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Патент USA US2368657

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Patented Feb. 6, 1945
I 2368,65?‘
Norman Hulton Haddock, Blackley, Manchester, '>
" England, assignor to Imperial Chemical In
‘ -~Adustries‘Lin1ited, a'corporation of Great Britain
‘No‘DraWing; Application May 22,1942,.Serial ‘Na
chlorr'd'eifin a "solvent-Qsucheasiiloenzene.hrv o-di._
The present vinvention relates to‘themanufa‘c
ture'of 'dye'stu?s'f'andintermediates; therefor.
chlorlbenzene'. (‘preferably above 14’0'°- “C‘.'). onewof ‘
two, dislilp'honic' "acids of pr?C-i-dit? lni‘ethfylbenze ‘
According ‘to the vinvention we" cause ‘a ,pr-p'f
with a thi-ocyanoaryl-amine or -_an'N-mono-alkyl '
thiazyl) azoberize‘n'eiw‘h'ich are. obtained (1)‘ by.
sulphonating'v rp'gp"-di'?6;methylbenZtliiazylJaZo-~i
benzene'and "('2)" oxidising dehydrotlriioep-toluie
or -'aralkyl thiocyanoarylamine of the benzene
dineisulphoriic acid ‘with, ‘for; instance, I sodium~
chloride (made as described below) ‘to‘interact
hypo'ol'il'ofite. ‘(This latter ,disulphon‘ic 'ac‘idi‘sjtlie;
series,‘ thereby ‘obtaining ‘the ‘corresponding di
_ v
‘The invention "also 'cOmpriSes'the ‘steps of hy
dyestu?'”Chlora‘zo1 ‘Fast Yellow B,",'Coldur.lndex
10: No; Eli-and :is ‘given ‘the constitution: .p:_p" -di('6;
drolysing a- p : p”>-di"(’6 l-methylbenzthiazyl) a'zob'en
methylbenzthiazyl )1 'azob‘enz'ene-o ': o’ -‘clisulp‘lionic ; .
zene-di’(tliiocyanosulphonarylaniide) ‘obtained in
ac‘idi'). The‘ disulpnonyl chloride derivatives used.‘
the ' above‘ manner, ‘to the 1corresponding ' p : p"‘-Jdi
as starting‘ materials ‘are “accordingly two. innum
(6amethylbenzthi'azyl)*azobenzene,- di<mercapto -
positions di’?er'in'fconsti‘
occupied‘ by‘jthe disulplionlyji-chloride
respeet of
sulphonaryla-rr?de) and oxidisingv thedaftter to 115i ber-"anri'
the corresponding‘polydisulphide. '‘
groups'jwh'idh positions. viilepend ' on‘ whether
corresponding 'disulphol?'c _ 'a’c'idiiis made'fby» .‘(see
‘The present 'polydisulphidesrepresent sulphur»
con'ta‘iniing dyestuifsv which may beiapplied ‘to cel
lulosic material from sodium sulphide solution
according to the usual practice with sulphur dye
above) ‘ process "(1) ' or "(2);;
-aralkyl"thiocyanoarylaanines of ‘the bem‘zer'ie'‘.se-v
stu?'s. - .By-V-this means thereare obtained bright
ries there may be used, for instance,-p-thioc'yaiio
orange-yellow shades ‘possessing excellent :fast
N-methylaniline, vp - thiocyanoaniline,
p - thio
cyanoloeaminoanisole, ,2-:~5%dioh1ono~14:-ttiiocyano
ness l-to severev washing,- chemick ‘and light.
