Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-06-16
2002-09-10
Solola, T. A. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S497000, C558S315000
Reexamination Certificate
active
06448416
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates generally to electron acceptors (or withdrawing groups) which can be used in the preparation of polymeric thin films for waveguide media, and specifically to dicyanomethylendihydrofuran-based electron acceptors, and methods of making the same.
BACKGROUND OF THE INVENTION
Thin films of organic or polymeric materials with large second order nonlinearities in combination with silicon-based electronic circuitry can be used in systems for laser modulation and deflection, information control in optical circuitry, as well as in numerous other waveguide applications. In addition, novel processes through third order nonlinearity such as degenerate four-wave mixing, whereby real-time processing of optical fields occurs, have utility in such diverse fields as optical communications and integrated circuit fabrication. The utility of organic materials with large second order and third order nonlinearities for very high frequency application contrasts with the bandwidth limitations of conventional inorganic electrooptic materials currently in use.
Numerous optically responsive monomers and polymers have been developed for use in organic materials which, in turn, can be used in the waveguide applications described above. For example, U.S. Pat. No. 5,044,725, which is incorporated herein by reference in its entirety, describes numerous polymer compositions which provide suitable nonlinear optical response. U.S. Pat. No. 5,044,725 describes, for example, a preferred polymer composition comprising an organic structure containing an electron donating group and an electron withdrawing group at opposing termini of a bridge. To achieve nonlinear optic (NLO) stability, however, thermally stable electron acceptors must be obtained.
The synthesis of thermally stable electron accepting (or withdrawing) groups for organic nonlinear optical applications are generally known in the art. Although many different electron acceptors have been reported in the literature, few, if any, have showed both suitable thermal stability and very high electron acceptance at the same time. Accordingly, electron acceptors which exhibit both thermal stability and very high electron acceptance are desired.
SUMMARY OF THE INVENTION
The present invention is directed to compounds which can serve as electron acceptors in, for example, thin films for waveguides. Preferred compounds of the invention have Formula I
where R
1
and R
2
are base stable moieties. R
1
and R
2
each, independently, are H, substituted and unsubstituted C
1
-C
10
alkyl, substituted and unsubstituted C
1
-C
10
alkenyl, substituted and unsubstituted C
1
-C
10
alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylaryl, substituted and unsubstituted carbocycles, substituted and unsubstituted heterocycles, substituted and unsubstituted cyclohexyl, or (CH
2
)
n
—O—(CH
2
)
n
where n is 1-10. Alternatively, R
1
and R
2
together form a ring structure or a substituted ring structure. R
3
is either substituted and unsubstituted C
1
-C
5
alkyl, substituted and unsubstituted C
1
-C
5
alkenyl, substituted and unsubstituted C
1
-C
5
alkynyl.
The present invention is also directed to a method of preparing compounds having Formula I comprising the steps 1) providing an alkylvinylether, 2) contacting the alkylvinylether with a strong base to form a first intermediate compound, 3) contacting the first intermediate compound with a ketone to form a second intermediate compound, and 4) reacting the second intermediate compound with dicyanomethane in the presence of a metal alkoxide base, or other appropriate base known to those skilled in the art, to form a compound having Formula I.
DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
The present invention relates, in part, to novel electron acceptors which have utility in organic nonlinear optical applications and methods of preparing the same. The compounds of the invention function as electron acceptors (or as electron withdrawing groups) which exhibit both thermal stability and very high electron acceptance simultaneously. The compounds of the invention can be used in, for example, polymeric organic materials for optical waveguides. Such polymeric organic materials are described in, for example, U.S. Pat. Nos. 5,044,725, 4,795,664, 5,247,042, 5,196,509, 4,810,338, 4,936,645, 4,767,169, 5,326,661, 5,187,234, 5,170,461, 5,133,037, 5,106,211, and 5,006,285, each of which is incorporated herein by reference in its entirety.
The phrase “electron acceptor” is used synonymously with “electron accepting group” and “electron withdrawing group” and refers to electronegative organic compounds or substituents which attract electron density from the pi-electron system when the conjugated electron structure is polarized by the input of electromagnetic energy.
In preferred embodiments of the invention, the electron acceptor compounds are dicyanomethylenedihydrofuran-based compounds comprising Formula I:
Preferably, R
1
and R
2
each, independently, are selected from the group consisting of H, substituted and unsubstituted C
1
-C
10
alkyl, substituted and unsubstituted C
1
-C
10
alkenyl, substituted and unsubstituted C
1
-C
10
alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylaryl, substituted and unsubstituted carbocycles, substituted and unsubstituted heterocycles, substituted and unsubstituted cyclohexyl, and (CH
2
)
n
—O—(CH
2
)
n
where n is 1-10.
“C
1
-C
10
” refers to C
1
, C
2
, C
3
, C
4
, C
5
, C
6
, C
7
, C
8
, C
9
, C
10
, and all combinations of ranges thereof.
The substituted alkyl, alkenyl, alkynyl, carbocyclic, and heterocyclic groups can comprise one or a plurality of substituents including, for example, fluorine, chlorine, D, and the like. In addition, the heterocyclic groups can comprise O, N, S, and the like.
The aryl groups preferably include, but are not limited to, benzyl, phenyl, fluorenyl, and naphthyl. The aryl groups, carbocycles, heterocycles, and cyclohexyl can also be substituted by one or a plurality of substituents including, for example, D, halides, including fluorine, chlorine and bromine. The alkylaryl groups preferably comprise C
1
-C
10
alkyl and the substituted alkylaryl groups comprise the substitutions for the alkyl and aryl groups described above.
In more preferred embodiments of the invention, R
1
and R2 each, independently, are selected from the group consisting of benzyl, carbocycle, heterocycle, cyclohexyl, phenyl, cycloalkyl, cycloalkenyl, and substituted phenyl. Additional moieties for R
1
and/or R
2
, independently, include, but are not limited to the following:
and the like.
In even more preferred embodiments of the invention, R
1
is CH
3
and R
2
is a substituted phenyl. Preferably, the substituted phenyl is selected from the group consisting of, but not limited to:
and the like.
Alternatively, R
1
and R
2
together form a ring structure or a substituted ring structure from 3 to 7 atoms total with 5 or 6 atoms being preferred. Preferably, the ring structure is substituted or unsubstituted carbocycle, substituted or unsubstituted heterocycle, or substituted or unsubstituted cyclohexyl. The substituted ring structure can comprise substituents including, but not limited to, halides, including fluorine, chlorine and bromine. A preferred compound having a ring structure formed by R
1
and R
2
comprises
R
3
is preferably selected from the group consisting of substituted and unsubstituted C
1
-C
4
alkyl, substituted and unsubstituted C
1
-C
4
alkenyl, substituted and unsubstituted C
1
-C
4
alkynyl. More preferably, R
3
is C
3
alkenyl (—CH═CH—CH
3
), C
5
alkenyl (—CH═CH—CH═CH—CH
3
), C
2
alkynyl (—C≡CH), or C
4
alkynyl (—C≡C—C≡CH). Most preferably, R
3
is CH
3
. The substituted alkyl, alkenyl, and alkynyl groups can comprise one or a plurality of substituents including, for example, F, D, or Cl.
In preferred embodiments of the invention, R
3
is selected from the group consisting of C
1
-C
4
alkyl, C
1
-C
4
alkenyl, a
He Mingqian
Leslie Thomas M.
Corning Incorporated
Nwaneri Angela N.
Solola T. A.
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