Fluorescent diketopyrrolopyrroles

Details Fluorescent diketopyrrolopyrroles Fluorescent diketopyrrolopyrroles

2000-09-07

2003-08-05

McKane, Joseph K. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C524S092000, C548S443000

Reexamination Certificate

active

06603020

ABSTRACT:

The present invention relates to fluorescent diketopyrrolopyrroles (“DPPs”) of the formula I
wherein R
1
and R
2
, independently from each other, stand for C
1
-C
25
-alkyl, allyl which can be substituted one to three times with C
1
-C
3
alkyl or Ar
3
, —CR
3
R
4
—(CH
2
)
m
—Ar
3
, wherein R
3
and R
4
independently from each other stand for hydrogen or C
1
-C
4
alkyl, or phenyl which can be substituted on to three times with C
1
-C
3
alkyl,
Ar
3
stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C
1
-C
8
alkyl, C
1
-C
8
alkoxy, halogen or phenyl, which can be substituted with C
1
-C
8
alkyl or C
1
-C
8
alkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, and wherein C
1
-C
25
-alkyl or —CR
3
R
4
—(CH
2
)
m
—Ar
3
, preferably C
1
-C
25
-alkyl, can be substituted with a functional group capable of increasing the solubility in water such as a tertiary amino group, —SO
3
—, or PO
4
2−
,
Ar
1
and Ar
2
, independently from each other, stand for
 wherein
R
5
stands for C
1
-C
6
alkyl, —NR
8
R
9
, —OR
10
, —S(O)
n
R
8
, —Se(O)
n
R
8
, or phenyl, which can be substituted one to three times with C
1
-C
8
alkyl or C
1
-C
8
alkoxy,
wherein R
8
and R
9
, independently from each other, stand for hydrogen, C
1
-C
25
-alkyl, C
5
-C
12
-cycloalkyl, —CR
3
R
4
—(CH
2
)
m
—Ph, R
10
, wherein R
10
stands for C
6
-C
24
-aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein Ph, the aryl and heterocyclic radical can be substituted one to three times with C
1
-C
8
alkyl, C
1
-C
8
alkoxy, or halogen, or R
8
and R
9
stand for —C(O)R
10
, wherein R
11
can be C
1
-C
25
-alkyl, C
5
-C
12
-cycloalkyl, R
10
, —OR
12
or —NR
13
R
14
, wherein R
12
, R
13
, and R
14
stand for C
1
-C
25
-alkyl, C
5
-C
12
-cycloalkyl, C
6
-C
24
-aryl, or
a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the aryl and heterocyclic radical can be substituted one to three times with C
1
-C
8
alkyl or C
1
-C
8
alkoxy, or —NR
8
R
9
stands for a five- or sixmembered heterocyclic radical in which R
8
and R
9
together stand for tetramethylene, pentamethylehe, —CH
2
—CH
2
—O—CH
2
—CH
2
—, or —CH
2
—CH
2
—NR
5
—CH
2
—CH
2
—, preferably —CH
2
—CH
2
—O—CH
2
—CH
2
—, and n stands for 0, 1, 2 or 3,
and wherein R
6
and R
7
, independently from each other, stand for hydrogen or R
5
, but do not stand simultaneously for hydrogen, preferably R
6
stands for R
5
and R
7
for hydrogen.
U.S. Pat. No. 4,579,949 describes a process for the preparation of DPPs which are unsubstituted at the nitrogen atoms of the pyrrolo-rings. Especially example 45 describes the DPP-compound of the formula II
DPP-compound II, however, is violet, exhibits only insufficient fluorescence and solubility.
Further, EP-A 133,156 claims generically DPP-compounds, however, compounds of formula I are not mentioned explicitly and no teaching is given that DPP-compounds of formula I could exhibit a red or orange fluorescence.
EP-A 499,011 describes electroluminescent devices comprising DPP-compounds. Particularly, in example 1 the DPP-derivative of formula III
is disclosed. However, no teaching is given with regard to the fluorescence of DPP-compounds and a way to obtain DPP-compounds exhibiting a red or orange fluorescence.
WO 98/33862 describes the use of the DPP-compound of formula IV
as a guest molecule in electroluminescent devices. However, no teaching is given with regard to the fluorescence of DPP-compounds and a way to obtain DPP-compounds exhibiting a red or orange fluorescence.
In addition, commercially available red fluorescent dyes such as thioindigo derivatives do not show superior light stability when incorporated in plastics. In addition, commercially available red fluorescent dyes cannot be applied to colour polyamides, because they decompose during the manufacturing process.
Hence, the object of this invention was to provide red or orange fluorescent compounds with a high heat stability, a good solubility in polymers, hydrocarbon based fuels, lubricants, and water, a high light stability, and the ability to be used in plastics, especially polyamides, without decomposition and loss of lightfastness, and in paints.
Accordingly, the abovementioned DPP-compounds I were found.
In addition, a process for its preparation and its use were found, too.
Red or orange fluorescent compounds means that the inventive compounds preferably have a fluorescence emission maximum in the range of from 520 to 780, more preferably from 550 to 700, more preferred from 580 to 650 nm. Further, the inventive compounds preferably exhibit an absorption in the range of 480 to 580 nm.
The inventive compounds I usually exhibit a fluorescence quantum yield (“FQY”) in the range of from 1>FQY≧0.3 (measured in aerated toluene or DMF). Further, in general, the inventive compounds I exhibit a molar absorption coefficient in the range of from 5000 to 100000.
A preferred embodiment relates to DPP-compounds I, wherein R
1
=R
2
, and R
5
=R
6
, R
7
=hydrogen, and Ar
1
=Ar
2
, particularly preferred wherein in addition to the above R
3
=R
4
=H, m=0 and n=0, most preferred are DPP-compounds in which
(a) R
1
=R
2
=C
1
-C
8
alkyl, Ar
1
=Ar
2
=phenyl or stilbene, R
5
=R
6
=—NR
7
R
8
in 4-position, R
7
=hydrogen, and R
8
=R
9
=C
1
-C
8
alkyl or phenyl, or
(b) R
1
=R
2
=C
1
-C
8
alkyl, —(CH
2
)
m
—Ph, Ar
1
=Ar
2
=phenyl or stilbene, R
5
=R
6
=—SR
7
or unsubstituted or substituted phenyl in para-position, and R
8
=C
1
-C
8
alkyl, phenyl or a heterocyclic radical, both unsubstituted or substituted, or C
5
-C
12
-cycloalkyl, or
(c) R
1
=R
2
=—CH
2
—Ph, wherein phenyl can be substituted with phenyl, naphthyl or C
1
-C
4
alkyl up to two times, Ar
1
=Ar
2
=phenyl or 1- or 2-naphthyl, R
5
=R
6
=R
7
=hydrogen, in case where Ar
1
=Ar
2
=1- or 2-naphthyl, or, in all other cases, C
1
-C
8
alkyl or phenyl.
Particularly preferred DPP-compounds I are the following compounds:
C
1
-C
25
alkyl is typically linear or branched—where possible—methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, preferably C
1
-C
8
alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, more preferably C
1
-C
4
alkyl such as typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl; C
1
-C
3
alkyl stands for methyl, ethyl, n-propyl, or isopropyl; C
1
-C
6
alkyl stands for methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, or n-hexyl.
C
1
-C
8
alkoxy is typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C
1
-C
4
alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy.
C
6
-C
24
aryl is typically phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, 2- or 9-fluorenyl or anthracenyl, preferably C
6
-C
12
aryl such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl.
C
7
-C
24
aralkyl is

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