Note: Descriptions are shown in the official language in which they were submitted.
Case 150-3698
106~3263
IMPROVEMENTS IN OR RELATING TO ~RGA~IC COMPOUNDS
: The invention concerns disazo compounds.
The invention provides compounds of formula I,
R3 R4
"~"~N = N~ ~ R2 ~ ~ N R~2 ~ N--N_"~
I lol lol 11 To~ loTol
: ~ R N N N~ ~ R ~
(~O3M)n \ 1 H H 11 / (SO3M)
~SO3M)m 1 (SO3M)p-l
.~ in which Rl and Rll, independently, are hydrogen,
r~ methyl, methoxy, chlorine, -N~COCH3
; 5 or -NHCONH2,
,,~ ,
! R2 and Rl2, independently, are hydrogen,
~A, methyl or methoxy,
R3 is hydrogen, C1 4alkyl, hydroxy-C2 3-
alkyl or hydroxy-(C2 3alkoxy)-C2 3-
alkyl,
R4 is Cl_4alkyl~ hydroxy-c2-3-alkyl or
~: hydroxy (C2_3alkxY)-c2-3-alkyl~
the M's, independently, are hydrogen, li~hium,
sodium, potassium, NH4~ NH2R3'R4' or
; NR5R6R7R8~
. . ~ 15 R3' and R4', independently therefrom, have
the significances of R3 and R4~ above,
respectively,
R5 is hydrogen, Cl 4alkyl or hydroxy-C2 3-
~ : alkyl,
,''~ ' :
1068Z63
- 2 - 150-36~8
-
R6, R7 and R8, independently, are
Cl 4alkyl or hydroxy-C2 3alkyl, and
m, n, p and q, independently, are 1 or 2.
The Cl 4alkyl groups in the compounds of formula
I are preferably methyl or ethyl, particularly the former.
Any hydroxy or hydroxyalkoxy substituent on any
C2 3alkyl radical or moiety is on the 2- or 3-position thereof.
-; The preferred hydroxyalkyl radicals are 2- and 3-hydroxypropyl
:
and 2-hydroxyethyl, particularly the latter. The preferred
hydroxyalkoxyalkyl radical is 2-(2'-hydroxyethoxy~-ethyl.
,................................................................... ~
Y The preferred M's are sodium, lithium, ammonium
....
and diethanolammonium. The preferred significances of Rl and
~
~11 are hydrogen and methyl, particularly hydrogen. The
preferred significances of R2 and R12 are hydrogen and
methoxy, particularly hydrogen.
Preferably at least one of R3 and R4 is hydroxy-
alkyl or hydroxyalkoxyalkyl, the preferred significances of
R3 being hydrogen, methyl and 2-hydroxyethyl and those of R4
being 2-hydroxyethyl, 2- or 3-hydroxypropyl or 2-~2'-hydro~y-
ethoxy)-ethyl. It is also preferred that R3 and R4 are
identical; thus in the most preferred compounds, R3 and R4
, " ~
`~ are both 2-hydroxyethyl.
R ~ R and Rn preferably are the same.
6 7 ~
Where a single sulpho group is borne by either of
25~ the naphthyl radicals, such is preferably in the 6-position
thereof.~ Where two sulpho groups are borne by either of the
naphthyl radicals, such may, for example, be borne on
positlons~ 1,5; 1,6; 1,7; 3,6; 3,7; 3,8; 4,7; 4~8; 5,7 or 6,8;
~3~
;,~
-- 1068263
- 3 - 150-3698
the preferred positions being 4,8; 5,7 and 6,8, particularly
positions 4,8 and 6,8.
Where three sulpho groups are borne by either
of the naphthyl radicals, such may, for example, be in
; 5 positions 3, 6, 8 or 4, 6, 8.
The preferred compounds of for~ula I bear a total
~ of four sulpho groups.
.. In the compounds of formula I, the two naphthyl-
azo phenyl amino groups are preferably identical, i.e. Rl
and Rll, R2 and R12 and the number and positioning of the
.~ sulpho group(s) in each naphthyl nucleus are preferably the
, .
same.
