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Synthesis 2007(6): 893-901  
DOI: 10.1055/s-2007-965947
PAPER
© Georg Thieme Verlag Stuttgart · New York

New Anthracenyl-Substituted Phosphonates: Synthesis and Utility

K. C. Kumara Swamy*, Venu Srinivas, K. V. P. Pavan Kumar, K. Praveen Kumar
School of Chemistry, University of Hyderabad, Hyderabad 500046, India
Fax: +91(40)23012460; e-Mail: kckssc@uohyd.ernet.in;
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Publication History

Received 26 October 2006
Publication Date:
20 February 2007 (online)

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Abstract

Chlorination of α-hydroxyphosphonate anthracen-9-yl(5,5-dimethyl-2-oxo-2λ5-1,3,2-dioxaphosphinan-2-yl)methanol (11) using thionyl chloride unexpectedly yields 10-(5,5-dimethyl-2-oxo-2λ5-1,3,2-dioxaphosphinan-2-ylmethylene)anthracen-9(10H)-one (13), 2-(10-chloroanthracen-9-ylmethyl)-5,5-dimethyl-2λ5-1,3,2-dioxaphosphinan-2-one (14), and 10-(5,5-dimethyl-2-oxo-2λ5-1,3,2-dioxaphosphinan-2-ylmethylene)-9,10-dihydroanthracen-9-ol (15) in addition to 2-[anthracen-9-yl(chloro)methyl]-5,5-dimethyl-2λ5-1,3,2-dioxaphosphinan-2-one (12). The reaction of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane (5) with 9-anthraldehyde leads to 2-chloro-1,1-dimethylethyl hydrogen 10-(5,5-dimethyl-2-oxo-2λ5-1,3,2-dioxaphosphinan-2-ylmethylene)-4a,9,9a,10-tetrahydroanthracen-9-ylphosphonate (20) in addition to 12. Bromination of 11 with phosphorus tribromide affords the 10-bromoanthracen-9-yl product, 2-(10-bromoanthracen-9-ylmethyl)-5,5-dimethyl-2λ5-1,3,2-dioxaphosphinan-2-one (22). Reaction of 12 with 4-chloro- or 4-nitrobenzaldehyde in the presence of sodium hydride affords the products, 9-(2-arylvinyl)anthracenes 23 and 24 in an uncommon Horner-Wadsworth-Emmons-type reaction. Compound 22 underwent the normal Horner-Wadsworth-Emmons reaction with benzaldehydes or ferrocenecarbaldehyde to afford disubstituted alkenes. One of these alkenes, (E)-9-bromo-10-[2-(4-bromophenyl)vinyl]anthracene (26), undergoes Sonogashira coupling with terminal alkynes to afford the conjugated alkynes (E)-9-bromo-10-[2-(4-ethynylphenyl)vinyl]anthracenes 30-32 in moderate yields. X-ray crystal structures of 12-15, 20, 23 and (E)-9-bromo-10-[2-(4-methoxyphenyl)vinyl]anthracene (27) have been determined.

Key words

phosphonates - arenes - halogenation - Horner-Wadsworth-Emmons reaction - cross-coupling

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12

In normal Horner-Wadsworth-Emmons reactions, hydrogen is eliminated by the base to produce the carbanion, which then reacts with the aldehyde.

17

We have also observed two butadiene products of very close TLC R f values from the reaction of 12 with using cinnamaldehyde. One of these contains hydrogen at the C10 (product a) and the second one (product b) does not [1H NMR (400 MHz, CDCl3): product a: δ = 6.75 (d, J = 16.0 Hz, 1 H, olefinic-H), 6.84 (dd, J = 10.8, 16.0 Hz, 1 H, olefinic-H), 7.25-7.58 (m, 11 H, phenyl-H, anthryl-H), 8.03, 8.37 (d with virtual coupling, 4 H, anthryl-H), 8.42 (s, 1 H, anthryl-H). Product b: δ = 6.74-6.82 (m, 2 H, olefinic-H), 7.25-7.66 (m, 11 H, phenyl-H, anthryl-H, olefinic-H), 8.38 (d, J = 8.8 Hz, 2 H, anthryl-H), 8.58 (d, J = 8.8 Hz, 2 H, anthryl-H)].