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Synthesis 2003(8): 1279-1285
DOI: 10.1055/s-2003-39414
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Convenient and Convergent Syntheses of Long-Chain α,ω-Dibromides and Diphosphines of the Formula X(CH2)nX (n = 18-32)

Wolfgang Mohr, Clemens R. Horn, Jürgen Stahl, J. A. Gladysz*
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054 Erlangen, Germany
Fax: +49(9131)8526865; e-Mail: gladysz@organik.uni-erlangen.de;
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Publication History

Received 21 March 2003
Publication Date:
26 May 2003 (online)

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Abstract

The known tetrahydropyranyl ethers Br(CH2)yOTHP (y = 6, 9, 11), which are easily prepared from commercial bromoalcohols, are sequentially treated with Mg, Li2CuCl4, and X(CH2)zX (z/X = 6/Br, 7/Br, 8/Br, 10/Br, 10/I) to give the diethers THPO(CH2)nOTHP in 68-40% yields (n = 2 y + z = 18, 19, 20, 22, 24, 28, 32). Subsequent reactions with Ph3P and 2,4,4,6-tetrabromocyclohexa-2,5-dienone give the title compounds Br(CH2)nBr in 91-75% yields. Reactions with commercial K+ -PPh2 give the diphosphines Ph2P(CH2)nPPh2 in 95-74% yields.

Key words

THP ethers - Grignard reagents - cross-coupling - bromination - phosphines

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The PCH2CH2CH2 linkages of the free phosphines exhibit a characteristic pattern of 13C signals. A 1H-1H COSY experiment with Ph2P(CH2)14PPh2 was used to make definitive assignments of the corresponding 1H signals, and a 1D-NOE experiment (DPFGSE-NOE) confirmed the PCH2 signal (close contact to the ortho protons of the phenyl ring). A 1H-13C COSY experiment in turn gave a definitive assignment of the PCH2 13C signal. A selective 1D-13C-INADEQUATE spectrum verified this conclusion and enabled assignments of the remaining signals.