Fluorescent pigments

Details Fluorescent pigments Fluorescent pigments

1998-06-11

2001-07-17

Raymond, Richard L. (Department: 1624)

Compositions: coating or plastic

Materials or ingredients

Pigment, filler, or aggregate compositions, e.g., stone,...

C106S031130, C106S031160, C106S493000, C106S494000, C106S495000, C106S496000, C106S498000, C523S160000, C523S161000, C523S205000

Reexamination Certificate

active

06261359

ABSTRACT:

The present invention relates to novel soluble chromophores containing carbamate groups, to their preparation and to the use thereof as fluorescent pigments and as pigment precursors which can be readily converted into the corresponding pigments.
N-substituted pyrrolo[3,4c]pyrroles are disclosed in U.S. Pat. Nos. 4,585,878 and 4,791,204. From the generic definition of all substituents it can be inferred that the N-substituents may also be, inter alia, alkoxycarbonyl groups, which are defined in U.S. Pat. No. 4,791,204 as including methoxycarbonyl, ethoxycarbonyl n-propoxycarbonyl, n-butoxycarbonyl and n-hexyloxycarbonyl. U.S. Pat. No. 4,585,878 teaches that the N-substituted pyrrolo[3,4-c]pyrroles disclosed therein exhibit high fluorescence in dissolved form in polymers.
The invention provides novel carbamate group-containing soluble chromophores which, surprisingly, exhibit a very high solid state fluorescence, especially in the UV range, and which are readily convertible into the corresponding pigments with simultaneous displacement of the absorption spectrum, and hence open the way to unexpected applications.
Accordingly, the invention relates to compounds of formula
A(B)
x
,   (I),
wherein x is an integer from 1 to 4,
A is the radical of a chromophore of the quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine or azo series, which radical contains x N-atoms attached to B, preferably with at least one directly adjacent or conjugated carbonyl group,
B is a group of formula
and, if x is 2, 3 or 4, may also be one, two or three hydrogen atoms, in which formulae (II), (III) and (IV)
m, n and p are each independently of one another 0 or 1,
X is C
1
-C
14
alkylene or C
2
-C
8
alkenylene,
Y is a group —V—(CH
2
)
q
—,
Z is a group —V—(CH
2
)
r
—,
V is C
3
-C
6
cycloalkylene,
q is an integer from 1 to 6, and
r is an integer from 0 to 6,
R
1
and R
2
are each independently of the other hydrogen, C
1
-C
6
alkyl, C
1
-C
4
alkoxy, halogen, CN, NO
2
, unsubstituted phenyl or phenoxy or phenyl or phenoxy which are substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen,
Q is hydrogen, CN, Si(R
1
)
3
, is a group C()(R
5
)(R
6
)(R
7
), wherein R
5
, R
6
and R
7
are each independently of one another hydrogen or halogen and at least one of R
5
, R
6
and R
7
is halogen,
wherein R
1
and R
2
are as defined above,
a group SO
2
R
8
or SR
8
, wherein R
8
is C
1
-C
4
alkyl,
is a group CH(R
9
)
2
, wherein R
9
is unsubstituted phenyl or phenyl which is substituted
by C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen, or
is a group of formula
R
3
and R
4
are each independently of the other hydrogen, C
1
-C
18
alkyl, a group
wherein X, Y, R
1
, R
2
, m and n are as defined above, or R
3
and R
4
, together with the linking nitrogen atom, form a pyrrolidinyl, piperidinyl or morpholinyl radical.
A is the radical of a known chromophore having the basic structure
A(H)
x
,
for example
and all known derivatives thereof.
X is the significance of C
1
-C
14
alkylene is straight-chain or branched alkylene, typically methylene, dimethylene, trimethylene, 1-methylmethylene, 1,1-dimethylmethylene, 1,1-dimethyldimethylene, 1,1-dimethyltrimethylene, 1-ethyldimethylene, 1-ethyl-1-methyldimethylene, tetramethylene, 1,1-dimethyltetramethylene, 2,2-dimethyltrimethylene, hexamethylene, decamethylene, 1,1-dimethyldecamethylene, 1,1-diethyldecamethylene or tetradecamethylene.
X in the significance of C
2
-C
8
alkenylene is straight-chain or branched alkenylene, typically vinylene, allylene, methallylene, 1-methyl-2-butenylene, 1,1-dimethyl-3-butenylene, 2-butenylene, 2-hexenylene, 3-hexenylene or 2-octenylene.
Halogen substituents may be iodo, fluoro, preferably bromo and, most preferably, chloro.
C
1
-C
6
