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Патент USA US3082224

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United States Patent 0 ’
ce
3,082,215
Patented Mar. 19, 1963 '
1
As speci?c examples of the pigments of our invention
3,082,215
LlN-BENZOBISTHEACHROMONE PIGMENTS
Donald Graham Wilkinson, Manchester, England, as
sigrror to Imperial Chemical industries Limited, Lon
don, England, a corporation of Great Britain
there may be mentioned lin-benzobisthiachromone, 2:9
dimethyl-limbenzobisthiachromone, 2:9 - dichloro - 4: 11
dirnethyl - lin - benzobisthiachromone,
1:3:8z10 - tetra
chloro-linabenzobisthiachromone, 114:8:11 - tetramethyl
No Drawing. Filed July 22, 1959, Scr. No. 828,728
Claims priority, application Great Britain July 30, 1958
3 Claims. (Cl. 260—328)
2 : 9-dichloro-lin-benzobisthiachromone, *1 :2: 8 :9‘ - di'benz
lin - benzobisthiachromone, 2:9 - dimethoxy-lin-benzobis
thiachromone, 3: 10 - di(methanesulphonyl) -lin-benzobis
This invention relates to new pigments and more par
thiachrom‘one,
2.:9-‘diamino - lin - benzo‘bisthiachromone,
ticularly it relates to new pigments suitable for the 10 2:9-diacetylarnido - lin - benzobisthiachromone, 2:9-di
benzoylamido-lin-benzobisthiachromone, 2:9 - di(phenyl
colouration of paints, printing inks, rubber and arti?cial
polymeric materials and for the mass colouration of
thioureido)-lin<benzobisthiachromone, 2:9 - di(naphthyl
?bre-forming materials.
1’-nreido) -lin-benzobisthiachromone, 2 : 9’-di(benzylidine
The pigments of the invention are of a new polycyclic
amino) -lin-benzobisthiachromone, 3: lO-dibenzoylamido
type which we designate as lin-benzobisthiachromones 15 lin-benZobisthiachromone, 2:9 - di(dimethylarnino) - lin
and in this speci?cation the following system of number
ing is used for the parent ring system of these new poly
cyclic ‘compounds
182
13
/
9
8
\/
II
6
II
10: 1 l-dibenz) ~lin~benzobisthiachromone.
According to a further ‘feature of the invention we
provide a process for the manufacture of new pigments
20 as ‘hereinbefore de?ned which comprises cyclising a di
14
'0
10
benzobisthiachromone and 2:9 - dibenzoylamido - (3:4:
1
/\
2
S/
5
3
canboxylic acid of the formula
‘
25
O
7
wherein X and Y have the meanings'ascribed above by
According to the invention we provide new pigments
of the formula:
treating said dicanboxylic acid with a dehydrating or con
30
densing agent.
The \cyclisation may be carried out for example by
heating with dehydrating agents such as sulphuric acid,
polyphosphoric acid or chlorosulphonic acid. In carry
ing out the process of the invention the dicarbcxylic acid
may, for example, be dissolved in concentrated sulphuric
" acid and the solution heated for example at between 70°
C. and 100° C. [for between 1/2 and 2 ‘hours.
wherein X and Y each represent the atoms necessary to
When polyphosphoric acid is used as dehydrating
complete a benzene ring or a system of [fused 6-, or 6
agent it is usually necessary to heat the solution of the
and S-membered rings and wherein the rings or ring sys
dicarboxylic acid at a higher temperature and for ‘a
tems represented by X and Y may carry non-ionic 40 longer time, for example at between 160° C. and 170°‘
substituents.
C. for 10 hours. When chlorosulphonic acid is used as:
As examples of systems of fused rings which may be
completed bythe atoms represented by X and Y there
dehydrating agent it is not usually necessary to heat thev
solution of the dicarboxylic acid at all, cyclisation being
usually complete after stirring for a few minutes at 20°
may be mentioned naphthalene, pyrene and carbazole.
Such ring systems must be free from ionic solubilising 45 C. or for 1 hour at between -5° and 0° C.
groups such as sulphonic acid, canboxy-lic acid and qua
After the cyclisation has taken place the pigment may
ternary ammonium groups.
be precipitated from solution in sulphuric, polyphos
As examples of non-ionic substitnents which may be.
phoric or chlorosulphonic acid by pouring the solution
carried by' X and Y there may be mentioned halogeno
into ‘water and it may then be isolated by ?ltration and
for example chloro and bromo; nitro; alkyl for example
washing.
‘
methyl and ethyl; substituted alkyl for example tri?uoro
Other dehydrating or ‘condensing agents such as phos
methyl; aryl for example phenyl and p~tolyl; carbamyl
phorus tri- and penta-chloride and aluminium chloride
and substituted carbamyl for - example Nmethylcar
may be employed for the cyclisation of the dicarboxylic
bamyl, N:N-dimethylcarbamyl and N-phenylcarbamyl;
carbalkoxy for example carbomethoxy; sulphamyl and
substituted sulphamyl for example N-methylsnlphamyl,
acid. It is sometimes advantageous to employ a reagent
commonly used for the production of acid chlorides, for
example thionyl chloride, in conjunction with a condens
N - B - hydroxyethylsulphamyl
ing agent such as aluminium chloride.