aniline ror,p-thiocyanoiNebenzyglaniliner‘ '
di(thiocyanosulphonarylam-ide)i r ‘ deriva- ‘
tives of pvzzphdi(6emethylbenzthiazyli azobenzene
The invention “ [is illustrated
referred-to abovepnot only ‘constitute interme
?ned to , the : following’, examples fine
diates in the, described_manufacture of sul
phur-containing :dyestu?si but may themselves ‘be ‘
Example! ’
applied to cellulosic material from :sodiiunsul-j
phide :solut-ion.~according,_to the usual :pract-ice 30 ' m paptsof pm;ananaesthesia»ea;i ‘
benzene disulphonyl “chloride; (prepared;
withesulphur dyestuffs. .‘By‘this procedurelrthe
di(thiocyanosulphonarylamide) "derivatives" be» low); are .added‘ to, 30K partsMof:moltenypstmoe
cyano-Nemethylanil-ineLand thefmixture stirred;
come- hydrolysed inv ‘the sodiwn-sulphide- so1u.-»
.. tionyto. the corresponding di(mercaptosvilphon
arylamide) derivativea Thevlatter subsequently -'
C. H0170. parts of;ialcoholiftareeiaddedsandithe;
' orange precipitate; is ,?ltemed; and-.‘washed ~ - with:
become ‘oxidised toopolydisulphides on the, ?bres.
,Thus by the dyeing technique commonly employed
withsulphur dyestu?s there are producedxon the.
?brevthe sulphur dyestuffs, to [the productionin.
substance of which the‘ above-mentioned ‘proc
esses‘relatea In, this wayalso, ,dyeings are obn-v-i
tained having the properties already described.
alcohol“ ‘11 pants"of:>p:p'-di»(6emethylbenzthia¢~
zyDiazobenzene-di?N 1- methyl . -*4-;- thiocyanosul- » '
phon'an'ilidet are obtained.‘ .i Thembove product:
40 isildissolv'edfin ‘10D wager boiIi-ngaI-aloohol
v '
' taming f2'0 parts-tofusodiumesulphide-fcmstalsi-p
p'honani'lidé) derivativeitoFthe'iconrespondih?rdip
Accordingly,lthispinvention is to beregarded
as, relating?notionlywto the manufacture by the.‘
(N - methyl-4emercapizosulphonanilide)l '
' stii?sinsubstancewbut also, to their production» ’
aforesaid ‘processes‘of sulphur-containing dye
onvilthe ?bre, that lisp-Von the cellulosic material‘
directly, by employing-inzthe technique usual inj
dyeing with sulphurqdyestuffs, thesabove- inter‘;
Hydrolysis of’ the. diiNvme‘thylale-thiocyanosmeea '
‘s't'reamgo'f: air is passedithnouglii
di'(N minetliiylmercantosulphonanilide) '..
‘ oxidised .therehyito the .icorres'pondinggm?lydisule = .
pliidegwh'ich is thrown db-wnia's'a precipitate; "Elie I
mediate products, namely the di(thiocyanosu1~ 50
phonarylamide) r-derivatiyes of pzp'i-d?l?enethyl;
_ The starting material. whic
methylbenzthiazyl) azobenzene. disulphonyl |chlo+
dark brown powder, soluble‘in concentrated 5111;. ‘if? .
phuric acid to give a brié-ht-‘orange-red solution;- I I _ i
and in » boiling‘ ail-wus-zsediumi sulphide.‘ to“ an’
’ rldefis madeby-treatirrglwithphesphoruspentars-? imshades-Whichl after oiddising-inthesairflvareqr
bright yellow, and possess excellent tastness to
severe washing, chemick and good fastness to
' The
cyanoaniline are heated with stirring at 135° C.
for 2% hours. The dark coloured mixture is
cooled to 90-100° and treated with 100 parts of
p:p'-di(G-methylbenzthiazyl) azobenzene
ethanol. ‘ The brownish-yellow precipitate of
disulphonyl chloride used above is prepared as
follows: 12 parts of Chlorazol Fast Yellow "B
(Colour Index No. 814), 15 parts of phosphorus
dichloro-‘l-thiocyanosulphonanilide) is ?ltered
pentachloride‘and1150{parts of nitrobenzene are '
The yellow powder dissolves readily'in boiling
heated at>1~50-l55° C. for-2 hours. The solution ‘is
cooled and the precipitate which forms is, ?l
aqueous ‘sodium'sulphide solution containing a
little 'cellosolve, from which solution cotton is
tered, washed with benzene and dried. The prod
dyed in shades which after oxidation’ in the air,
o?‘, washed. with ethanol and’ waterand dried.
uct, p:p'-di (6-methylbenzthiazyl) azobenzene di
are yellow and possess very good fastness to se
sulphonyl chloride, is a brown crystalline powder, '
vere washing, chemickand good fastness to light.