As a preferred class of compounds of formula I
., .
may be given the compounds of formula I'~
N= N ~ NH - 1 N~0
3M)3 t 3 )t-l ~2
. ., .:
`~; 15 wherein M is as defined above,
, .
Rl' is hydrogen or methyl, preferably
hydrogen,
R2' is hydrogen or methoxy, preferably
hydrogen,
R3" is hydrogen, methyl or 2-hydroxyethyl,
.,.~ .
, . .
::J
~s~
.;,,1, .
,;': .
1068Z~3
4 ~ 150-3698
R4 n is 2-hydro~yethyl, 2- or 3-hydroxy-
: propyl or 2-(2'-hydroxyethoxy)-ethyl,
preferably 2-hydroxyethyl,
t is 1 or 2 and the sulpho groups are
, 5 ln positions 4,8; 5,7 or 6,8, preferably in positions 4,8 or
6,8.
. The invention also provides a process for the
production of compounds of formula I, comprisin~ reacting,
.~
` in any desired order, a cyanuric halide with an aminoazo
compound of formula II,
.. .
~:, R
~ ,~N N~N1~2 II
3 n ~S03M)m_l
an aminoazo compound of formula III `
N1l2 III
(S03M~q (S03M)p_l
and with an amine. HNR3R4 IV.
The preferred mol ratio of cyanuric halide :
compound II : compound III : amlne HNR3R4 is 1 ~
5 ~ The~above process may be carried out in conven-
tlonal manner. The preferred cyanuric halides are the
, ~: . ~ , : : ` `
-- 1068263
_ 5 - 150-3698
chloride and bromide, particularly the former. For the
first reaction between the cyanuric halide and a compound II,
III, or IV a suitable temperature is from 0 to 20C, prefer-
ably 20C and a suitable pH is from 3 to 6. For the second
reaction (exchange of the second halogen on the cyanuric
halide) a suitable tempera~ure is from 20 to 70C, prefer-
ably 60 to 70C, a suitable pH being from 5 to 7. For the
third reaction, the temperature is suitably from 70 to
` 105C, preferably 95 to 100C, and the pH from 5.5 to 7.5.
In the preferred sequence of reaction, the amine
: .,,
IV is reacted finally with the compound V
r~
Hal R
R~ ~ N 12
, ~ N=N ~ ~ N ~ ~ N=N- ~ ~sO3M) V
~ (SO3M)n (S03M)m-1 (S03M)p-l
~ in which Hal signifies a halogen atom, prefer-
~ ably chlorine or bromine, more
. ,', . .
preferably the former.
This sequence is particularly preferred where the compounds
II and III are identical, i.e. compound V is symmetrical.
In this case, compound V is conveniently produced by simul-
taneous reaction of the cyanuric halide with two mols of
compound II or III, suitably under the conditions above
5 - -
, ;~
, 1, ~ ;,
- 1068Z63
- 6 ~ 150-3698
; described for replacement of the second halogen of the
cyanuric halide.
- The compounds of formulae II, III and IV are
either known or may be obtained in conventional manner from
available starting materials.
The resulting compounds of formula I may be iso-
lated and purified in conventional mannex.
As will be appreciated, where the compound of
formula I is obtained in free acid form, such may be con-
verted into salt form, and vice versa, as desired, as can
interconversion from one salt form to another.
The compounds of formula I wherein at least one
and preferably all the sulpho groups are in 0NH2R3R4 form
~.~
;; are advantageously prepared by reaction of an appropxiate
.,
amine IV with the compound of formula V in free acid form,
the amine IV being employed in an amount sufficient for
~... .
~ both replacement of the halo atom in the compound V and
., .
neutralisation of the free sulpho group(s) therein. Such
process is particularly preferred when the amine IV is
~i .~3` ~ ~ . 20 ~ an alkanolamine or hydroxyalkoxyalkylamine, since such
enables the direct production of agueous liguid preparations
of the compounds of formula I, particularly where the
J,~ a1kanolamine or hydroxyalkoxyalkylamine is employed in
excess, the excess being present in the final liquid
preparation and serving as solubilising aid for the com-
pound of formula I.
., ~
x~
, , ~ .