As examples of dicarboxylic acids which may be
cyclised in the process of the invention there may be men
and
N:N - dimethylsul
phamyl; amino; alkylamino for example methylamino;
dialkylamino for example dimethylamiuo; arylarnino for
example anilino; acylamido for example acetylamido, a
vfuroylamido, p-toluene sulphonamido and aroylamido such
as benzoylarnido and substituted benzoyl amido (for ex
ample 0-, m- and p-chloro, -methoxy or ~nitro benzoyl
60
tioned 2:5-di(phenylmercapto)terephthalic acid, 2:5-di
(p-tolylmencapto)terephthalic acid, 2:5-di(4’-chloro-2'
methyl-phenylmercapto)terephthalic acid, 2:5-di(3’:5'
dichlorophenylmiercapto)terephthalic acid, 2:5 - di(4’
amido), phthalimido and ?-naphthoylamido; alkyl and
acetylamidophenylmercapto)terephthalic acid and 2:5
aryl-ureido and -thionreido for example nebuty-l- and 65 di(naiphthyl-2’-mercapto)terephthalic acid.
phenyl-ureido and -thioureido; arylideneamino for ex
The dicarboxylic acids used in the process of the in
ample benzylidineamino; alkanesulphonyl for example
vention may be obtained for example ‘by hydrolysis of the
methanesulphonyl and chloromethanesulphonyl; hy
corresponding esters with alcoholic potassium hydroxide
droxy; alkoxy, for example methoxy, ethoxy and p-hy
solution. The esters may be obtained for example by
droxy ethoxy; and aryloxy for examiple phenoxy and 70 reaction of a 2:S-dihalogenoterephthalic ester with the
cresoxy. It is to be understood that more than one of
appropriate thiophenol, thionaphthol or thiol derivative
these substituents may be present.
of a carboxylic or heterocyclic ‘compound, by heating if
3,082,215
3
4
contain 69.1% of carbon, 2.9% of hydrogen and 17.2%
desired in a solvent such as pyridine, for 20 hours in the
of sulphur. CZOHIOOZSZ requires carbon 69.3%, hydro
presence of potassium hydroxide.
gen 2.9% and sulphur 18.5%.
Those new pigments as hereinbefore de?ned in which
2.5 parts of the product is added gradually to 50 parts
the rings or ring systems represented by X and Y carry
of
90% sulphuric acid which is stirred at room tempera
as substituents ureido, thioureido, benzoylamino, or acyl
ture and the deep blue-green solution is then stirred for 1
amide groups may be manufactured by an alternative
hour. It is then added dropwise to 550 parts of a 10%
process comprising treatment of a pigment as herein
aqueous solution of sodium carbonate at 65° C., with
before de?ned in which the rings or ring systems repre
good stirring. The pigment is then ?ltered off, washed
sented by X and Y carry amino groups as substituents,
with an isocyanate, isothiocyanate, aldehyde or a func 10 free from alkali, intimately mixed with 0.12 part of pine
oil and ?nally dried at 50° C. The product forms a
tional derivative of an organic acid such as an acid halide,
bright golden yellow pigment of excellent fastness to
anhydride or ester, and this alternative process forms a
heat, light and solvents which can be used for the prep
further feature of our invention.
aration of paints and lacquers and the colouration of
The alternative process of our invention may con
plastics. It can also be used ‘for the mass-colouration of
veniently be carried out by treatment of a ?nely divided
?bre forming materials such as polyesters and polyamides.
suspension of the amino substituted pigment in a suitable
The 2:5-di(phenylmercapto)terephthalic acid used in
solvent, for example pyridine, with the appropriate re
the above example may be obtained as follows:
agent, for example n-butylisocyanate, phenyl isothio
A mixture of 4.65 parts of diethyl-2:S-dichlorotereph
cyanate, benzaldehyde, benzyl chloride, acetic anhydride,
thalate, 4.43 parts of thiophenol and 2.28 parts of pow
phthalic anhydride, or p-toluene sulphonyl chloride, at
dered potassium hydroxide is stirred with 25 parts of dry
an elevated temperature, for example between 100° and
pyridine under a re?ux condenser at between ‘115° and
150° C. The product may then be isolated by ?ltration
120° C. for 20 hours.
and washing.
The reaction mixture is added to
water and the pyridine is removed by steam-distillation.
The residue in the reaction vessel is then made just acid by
the addition of hydrochloric acid and the unreacted thio
phenol is steam distilled off. The insoluble yellow solid
The products obtained by carrying out one of the
processes of the invention are usually crystalline in na
ture and may be converted into a ?nely divided pig~
mentary form in known manner, for example by grind
residue is ?ltered off and boiled with dilute sodium carbo
nate solution and the undissolved ester is ?ltered off, and
ing, acid pasting, salt milling or treatment with an or
ganic liquid such as phenol, cresol, xylene or dimethyl
formamide, if desired at an elevated temperature. In 30 hydrolysed to form 2:5-di(phenylmercapto)terephthalic
acid by boiling it with a 5% solution of potassium hy
some cases the crystalline form of the pigments of the
droxide in ethanol. The 2:5-di(phenylmercapto)tereph
invention can be modi?ed by the application of such
procedures.
thalic acid so formed is a bright yellow compound melting
‘
The pigments of the invention are useful for incor
poration in printing inks, paints, lacquers and stoving
enamels and ‘for the colouration of rubber and arti?cial
polymeric materials such as cellulose acetate, polyvinyl
at 342-344° C.
