Polycyclic dyes

Details Polycyclic dyes Polycyclic dyes

2001-09-25

2002-10-08

Owens, Amelia (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C008S578000

Reexamination Certificate

active

06462204

ABSTRACT:

This invention relates to polycyclic dyes, especially 3,7-diphenyl benzodifuranone dyes.
EP-A-0363034 discloses the preparation of 3,7-diphenyl benzodifuranone dyes and EP-A-0469723 discloses the use of such dyes in thermal transfer printing. The dyes disclosed in EP-A-0363034 have the general formula.
wherein
W is —NR
1
R
2
or —OR
3
R
3
is H or an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group;
each of R
1
and R
2
independently is H, or an optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl group; or
R
1
and R
2
together with the nitrogen atom to which they are attached form a heterocyclic ring; or
R
1
or R
2
together with the nitrogen atom and the adjacent carbon atom of Ring B form a heterocyclic ring;
Ring A is unsaturated or is substituted by from one to three groups
Ring B is unsubstituted, apart from the group W, or is substituted by one or two further groups;
each of Z
1
and Z
2
independently is —O—, —S— or —NY— in which Y is H, an optionally-substituted hydrocarbon group or an acyl group; and
each of X
1
and X
2
, independently, is hydrogen, halogen, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH and carboxylic acid esters.
One of the many groups additional to the group W which may be substituted on the Ring B is a hydroxyalkyloxy group.
EP-A-0492893 discloses a mixture of dyes each of the formula
wherein
each of R
1
and R
2
independently is hydrogen, nitro, halogen, C
1-6
-alkyl, C
1-6
-alkoxy, phenyl, phenoxy, C
1-6
-alkoxyphenyl, cyano, —COOR and —SR, hydroxy, OCO.C
1-6
-alkyl, —SO
2
OH, —SO
2
Cl, —SO
2
C
1-6
-alkyl, —NR
2
and —CONR
2
, —OC
1-6
-alkyl-COOR
5
, —OC
1-6
-alkylOR
5
, —OC
1-6
-alkylOR
5
OR
5
, and —OC
1-6
-alkylOCOR
5
, —OC
2-6
-alkenyl, —OC
1-6
alkyl-Z, —OC
1-6
-alkylOC
1-6
alkyl-Z and —OC
1-6
-alkylSC
1-6
-alkyl-Z in which Z is a 5-, 6- or 7-membered saturated or unsaturated heterocyclic residue; and
each of R
3
, R
4
, R
5
and R
6
, independently, is hydrogen, C
1-6
-alkyl, halogen and C
1-6
-alkoxy,
in which each R independently is —H, C
1-6
-alkyl or phenyl and
in which each R
5
independently is H, C
1-6
-alkyl, —C
1-6
-alkyl-C
1-6
-alkoxy or phenyl except where the mixture contains one compound of Formula (XI) in which R
2
is —OC
2
H
5
and R
1
, R
3
, R
4
, R
5
and R
6
are all absent, one compound of Formula (XI) in which R
2
is n-propoxy and R
1
, R
3
, R
4
, R
5
and R
6
are all absent and 4-[1-cyano-methyl-4,5-dicyano imidaz-2-ylazo] N-ethyl-N-(ethoxycarbonyl-propyl)amino-benzene.
EP-A-0371223 discloses a range of 3,7-diphenyl benzodifuranone dyes of the formula
wherein
each of A and B, independently, is hydrogen, a C
1
-C
4
alkyl group or a C
1
-C
4
alkoxy group;
Y is hydrogen, a C
1
-C
4
alkyl group, a C
1
-C
4
alkoxy group or a group of the formula —O—R
2
—X—R
1
,
or Y and B are taken together with each other to form a methylenedioxy group;
R
1
is a C
1
-C
4
alkyl group, a phenyl group or a C
3
or C
4
alkenyl group; R
2
is an ethylene group unsubstituted or substituted by a methyl, methoxymethyl or ethoxymethyl group, a propylene group unsubstituted or substituted by a hydroxy, C
1
-C
4
alkylcarbonyloxy or methyl group, or a C
4
-C
8
alkylene group unsubstituted or substituted by a hydroxy, C
1
-C
4
alkylcarbonyloxy or C
1
-C
4
alkoxy group; and
X is a divalent group of —O—,—S—,—SO—,—SO
2
— or —N(R
3
)— in which R
3
is a hydrogen atom or a C
1
-C
4
alkyl group;
with the proviso that when X is a divalent group of —O— or —S— and Y and B are not taken together with each other to form a methylenedioxy group, and when R
2
is an unsubstituted ethylene or unsubstituted propylene group, R
1
is a C
3
or C
4
alkyl or alkenyl group, or a C
1
-C
4
alkyl group, respectively. In such dyes, the group —O—R
2
—X—R
1
may be an alkoxyalkoxy group.
