Organic compounds -- part of the class 532-570 series – Organic compounds – Chalcogen in the nitrogen containing substituent
Reexamination Certificate
1999-03-09
2001-09-04
Shah, Mukund J. (Department: 1611)
Organic compounds -- part of the class 532-570 series
Organic compounds
Chalcogen in the nitrogen containing substituent
Reexamination Certificate
active
06284889
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel chromophoric compounds and to a process for their preparation.
2. Description of the Related Art
Chromophoric compounds, in particular nonlinear optical chromophores, represent the essential component for so-called organic conductors, i.e. for electrically conductive materials. Organic conductors are used for electrooptical and photonic components, in particular switches, and in areas of information processing and integrated optics, such as optical chip-to-chip connections, waveguiding in electrooptical layers, in the optical signal processing in sensors, and the like.
In general, chromophoric systems have conjugated &pgr;-electron systems in the molecule and carry electron donors or acceptors in suitable positions of the &pgr;-electron system. NLO-active chromophores attracting great interest are those having a high dipole moment &mgr;, a high hyperpolarizability &bgr; and suitable absorption properties &lgr; as well as a high nonlinear optical activity. For the various areas of use, they should also have high thermostability. However, the systems known from the prior art are very sensitive to high temperatures.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide novel nonlinear optical chromophores having the above-mentioned properties, which can be prepared in high purity and in a simple manner from readily obtainable starting materials.
This object is achieved by the oxazine compounds according to the invention, particularly novel benzoxazine and phenoxazine compounds, and the process for their preparation.
The present invention accordingly provides chromophoric compounds of the general formula 1
where
R
1
, R
4
, R
5
are each a hydrogen atom, a linear or branched C
1
- to C
20
-alkyl radical which is optionally interrupted by 1 to 5 ether oxygen atoms, or an aryl or heteroaryl radical;
R
2
, R
3
, which can be the same or different, are each a hydrogen atom, a linear or branched C
1
- to C
20
-alkyl radical which is optionally interrupted by 1 to 5 ether oxygen atoms, a benzyl radical or an aryl or heteroaryl radical, where one of the radicals R
2
and R
3
optionally has a hydroxyl or carboxyl group;
Z is an electron-acceptor-substituted methylene or imino group;
X denotes S, O, NR
6
or a ring double bond or denotes
where R
6
is a hydrogen atom, a linear or branched C
1
- to C
20
-alkyl radical or a phenyl or naphthyl radical and T denotes CH or N or Z and T together optionally form a structure of the type ═N—SO
2
—C≡, ═N—CS—C≡ or ═N—CO—C≡; and
Y is a CH or CR
7
group or N where R
7
is a linear or branched C
1
- to C
20
alkyl radical or a phenyl or a naphthyl radical.
The present invention therefore also provides a process for preparing chromophoric compounds of the general formula 1
by heating an appropriate 5-amino-2-nitrosophenol or a mineral acid salt of the general formula 2 with a methylene-active compound of the general formula 3A or the tautomeric form 3B
in a polar solvent, and in the presence of a base, for example, triethylamine.
In the formulae 2 and 3A or 3B shown above, the radicals R
1
, R
2
, R
3
, R
4
and R
5
and X, Y and Z are as defined for formula 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a preferred embodiment of the present invention, the radicals R
1
, R
4
and R
5
each denote a hydrogen atom. The radicals R
2
and R
3
preferably denote—independently of one another—a C
2
- to C
7
-alkyl radical, most preferably an ethyl, butyl or heptyl group. One of the radicals R
2
and R
3
advantageously has a functional group in the form of a hydroxyalkyl or carboxyalkyl group (having a terminal OH or COOH group), for example a hydroxyethyl group.
Where R
1
, R
2
, R
3
, R
4
and/or R
5
denote a heteroaryl radical, this s preferably selected from the group consisting of thiophenes, thiazoles and pyridines, i.e. a thienyl, thiazolyl or pyridyl radical is present; preferred aryl radicals are phenyl or naphthyl radical.
In the context of the present invention, preference is given to those compounds of the general formula 1 shown above in which the radicals R
1
and R
2
have suitable functional groups so that they can jointly form a 5- or 6-membered ring.
