Dibromomethane → HCID 67160121, compound

HRID 2098434Notes

Reaction equation

HRID 2098434 reaction equation
[CH:1]([C:3]12[O:11][CH:10]1[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4]2)=[CH2:2].[CH2:12]([Li])[CH2:13][CH2:14][CH3:15].[CH3:17]CCCCC.BrCBr.C([Mg]Cl)CCC>>[CH2:2]([CH:1]1[C:3]2([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH:10]2[OH:11])[CH2:17]1)[CH2:12][CH2:13][CH2:14][CH3:15]

Participants

6

Reactant 5

HCID 3024DibromomethaneHCID 8058HexaneHCID 57483484HCID 57483484, compoundHCID 178418265HCID 178418265, compoundHCID 178418339Butyllithium

Product 1

HCID 67160121HCID 67160121, compoundYield 65%

Procedure

Prepared as described in Example 24 from 1-vinyl-9-oxabicyclo[6.1.0]nonane (J P Kokai S49-047345, Takasago Perfumery Co., Ltd.) (3 g, 18 mmol), n-butyl lithium 1.6 M in hexane (11 ml, 18 mmol), dibromomethane (12.5 g, 72 mmol) and tent-butyl magnesium chloride (36 ml, 72 mmol). Work-up and bulb-to-bulb distillation at 98° C./0.05 mbar gave 2.6 g (65%) of a colorless oil (dr=93:7). 1H NMR (CDCl3): δ 0.3 (m, 1H), 0.5 (m, 1H), 0.8 (m, 1H), 0.8-1.1 and 1.2-2.4 (22H), 3.25 (1H) ppm. 13C-NMR (CDCl3): δ 14.1 (q), 20.7 (t), 22.7 (t), 23.3 (t), 23.5 (t), 24.3 (d), 26.5 (t), 26.8 (t), 28.9 (t), 29.4 (s), 29.7 (t), 30.4 (t), 31.2 (t), 31.7 (t), 73.7 (d). cis-configuration assigned by COSY, HMBC, HSQC, NOESY in DMSO-D6. MS (EI): m/z (%) 224 (M+, 1), 206 ([M-18]+, 10), 178 (4), 163 (5), 149 (12), 135 (22), 126 (24), 109 (22), 107 (24), 98 (58), 97 (33), 96 (80), 95 (46), 93 (54), 69 (41), 68 (42), 67 (84), 55 (100), 41 (80). IR (film): 3362 (br, OH), 2919 (s), 2852 (m), 1456 (m), 1364 (w), 1106 (w), 1029 (m), 989 (m), 811 (w), 741 (w), 726 (w).

Workup

  1. customPrepared
  2. distillationbulb-to-bulb distillation at 98° C./0.05 mbar

Sources & evidence

ORD record
ord-57e215930b3d48b285ab9db57c84660e
Source dataset
uspto-grants-2013_05
Patent number
US08450533B2

Reaction notes

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