Dibromomethane → HCID 67159854, compound

HRID 2098431Notes

Reaction equation

C[Li].[CH2:3]([C:9]1[C:10](=O)[CH2:11][CH2:12][CH:13]=1)[CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].BrCBr.C([Mg]Cl)(C)(C)C.C([O:26][CH2:27][CH3:28])C>>[CH2:3]([C@@:4]12[CH2:5][C@@H:6]1[CH2:7][CH2:8][C:27]2([CH3:28])[OH:26])[CH2:9][CH2:10][CH2:11][CH2:12][CH3:13]

Participants

Reactant 5

HCID 3024Dibromomethane

HCID 3283Diethyl Ether3×

HCID 667682-Hexyl-2-cyclopenten-1-one

HCID 178418310HCID 178418310, compound

HCID 178418348HCID 178418348, compound

Product 1

HCID 67159854HCID 67159854, compoundYield 60%

Procedure

Methyl lithium 1.6 M in diethyl ether (4 ml, 7 mmol) is added dropwise to 2-hexylcyclopent-2-enone (Isojasmone B11) (1 g, 6 mmol) in diethylether (4 ml) at −78° C. At 0°-5° C. dibromomethane (3×0.6 ml, 24 mmol) and tert-butyl magnesium chloride 2M in diethyl ether (3×4 ml, 24 mmol) are added. Work-up after 18 h at 25° C. (as described in example 1) and bulb-to-bulb distillation gives 0.7 g (60%) of a colorless oil (cisltrans=93:7). 1H NMR (CDCl3): δ 0.3 (m, 1H), 0.7 (m, 1H), 0.9 (t, 3H), 1.05 (m, 1H), 1.2-2 (15H), 1.3 (s, 3H) ppm. 13C-NMR (CDCl3): δ 11.0 (t), 14.0 (q), 22.6 (t), 23.4 (d), 24.7 (t), 25.15 (q), 27.5 (t), 29.9 (t), 31.2 (t), 31.8 (t), 34.3 (s), 37.9 (t), 81.05 (s). cis-configuration assigned by COSY, HMBC, HSQC, NOESY in CDCl3. MS (EI): m/z (%) 196 (M+, 2), 181 ([M-15]+, 14), 155 (24), 138 (15), 135 (27), 125 (32), 110 (34), 107 (38), 93 (92), 79 (50), 57 (14), 43 (100).

Workup

distillationWork-up after 18 h at 25° C. (as described in example 1) and bulb-to-bulb distillation

Sources & evidence

ORD record: ord-cb4e8772ca894baa88a9c4666edf1ba0
Source dataset: uspto-grants-2013_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08450533B2

Reaction notes

Loading…