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Patented Oct. 22, 1946
-
2,409,851
UNITED STATES PArEuroFFmE ‘f
PEItYLENE DERIVATIVES '
Norman Hulton Haddock, Blackley, Manchester,‘
England, assignor to Imperial Chemical Indus
tries Limited, a corporation of Great Britain
No Drawing. Application March 2, 1942, Serial
N0. 433,103. InGreat Britain March 12, 1941_
10 Claims.
1
t
a
(Cl. 260-281)
2
,
This invention relates to the manufacture of
new perylene derivatives containing sulphur.
tween more than two molecules ‘of the mercap
tans.
'
phur dyes and others of them substances which,
are, as stated, sulphur dyes and can be dyed from
as will be explained below, can be used as sulphur
sodium sulphide vats. They yield bright red dye
ings which have very good fastness to light,
dyes. They are all'derivatives of perylene-3z4:
9: IO-tetracarboxy-di- (phenylimides) ,
the
sul
chemic and washing with soap at the boil. ' The
phur dyes being mercaptans and the correspond
ing disulhpide derivatives, and the others being
sulphur dyes already in use do not include any
which dye in red shades of as good brightness
thiocyano and xanthic ester derivatives. All of 10
them, therefore, may be represented by the gen
and fastness.
eral formula
'
The thiocyano and xanthic ester derivatives are
. not strictly speaking dyes, but they can‘neverthe
less be used as if they were sulphur dyes, because
under the conditions of the sodium sulphide‘ vat
‘
they are hydrolysed to'the mercaptans. When
so used they give dyeings like those obtained from
wherein Q is the radical of perylene-3,4,9,l0
tetracarboxy-diimide, R, R’ represent phenylene
(y,
‘
The mercaptans and the disulphide derivatives
These new derivatives are some of them sul
the mercaptans and disulphide derivatives} l‘ ‘ "
radicals selected from the group consisting'of,
The invention includes the application of the
phenylene, alkyl phenylenes having not‘ more
new derivatives as sulphur dyes.
’ ‘
‘
than 4 carbon atoms in‘ the side chain, and al-‘
koxy-phenylenes having not more than 4 car 20 ‘ In making the thiocyano and xanthic'ester de
rivatives, ‘the tetrazotisation can be effected con
bon atoms in theside chain, said radicals ‘R and
veniently by dissolving the amine in concentrated
B’. being attached tothe radical Q through the
sulphuric acid and adding a’ sulphuric acid solu‘-'
N-atoms of the imide groupings, while X, X’
tion, of sodium nitrite. After tetrazotisation, the
designate radicals which are reducible by alkali
metal sul?des in alkaline medium to mercaptanv 25 sulphuric acid‘ solution may be poured on to ice
radicals. The presence of these radicals causes“ and ?ltered, thetetrazo compound is thus ob
tained as ‘a paste, whichmcan? be added ‘towater
the entire compound to become applicable to tex
and treated for the replacement of the diazonium
tile ?ber as a sulfur dye, that is by reduction in’
substituents by thiocyano or xanthic ester sub
an alkaline sul?de vat followed by oxidation on
the ?ber. In a more speci?c sense, X, X’ are 30 stituents. When making thiocyano derivatives
the ?ltration may conveniently be omitted. The
substituents selected from the group consisting
treatment of the terazo compound With “thio
of the thiocyanate radical (—SCN), the disul?de
cyanates and xanthates is effected according to
radical ,(-S—S-—), and alkyl-xanthate radicals
the known methods of replacing diazonium sub
(-S—CS—‘-O—a1kyl). In the case of the disul
?de radical, the second bond of the S--S group 35 stituents with thiocyano and xanthic ester ones.
Sodium thiocyanate can be conveniently used for
may be attached to the same perylene-diimide
making the thiocyano derivatives and potassium
molecule or it may bridge two such molecules.
ethyl xanthate for making the xanthic ester ones.
According to the invention We make the thio
When using potassium ethyl xanthate
cyano and xanthic ester derivatives by tetrazotis
ing perylene-3z1lz9:IO-tetracarboxy-di-(m- or p 40
(KS.CS.OC2H5)
aminophenylimides), which may carry alkyl or
the ethyl xanthic ester substituent
alkoxy substituents with not morethané carbon
atoms, in the phenylene nuclei, and then treating
the resulting tetrazotised compounds with thio
cyanates or xanthates, so as to replace the di
. (—S.CS.OC2H5)
5
azonium substitutents with thiocyano or‘xanthic
ester substituents respectively.
‘
is introduced. Using other esters, othercorre
sponding ester substituents are introduced.