Surprisingly, we find that 3,7-diphenyl benzodifuranone dyes having a hydroxyalkoxy group at the 4-position of at least one of the 3- and 7-phenyl groups show improved levelling properties as compared with the corresponding dyes containing a 4-alkoxy groups and improved build up as compared with the corresponding dyes containing a 4-hydroxy group.
Thus, the present invention provides a polycyclic dye of the formula (I)
wherein
each of R
1
, R
2
, R
4
and R
5
, independently, is hydrogen, alkyl or alkoxy;
R
3
is hydrogen, alkyl, optionally substituted alkoxy or amino; and
Y is a straight or branched C
1-8
alkylene group.
The alkyl group or the alkyl moiety of the alkoxy group of each of R
1
-R
5
is preferably a C
1-6
alkyl, more preferably a C
1-4
alkyl group or moiety. A C
1-4
alkyl group or moiety can be straight-chained or branched and be for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.butyl or tert.-butyl.
Preferably, ih the formula (I),
each of R
2
, R
4
and R
5
is hydrogen;
R
1
is hydrogen, methyl or ethyl;
R
3
is hydrogen, alkyl or alkoxy; and
Y is a straight or branched C
2-5
alkylene group.
Especially preferred 3,7-diphenyl benzodifuranone dyes have the respective formulae (Ia), (Ib) and (Ic)
In another preferred range of dyes within the formula (I), R
3
is a substituted alkoxy group
(a) of the formula —OR
6
CO
2
R
7
OR
8
, wherein each of R
6
, R
7
and R
8
independently is a straight or branched C
1-6
alkylene group; or
(b) of the formula —OR
9
OH, wherein R
9
is a straight or branched C
1-8
alkylene group; or
(c) wherein the substituent is a tetrahydrofurfuryl or tetrahydropyran-2-ylmethyl group, an especially preferred substituted alkoxy group being the fur-2-ylmethoxy group.
A 3,7-diphenyl benzodifuranone dye of the formula (I), defined above, may be prepared, in accordance with a process aspect of the invention, by a process which comprises reacting a compound of the formula
wherein
each of R
3
, R
4
and R
5
is as defined above, with a mandelic acid derivative of the formula
 wherein
A is hydroxyl, (C
1-4
alkyl) carbonyloxy or halogen;
B is hydrogen, C
1-4
alkyl or aryl;
R
10
is a C
1-4
alkyl or phenyl group; and
each of R
1
, R
2
and Y is as defined above to form a 2,6-dioxo-2,3,6,7-tetrahydro benzodifuranone derivative (IV) oxidising the derivative (IV) to obtain the corresponding 2,6-dioxo-2,3-dihydrobenzodifuranone derivative (V) and deacylating the derivative (V) to provide the polycyclic dye of the formula (I).
Halogen is preferably fluorine, chlorine or bromine. Aryl is preferably phenyl or substituted phenyl.
Especially preferably, in the formula (III), A is hydroxyl, B is hydrogen and R
10
is methyl.
The reaction of the compound of the formula (II) with the mandelic acid derivative of the formula (III) is preferably carried out in the presence of an acid catalyst, e.g. sulphuric acid, p-toluene sulphonic acid or dodecylbenzene sulphonic acid, and preferably at a temperature of from 50 to 70° C. and preferably for a period of from 3 to 5 hours.
The oxidation reaction is preferably carried out at a temperature of from 40 to 60° C. and preferably from a period of from 15 to 45 minutes. Especially preferred oxidising agents are chloranil, hydrogen peroxide and ammonium persulphate.
The deacylation treatment is preferably carried out at a temperature of from 80 to 100° C. and preferably for a period of from 2 hour to 2 hours, and more preferably in a polar solvent such as 2-ethoxyethanol or dimethyl formamide. An especially preferred deacylating agent is hydrochloric or sulphuric acid.
An alternative process for preparing a polycyclic dye of the formula (I), given and defined above, comprises reacting a compound of the formula
wherein
each of R
1
, R
2
, R
3
, R
4
and R
5
is as defined above; with an alkylating agent of the formula
 wherein
Y is as defined in above;
R
10
is a C
1-4
alkyl or phenyl group; and
X is a halogen atom;
to obtain an acyl-2,6-dioxo-2,3,6,7-tetrahydrobenzodifuran derivative of the formula
 wherein
each of R
1
, R
2
, R
3
, R
4
, R
5
, R
10
and Y is as defined above; and deacylating the derivative (VIII) to provide the polycyclic dye of the formula (I).
Preferably, in the formula (VII), X is bromine and R
10
is

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