The radicals R
3
and R
4
in the general formula 1 may likewise have suitable functional groups so that they can jointly form a 5- or 6-membered ring. In addition, the radicals R
1
and R
2
and also R
3
and R
4
together may in each case denote such a saturated or unsaturated substituted or unsubstituted 5- or 6-membered ring.
In another preferred embodiment of the invention, the radicals R
2
and R
3
in the general formula 1 shown above likewise comprise functional groups which are suitable for jointly forming a 5- or 6-membered ring; this ring optionally has a directly bonded OH or COOH group or an OH or COOH group which is bonded via an aliphatic hydrocarbon radical. As in the case of R
1
and R
2
and also R
3
and R
4
, 5- or 6-membered rings can be formed which may be substituted or unsubstituted and saturated or unsaturated. However, the ring system is preferably saturated and has, in a further preferred embodiment, at least one other nitrogen or oxygen atom in the ring, in addition to the original nitrogen atom. Again, as before, this ring may be substituted or unsubstituted.
If there are substituents present on the ring, these are, in another preferred embodiment, additional functional groups, such as, for example, hydroxyalkyl or carboxy-alkyl groups. By appropriately selecting the functionalities of the radicals R
2
and R
3
, these may give ring groupings of the morpholine or piperazine type. Here, preference is given to morpholin-4-yl, piperazin-1-yl and 4-(C
1
- to C
4
-alkyl)piperazin-1-yl groups, for example to the 4-methylpiperazin-1-yl and the 4-(2-hydroxyethyl)piperazin-1-yl group.
Particularly preferred radicals or atom groups in the above-mentioned formula 1 are hydrogen atoms for R
1
, R
4
and R
5
, ethyl, butyl, heptyl or hydroxyethyl groups for R
2
and R
3
, sulfur or an unsubstituted 1,2-fused benzene ring for X, the group —CH for Y, a dicyanomethylene, alkoxycarbonylcyanomethylene, cyanoimino or alkoxy-carbonylimino group for Z and the group ═N—SO
2
—C≡ for Z and T together.
Particularly preferred compounds of general formula 1 are those whose preparation is described in the examples. These are:
benzo[a]-5-dicyanomethylene-9-[N,N-diethylamino]-7,12-phenoxazine
benzo[a]-5-dicyanomethylene-9-[N,N-di(n-butyl)amino]-7,12-phenoxazine
benzo[a]-5-dicyanomethylene-9-[N-(n-butyl)-N-(2-hydroxyethyl)amino]-7,12-phenoxazine
benzo[a]-5-dicyanomethylene-9-[N-(n-heptyl)-N-(2-hydroxyethyl)amino]-7,12-phenoxazine
2-dicyanomethylene-6-[N,N-diethylamino]thieno[4,5-b]-benzo-4,9-oxazine
9-[N-(n-heptyl)-N-(2-hydroxyethyl)amino]benzo[d]isothiazolo[3,3a,4-ab]phen-7,12-oxazine 4-dioxide.
Thus, the compounds according to the invention can be seen as oxazine derivatives, in particular as benzoxazines and phenoxazines.
The above-mentioned compounds are so-called nonlinear optical chromophores having a high &mgr; value and at the same time high &bgr; and suitable &lgr;
max
values. Suitable &lgr;
max
values are greater than 600 nm and are preferably about 700 nm. The chromophores can be obtained in high purity in a simple and economical manner from easily accessible starting materials.
Both the aminonitrosophenol compounds of formula 2 and the methylene-active compounds of formula 3A or their tautomeric form 3B are easily accessible starting materials, so that the preparation of the compounds of the formula 1 can be carried out with an economical yield. The 5-amino-2-nitrosophenols of the formula 2 can be prepared in a simple manner by nitrosation of the corresponding 3-aminophenols. The resulting 5-amino-2-nitrosophenols are preferably reacted in an equimolar ratio with the appropriate meth
Fricke Christian
Hartmann Horst
Kanitz Andreas
Greenberg Laurence A.
Lerner Herbert L.
Liu Hong
Shah Mukund J.
Siemens Aktiengesellschaft
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