35
Example 2
2.6 parts of 2:5-di(p-tolylmercapto)-terephthalie acid
(which may be made as described below) is added grad
chloride, polythene and polystyrene and ?bre forming
ually to 60 parts of 98% sulphuric acid which is stirred
materials such as polyesters and polyamides. They give 40 at room temperature. The solution is then heated to 70°
bright yellow to purple shades of high fastness to light,
C. and stirred at this temperature for 1 hour and ?nally
heat and solvents.
Those pigments of the invention wherein X and Y
each represent the atoms necessary to complete a benzene
ring which carries one or more halogen atoms as sub
stituents give bright yellow shades of high fastness to
light, heat and solvents, and in particular 123:8:10-tetra
chloro-lin-benzobisthiachromone is a valuable pigment
which has very good fastness to out-door atmospheric ex
posure when incorporated in paints.
Those pigments of the invention wherein X and Y each
represent the atoms necessary ‘to complete a benzene
ring which carries an acylamino group as a substituent
give bright red shades of excellent fastness properties
and in particular 2:9-di(4f-chlorobenzoylamido)-lin
heated to 80° C. and stirred at this temperature for 1/2
hour. The reaction mixture which is dark green in colour
is added gradually to 500 parts of hot 10% aqueous
sodium carbonate solution, when a bright golden yellow
suspension of 229-dimethyl-lin-benzobisthiachromone is
formed. The pigment is ?ltered off, washed free from
alkali, dried and recrystallised vfrom chlornaphthalene
when it forms bright orange micro plate-shaped crystals
50 which melt at from 370° to 374° C.
The crystalline
product may be converted into a ?nely divided pig
mentary form as previously described for the product of
Example 1.
The 2:5-di(p-tolylmercapto)-terephthalic acid used in
the above example may be made as follows:
A mixture of 3 parts of diethyl 2:5-dichloroterephthal
cellent fastness to heat, light and solvents, especially
ate, 3.2 parts of p-thiocr'esol and 1.45 parts of powdered
when used for the colouration of arti?cial polymeric
potassium hydroxide is stirred in 15 parts of dry pyridine
materials such as polythene and polystyrene.
under a re?ux condenser at between 115° and 120° C. for
The invention is illustrated but not limited by the 60 20 hours. The diethyl ester of 2:5-di(p-tolylmercapto)
following examples in which the parts are by weight.
terephthalic acid is isolated and hydrolysed as described
in Example. 1 for the corresponding diphenyl mercapto
Example 1
compound.
3.5 parts of 2:5-di(phenylmercapto)terephthalic acid
Example 3
(which may be made as described below) is added grad
ually during 1/2 hour to 30 parts of polyphosphoric acid 65 5 parts of 2:S-di(4'-chloro-2’-methyl-phenylmercapto)
terephthalic acid (which maybe made as described below)
which is stirred at between 160° and 170° C. and the
benzobisthiachromone is a valuable red pigment of ex
is added gradually over 20 minutes to 80 parts of 100%
sulphuric acid which is stirred well at between 50° and
60° C. The reaction mixture is then heated at 100° C. and
to water, the yellow product in suspension is ?ltered off,
boiled with 250 parts of 5% aqueous caustic soda solu 70 stirred at 100° C. for 11/2 hours. The deep green coloured
reaction mixture is then added to 500 parts of water and
tion and again ?ltered and washed to remove uncyclised
the bulk of the acid is removed by ?ltration. The yellow
material. The lin-benzobisthiachromone thus obtained is
pigment is then stirred with dilute aqueous ammonia solu
crystallised from chloronaphthalene when it forms ?at
tion at 70° C., ?ltered off, washed neutral and dried. The
golden yellow needle-shaped crystals which melt at from
bright yellow pigment so obtained is puri?ed by crystal~
390° to 395° C. On analysis the product is found to
mixture is then stirred at between 160° and 170° C. for
a further 10 hours. The reaction mixture is then added
3,082,215
6
lisation from chlornaphthalene.
2:9-dichloro - 4:11 - di
methyl-lin-benzobisthiachromone is thus obtained in the
form of ?ne yellow needle-shaped crystals which melt with
decomposition at from 435° to 440° C.
temperature for a further 1 hour and is then added slowly
to crushed ice. The crude yellow 3: l0-dichloro-lin-benzo
'bisthiachromone which is precipitated is ?ltered off and
freed from uncyclised material by extraction with hot 2%
A mixture of 2 parts of the product and 15 parts of
aqueous sodium carbonate solution. After drying, it is
anhydrous sodium carbonate is ball~milled for 20 hours
puri?ed by crystallisation from chloronaphthalene when it
with steel balls. The mixture of sodium carbonate and
is obtained as a bright yellow crystalline powder. The
pigment is separated from the steel balls and stirred with
product is converted into a ?nely divided pigmentary form
hot water and the pigment is ?ltered off and washed free
by milling with sodium carbonate as described for the
from alkali. The pigment paste is stirred with 0.1 part 10 product of Example 3. When the pigment is incorporated
of pine oil and dried at 50° C. A bright yellow powder of
into paints or used for colouring plastics, bright yellow
soft texture is obtained which is slightly greener in shade
than the pigment of Example 1. It has excellent fastness
obtained.
properties.
