Dibromomethane → (RS)-1-((1RS,2SR)-2-((E)-hex-1-enyl)cyclopropyl)ethanol

HRID 2098430

Reaction equation

HRID 2098430 reaction equation
C[Mg]Cl.O1CCCC1.[CH:9](=O)/[CH:10]=[CH:11]/[CH:12]=[CH:13]/[CH2:14][CH2:15][CH2:16][CH3:17].BrCBr.C([Mg]Cl)(C)(C)C.C([O:30][CH2:31][CH3:32])C>>[CH:14](/[CH:15]1[CH2:17][CH:16]1[CH:31]([OH:30])[CH3:32])=[CH:13]\[CH2:12][CH2:11][CH2:10][CH3:9]

Participants

7

Reactant 6

HCID 3024DibromomethaneHCID 3283Diethyl EtherHCID 8028TetrahydrofuranHCID 52833392,4-NonadienalHCID 178418310HCID 178418310, compoundHCID 178418332HCID 178418332, compound

Product 1

HCID 67160751(RS)-1-((1RS,2SR)-2-((E)-hex-1-enyl)cyclopropyl)ethanolYield 87.7%

Procedure

Prepared as described in Example 1 (System B) from methyl magnesium chloride 3M in tetrahydrofuran (7.3 ml, 21 mmol), (2E,4E)-nona-2,4-dienal (3 g, 21 mmol), dibromomethane (15 g, 87 mmol) and tert-butyl magnesium chloride 2M in diethyl ether (43 ml, 87 mmol) at 0°-10° C. Work-up after 18 h and bulb-to-bulb distillation at 80° C./0.05 mbar gave 3.1 g (77%) of a colorless oil (syn/anti=83:17). Odour: fruity, pear, green. 1H NMR (CDCl3): δ 1H NMR (CDCl3): δ 0.5 (m, 1H), 0.7 (m, 1H), 0.8-1 (2H), 0.9 (t, 3H), 1.2-1.4 (6H), 1.8-2.0 (3H), 3.2 (m, 1H), 5.0 (m, 1H), 5.5 (m, 1H) ppm. 13C-NMR (CDCl3) syn-isomer: δ 11.5 (t), 13.9 (q), 18.8 (d), 22.2 (d), 22.5 (q), 28.1 (d), 31.7 (t), 32.1 (t), 71.5 (d), 128.9 (d), 131.7 (d). 13C-NMR (CDCl3) anti-isomer: δ 10.8 (t), 14.0 (q), 19.6 (d), 22.2 (d), 22.5 (q), 28.3 (d), 31.7 (t), 32.1 (t), 72.0 (d), 128.7 (d), 132.0 (d). syn-configuration assigned by GC retention time. MS (EI): m/z (%) 168 ([M]+, 1), 150 ([M-H2O]+, 7), 113 (48), 95 (47), 82 (33), 81 (80), 68 (72), 67 (100), 57 (43), 55 (45), 54 (80), 45 (75), 43 (56), 41 (64). IR (film): 3340 (br, OH), 2958 (m), 2925 (m), 2871 (m), 2858 (m), 1455 (m), 1414 (w), 1366 (m), 1290 (w), 1180 (w), 1103 (m), 1076 (m), 1029 (m), 959 (s), 897 (m).

Workup

  1. customPrepared
  2. distillationbulb-to-bulb distillation at 80° C./0.05 mbar

Sources & evidence

ORD record
ord-06711dd686524d78af01e4bf51005024
Source dataset
uspto-grants-2013_05
Patent number
US08450533B2

Linked notes

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