Allyl bromide → 3-(Allyloxy)-5-methylhex-1-yne

A solution of 5-methylhex-1-yn-3-ol (2.11 g, 18.81 mmol) in DMF (30 ml) was cooled (0° C. ice bath) and treated with 60% NaH (0.903 g, 22.57 mmol). The reaction was stirred for 20 min, then warmed to room temperature and stirred for 1 hr. To this was added allyl bromide (4.9 ml, 56.6 mmol) over 5 min. The reaction was stirred overnight. The reaction was diluted with Et2O (100 mL), washed with water (4×25 mL), brine (25 mL), dried (MgSO4), filtered and concentrated to give the product, 3-(allyloxy)-5-methylhex-1-yne (2.83 g, 13.94 mmol, 74.1% yield) as a yellow mobile oil. 1H NMR consistent with expected product, contains ca. 4:1 product/SM. Used as-is without further purification. 1H NMR (CDCl3) δ: 5.89-6.00 (m, 1H), 5.34 (dq, J=17.2, 1.6 Hz, 1H), 5.22 (dq, J=10.3, 1.4 Hz, 1H), 4.29 (ddt, J=12.6, 5.1, 1.5 Hz, 1H), 4.14 (ddd, J=7.6, 6.7, 2.0 Hz, 1H), 3.99 (ddt, J=12.6, 6.3, 1.3 Hz, 1H), 2.44 (d, J=2.0 Hz, 1H), 1.90 (dsxt, J=13.5, 6.8 Hz, 1H), 1.64-1.80 (m, 2H), 1.56-1.64 (m, 2H), 0.95 (d, J=4.6 Hz, 3H), 0.94 (d, J=4.6 Hz, 3H).

1. stirringstirred for 1 hr
2. stirringThe reaction was stirred overnight
3. washwashed with water (4×25 mL), brine (25 mL)
4. dry with materialdried (MgSO4)
5. filtrationfiltered
6. concentrationconcentrated

ORD record

ord-5c0be43332e3466ea6fe470308063277

Source dataset

uspto-grants-2016_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09273067B2