- The 2:S-di(3'-chlorophenylmercapto)-terephthalic acid
'
The starting material used in the above example may 15
A mixture of 21.75 parts of diethyl 2:5-dichlorotereph
thalate, 29.7 parts of 4-chloro-2-methyl-thiophenol and
10.65 parts of powdered potassium hydroxide is stirred
with 120 parts of dry pyridine under a re?ux condenser 20
be prepared as follows:
at between 115° and 120° C. for 20 hours. The diethyl
ester of 2 : 5 -di ( 4'-chloro-2'-methylphenylmercapto) -ter
ephthalic acid is isolated and hydrolysed as described in
shades of excellent fastness to heat, light and solvents are
'
used in this example may be obtained by condensation of
dimethyl-2:S-dibromoterephthalate with m-chlorothiophe;
nol followed by hydrolysis of the product, the procedure
being similar to that described in Example 1 for obtain
ing 2:S-diphenylmercaptoterephthalic acid.
Example 6
5 parts of 2:5-di(2’-chlorophenylmercapto)-terephthalic
acid is stirred with a solution of 16 parts of thionyl chlo
ride
in 55 parts of monochlorobenzene for 1 hour at 100°
Example 1 for the corresponding diphenyl mercapto com
C. in a closed vessel ?tted with a re?ux condenser. The
pound.
25 solution is cooled to room temperature and 10 parts of
Example 4
4.1 parts of 2:5-di(3’:5’-dichlorophenylmercapto)-ter
powdered aluminium chloride is gradually added. The
colour changes through purple to green. The reaction
ephthalic acid (which may be made as described below)
mixture is then heated at 130° C. for 3 hours. It is then
is added gradually over 30 minutes to 80 parts of 98% sul
cooled and the insoluble reaction product is ?ltered and
phuric acid stirring at between 95° C. and 105° C., and the 30 Washed with a little monochlorobenzene and then with
stirring continued for 1 hour at this temperature. The
alcohol. The product iswarmed with dilute hydrochloric
deep green coloured solution is then added to 500 parts
acid to free it from aluminium ‘compounds, ?ltered and
of water and the bright yellow precipitate is ?ltered off.
then extracted with hot dilute sodium carbonate solution
The ?lter-cake is then stirred with dilute aqueous ammonia
to free it from uncyclised material. After drying it is
at 70° and the puri?ed bright yellow pigment ?ltered off, 35 recrystallised ‘from chlornaphthalene. 4:11-dirohloro-lin
washed until free of ammonia and dried. It is then further
benzobisthiachromone is obtained in the form of golden
puri?ed by ‘crystallisation from the chlorn-ap'hthalene when
yellow needles. It may be converted into a ?nely divided
1 :3 :8 : 10¢tetrachloro-lin-benzobisthiachrornone is obtained
pigmentary form as described for the product of Example
as ?ne bright yellow needles which melt above 430° C.
3. When the pigment is incorporated into paints or used
The crystalline product is converted into a ?nely divided 40 for the oolouration of plastics, bright yellow shades of
pigmentary form as previously described for the pigment
excellent fastness to heat, light and solvents are obtained.
of Example 3.
The 2:5-di(2'-chlorophenylmercapto)-terephthalic acid
The 2 : 5 -bis ( 3 ’ : 5 '-di‘chlorophenylmercapto ) -terephthalic
used in this example may be obtained by a procedure
acid may be made as follows:
similar to that described in Example 1 for obtaining 2:5
A mixture of 6.0 parts of 3:5-dichlorothiophenol, 4.4 45 diphenylmercaptoterephthalic acid, thiophenol being re
parts of dimethyl-2:5-dichloroterephthalate and 1.9 parts
of powdered potassium hydroxide is stirred with 25 parts
placed by 2-chlorothiophenol.
of pyridine at the boil under a re?ux condenser for 20
hours. The product is isolated and hydrolysed as described
reagent and conditions used to obtain other lin-benzobis
and —5° C. The intense green solution is stirred at this
condensate.
The following table brie?y indicates in column 2 the
thiachromone-s from the appropriately substituted 2:5-di
in Example 1 for the corresponding diphenylmercapto 50 (phenylmercapto) terephthalic acids and in column 4 the
compound.
shade of each product when converted into a ?nely divided
Example 5
pigmentary form. The terephthalic acids listed in column
3 parts of 2:S-di(3’-chlorophenylmercapto)-terephthalic
1 may all be obtained by condensation of dimethyl 2:5
acid is added gradually during 15 minutes to 45 parts of
dichloro- (or bromo-) terephthalate with the appropriately
chlorosulphonic ‘acid which is stirred at between 0° C. 55 substituted thiophenol, followed by hydrolysis of the
Starting material
Method of oyclisation ‘
Lin-benzobisthiachromone obtained
Colour
‘
2:d?g’io?di?ethylphenylmercapto)tere13
a 10 ac .
98% sulphuric acid, 2 hours at'100° C.-__ 1:3:8:10-tetramethyl _______________ __ Yellow.
2:5t-di(‘$3111pro-2zdddimethylphenylmercapto)
erep
a 10 act .
100% sulphuric acid, 2 hours~ at 100° C... 2:9-dichlor0-1z4z8zllftetramcthyl-____
2:5-d§4’-chi0ropheny1rnercapto)tcrephthalic
98:41,ospléahuric acid, 15 minutes at 100° to 2:9-dichloro _____________________ _. Reddish yellow.
2:5-di(3’-chloro-2-mcthylphenylmcrcapto)terephthalic acid.
Chlcrosulphonie
acid, 1 hour at 0° to
—5‘’ C.
2:5-di(2’:5’-dichl0rophenylmercapto)
terephthalic acid.
Chlorosulphonic
acid, 10 minutes at 20°
0.
