Compositions – Light transmission modifying compositions
Reexamination Certificate
1994-12-02
2002-04-30
Tucker, Philip (Department: 1712)
Compositions
Light transmission modifying compositions
C549S020000, C549S022000, C549S035000, C549S039000, C549S333000, C549S341000, C549S551000, C549S554000, C549S561000, C549S563000, C564S315000, C564S323000, C560S009000, C560S021000, C560S022000, C560S023000, C560S036000, C560S037000, C560S045000, C560S102000, C560S141000, C558S418000, C558S420000, C558S423000, C558S388000, C558S401000, C558S414000, C558S416000, C558S427000, C568S028000, C568S029000, C568S030000, C568S031000, C568S032000, C568S033000, C568S034000, C568S035000, C568S038000, C568S039000, C568S
Reexamination Certificate
active
06379590
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an improved method of making unsymmetrically substituted fluorenyl compounds having strong second order nonlinear optical activities. More specifically, one step of this method further comprises the preparation of unsymmetric 2,7-disubstituted fluorenyl compounds via nucleophilic replacement of at least one of the substituents in a 2,7-disubstituted fluorenyl precursor with another functional group.
2. Prior Art
Organic polymer materials which have large second order nonlinear optical (“NLO”) response are of interest for optical applications including data storage, communications, and computing. Important applications include waveguides, interconnects, switches, and the like. The advantages over the conventionally employed inorganic materials, e.g., LiNbO
4
, in such applications include fast response time, large electro-optical response over a wide frequency range, low dielectric constant, compatibility with silicon wafer technology and others. However, because known NLO active polymers suffer from lack of long term stability under working temperature conditions, their practical utility is limited.
In our '065 Application, we have described thermal stable fluorene-based compounds which are highly NLO active through their unsymmetrical substitution at the aromatic rings of the general formula A:
wherein
m and n are independently integers of from 1 to 4;
R
1
and R
2
which are the same or different in groups D—R
1
— and A—R
2
—, each are optionally present and independently —Ar—, —Ar—H═CH— or —Ar—C≡C—, where in Ar is a divalent bridging group selected from the group consisting of phenylene, biphenylene, naphthalene, and thienylene;
A is an electron accepting group selected from —NO
2
, —CN, —CO
2
R, —C(O)R, —SO
2
R, —SO
2
R
F
, —C(CN)═C(CN)
2
or —CH═C(CN)
2
;
R
F
is —C
p
F
2p+1
;
p is an integer of from 1 to 10;
R is an straight, branched or cyclic aliphatic alkyl group having about 1 to 10 carbon atoms, or an aromatic group such as phenyl or naphthyl;
is an electron donating group selected from —NH
2
, —NHR, —NR
2
, —OH, —OR, —SH, or —SR, wherein R is same as defined above;
X and Y are groups capable of partaking in polymerizations reactions and are independently selected from the group consisting of —H, —NH
2
, —NHR, —NR
2
, —OH, —OR, —SH, —SR, —COOH, —NCO,
wherein
R is same as defined above, and
y is an integer from about 1 to about 10.
As used throughout, the terms m, n, R
1
, R
2
, A, R
F
, p, R, D, y, X and Y are defined as described above in connection with the compounds of formula A unless otherwise indicated.
These unsymmetrically substituted fluorenyl compounds can be used to make high glass transition temperature nonlinear optical polymers. By “unsymmetrical”, it is meant that substituents on the two opposite phenyl rings of the fluorenyl moiety are non-identical. Some of these fluorenyl compounds can be grown into non-centrosymmetric crystals, while all of such compounds can be used as additives in host-guest polymer systems.
In U.S. patent application Ser. No. 028,921, filed Mar. 8, 1993, (pending), we have disclosed various polymers exhibiting nonlinear optical properties and high glass transition temperatures made from either the unsymmetrically substituted fluorenyl compounds or monomers described above.
In the simple case wherein both R
1
and R
2
are not present, formula A may be rewritten as indicated below in formula B:
These unsymmetrically substituted fluorenyl compounds of the formula B are usually prepared from a 2,7-disubstituted fluorene derivative, preferably a 2,7-disubstituted 9-fluorenone derivative such as 2-fluoro-7-nitro-fluoren-9-one and the easily available 2,7-dinitrofluoren-9-one or its ketal, 2-(2,7-dinitro-9-fluorenyl)1,3-dioxolane. However, the replacement of a nitro group on these molecules by other functional groups is usually a low-yield, time-consuming, multi-step process which includes the reduction of the nitro group to an amine group followed by subsequent reactions. See, e.g., '065 application, “Step 2”.
