Triazinylaminostilbene derivative as fluorescent whitening...

Details Triazinylaminostilbene derivative as fluorescent whitening... Triazinylaminostilbene derivative as fluorescent whitening...

2002-03-06

2004-04-20

Balasubramanian, Venkataraman (Department: 1624)

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

Organic compounds

Four or more ring nitrogens in the bicyclo ring system

C252S301210, C252S301230, C427S411000, C427S412000, C427S158000, C008S119000, C008S648000, C008S919000

Reexamination Certificate

active

06723846

ABSTRACT:

The present invention relates to new 4,4′-diaminostilbene-2,2′-disulfonic acid compounds which are useful as fluorescent whitening agents or for removing stain in photographic materials.
In WO 96/00221, there are described optical brightening agents for textiles, paper etc. The disclosed compounds have the formula:
in which R
a
and R
b
are the same or different and each has the formula —NR
c
R
d
in which R
c
is hydrogen; C
1
-
6
alkyl which is optionally substituted by at least one of mercapto, C
1
-C
6
thioalkyl, OH and SO
3
M′ in which M′ is hydrogen, a colourless cation or an amine-derived cation; or —R
e
(CO
2
M′)
x
in which R
e
is an aliphatic moiety having 1-6 carbon atoms, those valencies not bonded with groups CO
2
M′ being bonded with at least one of hydrogen, mercapto, C
1
-C
6
thioalkyl, OH and SO
3
M′ in which M′ has its previous significance and x is an integer from 1 to 4, provided that, when R
c
is C
1
-C
6
alkyl which is optionally substituted by at least one of mercapto, C
1
-C
6
thioalkyl, OH and SO
3
M′, R
c
is substituted with at least both of OH and SO
3
M′; R
d
is R
c
, hydrogen or C
3
-C
6
alkyl, provided that R
c
and R
d
cannot both be hydrogen and that, when one of R
c
and R
d
is hydrogen, the other cannot be —(NHCH
2
CO
2
H); or R
c
and R
d
, together with the nitrogen atom, form a ring having from 5-6 members only, one of which is heterocyclic, which ring is singly substituted with —COOM′ or —SO
3
M′; and each R
f
, independently, is hydrogen, methyl, C
1
-C
6
alkoxy or halogen.
Furthermore, WO 98/42685 describes similar compounds having the formula:
in which X is O or, preferably, NH; M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine; each R
1
, independently, is an amino acid residue from which a hydrogen atom on the amino group has been removed; n is 1 or 2; and each R
2
, independently, is hydrogen, C
1
-C
3
alkyl, halogen, cyano, COOR in which R is hydrogen or C
1
-C
3
alkyl, CONH—R in which R has its previous significance, SO
2
NH—R in which R has its previous significance, NH—COR in which R has its previous significance, SO
3
M in which M has its previous significance or, when n is 1, R
2
can also be CO—R
3
in which R
3
is C
1
-C
3
alkyl or phenyl, certain compounds being excluded, and their use as fluorescent whitening agents.
A new class of 4,4′-diaminostilbene-2,2′-disulfonic acid compounds has now been found most of which are useful as fluorescent whitening agents and which have superior properties to, and are more readily prepared than the compounds disclosed in WO 96/00221 and in WO 98/42685. Furthermore, the new compounds are useful for removing stain in photographic materials.
Accordingly, the present invention provides new compounds having the formula:
wherein each
R
1
represents, independently, a linear C
1
-C
4
-alkylene residue which is unsubstituted or substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy- or alkoxy-alkoxy, —OCOM, —OCOC
1
-C
4
-alkyl, or an amino acid residue from which a hydrogen atom on the amino group has been removed; each
R
2
represents, independently, a linear C
1
-C
4
-alkylene residue which is unsubstituted or substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy- or alkoxy-alkoxy, —OCOM, —OCOC
1
-C
1
-C
4
alkyl, —CO
2
M, CO
2
C
1
-C
4
-alkyl SO
3
M or phenoxy which is unsubstituted or substituted by halogen, C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy, —CO
2
M or —CO
2
C
1
-C
4
-alkyl, NH
2
or mono- or disubstituted amino; or phenyl which is unsubstituted or substituted by 1 to 3 SO
3
M, SO
2
NHC
1
-C
4
-alkyl, —SO
2
NH
2
, —CO
2
M, —CO
2
C
1
-C
4
-alkyl —CONH
2
, —CONHC
1
-C
4
-alkyl, —NHCOC
1
-C
4
-alkyl or mono- or disubstituted amino groups; each
R
3
represents, independently, hydrogen, C
1
-C
4
-alkyl, halogen, cyano, SO
3
M, —SO
2
NH
2
, SO
2
NHC
1
-C
4
-alkyl, —CO
2
M, —CO
2