2:5-di(2’:4'-dichlorophenylrnercapto)
_____do ________________________________ _.
2:9:4z11-tetrachloro ________________ -_
Do,
2:5-di(3’:4’-dichlorophenylmereapto)
_____d0 ________________________________ ._
2:3:9zl0-tetrachloro ________________ __
Orange.
aci
.
terephthalic acid.
terephthalic acid.
2:5-dgly-methoxyphenylmercapto)terephthalic
.
3:10-dichloro-4:11-dimcthyl ________ __ Greenish yellow.
1:428:11-tetrachloro ________________ ._ Yellow.
Method of Example 6 _________________ __ 2:9-dimethoxy _____________________ __ Bright yellowish
aci .'
2:5-di(5’-chl0r0-2-methoxyphenylmercapto)
terephthalic acid.
Do.
red.
Chlorosulphonie
acid, 10 minutes at 20°
0.
1:8-dich1or0-4zll-dimethoxy________ __ Orange.
2zi-di(3gp?pro~4-rgethoxyphenylmercapto)
erep
a 1C BC! .
Chlorosulphonic
acid, 5 minutes at 15°
.
3:l0-dichloro-2:Q-dimethoxy ________ __
2:5~di(3’-methanesulphonylphenylmercapto)
98% sulphuric acid. 1 hour at 100° to
3:10-di(methanesulphonyl) ________ __ Bright orange.
terephthalic acid.
105° C.
Do.
'
8,082,215
7
8
Example 7
resulting colourless solution is diluted with 500 parts of
In place of the 5 parts of 2:5~di(2'-chlorophenylmer
capto)terephthalic acid used in Example 16 there is used
5 parts of 2:S-di(naphthyl-2'-rnercapto)terephthalic acid.
hydrochloric acid. The bright yellow precipitate of 2:5
di(4’-acetylamidophenylmercapto)-terephthalic acid is ?l
hot water and acidi?ed to Congo red with concentrated
tered off, washed acid free with boiling water and dried
l:2:8:9-dibenz-linbenzobisthiachromone is obtained. Af
ter conversion to a ?nely divided pigmentary form it
forms a yellow pigment.
2:5-di(naphthyl-2'-mercapto)terephthalic acid may be
obtained by condensation of dimethyl 2:5-dibromotereph
thalate with naphthalene-Z-thiol followed by hydrolysis
at 100° C.
Example 9
1.9 parts of 2:9-diamino-lin-benzobisthiachromone are
ground to a ?ne paste with 50 parts of pyridine. The re
10
sulting suspension is diluted with 100 parts of pyridine and
40 parts are distilled off to remove traces of water.
of the condensate.
The
resulting suspension is cooled to 80° C. and 3.5 parts of
p-chlorobenzoyl chloride is added. The mixture is again
heated to boiling and is stirred and boiled under re?ux
Example 8
1.9 parts of 2:9-diamino-lin-benzobisthiachromone are
ball-milled for 20 hours with 100 parts of pyridine. The 15 for 3 "hours during which time the maroon colour of the
resulting suspension is diluted with 50 parts of pyridine
suspension changes to bright scarlet. The 2:9-di(4'-chlo
and heated to 100° C. 6 parts of benzoyl chloride are
robenzoylamido) - lin - benzobisthiachromone which is
added with stirring to the hot suspension which is then
boiled under re?ux for 3 hours. The bright orange red
formed is ?ltered from the hot reaction mixture, and is
washed with 25 parts of boiling pyridine. It is then con
suspension of 2:9 - di(benzoylamido) - lin - benzobisthia 20 tinuously extracted with boiling acetone for 3 hours and
chromone obtained in this way is cooled and poured
?nally dried at 100° C.
with stirring into a. mixture of 500 parts of ice and 150
2 parts of the crystalline product are mixed with 20
parts of concentrated hydrochloric acid. The orange~red
parts of sodium chloride, 350 parts of steel balls and 20
precipitate is ?ltered oil, washed with water until free
parts of nails and milled for 40 hours. The salt-pigment
from acid, and dried. It is continuously extracted for 1 25 mixture is separated from the steel balls and nails and is
hour with hot acetone and dried. The product may be
stirred with 25 parts of dimethyl formamide for 12 hours,
puri?ed, if desired, by recrystallisation from boiling di
during which time its shade becomes appreciably brighter.
methyl formamide whence it is obtained as copper
The mixture is diluted with 120 parts of hot water, stirred
coloured plates which melt with decomposition above
at 70° C. for 1/2 hour and then ?ltered. The ?lter cake
370° C. Found C, 69.4; H, 3.3; N, 4.7%. C34H2OO4N2SZ 30 is stirred with 150 parts of water and 5 parts of 98% sul
phuric acid at 70° C. for 1/2 hour, ?ltered, washed acid free
requires C, 70.0; H, 3.4; N, 4.8%.
2 parts of crystalline 2z9-di(benzoylamido)-lin-benzo
with hot water and the moist ?lter cake is mixed intimate
bisthiachromone are ball-milled for 17 hours with 20 parts
ly with 0.1 part of pine oil and dried at 60° C.
The resulting bright scarlet pigment when incorporated
of anhydrous sodium carbonate. The mixture is extracted
with hot water and ?ltered, the ?lter cake washed alkali 35 into paint media and into polymeric materials such ‘as poly
thene and polystyrene has excellent fastness properties es
free with water, mixed intimately with 0.1 part of pine
oil and dried at 50° C. The resulting bright mid-shade
pecially to heat and solvents.