--~ 106~3Z63
- 7 - 150-3698
The compounds of formula I are anionic dyes and
are useful for dyeing anionic dyeable substrates, such as
cellulosic substrates, e.g. cotton and particularly paper,
and leather. The substrates may be dyed in conventional
manner, employing conventional amounts of dyestuff.
The good water solubility, even in cold water, of
the compounds of formula I, particularly when in salt form,
makes them eminently suitable for use in aqueous liquid
, dyestuff preparations, which have particular utility in the
,~ 10 paper dyeing industry. Such liquid dyestuff preparations
s ~ may be prepared in conventional manner and contain conven-~J tional additives such as solubilising aids and stabilisers,
i;~ .
e.g. alkanolamines, diglycolamines and acid amides, such as
formamide and dimethylformamide, and urea. Such liquid dye-
- 15 stuff preparations, as is normal, preferably have a low
.,.
~$~ salt content, to which end, any press-cake employed for
their production should preferably have as low a salt con-
..
~ tent as possible, i.e. only the minimum amount of salt fox,~
salting out the compounds should preferably be employed.
, ~
Typical dyestuff preparations contain the following:-
; 100 parts by-weight compound of formula I or
mixture thereof,
. ~ ~ ~
100, preferably 1-10, parts by weight salt,
; 100-800 parts by weight water,
0-500 parts by weight of a solubilising agent
(alkanolamine, hydroxyalkoxyalkylamine, e.g.
1 ~ ~
.~:
- ~ 1068263
~ - 8 - ` 150-3698
.~ .
of formula IV, acid amide, e.g. formamide or
dimethylformamide), and
~; urea in an amount up to 30~ by weight of the
water contained in the preparation.
The liquid aqueous preparations may be suspensions
or, preferably, true solutions, which solutions may be
obtained either by employing such amounts of the ingredi-
.;, .
ents as to obtain a true solution or by filtration of a
solid-containing solution. ~3
,~ 10 The compounds of formula I are also suitable for
.. i .
incorpOration in solid dyestuff preparations, preferably
,, .
granulate preparations in which the average particle size
is greater than 20~u. Again, the salt content is prefer-
ably kept low. Typical solid dyestuff preparations contain
the following:-
~,~ 100 parts by weight compound of formula I or
mixture thereof,
100, preferably 1-10, parts by weight salt
0-800 parts by weight extender, e.g. starch,
20~ starch degradation products, dextrin, urea,
soda, sugar, etc.
0 to 10% by weight residual moisture.
Such~granulate preparations are conveniently prepared by
; homogenising the dyestuff in press-ca~e form (i.e. contain-
~ y~
~ 25 ing salt) with any extender, in water, and then spray
~ ,~ ,. ..
-- 1068263
- 9 - 150-3698
drying.
The above-described liquid and solid dye prepara-
tions show good storage stability.
On paper, the compounds of formula I give yellow
to reddish yellow dyeings of good fastness to water and to
.,
milk, fruit juices, sweetened mineral waters and alcohol.
The dyed papers may be bleached using either oxidative or
reductive techniques, which is of advantage in paper re-
cycling. The dyeings are brilliant in hue and show good
i'
~, 10 fastness to light, any fading upon prolonged exposure to
`,~ light belng tone-in-tone. The dyes do not produce mottled
e~fects and are largely unaffected by pH. They may be
employed in the dyeing of paper in their dry form, i.e.
,~
added to the stock in powder or granule form without prior
dissolving and without loss of brilliance or yield.
Paper can, of course, be dyed after sheet forma-
. tion, preferably before sizing, as well as in the stock.
The following Examples, in which all temperatures
are in degrees Centigrade, illustrate the invention.
