Substituted tetraarylethylene compounds

Details Substituted tetraarylethylene compounds Substituted tetraarylethylene compounds

2002-06-21

2003-12-30

Keys, Rosalynd (Department: 1621)

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

Organic compounds

Oxygen containing

C568S723000, C568S640000, C568S646000, C560S140000, C560S144000, C560S146000, C562S087000, C562S088000, C562S089000, C562S115000

Reexamination Certificate

active

06670512

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to tetraarylethylene compounds. More particularly the present invention relates to substituted tetraaryl compounds, preferably which contain functional groups, most preferably terminal functional groups. Such compounds have the potential to act as molecular “templates” for metal complexation. That is, for example, a tetraaryl ethylene compound having at least one, preferably at least two functional substituents on either side of the plane defined by the sigma bonds attached to the ethylenic carbon atoms could form a “supramolecular assembly” comprising alternating layers of a metal atom and the tetraaryl compound.
BACKGROUND OF THE INVENTION
Chemische Berichte, 1872, 5, 278 reports work by A. Behr to make a substituted tetraphenylethylene. The compound was manufactured from benzophenone and the resulting compounds are hydroxyl substituted in the aromatic (aryl) ring para to the ethylenic carbon atoms. There are a number of subsequent references to this paper, including Kogyo Kagaku Zasshi, 61, 481-2 (1958) by Yoshiro Nakamura, which clearly establishes that the oxidation and subsequent alkylation is para to the ethylenic carbon atoms. The reference fails to clearly teach ortho substituted tetraarylethylenes. Further, the references also fail to teach tetraarylethylene which is substituted both above and below the plane defined by the sigma bonds attached to the ethylenic carbon atoms.
Accordingly, the present invention seeks to provide novel tetraarylethylene compounds.
SUMMARY OF THE INVENTION
The present invention provides a compound of formula I:
wherein at least two R
1
are the same and not a hydrogen atom; and R
1
, R
2
, R
3
, R
4
and R
5
are independently selected from the group consisting of a hydrogen atom; a halogen atom; a hydroxyl radical; a C
1-20
alkyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; a C
3-20
allyl radical; a C
1-20
alkoxy radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; a C
3-20
allyloxy radical; a carbalkoxy radical of the formula —COOR
20
wherein R
20
is a hydrogen atom or a C
1-20
alkyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; a carboxylate radical of the formula —OCOR
30
wherein R
30
is a C
1-20
alkyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; a C
6-10
aryl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; a C
6-10
aryloxy radical or a C
7-11
benzyloxy radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; an acyl R
6
CO— radical wherein R
6
is a C
1-20
alkyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom, a hydroxyl radical or a carboxyl radical; an amido radical which is unsubstituted or substituted by up to two C
1-20
alkyl radicals; a (—O—)
n
—P(R
7
)
2
radical wherein each R
7
is independently selected from the group consisting of a C
1-20
alkyl radical, a C
1-20
alkoxy radical, a C
6-10
aryl radical and n is 0 or 1; a (—O—)
n
—PO(R
8
)
2
radical wherein each R
8
is independently selected from the group consisting of a C
1-20
alkyl radical, a C
1-20
alkoxy radical, a C
6-10
aryl radical and n is 0 or 1; a —Si(R
9
)
3
radical wherein each R
9
is independently selected from the group consisting of a C
1-20
alkyl radical, a C
6-10
aryl radical, a hydrogen radical and an alkoxy radical; a trifluormethanesulfonyloxy radical; or two or more of adjacent substituents R
2
, R
3
, R
4
and R
5
may be taken together to form a fused ring.
The present invention also provides a process for the preparation of a 2,2′,2″,2′″-(tetra C
1-6
alkoxy)tetraphenylethylene comprising acid catalyzed decomposition of the diazo derivative of 2,2′-di C
1-6
alkoxybenzophenone hydrazone at a temperature of less than 25° C. in the absence of light.
The present invention also seeks to provide a process for the preparation of 2,2′,2″,2′″,6,6′,6″,6′″-octa C
1-4
alkoxy tetraphenylethylene comprising the controlled oxidation of 1,1,2,2,-tetrakis(2′,6′-di C
1-6
alkoxyphenyl)ethane. Typically the oxidation takes place in the presence of triphenylmethyl hexafluorophosphate in an inert solvent at low temperatures typically from about 0° C. to about 25° C. It is believed that the resulting 2,2′,2″,2′″,6,6′,6″,6′″-octa C
1-6
alkoxy tetraphenylethylene compound may be dealkylated to 2,2′,2″,2′″,6,6′,6″,6′″-octahydroxy tetraphenylethylene.
In a further embodiment the present invention provides a process for the preparation of 1,1,2,2-tetrakis(2′,6′-di C
1-6
alkoxyphenyl)ethane comprising the radical coupling of bis(2,6-di C
1-6
alkoxyphenyl)methanol and bis(2,6-di C
1-4
alkoxyphenyl)methane in equimolar amounts in an inert solvent in the presence of p-toluene sulphonic acid.
A second method of preparation of 1,1,2,2-tetrakis(2′,6′-di C
1-6
alkoxyphenyl)ethane is provided by the reductive radical coupling of bis(2,6-di C
1-6
alkoxyphenyl)methanol using chromous ion (CrCl
2
) in an acidic medium (HCl).
A further aspect of the present invention provides a process for the synthesis of unsymmetrically substituted tetraphenylethylene compounds of formula 1 wherein two R
1
substituents on opposite ends of the central ethylene moiety are C
1-20
alkoxy radicals (as defined above) and two R
1
substituents on opposite ends of the central ethylene moiety are benzyloxy radicals (as defined above) comprising acid catalyzed decomposition of the diazo derivative of 2-C
7-11
benzyloxy, 2′-C
1-20
alkoxy benzophenone.
In the diazo-coupling reaction of 2-benzyloxy-2′-methoxybenzophenone hydrazone to give the dibenzyloxydimethoxytetraphenylethylene, both double bond isomers are produced, giving a mixture of E and Z—1,2-di(2′-benzyloxyphenyl)-1,2-di(2′-methoxyphenyl)ethane. The subsequent hydrogen resulted in the separable E and Z—1,2-di(2′-hydroxyphenyl)-1,2-di(2′-methoxyphenyl)ethylene.
In a further aspect of the present invention the resulting unsymmetrically substituted tetraphenylethylene compounds of formula I wherein two R
1
substituents on opposite ends of the central ethylene moiety are C
1-20
alkoxy radicals (as defined above) and two R
1
substituents on opposite ends of the central ethylene moiety are C
7-11
benzyloxy radicals (as defined above) may be subjected to catalytic hydrogenolysis (hydrogenation) to convert the benzyloxy radicals to hydroxyl radicals. Preferably the catalyst is palladium on carbon. Both E and Z isomers can be produced in this way and either separated and used individually or used as a mixture.
In a further embodiment the present invention provides a process for producing compounds of formula I above wherein all R
1
substituents are C
3-20
allyloxy radicals comprising reacting the compounds of formula I above wherein all R
1
substituents are hydroxyl radicals with excess 1-halo C
3-20
allyl compound. Preferably the halo substituent is a bromine atom. The resulting compound may be subject to a high temperature Claisen rearrangement to yield the compounds of formula I wherein all R
1
substituents are hydroxy radicals and all R
2
substituents are C
3-20
allyl radicals. The resulting compounds may then be catalytically h

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