‘
If in place of p-chlorobenzyl chloride in the above ex
red pigment has excellent fastness properties especially to
ample there is used a chemically equivalent quantity of
heat and solvents when incorporated into paint media.
The 2:9-diaminobenzobisthiachromone used in this 40 other acid chlorides or anhydrides, other 2:9-di—(acyl
amido)-lin-benzobisthiachromones may be obtained, such
example may be obtained as follows:
as those listed in the following table. The shades of the
8.5 parts of 2:5 - di(4’ - acetylamidophenylmercapto)
products, after conversion into a ?nely divided pigmentary
terephthalic acid (which may be made as described below)
form are listed in column 3.
are added gradually during 10 to 15 minutes with stirring
to 170 parts of 98% sulphuric acid without external cool 45
ing. The resulting orange solution is heated to between
Acid chloride or
Lin-benzobisthiachromone
Shade
100° C. and 110° C. during 15 to 20 minutes and is main~
anhydride
obtained
tained at this temperature for a further 45 minutes. Dur
ing the heating the colour of the solution changes ?rst
p-‘vlethoxybenzoyl
chloride.
2z9-dl(4’-methoxybenzoyl- Bright red.
amido).
to violet and ?nally to bright blue. The solution is cooled 50
to room temperature and added dropwise to a stirred solu
tion of 350 parts of sodium carbonate in 2000 parts of
p-Toluyl chloride ____ __ 2:9-d(i1(4)’-methy1benzoyla-
water. The magenta solid which is thereby precipitated
o-Bromobenzoylchlo- 2:9-d(i1(2’-br0mobenzoyla-
Acetic anhydride ____ _-
mi
is ?ltered oil, washed free from alkali with hot water
and dried at 100° C. If desired, it may be puri?ed by 55 m-Nitrobenzoylchlor1 e.
r
e.
1
recrystallisation from boiling mono-chloro-naphthalene.
p-Nétrobenzoylchlo-
Long purple needles are obtained. Found C, 64.2; H,
a-Ftll'flyl chloride”..p-Dirnethylaminobenzoyl chloride.
?-Naphthoyl chl0rldc._
60 2:4-dichlorobenz0ylchloride.
3:4-dich1orobenzoyl
chloride.
Diphenyl-icarboxy
3.4; N, 7.1%. CZOHHOZNZSZ requires C, 63.9; H, 3.2;
N, 7.4%.
2 : 5‘di‘( 4'-acetylamidophenylmercapto) terephthalic acid
may be prepared as follows:
42 parts of p-acetylamidothiophenol are added rapidly
to a stirred suspension of 14.4 parts of powdered potas
sium hydroxide in 350 parts of pyridine at 65° C. in a
r1 e.
chloride.
Orange.
Do.
Bright orange.
0 .
m1
.
Do.
2:tz1’di(3'-nitrobenzoylarnl- Reddish orange.
.
2:%-di(4’-nitrobenzoylaml- Bright orange-red.
.
2:9-dl(rz-furoylamido)_.__.
2:9-di(4-’dimethylamlnobcnzoylamido).
2:9-di(?-naphthoy1amido)_
2:9-di(2':4’-dichloro benzoylamido).
2:9»di(3’:4’~dichlcro benzoylamid .
2:9-dl(4’-pheny1beuzoyla.
Bright orange.
Bluish red.
Bright scarlet.
Rcddlsh orange.
Yellowish red.
Do.
mido .
m-To1uylchloride.___. 2:9-d(i1(I<l)’-methylbenzoyla- Orangeyellow.
?ask from which the air has been excluded by a current of 65 [rTolucnesulphonyl
nitrogen. The mixture is stirred for 15 minutes and then
45.2 parts of diethyl-2:S-dibromoterephthalate and 100
pants of pyridine are added. The mixture is stirred and
boiled under re?ux in an atmosphere of nitrogen for 16
2:9-di(acetylamldo) ..... _-
Phthalic anhydride--- 2:9-d1(phthalimldo) _____ __
chloride.
m1
0 .
2:9-di(4’-mcthylbenzcne
sulphonamido).
Red.
Example 10
In
place
of
3.5
parts
of p-ehlorobenzoyl chloride in Ex
hours. The resulting thick yellow suspension is poured 70
ample 9 there are used 2.9 parts of phcnylisothiocyanate.
into 2000 parts of cold water and the insoluble yellow
The 2:9 - di(phenylthioureido)-lin-benzobisthiachrornone
solid is ?ltered off, washed with water and then with 100
which is obtained may be converted into a ?nely divided
parts of ethanol. It is mixed with 450 parts of 10% aque~
pigmentary form by the method used for the product of
ous sodium hydroxide solution and 500 parts of 95%
ethanol and boiled under re?ux for 90 minutes. The 75 Example 9 and then forms an orange-red pigment.
3,082,215
Example 11
In place of 3.5 parts of p-chlorobenzoyl chloride in
Example 9 there are used 2.2 parts of a-naphthylisocya
nate.
The 2:9~di(naphthyl-l’—ureido)-1in - benzobisthia
10
with stirring into 5100 parts of cold water. Sodium hy
droxide solution is added until the liquid is no longer
acid to Congo red indicator and the purple precipitate
of 2:9-di(dimethylamino)-lin-benzobisthiachromone is
chromone which is obtained may be converted into a 5 ?ltered offfwashed with hot water until washings are
neutral and continuously extracted for 2 hours with
boiling acetone and dried. If desired the product may
be crystallised from chloronaphthalene, violet needles be
pigment.
ing obtained. It may be converted into a ?nely divided
Example 12
10 pigmentary form by the method used for the product of
In place of 3.5 parts of p-chlorobenzoyl chloride in
Example 9 and then forms a purple pigment.