‘ Hydrolysis of the thiocyano and-the'xanthic
Also according to the invention we make the
ester derivatives is conveniently effected with so
mercaptans by hydrolysing the thiocyano and
dium sulphide. In fact as has already been men!
50 tioned, hydrolysis is eifected‘ under the condi
xanthic ester derivatives.
‘
. Also according to the invention we make the
tions of use in the sodium sulphide sulphur vat.
disulphide derivatives by oxidising the mercap
This effect is verysurprising, because in the case
tans. The disulphide derivativesv will in general
of the simpler .aryl compounds it has been ‘our.
experience that their thiocyanates do not _hy-,
contain more than one disulphide i. e. ——S.S—'
group, and may be formed by combination be
55
drolyze readily except‘ under, ‘drastic conditions,‘
2,409,851
3
4
involving for instance re?uxing for six hours with
very strong aqueous or alcoholic caustic soda. It
is very surprising, therefore, that the relatively
cool and weakly alkaline aqueous sodium-sul?de
vat is capable of hydrolyzing the thiocyanates of
aminophenylimide) in the process of that ex
ample.
Erample 3
6.4 parts of perylene-3z4z9:IO-tetracarboxy-di
(m-aminophenylimide) are dissolved in 90 parts
of 98% sulphuric acid below 25° (3., and a solu
tion of 2.06 parts of sodium nitrite in 18 parts
of 98% sulphuric acid is added. The mixture is
heated at 30—35° C., for half an hour and then
Poured on to 500 parts of ice and water. 100
parts of sodium chloride are added, and the
bright red diazonium salt which is precipitated
is ?ltered off and washed several times with 20%
this invention so readily as to produce a satis
factory dyeing on the ?ber.
’
The mercaptans oxidise easily to the disulphide
derivatives. In fact they are di?icult to preserve
as mercaptans, as they oxidise on contact with
air. In manufacture, air is the most convenient
oxidising agent touse, although other oxidising
agents, e. g., sodium m-nitrobenzene-sulphonate
may be used if desired.
For use as sulphur dyes, the disulphide deriva
tives appear to be the most convenient.
The following examples in which ‘parts are by
sodium chloride solution.
The diazonium salt is '
made into a thin paste with water and gradually
' poured into a solution of 10- parts of potassium
ethyl xanthate in 100 parts of water, keeping the
temperature between 40 and 50° C., and adding
sodium carbonate in small portions to keep the
mixture alkaline to Brilliant Yellow paper. The
red suspension is heated to 90° C., {and maintained
weight illustrate but do not limit the invention. ’
Example 1
5 parts of perylene-3r4z9:10-tetracarboxy-di
(m-aminophenylimide) (prepared by heating
perylene-3:4:9:10-tetracarboxy anhydride with
at 80—90° C., for about a quarter of an hour until
the evolution of nitrogen ceases. The bright red
m'-pheny1enediamine-—see British Patent No.
201,786) are dissolved in 72 parts of 98% sul 25 suspension is ?ltered and washed alkali-free.
The product is hydrolysed to the mercaptan by
phuric acid. The solution is stirred at 30° C. A
dissolving in aqueous sodium sulphide solution.
solution of 1.6 parts of sodium nitrite in 7.2 parts
Either as such or after oxidising to the disul
of 98% sulphuric acid is added during a quarter
of an hour and the mixture is stirred at 30° C.,
phide it yields violet shades on cotton from a so
is evolved during this operation. The bright red
compound in suspension is ?ltered, washed with
5' parts of perylene-3z4z9:IO-tetracarboxy-di
(m-amino-p-methylphenylimide) (prepared by
until diazotisation is complete. The red solution 30 dium sulphide vat and these oxidise in'the air to
bright bluish-red.
is then poured on to and stirred up with 300 parts
In the ?rst part of this example, the potassium
of crushed ice. The diazonium sulphate is thus
ethyl xanthate may be replaced by the corre
obtained as a colloidal red precipitate. To this
sponding isopropyl or n-butyl esters.
there is added a solution of 15 parts of sodium
thiocyanate in 50 parts‘of water and the mixture 35
Example 4
is stirred and slowly warmed to 95° C. Nitrogen
heating perylene-3-: 4 : 9 : IO-tetracarboxylic acid
.
The resulting perylene-3 :4; 9 : lO-tetracarboxy 40 anhydride with m-toluylenediamine) are .dis
solved in 22 parts of 98% sulphuric acid at 25° C.
di-(m-thiocyanophenylimide) is a ‘red powder,
Asolution of 1.6 parts of sodium nitrite‘in 22
insoluble in water. Its structure may be ex
parts of ice-cold 98% sulphuric acid is added
pressed by the formula
water and dried.
