A Simple and Efficient Conversion of Tertiary Cyclopropanols to 2-Substituted Allyl Halides

Abstract

Readily available sulphonates of tertiary cyclopropanols are converted into 2-substituted allyl bromides in high yields under the action of magnesium bromide in diethyl ether. Magnesium chloride, aluminium chloride and titanium tetrachloride also induce effectively the transformation of cyclopropyl sulphonates into the corresponding allyl chlorides.

cyclopropanols - sulphonic esters - ring cleavage - allyl halides - magnesium halides

References

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<A NAME="RG34301ST-13">13</A> We have obtained this finding quite accidentally. A search in the literature revealed that magnesium halides have been earlier proposed by Gore and co-workers as an efficient reagent for nucleophilic displacement of p-tosyloxy or mesyloxy groups by halogen atoms: Place P. Roumestanant M.-L. Gore J. Bull. Soc. Chim. Fr.  1976,  169 

<A NAME="RG34301ST-14">14</A>

Typical Procedure: A solution of 1-hexylcyclopropyl methanesulfonate 2a 7.65 g (35 mmol) in 10 mL Et₂O was added slowly into MgBr₂ (52 mmol) solution (prepared from 1.26 g magnesium turnings and 4.5 mL 1,2-dibromoethane in 30 mL Et₂O) at r.t. When the reaction was completed (control by TLC), water was added to the mixture until precipitate was dissolved. Water layer was extracted with Et₂O, washed with 5% NaCl solution and dried over Na₂SO₄. After evaporation of the solvent, the resulting crude product was purified by column chromatography, using petroleum ether eluent and silica gel (Merck 70-230), yielding 6.82 g (95%) of pure allyl halide 3.

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<A NAME="RG34301ST-17">17</A>

Entry 11: ¹H NMR (200 MHz, CDCl₃) δ = 0.60-0.74 (m, 1 H), 0.80-0.92 (m, 1 H), 1.06-1.22 (m, 2 H), 1.74 (d, J = 6.5 Hz, 3 H), 2.09 (dd, J ₁ = 15 Hz, J ₂ = 8 Hz, 1 H), 2.45 (s, 3 H), 2.49 (dd, J ₁ = 15 Hz, J ₂ = 6 Hz, 1 H), 4.28-4.50 (m, 1 H), 7.35 (d, J = 8 Hz, 2 H), 7.77 (d, J = 8 Hz, 2 H). Entry 19: ¹H NMR (200 MHz, CDCl₃) δ = 0.92 (t, J = 6 Hz, 1 H), 1.04-1.40 (m, 2 H), 1.58 (dd, J ₁ = 12 Hz, J ₂ = 8 Hz, 1 H), 1.66-2.06 (m, 3 H), 2.10-2.44 (m, 2 H), 3.02 (s, 3 H).

<A NAME="RG34301ST-18">18</A>

Entry 11: ¹H NMR (200 MHz, CDCl₃): δ = 1.76 (d, J = 6.5 Hz, 3 H), 2.61-2.89 (m, 2 H), 4.01 (s, 2 H), 4.17-4.28 (m, 1 H), 5.08 (d, J = 1 Hz, 1 H), 5.32 (s, 1 H). n _D ²⁰ = 1.5235. Entry 19: ¹H NMR (200 MHz, CDCl₃): δ = 1.86-2.06 (m, 2 H), 2.28-2.50 (m, 4 H), 4.08 (s, 1.8 H), 4.88-4.95 (m, 0.1 H), 5.07 (s, 0.1 H), 5.30 (s, 0.1 H), 5.78 (s, 0.9 H).