A nitro group has long been known to activate another functional group in the same aromatic moiety towards nucleophilic displacements (“SNAr reactions”). See, e.g., Bunnett, J. F., 12 Q.
Rev. Chem. Soc.
1 (1958); Miller, J., Aromatic Nucleophilic Substitution, (1968); and Terrier, F., Nucleophilic Aromatic Displacement: The Influence of the Nitro Group, (1991). In all three of these references, the activation of the nitro group is localized in the same aromatic ring containing the substituent group. By contrast, examples in which the transmission of nitro activation in one ring to another ring attached thereto are rare, if any. To our knowledge, there is no successful example of nucleophilic replacement of a substituent on one ring of a biphenyl or fluorenyl molecule activated by a nitro group attached on the opposite ring.
It would be desirable to provide an improved method for preparing these unsymmetric substituted fluorenyl compounds of general formula B in high yield, wherein the method would involve only a minimal amount of steps.
SUMMARY OF THE INVENTION
In accordance with this invention, there is provided a method for preparing unsymmetrical 2,7-disubstituted fluoren-9-one derivatives, said method comprising:
reacting a compound of the formula D:
wherein
A′ is the same as or different from A, and is a leaving group selected from the group consisting of —Br, —Cl, —F, —NO
2
, and —CN;
is a carbonyl or a protected carbonyl, wherein said protected carbonyl is a ketal or thio-ketal selected from the group consisting of
wherein
R′ is —C
r
H
2r+1
;
R″ is —(CH
2
)
r
; and
r is independently an integer of 2 or 3;
A is an electron accepting group selected from the group consisting of NO
2′
—CN, —CO
2
R, —C(O)R, —SO
2
R, —SO
2
R
F
, —C(CN)═C(CN)
2
and —CH═C(CN)
2
;
R
F
is —C
p
F
2p+1
;
p is an integer of from about 1 to about 10;
R is selected from the group consisting of phenyl, napthyl, and a straight, branched and cyclic aliphatic alkyl group having from about 1 to about 10 carbon atoms;
with a nucleophilic reagent in the presence of an aprotic solvent and under conditions sufficient to form a compound of the formula C
wherein
A is as previously defined in formula D;
D is an electron donating group selected from the group consisting of —NH
2
, —NHR, —NR
2
, —OH, —OR, —SH, and —SR;
R is as previously defined in set A of formula D; and
is as previously defined in formula D.
Another aspect of this invention is directed to an improved process for producing unsymmetrically substituted fluorenyl compounds, said process comprising
a) reacting a compound of the formula D′
with a protection reagent selected from the group consisting of (CH
2
OH)
2
,
and (CH
3
O)
3
CH in the presence of an acid catalyst and a solvent under conditions sufficient to produce a protected carbonyl compound of the formula E:
wherein
is
b) reacting said protected carbonyl compound with a nucleophilic reagent in an aprotic solvent and under conditions sufficient to produce a protected 2,7-disubstituted fluoren-9-one derivative thereof of the formula F:
wherein
D is selected from the group consisting of —NH
2
, —NHR, —NR
2
, —OH, —OR, —SH, and —SR;
R is selected from the group consisting of phenyl, naphthyl, and a straight, branched and cyclic aliphatic alkyl group having from about 1 to about 10 carbon atoms; and
is
c) deprotecting said 9-carbonyl of said 2,7-disubstituted fluoren-9-one derivative in the presence of both the acid catalyst of step a and active aromatic compounds under conditions sufficient to yield a 2,7-disubstituted fluorenyl compound geminately alkylated at a 9-carbon, as shown in the formula G:
wherein
m and n are independently from about 1 to about 4;
X′ and Y′ are independently selected from the group consisting of H, —NH
2
, —NR
2
, —NHR, —OH, —SR, —OR and —SH;
Shan Jianhui
Wu Chengjiu
Allied-Signal Inc.
Criss Roger H.
Szuch Colleen D.
Tucker Philip
LandOfFree
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