Example 9 there are used 10 parts of n-butyl isocy-anate.
2:5 - di(4’-dimethylaminophenylmercapto)terephthalic
?nely divided pigmentary form by the method used for
the product of Example 9 and then forms a bright red
The 2:9-di(n-butylureido) - lin - benzobisthiachromone
which is obtained may be converted into a ?nely divided
acid may be obtained as follows:
A mixture of 7.6 parts ‘of diethyl 2:5-dibromotereph
pigmentary form by method used for the product of Ex 15 thalate, 9.8 parts of S-acetyl-p-dimethylaminothiophenol,
ample 9 and then forms a bright scarlet pigment.
5.1 parts of powdered potassium hydroxide and 25 parts
of pyridine is stirred and re?uxed for 18 hours.‘ The
Example 13
mixture is poured into water and the pyridine is steam
In place of 3.5 parts of p-chlorobenzoyl chloride in
distilled off. The aqueous liquor is then acidi?ed with
Example 9 there are used 2.8 parts of phenylisocyanate.
20 acetic acid and the mixture is steam distilled for a fur
The 2:9-di(phenylureido) - lin - benzobisthiachromone
ther short period to remove any p-dimethylaminothio
which is obtained may be converted into a ?nely divided
phenol. The aqueous residue is ?ltered. The ?lter cake
pigmentary form by the method used for the product of
is stirred and boiled under re?ux for 21/2 hours with
Example 9 and then forms an orange-red pigment.
a mixture of 180 parts of ethanol and 40 parts of 10%
A red modi?cation of this pigment is obtained by dis
aqueous potassium hydroxide solution.
solving the orange red pigment in cold 98% sulphuric acid 25 The solution is diluted with an equal volume of water,
and pouring the solution into a large volume of Walter,
?ltered and the ?ltrate is acidi?ed with acetic ‘acid. 2:5
?ltering oil the precipitated solid, Washing acid-free and
di(4' - dimethylaminophenylmercapto)terephthalic acid
drying. The orange-red and red modi?cations of this
separates as an orange precipitate which is ?ltered off,
pigment give di?erent X-ray powder photographs and 30 washed with water and dried at 100° C.
infra-red absorption spectra.
S-acetyl-p-dimethylaminothiophenol may be obtained by
Example 14
reduction of p-p'-bis(dimethylaminophenyl)disulphide
16 parts of benzaldehyde are added to a stirred, ?nely
(prepared as described in Berichte der Deutsche Chemi
divided suspension of ‘1.9 parts of 2:9-diaminobenzobis 35 schen Gesellschaft, volume 19, page 1570) with.zinc in
a mixture of acetic acid and acetic anhydride. It is a
thiachromone in 125 parts of pyridine. The mixture is
stable crystalline solid of melting point 80° to 83° C.
stirred and boiled under re?ux for 8 hours, during which
time the suspension changes from violet to orange. The
Example 117
suspension is ?ltered hot, washed with 20 parts of hot
2
parts
of
the
~diamino-(l:2:8:9-dibenz)-lin-bcnzo
pyridine and is then continuously extracted with boiling 40
bisthiachromone obtained as described below is ?nely
acetone for 4 hours. The 2:9-di(benzylidineamino)-lin
ground in 140 parts pyridine. 40 parts of pyridine
benzobisthiachromone which is obtained may be converted
are distilled oil to remove traces of water, the sus
into a ?nely divided pigmentary form by the method
pension is cooled to about 80° and 4.0 parts of hen
used for the product of Example 9 and then forms a
zoyl chloride added with stirring. The mixture is
bright orange pigment.
45 boiled under re?ux for 4 hours. The resulting yellow
Example 15
suspension is ?ltered while still hot, the insoluble frac
tion is washed with hot pyridine, then methanol, and is
3.2 parts of benzoyl chloride are added to a suspension
then continuously extracted for 2 hours with boiling
of 2 parts of ?nely ground 3:IO-diamino-lin-benzobis
acetone. The yellow brown powder which is obtained
thiachromone in 100 parts of pyridine, and the mixture
may be converted to a ?nely divided pigmentary form
is stirred and re?uxed for 3 hours. The resulting orange
as described for the product of Example 9 and then
suspension is ?ltered while still hot, washed with 20
forms a yellow-brown pigment.
parts of hot pyridine and is then continuously extracted
The product has the formula:
with boiling acetone for 3 hours and dried at 100° C.
The 3 : 10-bis( benzoylamido)-lin-benzobisthiachromone so
obtained may, if desired, be crystallised from boiling 55
monochloronaphthalene, orange micro needles being ob
tained. Found N=4.6%; C34H2QO4N2S2 requires N:
4.8%.
The product may be converted into a ?nely divided
pigmentary form by the method used for the product of 60
Example 9 and then forms an orange pigment.