G
during a quarter of an hour and the mixture is
24 parts of the above thiocyano derivative are
stirred at 25° C., until diazotisation is complete.
mixed with 50‘parts of crystalline sodium sul
phide dissolved in 1000 parts of water. The mix
The solution is poured on to 300 parts of crushed
ice and a solution oi 15 parts of sodium thiocy
anate in 50 parts of Water is added and the mix
ture stirred and slowly heated to boiling, The
resulting perylene-3 :4 :9 : 10-tetracarboxy-di-(m
ture is heated to the boil. A violet solution of
perylene-3 :4: 9 : 10-tetracarb oxy-di- (m-mercapto
phenylimide) is obtained, this being probably
present as a leuco derivative.
thiocyano-p—methylphenylimide) is ?ltered 01f,
The solution is treated at about 50° C., by pass
ing through a stream of air, when a precipitate 30 washed with water and dried. It is a bright red
powder insoluble in water.
I
of the disulphide derivative is formed. This pre
20 parts of the above thiocyano derivative are
cipitate is ?ltered off, washed with water and
stirred with a solution of 50 parts of sodium sul
dried.
phide crystals in 800 parts of Water and the mix
It is red in colour, insoluble in water,‘ soluble
ture raised to the boil. The thiocyano compound
in concentrated sulphuric acid with a red colour
dissolves completely giving a deep ‘violent solu
and in aqueous sodium sulphide solution with a
violet colour. It dyes cotton in. red shades from
a sodium sulphide bath, and the dyeings have
very good fastness to light, chemic and washing
tion of the mercaptan. The solution is oxidised
at 40—50° C., by air-blowing and the red precipi
tate of the disulphide derivative is ?tlered oiT,
with soap at the boil.
washed and dried.
'
Example 2
Products similar to those of Example‘ 1 are ob
tained by using perylene-3;4::9:10—tetracarboxy-_
di-fpeaminophenylimide) instead or the di-(m-l
‘ ,
It dissolves in sulphuric acid with a purple col
our. It dyes cotton from a sulphide bath, in red
shades which have very good fastness to light,
chemic and wet treatments.
75
Sodium’ m-nitrobenzene sulphcnate may be
2,409,851
5
_
_
6
used instead of air in the above oxidation. Compounds corresponding to those obtained above ‘and
at room temperature for one hour,‘ warmed to
7 80° C., and ‘the red precipitate ?ltered on and
having very similar properties'are' ‘obtained ‘if
Washed with Water.-'
starting materials are used carrying ethyl, propyl
and butyl substituents instead of methyl.
‘
'
.
.
‘
'
reacting
I olaimz“
.
-_
l.
-
'
.
.
.25 43' A soluPlon of 4'35‘ parts of §odlqm.mtnte
‘
-
A
'
1' Acgmpound of the gemm'mrml?
perylene-3:4:9:10-tetracarboxylic
fifslgoljené‘sggngg 15:2: 3; §8digmS1f?g?1f§°§é d2‘;
o
‘
rivative as described in Example 4.
»
di-(m-amino-p-methoxyphenylimidei> \‘(prepared 10
by
' ‘
the mercaptan is oxidised to thedisulphide‘dee
_~
18.9 parts of perylene-3:4:9:10-tetracarboxy
-
‘
' 5 with dilute aqueous sodium sulphide solution and
a
Example 5
-
'
5
The ester is hydrolysed by warming to 90°‘ C.,
‘
.X—-R-Q-R’-X’ ~ ‘ ‘
.
v
wherein Q is the radicalofperylene-3,4,9,Ill-tetra;
carboxy-diimide, R, R" represent phenylene radi
cals selected from the group consisting ‘of phenyl
ln
parts of ice-cold 98% sulphurlcacid 15 add- 15 ene alkyl phenylenes having not more than 4
ed during a quarter of an hour and the mixture is
carbon atoms in the side chain and alkoxy
stirred until diazotisation is complete. The solu-
phenylenes having not more than
mm‘ is pwred °n t° 90° parts of crushed ice and
in the side chain said radicals R and R.’ being at
carbon atoms
a solution of 45 parts of sodium thiocyanate in
tached to the m'dical Q through the N_at'oms of
75 parts of water is added and the mixture stirred 20 the imide groupings while X X, designate new
3215;151:222_lg‘?ig?‘getggc:fgggi(mg?ogg?ff
cals which are reducible by alkali-metal sul?des
m th
in alkaline medium to mercaptan radicals where
‘
‘
'.
.
.
