Oligothiophenes and synthesis thereof

Details Oligothiophenes and synthesis thereof Oligothiophenes and synthesis thereof

2001-05-22

2003-02-04

Lambkin, Deborah C. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S043000

Reexamination Certificate

active

06515144

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to novel oligothiophenes and processes for the synthesis thereof, and more particularly, to such oligothiophenes in which the thiophene rings are cross-conjugated and annelated into a helix.
Five-membered ring unsaturated heterocycles, containing two double bonds and one heteroatom, are building blocks for conductive polymers. Polypyrrole and polythiophene are among the well-known conductive polymers with good stability and processability. These heterocycle polymers contain a pi- conjugated system (single and double bonds alternating) along a main polymer chain, linear or branched.
Pi-conjugated compounds, particularly thiophene-containing or furan-containing compounds, are used in various industrial applications. For example, they can be used as dyes or pigments, as (semi)conductors, (electro)luminescent material or in optical and electro-optical devices such as light emitting diodes, field-effect transistors, solar cells, polarizing optical elements and rechargeable batteries, and electrolytic capacitors. General background concerning the structure, properties and uses of redox active, electroactive, conductive polymers is described in an article entitled “Conductive Polymers” by Mercouri G. Kanatzidis published in Chemical and Engineering News, Dec. 3, 1990 and in U.S. Pat. Nos. 4,569,734; 4,640,749; 4,818,646; 4,987,042; 5,108,573; 4,758,634; 5,919,951; and 6,184,540, each of which is incorporated herein by reference.
There remains a need for improved oligothiophenes and processes for synthesizing them.
SUMMARY OF THE INVENTION
Among the several objects of the invention may be noted the provision of novel oligothiophenes and intermediates therefor; the provision of novel processes for preparing such oligothiophenes; the provision of such processes which produce oligothiophenes in the form of a helix; and the provision of such oligothiophenes which are produced by cross-conjugating and annelating thiophene rings into a helix. Other objects and features will be in part apprent and in part pointed out hereinafter.
Briefly, the present invention is directed to compounds of the formula:
wherein X is Br or I and R
1
is trialkyl with the alkyl group having from 1 to 6 carbon atoms.
The invention is also directed to intermediate compounds of the formula:
wherein X is Br or I and Y is H or SiR
1
wherein R
1
is trialkyl with the alkyl group having from 1 to 6 carbon atoms.
The invention is further directed to a process for preparing compounds of the first formula above comprising the steps of
(a) converting a compound of the formula:
wherein X is Br or I, to a compound of the formula:
wherein X is as defined above and R
1
is trialkyl with the alkyl group having from 1 to 6 carbon atoms;
(b) cross-conjugating compounds of the formula (3) above to a compound of the formula:
wherein X and R
1
are as defined above; and
(c) annelating a compound of the formula (4) above to produce an oligothiophene helix of the first formula above.


REFERENCES:
patent: 4569734 (1986-02-01), Naarmann et al.
patent: 4640479 (1987-02-01), Shely et al.
patent: 4758634 (1988-07-01), Jenekhe
patent: 4818646 (1989-04-01), Takakubo et al.
patent: 4987042 (1991-01-01), Jonas et al.
patent: 5108573 (1992-04-01), Rubinstein et al.
patent: 5519147 (1996-05-01), Swager et al.
patent: 5919951 (1999-07-01), Chmii et al.
patent: 6184540 (2001-02-01), Chmii et al.
patent: 6242561 (2001-06-01), Mohwald et al.
patent: 6403809 (2002-06-01), Holmes et al.
Gronovitz, Halogen-Metal Interconversion with Dibromobithienyls,Acta Chem. Scand., 1961,\pp. 1393-1395, vol. 15, No. 6. Chemical Societies in Denmark, Finland, Norway and Sweden.
Jong et al., The Synthesis, Oxidation, and Electronic Spectra of Four Dithienothiphenes,J. Org. Chem.,1971, pp. 1645-1648, vol. 36, No. 12, American Chemical Society, USA.
Kanatzidis, Conductive Polymers,Chemical&Engineering News, Dec. 3, 1990, pp. 36-54.
Meurer et al. Helical Molecules in Organic Chemistry,Top Curr. Chem.,1985, pp. 1-76.
Navaza et al., General Models for Helicenes,Bull. Soc. Chim. Belg.,1979, pp. 863-870, vol. 88, No. 11.
Suffert, Simple Direct Titration of Organolithium Reagents Using N-Pivaloyl-o-toluidine and/or N-pivaloyl-o-benzylaniline, J.Org. Chem.,1989, pp. 509-510, vol. 54, No. 2, Amer. Chem. Society, USA.

Affiliated with

Also associated with

Rating

Oligothiophenes and synthesis thereof does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Oligothiophenes and synthesis thereof, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Oligothiophenes and synthesis thereof will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3132391