Example 5
5 parts of p:p‘-di(6-methylbenzthiazyl)azoa'
benzene disulphonyl chloride (made as in Ex
soluble in hot organic solvents to give bright
yellow solutions.
Example 2
5 parts of p:p’-di(6-methylbenzthiazyl)azo
ample 1), 10 parts of p-thiocyano-N-benzylani- >
benzene disulphonyl chloride (made as described
line and 18 parts of dry nitrobenzene are heated
with stirring at 130-135° C. for one and a half
hours. .The dark coloured mixture’ is cooled to
‘in Example 1), 5 parts‘ of p-thiocyanoaniline and
10 parts of dry nitrobenzene are heated together
with stirring at 110-120" C. for 2 hours. ' The re
sulting melt is poured'into alcohol. The precipi
tate so formed is ?ltered‘ and washed. wellwith‘
The product,. p:p'-di(6-methylbenz
about 90° C. and treated with'100 parts of eth.-_
anol. The ‘brown solid p_:'p'-di(6-methylbenz
thiazyl) azobenzene -di(Nébenzyl-fl-thiocyanosul
phonanilide)) is?ltered off and washed with,
ethanol and Water.
lide) which is a yellowish-brown powder, is boiled
The above product is hydrolysed by boiling
for 14 hour with 50 parts of alcohol and 5"parts
with 100 parts of ethanol containing 10 parts of.
of‘ sodium sulphide crystals, a brownish-yellow‘
sodium sulphide crystals to :the corresponding
solution of the disodium salt of the ‘correspond 30. di (N - benzyl - 4 - mercaptosulphonanilide) . The
ing‘ p : p'-di ( G-methylbenzthiazyl) azobenzene-di
clear brown solution of the latter compound is
(mercaptosulphonanilide) being obtained‘. This is
then oxidised to the corresponding polydisulphide
diluted with water, and oxidised by' the addition
v by the addition of. vsodium m-nitrobenzene sul
of sodium m-nitrobenzene sulphonate at the boil
phonate at the boil-as in'Example 2. The yellow
until no more precipitation of the polydisulphide 35 precipitate of polydisulphide is ?ltered o?, washed‘
voccurs. The bright'yellow suspension is ?ltered,
and dried.‘ It’dyescotton (with airoxidation) .
washed with water and dried. This yellow pow
in yellow shades of .Verygood fastness proper
der dissolves in‘dilute sodium sulphide solution,
ties from boiling dilute ‘sodium sulphide solu
from which cotton is dyed in brownish-yellow
', Emample 6
shades, which on oxidising in air, become bright 40: tions. ‘ I ‘
5 parts of p:p’¢di(6-methylbenzthiazyl)azo-I
Example 3
L _ .
benzene disulphonyl chloride (made as described
10 parts of p:p’-di(Gemethylbenzthiazyl)azo
below), 10 parts of p-thio'cyanoaniline and 18'
benzene disulphonyl chloride ‘(made as described
parts of nitrobenzene are .heated with stirring at
in Example 1), .10 parts of 2-methoxy-4-thiocy
an'oanilineand 25 parts of dry nitrobenzene are
heated together, with stirring, at 130° C.»_for 2
hours. The mixture is diluted with 100 parts of
ethanol and the brownish-yellow precipitate ?l-.
tered'o? and washed with ethanol and water.
The so-obtain'ed p : p’--di ( 6y-methylbenzthiazyl) ‘-'
.' 130-135° C. for 11/2 hours.- ‘After cooling to 90
100° C., 200 parts of ethanol are ‘added and the
. yellow p : p’-di(6;methylbenzthiazyl) azobenzene;
di(4-thiocyanosulphonanilide) ?ltered on‘ and
_washed-with ethanol.
‘ The
above -di(4-thiocyanosulphonanilide)
hydrolysed by'boiling with 50 parts of ethanol
and 5 parts of sodium'sulphide‘ crystals for 11/;
hour to the corresponding di(4'-mercaptos_ulphon-'
azobenzene - di)(2’-methoxy- 4v-thiocyanosulphon
anilide) is hydrolysed by boiling with 100 parts of
ethanol and 10 parts of sodium sulphide crystals
anilide) By oxidising the latter by the addition
for 1Ahour‘ to the corresponding di(2-methoxy- " ‘of sodium. nitrobenzene sulphonate at the boil‘
4-mercaptosulphonanilide) .
