Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2003-02-11
2004-10-19
Huang, Evelyn Mei (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C252S299100, C252S299610, C252S301260, C430S078000, C430S058600, C106S498000
Reexamination Certificate
active
06806368
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel perylene-3,4:9,10-tetracarboxylic diimides (hereinafter referred to as perylimides for short) of the general formula I
where
R
1
, R
2
, R
3
and R
4
are independently hydrogen, chlorine, bromine or substituted or unsubstituted aryloxy, arylthio, arylamino, hetaryloxy or hetarylthio;
R
5
, R
6
, R
7
, R
8
, R
9
and R
10
are independently hydrogen or long-chain alkyl, alkoxy or alkylthio whose carbon chain may in each case contain up to four double bonds, with the proviso that at least four of these radicals are not hydrogen.
The invention also relates to the preparation of these perylimides and to their use as liquid-crystalline materials for electronic, optoelectronic and photonic applications, for coloration of macromolecular organic and of inorganic materials, as fluorescent dyes and as laser dyes and also as organic materials for solar collectors and electroluminescence applications.
2. Description of the Background
There are a multiplicity of technological applications, for example charge transport material applications, where the materials used have to have not only suitable molecular properties such as color and emission but also a supramolecular order, which is customarily determined by the relationship of the molecules in the crystal.
Particularly interesting arrangements of functional molecules are obtained in liquid-crystalline phases, which have substantial advantages in use over pigmentary solids. For instance, the mobility of the molecules in the liquid-crystalline phase makes it possible to prepare films of uniform thickness and of a macroscopic order induced by the substrate. When low viscosities are desired for the production process, films may also be prepared by raising the temperature above the melting point. On the other hand, liquid-crystalline orders which are stable over wide temperature ranges are also obtainable by attaching thermally or photochemically crosslinkable groups.
Perylimides have hitherto formed the basis for the following liquid-crystalline compounds:
Chem. Mater. 10, 1309-1319 (1998) describes perylimides which are derivatized at the imide nitrogen atoms with oligoethyleneoxy substituents as mesogenic groups. However, these groups tend to absorb atmospheric humidity, so that thin films of the liquid-crystalline phase in particular are not morphologically stable.
Angew. Chem. 110, 1463-1467 (1998) concerns liquid-crystalline coronenediimides which, however, form columnar liquid-crystalline phases only at above 150° C. and are preparable from perylene derivatives only by means of inconvenient processes.
EP-A-422 535 describes liquid-crystalline polymers which are partly functionalized with perylimide units in the side chains; that is, are not intrinsically liquid-crystalline low molecular weight dyes.
WO-A-97/22607 and 94/25504 disclose perylimides which are 1,7-disubstituted or 1,6,7,12-tetrasubstituted in the perylene structure, but which differ from the claimed perylimides of the formula I not least by the substitution on the imide nitrogen atoms and are not liquid crystalline.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide further liquid-crystalline dyes having advantageous application properties.
We have found that this object is achieved by the perylimides of the formula I defined at the beginning.
Preferred perylimides of the formula I are disclosed in the subclaims.
The invention also provides a process for preparing these perylimides, which comprises reacting a perylene-3,4:9,10-tetracarboxylic dianhydride of the general formula II
with identical or different primary amines of the general formulae III
in the presence of a polar aprotic solvent and of an imidation catalyst.
The invention further provides a process for preparing perylene-3,4:9,10-tetracarboxylic diimides of the general formula Ia
where Ar is substituted or unsubstituted aryloxy, arylthio, hetaryloxy or hetarylthio, which comprises reacting 1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic dianhydride (IIa) with identical or different primary amines of the general formulae III
in the presence of a polar aprotic solvent and of an imidation catalyst and reacting the resultant 1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic diimides of the general formula I′
with an aromatic alcohol or thioalcohol of the general formula IV
H—Ar IV
in the presence of an inert aprotic solvent and of a non-nucleophilic or only minimally nucleophilic base.
The invention further provides a process for preparing perylene-3,4:9,10-tetracarboxylic diimides of the general formula Ib
where Ar is substituted or unsubstituted aryloxy, arylthio, hetaryloxy or hetarylthio, which comprises reacting 1,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (IIb) with identical or different primary amines of the general formulae III
in the presence of a polar aprotic solvent and of an imidation catalyst and reacting the resultant 1,7-dibromoperylene-3,4:9,10-tetracarboxylic diimides of the general formula I″
with an aromatic alcohol or thioalcohol of the general formula IV
H—Ar IV
in the presence of an inert aprotic solvent and of a non-nucleophilic or only minimally nucleophilic base.
The invention further provides for the use of the perylimides of the formula I as liquid-crystalline materials in electronic, optoelectronic or photonic applications, for coloration of macromolecular organic and of inorganic materials, as fluorescent dyes and as laser dyes and also as organic materials for solar collectors and electroluminescence applications.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The variables in the formula I will now be more particularly described.
Examples of nonhydrogen radicals R
1
to R
4
are chlorine, bromine, phenoxy, phenylthio, phenylamino, 2-naphthyloxy, 2-naphthylthio, 2-, 3- and 4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and 2-, 4- and 5-pyrimidylthio, of which chlorine and bromine are preferred and phenoxy is particularly preferred.
When the perylene structure is to be substituted, preferably all or just two (especially 1,7-substitution) of the radicals R
1
to R
4
are identical ones of the abovementioned radicals. Aryl and hetaryl may each bear up to three, preferably one or two, substituents.
Examples of these substituents are:
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the alcohols obtained in the oxo process), of which C
1
-C
8
-alkyl radicals and especially tert-butyl are preferred;
2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-methylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 4,7-dithiaoctyl, 4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;
2-monomethyl- and 2-monoethylamino
Thalacker Christoph
Würthner Frank
BASF - Aktiengesellschaft
Huang Evelyn Mei
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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