Dibromomethane → HCID 67160199, compound

HRID 2098429Notes

Reaction equation

HRID 2098429 reaction equation
[C:1]12[CH2:9][CH:5]([C:6]1(C)C)[CH:4]([OH:10])[CH:3](C1(C3CC4CC(C4(C)C)=C3C)CC3CC(C3(C)C)=C1C)[C:2]=2[CH3:31].BrCBr.[CH2:35]([Mg]Cl)[CH2:36][CH2:37]C>C(OCC)C>[CH:36]([C:4]1([OH:10])[CH2:5][CH2:9][C@:1]2([CH3:6])[C@@H:2]([CH2:31]2)[CH2:3]1)([CH3:37])[CH3:35]

Participants

5

Reactant 3

HCID 3024DibromomethaneHCID 56924154HCID 56924154, compoundHCID 178418265HCID 178418265, compound

Product 1

HCID 67160199HCID 67160199, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

Prepared as described in Example 10 from Terpinen-4-ol (2 g, 13 mmol) and dibromomethane (9.15 g, 52 mmol) in diethyl ether by dropwise addition of tent-butyl magnesium chloride 2M in diethyl ether (26 ml, 52 mmol) at 10°-20° C. Work-up after 16 h at 25° C. and bulb-to-bulb distillation gave 2.1 g (85%) of a colorless oil. Odour: Agrestic. 1H-NMR (CDCl3): δ 0.3 (dd, 1H), 0.43 (dd, 1H), 0.6 (dddd, 1H), 0.89 (d, 3H), 0.91 (d, 3H), 1.03 (s, 3H), 1.1-1.2 (m, 2H), 1.2-1.3 (m, 1H), 1.5-1.7 (2 m, 2H), 1.75-1.9 (2H), 2.2 (m, 2H) ppm. 13C-NMR: δ 14.4 (s), 16.2 (q), 16.4 (q), 17.7 (d), 19.9 (t), 27.2 (q), 28.1 (t), 31.6 (t), 31.9 (d), 35.7 (t), 72.8 (s). syn-configuration confirmed by COSY, HSQC, HMBC, NOESY in CDCl3. MS (EI): m/z (%) 168 [M]+, 3), 150 ([M-18]+, 8), 125 (32), 107 (65), 86 (38), 71 (80), 43 (100). IR (film): 3419 (br), 2936 (m), 2863 (m), 1458 (m), 1379 (w), 1302 (w), 1225 (w), 1133 (m), 1049 (w), 992 (s), 957 (w), 906 (w), 863 (w).

Workup

  1. customPrepared
  2. distillationbulb-to-bulb distillation

Sources & evidence

ORD record
ord-55002bfcd8cf43d8bad5f88548c06b0c
Source dataset
uspto-grants-2013_05
Patent number
US08450533B2

Reaction notes

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