The clear brown
the corresponding polydisulphide is obtained as‘a
solution of the sodium salt of the latter compound
is diluted with 500 parts of water and oxidised to
the correspondingpolydisulphide either (a) by
addition of sodium m-nitrobenzene sulphonate at
the boil ‘asin Example 2 or (b) by aeration in
the cold as in Example 1. The'polydisulphide is
?ltered 017T, washed'and dried.
¢ , Both the polydisulphide and the di(2’—'methoxy
dye cotton from
aqueous . sodiumv sulphide solutions ,in' brownish
yellow shadeswhich on oxidising in the air be
yellow solid. Itis ?ltered off, washed with water
and dried. It dissolves in dilute aqueoussodium"
from which
which' become‘
cotton ‘isondyed
tion in the air and have good fastness proper~
p: p’ -di ( G-methylbe'nzthia‘zyl) ‘azobenz‘ene
disulphonchloride used above'is preparedasfiol
lows: 10 parts of p:p'-di(6-methylbenzthiazyl);
azobenzene are added'to 65' parts of‘ 20% voleum
_ during 10 minutes with stirringat 25° C." Stirring
is continued for 5 vminutesi'andltl‘ partsof 65%
come bright yellow. Theshades possess very,
oleum are added. . Thef'sulphonatio‘n mixture is
good 'fastness. to severe washing, chemick and
70 stirred at 25° C. until a sample is? readily and
' good .fastness to light.
completely soluble in dilute ammonia ; (‘one shak
ing vfor 10-15 minutes) and, pouredpn'tqjice.
5 parts of p:p'-di(6-methylbenzthiazyl) and
The: yellow’ precipitatev of the ,Ysulphonic‘ acid "is
benzene disulphonyl chloride (made as in Ex
ample ‘1),- and 10 parts of 2:5-dichlbro-4-thioi-1
?ltered ' off, washed with salt solutionj until ~vfree
‘from acid and dried. 15 parts cums sulpho‘nic' ‘ i
' 3
acid (passed through 100 mesh sieve), 100 parts
‘brownish-yellow precipitate ?ltered o?
of phosphorus pentachloride and 25 parts of
phosphorus oxychloride are heated with stirring
washed with ethanol and water.
The above product (p:p'-di(6-methylbenz
thiazyl) azobenzene-di(2 - methoxy-‘l-thiocyano
_in an oil bath at 161-l65° C. for 3 hours. After
sulphonanilide)) is hydrolysed to the correspond
ing mercapto compound and oxidised to the poly:
cooling overnight, the pasty mass is )added
gradually to crushed ice. The precipitated sul
phonchloride is ?ltered o?, washed thoroughly
with water and then with acetone and dried at
80° C.
Example 7 ‘
and ‘
disulphide as described in Example 3.
It dis-
-1 ,
solves readily in boiling dilute aqueous sodium
sulphide from which solution cotton is dyed in
10 yellow shades of very good fastness properties.
1. A‘sulfur dye made by heating a p:p'-di(6-v
5 parts of pzp’—di(6-methylbenzthiazyl)azo
methylbenzthiazyl) azobenzene - di(4- thiocyano
benzene disulphonchloride (made as described in I
Example 6), 10 parts of p-thiocyano-N-methyl- j
sulfonanilide) in a non-aqueous organic solvent
aniline and 18 parts of ‘dry _nitrobenzene are 15 with sodium sul?de until by hydrolization thev
corresponding di(4-mercaptosulfonanilide) is
heated at 130-135° C. for 1% hours. The mix
formed and then oxidizing ‘until the correspond
ture is ‘diluted with 200 parts of ethanol‘and the
ing polysul?de is formed.