,: ~
? ~ ~
1068263
- 10 - 150-3698
EXAMPLE 1:
81.4 Parts of the aminoazoic dye, produced by
weak acid coupling of diazotised 2-aminonaphthalene-5,7-
disulphonic acid with aniline-~-methane-sulphonic acid,
S followed by cleavage of the ~ -methane-sulphonic acid
group in alkali solution, are dissolved in 300 parts
water. 18.5 Parts cyanurochloride are added in small
amounts to this solution at 20, the pH being kept at 6 -
6.5 by the addition of sodium carbonate. On completion of
the reaction, the temperature is increased slowly to 60 -
70 and the second condensation starts. The pH is again
kept at 6 - 6.5. After approximately 2 hours the reaction
is practically complete. The pH is adjusted to 7 and 20
parts diethanolamine are added. The whole is then heated
to 9S - 100 and left to boil at this temperature for 3
hours. It is then cooled to 80 and 20 percent by volume
` sodium chloride is added. The whole is stirred cold and
the precipitated dye is filtered off with the aid o~ a
~-~ vacuum. When dry, the dye is distinguished by extremely
good solubility in cold water. It dyes paper and cellu-
losic fibres a yellow shade and is of formula:-
;'.~i
.' ~
'~:
.', ~ `
i~ .
, .
.. --10--
J
'i .
: `
1068Z63
~ - 11 - 150-369~'3~ 1
.~ ~
~':
, ' I .~:
HOCH2CH2 CH2CH2H ~:
NaO3S~ ~ ~NH ~ N 1 ~1 ~ ~ S03Na
S03Na S03Na . .
.-
EXAMPLE 2: :
: -
~., .
Following the procedure of Example 1 but employ- .
` ing an aminoazoic dye obtained employing diazotised 2~amino ¦
.,., .~
naphthalene-4,8-disulphonic acid in place of diazotised
2-amino naphthalene-5,7-disulphonic acid, a final dye having :
substantially the same properties as the final dye of ~ -
., Example 1 is obtained.
,.~ .
~ l .
EXAMPLES 3 T0 7: .
Following the procedures of Examples 1 or 2
above, but replacing the`20 parts diethanolamine by
a) 12 parts m~noethanolamine,
:.~
b~ 15 part5 N-methyl ethanolamine,
c) 20 parts 2-(2'-hydroxyethoxy)ethylamine,
d) 15 parts 2-hydroxypropylamine, or
15: e~ 15 parts 3-hydroxypropylamine,
~7'~ there are obtained dyestuffs of similar properties to
hose produced in Examples 1 and 2.
.'`1:~
.
, . . .
~068263
.
~ 150-3698
The following Table shows appropriate diazo
components and coupling components which are employed for
production of the starting aminoazo dyestuffs which may
be employed in similar way to the aminoazo dyestuff
starting materials used in the preceding Examples.
Exam- Diazo component Coupling component
` ple (diazotised
. No. amine)
:. 8 2-amino naphtha- 1-amino-2-methoxybenzene
; lene-5,7-disulph-
,, onic acid .
;' 9 ll 1-amino-3-methylbenzene
. 10 ll 1-amino-2-methoxy-5-methyl-
., benzene
.~ 11 ll 1-amino-2,5-dimethyl benzene
., 12 ll 1-amino-3-chlorobenzene
13 . . 3-aminoacetanilide
14 3-aminophenyl urea
.l 1-amino-2,S-dimethoxy benzene
16 2-amino naphtha- aniline
lene-6,8-disulph-
,~ ~ onic acid .
17 n 1-amino-2-methoxybenzene
18 ll 1-amino-3-methylbenzene
: 19 ll 1-amino-2-methoxy-5-methyl-
.J~ : ~ benzene
_.......... . _ l-amino-2,5-dimethyl benzene
. ~ ~
..
~? ~:
J
-' 1068263
- 13 - 150-3698
TABLE (continued)
. .Exam- Diazo component Coupling component
ple (diazotised
No. amine)
21 2-amino naphtha- 1-amino-3-chlorobenzene
: lene-6,8-disulph-
onic acid
22 .. 3-aminoacetanilide
, 2 3 .- 3 -aminophenyl urea
24 .. 1-amino-2,5-dimethoxy benzene
~ 25 2-amino naphtha- 1-amino-2-methoxybenzene
:~ lene-4,8-disulph-
onic acid .
~ 26 ll 1-amino-3-methylbenzene
^.~ 27 ll 1-amino-2-methoxy-5-methyl-
benzene
.3 28 1-amino-2,5-dimethyl benzene
~ 29 .l l-amino-3-chlorobenzene
.. 30 ll 3-aminoacetanilide
9~ 31 ll 3-aminophenyl uxea .
