 grams of 2-amino-6-thiocyanobenzothiazole, 160
grams of Na2S'9H-2O' and 700 cc; of water were re?uxed
together for ten minutes. A solution of 57.1 ‘grams of the
hydrochloride of 'y-dimethylaminopropyl chloride
Example 17
The general procedure set z?orth in Example 10 [was fol
lowed using 'yqdi-n-propylaminopropyl chloride hydrochlo
65
ride in place of whimethylaminopropyl chloride 'hydro
chloride. .2‘amino-6Jy-di-n-propylaminopropylthiobenzo
thiaz-ole was obtained as a. gummy solid.
Example 18
The general procedure set forth in Example 10 was fol
lowed using p-idi-nibutylaminoethyl chloride hydrochloride
in place of 'y-dimethylaminopropyl chloride hydrochloride.
Z-amino - 6 - 18-di-n-butylaminoethylthiobenzothiazole was
obtained as a gummy sol-id.
and 27.8 grams of NaHCOa in 400 cc. of water was added
The nonmetallized and metallized azo compounds of
over a period of about 15 minutes. Re?uxing was con 75
. "3,099,652 ..
our invention
‘I
,
8
applied‘to acrylonitrile polymers,
sistingpoif an ‘oxygen atom and the imino group, Y repre
such as polyacry'lonitrile ’ and 'acrylonitrile ‘ graft polymers,
sents a memberselected :?rom the group consisting of the
in the form of .anj-aqueous dispersion. '
‘ phenyl, chlorophenyl and tolyl radicals vand Z represents
a member selected from the group consisting of a methyl
The lfollowing’exa'mple illustrates one satisfactory way‘
in which the non-ime'tall-ized-azo compounds can he used
to dye an acrylonitrile' polymer textile, material. -0.1 gram
of dye is dissolved ‘by warming in 5 cc. of methyl Cello
‘group and the-amino group and the 1:2 nickel complex
thereof“
‘
v
-
'
.
2. The monoazo compounds having the formula:
solve. A 2% aqueous solution ofanonion'ic surfactant,
such as ‘Igepal CA (a polymerized ethylene oxide-alkyl
phenol icondensation product), is added slowly until ‘a ?ne '
emulsion is obtained and then the dye mixture is brought
to a volumeot200 cc.-with1warm‘water. v'5 cc.'of a 5%
aqueous solution of formic acid‘ :or acetic acid are added
and then 10 grams of fabric made from an acrylic ?ber
is entered 'and'in the case of Orlon 42 the dyeing is car- A
ried out at-theboil for one hour. In the case of mate
rials made iofiverelyacrylic ?ber the dye‘bathtempera-ture
should not-exceed 90°.C.- in order to avoid damage to
wherein R represents an alkylene radical having 2 to 3
the deer.‘ The dyed material is then washed well with
water and dried. The metallized dyeing can be obtained '20 carbon atoms and R1 and R2 each represents ‘an alkyl
radical having 1_to 4 ‘carbon atoms;
in accordance with the procedure described in Example 2.
A' 3% solution of a salt, other-than the 'thiocyanate salt,
3. The azo compound having the formula:
can be used. . However, we have ‘found the use of the thic
cyanates ‘of nickel, cobalt and ‘chromium to be particularly
advantageous.
1
v
~
-
-
i
a
‘9
~
.
I
The premetallized azo dyes can 'be applied in the same
general manner as the non-metallized azo dyes. However,
in order to mitigate- the possibility of demetallization .dur
ing dyeing ‘5 cc. of a 5% aqueous solution of a Weak acid
such as 'boric acid :is used instead v‘of formic ‘acid or acetic
acid. . Except for this change the dyeing conditions are the
same.
.
g
-
-
i
.
OH:
25
"30 ;
-
‘The nan-‘maniacs and ,metallized azo compounds of
our invention are devoid‘ of water solubilizing groups such
as the'carboxylic acid and the. sulfonic acid groups. Any
otherjsuitable method'known'to'i the art can Ibe used to
‘ '4. The azo compound having the formula:
35:
apply them to'acrylonitril'e- polymeric materials.‘ '
_ The dyein'gsobtainedmiththe ehromiumycomplexes of .»
CH3
our invention tend to ibeg'redder than‘those obtainedwith '
the nickel and cobalt complexes.
v I _
>
N
40
'7
1
The invention has been described in, detail with particu
lar reference vto’preferred'i‘emihodiments thereo?ibut it
will tie-understood that variations andvmodi?cations can
be effected Within‘ the spirit and scope of the invention as
described hereinahove-and' as v‘de?ned'cin the appended 45
claims.
H
~
.
i 5. The 1:2 nickel complex of the azo compound set
‘
iorthlin' claim/1.1...‘
We'claim:
_
.
.
..
ing of the inonoazo compounds, devoid of a water»so1u
bilizing group, having the formula:
3K .
_
/‘NRs"-_l
I
-.
.
, v’ »
v.
6. The azo compound having the formula:
1. The ‘azo compounds selected ‘from the group consist
.
I
_
N
'
N
/ '\\C N~N ii
0 z
55
- S
i
wherein R represents
alkylene radical "having 24:0 3..‘
carbon atoms, R1 and vRz'each represents an alkyl'radical 60
having 1 to 4 carbon atoms and-wherein
7. The ‘1:2 nickel complex of the azo compound set
forth in claim 6.
.
'
I.
v References Cited in the ?le of this patent
_ UNITED STATES PATENTS
65
2,128,256
Krzikalla et‘al _________ __ Aug. 30, 1938
taken together represents a 'member selected from the
group consisting of'the morpholinyl ‘and'piperidyl madi~
2,402,538
Dreyfus ____ _'_ ________ .._ June 25, 1945
2,832,761 ' . Straley et a1 ___________ __ Apr. v29‘, 1958
cals, X represents a member selected from the group con
2,916,482
Straley et al. __________ _.. Dec. 8, 1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 3,099,652
July 30, 1963
James M. Straley et al.
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 7, lines 52 to 58, the formula should appear- as
shown below instead of as in the patent:
2
1
Signed and sealed this 7th day of April 1964:
(SEAL)
Attest:
EDWARD J. BRENNER
ERNEST W. SWIDER
Attesting Officer
Commissioner of Patents
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