Ammonium Chloride → HCID 66731141, compound

HRID 1802834Notes

Reaction equation

HRID 1802834 reaction equation
[CH3:1][Li].[OH:3][CH:4]1[CH:9]2[C:10]([CH3:16])([CH3:15])[CH:11]3[CH2:14][C:8]2([CH2:13][CH2:12]3)[C:7]([CH3:18])([CH3:17])[CH2:6][C:5]1=[O:19].[Cl-].[NH4+]>C(OCC)C>[CH3:17][C:7]1([CH3:18])[CH2:6][C:5]([CH3:1])([OH:19])[CH:4]([OH:3])[CH:9]2[C:10]([CH3:15])([CH3:16])[CH:11]3[CH2:14][C:8]12[CH2:13][CH2:12]3

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 58240634HCID 58240634, compoundHCID 178418348HCID 178418348, compound2×

Product 1

HCID 66731141HCID 66731141, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

Methyllithium (63 ml of a 1.6M solution in diethyl ether, 0.10 mol) was added over 1 h to a solution of crude 5-hydroxy-2,2,7,7-tetramethyltricyclo[6.2.1.01.6]undecan-4-one (4, 20 g, obtained as in Example 1c) in diethyl ether (200 ml), cooled below 10° C. After 1.5 h stirring, an additional portion of methyllithium (50 ml of a 1.6M solution in diethyl ether, 0.080 mol) was added and stirring continued overnight at room temperature. The reaction mixture was poured onto a stirred mixture of saturated aqueous solution of ammonium chloride (200 ml) and ice (100 g), the phases separated and the aqueous phase extracted with MTBE (200 ml). The combined organic phases were washed with water (3×200 ml), dried (Na2SO4), concentrated in vacuo and the residue (21 g) purified by flash chromatography (MTBE/hexane 1:3 to 1:2) to afford 2,2,4,7,7-pentamethyltricyclo[6.2.1.01.6]undecane-4,5-diol (5b, 5.7 g, ˜46% yield starting from 3, white solid).

Workup

  1. temperaturecooled below 10° C
  2. stirringstirring continued overnight at room temperature
  3. customthe phases separated
  4. extractionthe aqueous phase extracted with MTBE (200 ml)
  5. washThe combined organic phases were washed with water (3×200 ml)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customthe residue (21 g) purified by flash chromatography (MTBE/hexane 1:3 to 1:2)

Sources & evidence

ORD record
ord-3747b5a34c804a3db8e912d3994fcbf2
Source dataset
uspto-grants-2013_01
Patent number
US08349890B2

Reaction notes

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