32 ll 1-amino-2,5-dimethoxybenzene
33 2-amino naphtha- aniline
lene-3,6,8-tri-
sulphonic acid
: 34 1-amino-2-methoxybenzene
: ~ 35 ll 1-amino-3-methylbenzene
36 : 1-amino-2-methoxy-5-methyl-
~: ~: :
'.- ~
~; ,
' 13-
1068263
:--
- 14 - 150-3698
T~BLE (continued)
Exam- Diazo component Coupling component
ple (diazotised
No. amine)
; 37 2-amino naphtha- 1-amino-2,5-dimethyl benzene lene-3,6,8-tri-
sulphonic acid
38 ll 1-amino-3-chlorobenzene
,
39 .. 3-aminoacetanilide
. 40 ll 3-aminophenyl urea
41 .. 1-amino-2,5-dimethoxy benzene
42 2-amino naphtha- aniline
lene-4,6,8-tri-
., sulphonic acid
43 ll 1-amino-2-methoxybenzene
44 ll 1-amino-3-methylbenzene
'. 45 1-amino-2-methoxy-5-methyl-
. benzene
~' 46 " . 1-amino-2,5-dimethyl benzene
;~ ~ 47 n 1-amino-3-chlorobenæene
48 ll 3-aminoacetanilide i~
. 49 .l 3-aminophenyl urea
. 50 ~ 1-amino-2,5-dimethoxybenzene
51 2-amino naphtha- aniline
lene-6-sulphonic
acid
~ 52 . 1-amino-2-methoxybenzene
s ~
d~: \
"'~''~
' !
I
. ~ I
1068Z63
- 15 - 150-3698
TABLE (continued~
Exam- Diazo component Coupling component
ple (diazotised
No. amine)
53 2-amino naphtha- 1-amino-2-methylbenzene
lene-6-sulphonic
acid
54 .. 1-amino-2-methoxy-5-methyl-
benzene
., 1-amino-2,5-dimethyl benzene
56 .. 1-amino-3-chlorobenzene
57 ll 3-aminoacetanilide
58 ll 3-aminophenyl urea
59 1-amino-2,5-dimethoxyben~ene `
,.,
.,~
:
~3 By the procedure of the above Examples symmetrical
compounds of formula I are, of course, produced. By step-
;~ ~
--~ wise condensation of the cyanuric halide, first with one
aminoazo dyestuff and then with a different one, followed
;5 by condensation with the amine IV, asymmetric compounds can
be obtained, e.g. condensation first with the aminoazo
dyestuff 2~amino naphthalene-6-sulphonic acid ~ aniline,~
followed by condensation with the dyestuff 2-amino naphtha-
lene-3,6,8-trisulphonic acid __~ aniline and finally with
' ~ 10 diethanolamine.
t ~ ;
'. -
' .
1068263
- 16 - 150-3698
EXAMPLE 60:
87.5 Parts of an aminoazoic dye, produced by
diazotisation of 2-amino naphthalene-4,8-disulphonic acid
and coupling to l-amino-2-methoxybenzene, are stirred into
500 parts water at 20 and 18.5 parts cyanurochloride are
then added in small amounts. During this time, the pH is
kept at 6 - 6.5 by the addition of sodium carbonate. On
completion of the reaction, the temperature is slowly
increased to 60 - ~0 and the pH is again kept at 6 - 6.5
until the reaction has finished. Sufficient 30~ hydro-
chloric acid i5 then added to bring the pH down to below 1.
After stirring cold, the completely precipitated disazo
dye is filtered off and washed with 2% hydrochloric acid
solution.
;~ 15 20 Parts of the disazo dye obtained are well
stirred, in the form of a strongly acid, approximately 50%,
presscake, with 45 parts water until a fine suspension is
achieved. The suspension is then neutralised to a p~ of
7 with 20 parts diethanolamine and a further 4 parts
; 20 diethanolamine are subsequently added. The suspension is
then heated to 95 - 100 and stirred for 1 hour at this
temperature. After this time, all reactions are complete
and a dye solution is obtained. The pH of this solution is
3 ~ approximately 7 - 7.5. The solution is stirred cold and
~ 25~ adjusted to 110 parts with water. In this way, a
;~ 1~ . .
