Dibromomethane → HCID 10933067, compound

HRID 2098428Notes

Reaction equation

HRID 2098428 reaction equation
[CH3:1]/[C:2](=[CH:5]\[CH2:6][C@H:7]1[CH2:12][C@H:11]2[C@:9]([CH3:13])([CH2:10]2)[C:8]1([CH3:15])[CH3:14])/[CH2:3][OH:4].[CH3:16][Mg]Cl.O1CCCC1.BrCBr.C([Mg]Cl)(C)(C)C>>[CH3:1][C:2]1([CH2:3][OH:4])[CH2:16][CH:5]1[CH2:6][C@H:7]1[CH2:12][C@H:11]2[C@:9]([CH3:13])([CH2:10]2)[C:8]1([CH3:15])[CH3:14]

Participants

6

Reactant 5

HCID 3024Dibromomethane3×HCID 8028TetrahydrofuranHCID 54768130HCID 54768130, compoundHCID 178418310HCID 178418310, compound3×HCID 178418332HCID 178418332, compound

Product 1

HCID 10933067HCID 10933067, compound

Procedure

System B: (E)-2-methyl-4-((1S,3S,5R)-1,2,2-trimethylbicyclo-[3.1.0]hexan-3-yl)but-2-en-1-ol (5 g, 24 mmol) (F. Schröder, WO 2006066436, priority 20.12.2005 to Givaudan) is added undercooling and stirring to methyl magnesium chloride 3M in tetrahydrofuran (8 ml, 24 mmol) under nitrogen. Dibromomethane and tert-butyl magnesium chloride are added at a temperature of 10°-20° C. The dibromomethane and tert-butyl magnesium chloride are each added in 3 portions, one portion of dibromomethane (4.2 g, 24 mmol) followed by a portion of tert-butyl-magnesium chloride (12 ml, 24 mmol). After the addition of each pair of portions (72 mmol) the mixture is stirred for an appropriate time at room temperature. When complete or nearly complete conversion is reached, as checked by GC, the mixture is quenched by addition of conc. NH4Cl. Tert-Butyl methyl ether extraction, washing of the organic phase with H2O until pH 7, drying over MgSO4 and concentration gives 16.6 g of an an oily residue, which is bulb-to bulb-distilled at 120° C./0.07 Ton giving 4.7 g (89%) of Javanol (dr=1:1), whose analytical data are consistent with the ones described for this compound in the literature (J. A. Bajgrowicz, G. Frater, EP 801049, priority 9.4.1997 to Givaudan-Roure).

Workup

  1. additionSchröder, WO 2006066436, priority 20.12.2005 to Givaudan) is added
  2. customthe mixture is quenched by addition of conc. NH4Cl
  3. extractionTert-Butyl methyl ether extraction
  4. washwashing of the organic phase with H2O until pH 7
  5. dry with materialdrying over MgSO4 and concentration
  6. customgives 16.6 g of an an oily residue, which
  7. distillationbulb-distilled at 120° C./0.07 Ton
  8. customgiving 4.7 g (89%) of Javanol (dr=1:1), whose analytical data

Sources & evidence

ORD record
ord-b0f74bf13d9c47559b328ef4b17f860b
Source dataset
uspto-grants-2013_05
Patent number
US08450533B2

Reaction notes

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