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

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.

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

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m/z for most intense peak of isotope envelope (relative intensity, %):

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33

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.

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