" 10~8Z63
- 17 - 150-3698
concentrated, ready-to-use, true d~e solution is
obtained which, even after a prolonged period, shows no
signs of separating out. The compound is o formula
.
~' ~OCH2CH2 ~CH2CH2oH
~ SO NH (CH~CH~OH)~
(HOCH2CH)2H2N03S . 1 1 3 2
~\~ NH~ N~ ~
(~1CH2cH2)2H2N3 CH30 OCH3 S03NH2(CH2cH20H)2
EXAMPLES 61 AND 62: :
If the procedure is carried out as in Example 60
but 15 parts monoethanolamine or 24 parts 2-( 2'-hydroxy-
.. . .
ethoxy)ethylamine are used in place of 24 parts diethanolamine,
105 parts or 80 parts, respectively, of a stable, concen-
trated true solution are obtained.
.
By the procedure of Examples 60 to 62 but employ-
ing the dyestuffs of Examples 1 to 24 or 26 to 59, can
1 similar liquid concentrated preparations be obtained.
-'t ~ :
EXAMPLE 63:
81.4 Parts of an aminoazoic dye, produced by
lS dlazotisation of 2-amino naphthalene-5,7-disulphonlc acid
and coupling to l-aminobenzene as in Example 1, are dis-
~-; solved in 300 parts water ~y stirring. 18.4 Parts cyanuro- -
chloric acid are then added in small amounts at 20. The
J~
-1
', ~ .
263
- 18 - 150-3698
.
pH is kept at 6 - 6.5 by the addition of sodium carbonate.
On completion of the reaction, the temperature is slowly
increased to 60 - 70 and the pH is again kept at 6 - 6.5
until the reaction is over. 90 Parts of a 30% hydro-
chloric acid are then added so that the pH drops to 1.
After stirring cold, the precipitated disazo dye is
filtered off with the aid of a vacuum.
46.3 Parts of the disazo dye obtained are
dissolved~ in the form of the acid presscake, in 450 parts
,.
water and neutralisea ~lith 8.5 parts lithi~ hydroxide
monohydrate. 10.5 Parts diethanolamine are then added and
, the solution is heated to 95 - 10~. After approximately
3 hours, condensation is complete. In this way, the
`i lithium salt of the dye in Example 1 is obtained and it is
extremely soluble in cold water.
XAMPLE 64:
46.3 Parts of the disazo dye in Example 63 are
; dissolved in 450 parts water and neutralised with 11 parts
potassium hydroxide. 10.5 Parts diethanolamine are then
added and the solution is heated to 95 - 100. After
approximately 3 hours, condensation is complete and 5
percent by volume potassium chloride is added to the
solution. After stirring cold, the precipitated dye is
filtered off with the aid of a vacuum. In this way, the
potassium salt of the dyestuff in Example 1 is obtained.
~i
r.
'i' '~ .~
,,.i,l ~ ~ .
.,~j:
..
1068263
- 19 - 150 3698
. .
Application E~ample A
70 Parts chemically bleached sulphite cellulose
(from pine) and 30 parts chemically bleached sulphite
cellulose (from beech) in 2000 parts water are beaten in a
; 5 Hollander beater. 0.5 Parts of the dye described in
Example 1 are sprinkled into this stock. After a mixing
time of 20 minutes, paper is produced from this stock.
` The absorbent paper obtained in this way is dyed yellow. The waste water is practically colourless.
.
~ 10 Application Example B
`, 0.5 Parts of the dye from Example 1 are dissolved
in 100 parts water. This solution is added to 100 parts
3 chemically bleached sulphite cellulose which has been
beaten together with 2000 parts water in a Hollander
lS beater. After 15 minutes mixing time, siæing is carried
out. The paper produced from this stock is yellow in
il.
~ colour and has very good wet fastness properties.
A~plication Example C
An absorbent paper sheet consisting of unsized
~ paper is drawn at 40 - 50 through a dye solution of the
ollowing composition:
0.5 Parts of the dye from Example 1
0.5 Parts starch and
99 Parts water,
, ~
The excess dye solution is squeeied off by two
. ~
roller. The dry paper sheet is dyed yellow.
