Diethyl Ether → HCID 20517423, compound

HRID 2059137Notes

Reaction equation

HRID 2059137 reaction equation
[N+](=[CH:3][CH3:4])=[N-].CCOCC.[OH:10][CH:11]1[CH2:16][CH2:15][C:14](=[O:17])[CH2:13][CH2:12]1>C(O)C.C(O)(=O)C>[OH:17][CH:14]1[CH2:13][CH2:12][C:11](=[O:10])[CH:3]([CH3:4])[CH2:16][CH2:15]1

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 70695Diazoethane2×HCID 5437064-Hydroxycyclohexanone

Product 1

HCID 20517423HCID 20517423, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 702EthanolSolvent

Procedure

To a freshly prepared solution of diazoethane in ether (~550 ml of 0.297 M =163 mmol) cooled to -10° C. and well stirred with a magnetic stirrer in an open 1 liter Erlenmeyer flask is added slowly a solution of 4-hydroxycyclohexanone (14.8 g, 13 mmol) in ethanol (150 ml) over a period of 15 minutes. The cooling bath is removed and the stirred reaction mixture is allowed to come to room temperature and stirred overnight. The excess diazoethane is discharged by adding a few drops of 10% aq. acetic acid and then the solvent is removed in vacuo. The residue is dissolved in ether, washed with a satd. aq. NaHCO3 solution, dried (Na2SO4) and the ether is removed in vacuo. Distillation of the residue in vacuo affords (±) 5-hydroxy-2-methylcycloheptanone which exists as an equilibrium mixture with its tautomeric bicyclic hemiacetal form (bp, 1.4 mm, 97°-99°, 17.51 g, 95%). IR (neat)μ: 2.93 (OH), 5.90 (C=O), NMR (CDCl3)δ: 0.91 (d, J=7 Hz, 2-CH of 2-y), 0.8 (d, J=7 Hz, 2-CH3), 3.4-4.5 (m, ##STR3## and ##STR4## GC-MS: RGC shows two components (~60:40) both of which show M+ 142 and identical fragmentations. MOX derivatization gave a single peak in RGC with M+ 171.

Workup

  1. customThe cooling bath is removed
  2. customthe stirred reaction mixture
  3. customto come to room temperature
  4. stirringstirred overnight
  5. customthe solvent is removed in vacuo
  6. dissolutionThe residue is dissolved in ether
  7. washwashed with a satd
  8. dry with materialaq. NaHCO3 solution, dried (Na2SO4)
  9. customthe ether is removed in vacuo
  10. distillationDistillation of the residue in vacuo

Sources & evidence

ORD record
ord-9d9c650027d547498f83a0ac95343d7f
Source dataset
uspto-grants-1982_03
Patent number
US04322357

Reaction notes

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