(p: p’-di(6-methylbenzthiazyl) azobenzene -di(N-methyl - 4 - thiocyanosulphon-
2. A sulfur dyetmade by heating p:p'-di(6
anilide)) ?ltered off and washed with ethanol 20
methylbenzthiazyl) azobenzene -di(2~methoxy-4
and water.
thiocyanosulfonanilide) in a non-aqueous or
The di(N-methyl-4-thiocyanosulphonanilide)
is hydrolysed by boiling with 50 parts of ethanol
ganic solvent ‘with sodium sul?de until by
hydrolization the corresponding di(4-mercapto
and 5 parts of sodium sulphide crystals for %
hour to the corresponding mercapto compound.
After‘ dilution with 500 parts of_ water, the solu
sulfonanilide) is formed and then oxidizing un-
tion is oxidised with sodium m-nitrobenzene sul
phonate at the boil (as in Example 2). The pre
4-thiocyanosulfonanilide) in a noneaqueous or
‘ i
3. A sulfur dye made by heating p:p'—di(6
methylbenzthiazyl) azob enezene-di (2-75'-dichloro-"
ganic solvent with sodium sul?de vuntil by
cipitated polydisulphide is ?ltered off, washed
hydrolization the corresponding di(4-'mercapto_
and dried. It is a yellowebrown powder, readily 30 sulfonanilide) is formedand' then oxidizing un
. soluble in aqueous sodium sulphide, from which
til the corresponding polysul?de is formed.
solution cotton is dyed in yellow shades, which
4. A sulfur dye made by heating p:p’-di(6
become brighter on oxidation in the air and have
methylbenzthiazyl) azobenzene - di(4 - thiocyano
good fastness properties.
Example 8
5 parts of p:p’-di(6-methylbenzthiazyl)azo
sulfonanilide) in a non-aqueous organic ‘solvent
35 with sodium sul?de until by hydrolization the .
corresponding di(ll-mercaptosulfonanilide) ' is
formed and then oxidizing until the correspond
benzene disulphonyl chloride (made as described
in Example. 6), 10 parts of p-thiocyano-N
ing polysul?de is formed.
5. The process of making a sulfur dye which
benzylaniline and 18 parts of vdry nitrobenzene 40 comprises heating a p:p'-di(6-methyl-'benz
are heated in an oil bath at 130-135° C. for 11/2
thiazyl) azobenzene-oi(4-thiocyanosulfonanilide)
hours. The dark coloured mixture after cooling
to 90—100° C. is treated with 200 parts of ethanol
_1 with sodium sul?de in a non-reactive liquid. or
ganiclsolvent until the corresponding p:p’-di(6
> and the brown precipitate- (the N-benzyl-4
methyl-benzthiazyl) azobenzene-diUi '- mercapto
thiocyanosulphonanilide) ?ltered off and washed 45 sulfonanilide) is formed, and then adding water -.
with ethanol and water. It is hydrolysed to the
and an oxidizing agent until the corresponding
corresponding mercapto compound and the lat
polydisul?de is formed.
ter oxidised to the polydisulphide as described
.6. Thepprocess in accordance with claim 5
in Example 5. The polydisulphide dyes cotton ' in which p:p'-(6 -‘- methyl -‘- benzthiazyl) azoben
from solution in aqueous sodium sulphide in yel 50 zene-di(2-methoxy-4-thiocyanosulfonanilide)
low shades of very good fastness to severe wash
ing, chemick and good fastness to light.
Example 9
5 parts of p:p'-di(6-methylbenzthiazyl)azo
benzene sulphonchloride (made as described in
heated with sodium sul?de.
7. The process in accordance ‘with claim 5
in which p:p’-(6 - methyl '- benzthiazyl) afzobene
zene-di(2-5-dichloro-4-thiocyanosulfonanilide is
55 heated with sodium sul?de.
Example 6), 7 parts of 2-methoxy-4-thiocyano
aniline and 18 parts of dry nitrobenzene are
heated at 125-30° C. for 2 hours and then at
135-40° C. for % hour. After cooling, the melt 60
is treated with 200 parts of ethanol and the
8. The process in accordance with. claim 5
in which p:p’-(6 - methyl - benzthiazy1)azoben-'
zenejdi(4-thiocyanosulfonanilide) is heated‘ with
sodium sul?de and the organic solvent is‘ alcohol; '
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