3:10-diamino-lin-benzobisthiachromone may be pre
pared in an exactly analogous way to the 2:9 isomer
described in Example 8 by using 2:5-di(3'-acetylamido~
phenylmercapto)terephthalic acid (from dimethyl 2:5-di 65 The diamino(1:2:8:9-dibenz) - lin - benzobisthiachro
mone used in this example may be obtained as follows:
bromoterephthalic and m-acetylamidothiophenol) in place
4 parts of 2:S-di(2’-acetylamidonaphthalene-6'-mer
of 2:5 - di(4' - acetylamidophenylmercapto)terephthalic
acid.
capto)terephthalic acid are added to 40 parts of 98%
sulphuric acid with stirring during 20 minutes at room
Example 16
70 temperature. The orange-brown solution is heated to
3 parts of 2:5-di(4’-dimethylaminophenylmercapto)
between 100° and 110° C. and stirred for 80 minutes when
terephthalic acid is added gradually with stirring to 55
it becomes cherry red in colour. It is cooled and poured
parts of 98% sulphuric acid at room temperature. The
slowly into'a stirred solution of 150 parts ‘of sodium car~
mixture is heated to 110° C. and stirred at that tempera
bonate in 1500 parts of water. The orange precipitate
ture for 1 hour. The solution is then cooled and poured 75 of diamino( l :2: 8 : 9'-dibenz) -lin-benzobisthiachromone is
3,082,215
11
12
After conversion to a ?nely divided pigmcntary form it
forms a yellow pigment.
?ltered otf, washed with hot water until the washings
are neutral and colourless, then washed with ethyl alcohol
The diamino(3 :4: 10: l'l-dibenz)-lin-benzobisthiachro
and ?nally the product is continuously extracted for 2
mone used in this example may be obtained from 2:5
di(5’ - acetylamido-napl1thalene-1'-mercapto)terephthalic
acid by treatment with 98% ‘sulphuric acid as described
hours with boiling acetone.
2:5 - di(2' - acetylamidonaphthalene - 6' - mercapto)
terephthalic acid is prepared by an analogous process to
that described in Example 8 for the preparation of 2:5
for the preparation of the isomeric compound of Ex
ample 17. 2:S-di(5’-acetylamidonaphthalene-l’-mercap
di(p-acetylamidophenylmercapto)terephthalic acid, re
to)terephthalic acid may be obtained by an analogous
placing p-acetylamidothiophenol with an equivalent
process
to that described in Example 8 for the prepara
10
amount of 2-acetylamido-naphthalene-6-thiol.
tion of 2:5-di(p-acetylamidophenylmercapto)terephthalic
Example 18
acid, replacing p-acetylamidothiophenol with an equiva
lent of 1-acetylamidonaphthalene-S-thiol.
In place of 2 parts of the diamino(1:2:8:9-dibenz)
What I claim is:
lin-benzobisthiachromone used in Example 17 there is
used 2 parts of the isomeric 2:9-diamino-(3z4z'l0z11 15
dibenz)-lin-benzobisthiachromone obtained as described
below. The product obtained has the formula
1. 1 :3 :8: 10-tetrachloro-lin-benzobisthiachromone.
2. 2:9-di(4' - chlorobenzoylamido) - lin - benzobisthia
chromone.
_
3. Pigments of the formula:
0
/S\
CO\
00/
\S/
CoHsCONH-
SA)‘
NBC 0 Cal-I5
A
C
l
S
l3
ll
0
wherein the rings A and B carry non-ionic substituents
selected from the group consisting of hydrogen, chlorine,
nitro, methyl, methoxy, methane sulfonyl, acetylamido,
After conversion to a ?nely divided pigmentary form
benzoylamido,
chlorobenzoylamido, bromobenzoylamido,
it forms an orange-brown pigment.
30
nitrobenzoylamido, methoxybenzoylamido, furoylamido,
The 2:9-diamino(3 :4: 10: ll-dibenz) ~lin-benzobisthia
phthalimido, dimethylaminobenzoylamido, naphthoyl
chromone used in this example may be obtained from
2:5 - di(4' - acetylarnidonaphthalene - 1'-mercapto)tereph
thalic acid by treatment with 98% sulphuric acid in the
manner described for the preparation of the isomeric
compound of Example 17. 2.:5-di(4’-acetylamidonaph
thalene-4'-mercapto)terephthalic acid may be obtained
amido, dimethylbenzoylamido, dichlorobenzoylamido,
phenylbenzoylamido, methylbenzoylamido, methylben
zene sulphonamido, pheuylthioureido, naphthylureido,
butylureido, phenylureido, benzylidineamino, dimethyl
amino and the divalent substituents.
by an analogous process to that described in Example 8
for the preparation of 2:5-di-(p-acetylamidophenylmer
capto)terephthalic acid, replacing p-acetylamidothio
phenol with an equivalent amount of l-acetylamino
naphthalene-4-thiol.
Example 19
In place of 2 parts of the diamino(l:2:8:9-dibenz)-lin
said divalent substituents being attached to two adjacent
carbon atoms of the rings A and B.
References Cited in the ?le of this patent
UNITED STATES PATENTS
benzobisthiachromone used in Example 17 there is used 2
parts of the isomeric diamino(3:4:10:11-dibenz)-lin
benzobisthiachromone obtained as described below. The
product has the formula:
1,880,490
2,521,676
Rosch ________________ __ Oct. 4, 1932
Schmidt-Nickels _______ __ Sept. 12, 1950
OTHER REFERENCES
Steikopf et al.: Leibigs Annalen, volume 527, pages
244-45 and 262-63 (1937).
Sidgwick: Organic Chemistry of Nitrogen, page 138,
00/
332, page 337 (1937).
55 page
Noller: Textbook of Organic Chemistry (1958), page
\S/
366.
NHCOCtHa
-
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