Method for the preparation of ferrocenyl substituted styrene

Details Method for the preparation of ferrocenyl substituted styrene Method for the preparation of ferrocenyl substituted styrene

2003-09-23

2004-10-05

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S140000, C502S224000

Reexamination Certificate

active

06800776

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a method for manufacturing ferrocenyl substituted styrene. More particularly, the present invention relates to a method for manufacturing ferrocenyl substituted styrene without heating or vacuum sublimation.
BACKGROUND OF THE INVENTION
A ferrocenyl double bond compound having the following structure can be utilized in various applications:
wherein Fc is ferrocenyl, for examples the applications disclosed in FR 2,567,890 (1986), U.S. Pat. No. 4,219,490 (1980) and Czech. 175,857 (1979). C. A. 90,138026c discloses that a ferrocenyl ethylene compound can be used to synthesize ferrocenyl derivatives.
JP 7-309915 (1995) discloses a high refractive index resin of a polyvinylferrocene copolymer.
JP 8-029372 (1996) discloses an enzyme electrode made from a copolymer of a vinyl monomer having a ferrocene and dodecyl methacrylate.
An article, Nature 330,360 (1987), discloses that the following compound has non-linear optical properties:
Another article, Inorg Chim. Acta, 242(1-2), 43 (1996), discloses a non-linear optical compound having the following structure:
A further article, J. Chem. Soc., Chem. Commun., 1122 (1987), discloses redox-active crown ethers having the following structure:
WO 96/11935 (1996) discloses compounds having the following structure, the methods of preparation and pharmaceutical compositions containing same:
The derivatives of this patent application are suitable for the preparation of antitumoral drugs for use, in particular, in the treatment of estrogen-dependent breast cancers.
An article, J. Org. Chem., 66, 3533 (2001), discloses a method for synthesizing ferrocenyl styrene by reacting ferrocenecarbonyl and toluene bromide, the reaction of which can be represented as follows:
In this method the reaction is carried out in tetrahydrofuran (THF) and in the presence of samarium diiodide as a catalyst, and then the reaction mixture is dehydrated under reflux in air to obtain ferrocenyl styrene. The catalyst used, samarium diiodide, is expensive and will undergo hydrolysis in air or moisture
U.S. Pat. No. 6,211,392B1 discloses a method of manufacturing ferrocenyl-1,3-butadiene, in which a ferrocenecarbonyl is reacted with an allyl halide in a polar aprotic solvent lacking a carbonyl group in the presence of samarium diiodide as a catalyst. The method of this US patent has a relatively high yield; however, the catalyst used, samarium diiodide, is expensive and will undergo hydrolysis in air or moisture.
There is still a need in the industry for developing an easier method for the preparation of ferrocenyl styrene.
SUMMARY OF THE INVENTION
The present invention provides a method for synthesizing ferrocenyl substituted styrene having the following Formula III, which comprises: a) reacting ferrocenecarbonyl having the following Formula I with toluene halide having the following Formula II in an ether solvent and in the presence of magnesium as a catalyst; b) introducing a liquid portion of the resulting reaction mixture into a silica gel column; c) eluting the silica gel column with a solvent of low polarity; d) collecting the resulting. eluate from the column; e) and evaporating the solvent from the eluate to obtain a solid comprising ferrocenyl substituted styrene (III):
wherein R is hydrogen or C1-C4 alkyl;
wherein X is a halogen; Y is a halogen, hydrogen or C1-C4 alkyl;
wherein R and Y are defined as above.
Preferably, X is bromine, and Y is hydrogen or C1-C4 alkyl.
Preferably, R is hydrogen or methyl.
Preferably, the ether solvent is tetrahydrofuran or ethyl ether, and more preferably, tetrahydrofuran.
Preferably, said solvent of low polarity is n-hexane, ethyl acetate or a mixture of them.
Preferably, said reaction in step a) is carried out at room temperature for a period of 3-48 hours.
Preferably, said liquid portion is kept in the silica gel column for a period of 6-96 hours in step b).
Preferably, a mole ratio of said toluene halide (II) to said ferrocenecarbonyl (I) in said reaction in step a) ranges from 0.1 to 20, and more preferably, is about 1.5.
Preferably, a mole ratio of said magnesium catalyst to said ferrocenecarbonyl (I) in said reaction in step a) ranges from 0.1 to 20, and more preferably, is about 3.
In the method of the present invention, the reaction mixture in step a) does not need to be heated under refluxing, and the catalyst used in a common alkaline earth metal.


REFERENCES:
patent: 2567890 (1951-09-01), Myklestad
patent: 4219490 (1980-08-01), Gotzmer, Jr.
patent: 6211392 (2001-04-01), Fang et al.
patent: WO 96/11935 (1996-04-01), None
Jong et al., Journal of Organic Chemistry, vol. 66, No. 10, pp. 3533-3537 (2001).

Affiliated with

Also associated with

Rating

Method for the preparation of ferrocenyl substituted styrene does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Method for the preparation of ferrocenyl substituted styrene, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for the preparation of ferrocenyl substituted styrene will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3284745