Alkyl will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl hexyl, and C
1
-C
18
alkyl may additionally be heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl hexadecyl or octadecyl.
C
1
-C
4
Alkoxy is typically methoxy, ethoxy, n-propoxy, isopropoxy or butoxy.
C
3
-C
6
Cycloalkylene is typically cyclopropylene, cyclopentylene and, preferably, cyclohexylene.
Particularly interesting compounds of formula I are those wherein x is 1 or 2 and B is a group of formula
and, if x is 2, may also be one hydrogen atom, and in formulae IV, V and VI
m is 0 or 1,
X is C
1
-C
4
alkylene or C
2
-C
5
alkenylene,
R
1
and R
2
are each independently of the other hydrogen, C
1
-C
4
alkyl, methoxy, chloro or NO
2
, and
Q is hydrogen, CN, CCl
3
, a group
SO
2
CH
3
or SCH
3
,
R
3
and R
4
are each independently of the other hydrogen, C
1
-C
4
alkyl or a group
or R
3
and R
4
, taken together, form a piperidinyl radical,
and preferably those wherein x is 2 and B may be twice a group of formula
Preferred compounds of formula I are
a) perylenecarboximides of formula
wherein D is hydrogen, C
1
-C
6
alkyl, unsubstituted or halogen- or C
1
-C
4
alkyl-substituted phenyl, benzyl or phenethyl or is B,
b) quinacridones of formula
wherein R
10
and R
11
are each independently of the other hydrogen, halogen, C
1
-C
18
alkyl, C
1
-C
4
alkoxy or phenyl,
c) dioxazines of formula
wherein R
12
is hydrogen, halogen or C
1
-C
18
alkyl,
d) isoindolines of formulae
wherein R
13
is a group
R
14
is hydrogen, C
1
-C
18
alkyl, benzyl or a group
R
15
has the same meaning as R
13
,
R
16
, R
17
, R
18
and R
19
are each independently of one another hydrogen, C
1
-C
18
alkyl, C
1
-C
4
alkoxy, halogen or trifluoromethyl,
e) indigo derivatives of formula
wherein R
20
is hydrogen, CN, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen,
f) azo compounds of formula
wherein R
21
and R
22
are each independently of the other hydrogen, halogen, C
1
-C
4
alkyl or C
1
-C
4
alkoxy,
g) anthraquinoid compounds of formula
and
h) phthalocyanines of formula
wherein
X
1
is H
2
, Zn, Cu, Ni, Fe or V,
X
2
is —CH(R
24
)— or —SO
2
—
R
23
is hydrogen, C
1
-C
4
alkyl, —N(E)R
24
, —NHCOR
25
, —COR
25
or
R
24
is hydrogen or C
1
-C
4
alkyl, R
25
is C
1
-C
4
alkyl and R
26
is hydrogen, halogen, C
1
-C
4
alkyl or C
1
-C
4
alkoxy,
z is 0 or 1 and y is an integer from 1 to 4,
in each of which formulae E is hydrogen or is B, with the proviso that E in each formula is at least one group B and B is as defined above, in respect of which definition the preferred meanings cited above apply.
Among the phthalocyanines, those of formula XVI, wherein X
1
is H
2
, Cu or Zn, X
2
is —CH
2
— or —SO
2
—, R
23
is hydrogen, —NHCOCH
3
or benzoyl and z is 1, are preferred
In U.S. Pat. No. 4,585,878 it is said in connection with the preparation of N-unsubstituted pyrrolpyrroles that they can be obtained by reacting a N-substituted pyrrolo-3,4-c-pyrrole with a compound that carries the corresponding N-substituents as leaving groups in an organic solvent. In the sole Example describing a compound containing a N-carbonyl group (Example 9: N-benzoyl), 1,4diketo-3,6diphenyl-pyrrolo[3,4-c]pyrrole is reacted with benzoyl chloride. In the experiment to prepare the desired carbamates in analogous manner by reaction with a corresponding acid chloride derivative, it was unfortunately found that it was only possible to obtain said carbamates in poor yield.
Very surprisingly, however, it was observed that when using appropriate trihaloacetates, azides, carbonates, alkylidene-iminooxyformates or, in particular, appropriate dicarbonates, the desired carbamates are obtained in very good yield. An improved yield is also obtained—even if only to a lesser degree—by carrying out the reaction with an aliphatic acid chloride derivative, conveniently butyl chloroformate, in the presence of a base as catalyst.
Accordingly, the invention further relates to a process for the preparation of compounds of formula I, which comprises reacting a compound of formula
A(H)
x
,   (XVII)
wherein A and x are as defined above, in the desired molar ratio with a dicarbonate of formula
B—O—B   (XVIII)
or with a trihaloacetate of formul

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