.
e Oxyphenyhmlde) 1s ?ltered o? wlth Water
b the entire compound becomes a plicabl to
and dried. It is a bright red powder insoluble in
tgx?le ?ber as a sulfur dye
p
e
Wag}; th.
.
.
25
2. A sulfur dye containing the nuclear struc
.
locyano derlvatlve can be converted to
ture of an NN,_di hen L3 4 9 10_tetracarb x _
?hgl?hfeddslrslgigsude denvatlve dyes cotton m
phenyl nuclei substituents which are convertible
the disulphide derivative as described in Example
pery1ene_d?mi’de m3; cairyi’nig’ further in laid
Compounds corresponding to those obtained
in an a1k?‘1ine.Su1?de Vat. to merca‘pto groups’
tained
above and
if there.
havingare
veryused
similar
as starting
propertiesmaterials
are ob- 30 fur
23f;figyvgési?gl?gngéiiggtga
dye to taxt?e ?ber Sa‘id gubstiwents
03111513112131;being
compounds carrying ethoxy, propoxy, isopropoxy
.
.
and butoxy substltuents Instead of methoxy‘
E$ample 6
5 parts of perylene-3:4:9:IO-tetracarboxy-di(m-aminophenylimide) are dissolved in 50 parts
”
'
'
radicals selected from the group consisting of
the thiocyanate radical, the disul?de radical and
35 alkyl-xanthate radicals.
3. A composition as in claim 2, wherein the
speci?ed phenyl radicals carry further substi
tuents selected from the group consisting of alkyl
of 98% sulphuric acid and the solution poured on
and alkyloxy of not more than 4 carbon atoms.
to crushed ice. The red precipitate is ?ltered 40 4. A compound of the general formula
0
X
C
@N/\0
i0
0/
1%
05 and Washed free of acid. The moist paste is
stirred with 800 parts of water containing 5 parts
of 36% hydrochloric acid and diazotised at 0~5°
C., by the addition of 1.6 parts of sodium nitrite
X)
ll
wherein X, X’ represent substituents which are
reducible in the manner of sulfur dyestuffs to
produce mercaptan groups in solution.
5. A compound of the general formula
0
0
H
II
o
0
in 10 parts of water. The red solution is ?ltered
from a trace of suspended material and run into
wherein X, X’ stand for thiocyanate radicals.
6. Acompound of the general formula
a solution of 20 parts of potassium isopropyl-'
xanthate and 20 parts of sodium carbonate in 300
wherein X, X’ stand for alkyl-xanthate radicals.
7. A compound of the general formula
i
<3?
parts of water at 60° C. The mixture is stirred
‘i
—
wherein X, X’ stand for disul?de radicals’.
XI
2,409,851
7
8
/ 8. vIn the process of manufacturing ‘a sulfur dye
step of dissolving the resulting sulfurrcontaining
of theperylene seriesLthe arrangement of steps
which consists of tetrazotizing a diamino-N,N'
compound in an aqueous vat containing analkali
sul?de, whereby to produce a, mercap-tan of N,N¢'
diphenyl-3,4,9,IO-perylene-tetracarboxye cliimide,
diphenyl-3,4,9,l0-perylene-tetracarboxy - diimide
in solution.
7
'
and coupling the resulting bis-diazoniurn com
10. A process as in claim 8 including further
pound to a, sulfur-containing compound of the
the steps of dissolving the resulting sulfur-con
group consisting of the alkali-metal thiocyan-ates
taining compound in an aqueous vat containing
and alkali-metal-alkyl-xanthates, said: coupling
an alkali sul?de, whereby to produce a mercaptan _
being achieved at a. moderately elevated tempera
ture whereby the diazoniumnitrogen is elimi 10 of N,N'-dipheny1-3,4,9,10-perylene-tetraoarboxy
diimide in solution, and then subjecting the said
nated and radicals from the group consisting of
solution to oxidation to precipitate Va, disul?de
thiocyanate and alkyl-xanthate are introduced
into the phenyl nuclei.
I
. 9. A process as in claim 8 including further the
form of said dye,
1
NORMAN HUL'IY'ON HADDO?K.
' -
Certi?cate of Correction
Patent ‘No. 2,409,851.
October 22‘, 1946.
NORMAN HULTON HADDOCK
’
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 6, lines 69‘ to 74 inclusive,
claim 7, for that portion of the formula reading
‘a i
ll
wag
l
0:0
l
0
and that the said Letters Patent should be read with this correction‘therein that the
same may conform to the record of the case in the Patent O?ice.
Signed and sealed this 24th day of December, A. D. 1946.
LESLIE FRAZER,
‘
First Assistant Oowwm'ssz'oner of Patents.
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