C
1
-C
4
-alkyl, —CONH
2
, —CONHC
1
-C
4
-alkyl, or —NHCOC
1
-C
4
-alkyl;
M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine and
m is an integer of 1 to 3.
Within the scope of the compounds of formula (1) both of the R
1
groups, the R
2
groups and the R
3
groups are preferably identical.
Further preferred compounds of formula (1) are those in which each of the amino acid residues R
1
is the same and each has the formula —NH—CH(CO
2
H)—R
4
in which R
4
is hydrogen or a group having the formula —CHR
5
R
6
in which R
5
and R
6
, independently, are hydrogen or C
1
-
4
-alkyl optionally substituted by one or two substituents selected from hydroxy, thio, methylthio, amino, carboxy, sulfo, phenyl, 4-hydroxyphenyl, 3,5-diiodo-4-hydroxyphenyl, &bgr;-indolyl, &bgr;-imidazolyl and NH═C(NH
2
)NH—.
Particularly useful compounds of formula (1) are those in which the amino acid from which the amino acid residues R
1
are derived is glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hyroxyphenylalanine), diiodotyrosine, tryptophan (&bgr;-indolyalanine), histidine ((&bgr;-imidazolylalanine), &agr;-aminobutyric acid, methionine, valine (&agr;-aminoisovaleric acid), norvaline, leucine (&agr;-aminoisocaproic acid), isoleucine (&agr;-amino-&bgr;-methylvaleric acid), norleucine (&agr;-amino-n-caproic acid), arginine, ornithine (&agr;,&dgr;-diaminovaleric acid), lysine (&agr;,&egr;-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (&agr;-aminoglutaric acid), threonine, hydroxyglutamic acid or taurine, or a mixture or an optical isomer thereof.
Especially preferred compounds are those in which the amino acid from which the amino acid residues R
1
are derived is sarcosine, taurine, glutamic acid or aspartic acid, aspartic acid or iminodiacetic acid being the most desirable.
Further preferred compounds of formula (1) are those in which R
1
is a linear C
1
-C
4
-alkylene residue which is unsubstituted or substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy- or alkoxy-alkoxy, —OCOM, —OCOC
1
-C
4
-alkyl, especially those in which R
1
is a linear C
1
-C
4
-alkylene residue which is unsubstituted or substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy- or alkoxy-alkoxy and, most preferably, those in which R
1
is a linear C
1
-C
4
-alkylene residue which is substituted by hydroxy or C
1
-C
4
-alkoxy, M being as previously defined.
With regard to the residue R
2
, this is preferably a linear C
1
-C
4
-alkylene residue which is unsubstituted or substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy or alkoxy-alkoxy, —OCOM, —OCOC
1
-C
4
-alkyl, —CO
2
M, —CO
2
C
1
-C
4
-alkyl, SO
3
M, phenoxy which is unsubstituted or substituted by halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, —CO
2
M or —CO
2
C
1
-C
4
-alkyl, NH
2
or mono- or disubstituted amino, most preferably, a methylene, ethylene or propylene residue which is substituted by hydroxy, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-hydroxy- or alkoxy-alkoxy, —OCOM, —OCOC
1
-C
4
-alkyl, —CO
2
M, —CO
2
C
1
-C
4
-alkyl, SO
3
M or di-C
1
-C
4
-alkylamino.
Compounds of particular interest are those in which R
2
is hydoxyethyl, hydroxypropyl, ethoxyethyl, hydroxyethoxyethyl, methoxyethoxyethyl, an acetic or propionic acid residue or methyl or ethyl esters thereof, an ethyl or methyl acetate, dimethylaminoethyl or ethyl sulphonic acid or the sodium salt thereof, an hydoxyethyl or a sodium acetate residue being most preferred.
Further interesting compounds are those in which each R
2
is phenyl which is unsubstituted or substituted by 1 to 3 SO
3
M, SO
2
NHC
1
-C
4
-alkyl, —SO
2
NH
2
, —CO
2
M, —CO
2
C
1
-C
4
-alkyl, —CONH
2
, —CONHC
1
-C
4
-alkyl, —NHCOC
1
-C
4
-alkyl or mono- or disubstituted amino groups.
Of especial interest are compounds in which each R
2
is phenyl which is unsubstituted or substituted by one SO
3
M, —SO
2
NH
2
or —NHCOC
1
-C
4
-alkyl group, however, the phenyl group is preferably unsubstituted.
Further preferred compounds of formula (1) are those in which each R
3

Affiliated with

Also associated with

Rating

Triazinylaminostilbene derivative as fluorescent whitening... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Triazinylaminostilbene derivative as fluorescent whitening..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Triazinylaminostilbene derivative as fluorescent whitening... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3201116