Ethylene Glycol → Methyl 8-(4-bromophenyl)-1,4-dioxaspiro[4.5]decane-8-carboxylate

HRID 881713Notes

Reaction equation

HRID 881713 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:15]([O:17][CH3:18])=[O:16])[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[CH2:19](O)[CH2:20][OH:21]>C1(C)C=CC(S(O)(=O)=O)=CC=1.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2([C:15]([O:17][CH3:18])=[O:16])[CH2:9][CH2:10][C:11]3([O:21][CH2:20][CH2:19][O:14]3)[CH2:12][CH2:13]2)=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 174Ethylene GlycolHCID 71742255Methyl 1-(4-bromophenyl)-4-oxocyclohexanecarboxylate

Product 1

HCID 86700820Methyl 8-(4-bromophenyl)-1,4-dioxaspiro[4.5]decane-8-carboxylateYield 100.1%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 1140TolueneSolvent

Procedure

To a round bottom flask containing methyl 1-(4-bromophenyl)-4-oxocyclohexanecarboxylate (4.64 g, 14.91 mmol) was added toluene (33 ml), ethylene glycol (8.32 ml, 149 mmol) and p-toluenesulfonic acid (85 mg, 0.45 mmol) at room temperature. The mixture was heated to 80 C. for 2 hours. The content was then cooled to room temperature and quenched with a saturated solution of sodium bicarbonate. The organic portion was washed with saturated sodium bicarbonate and the aqueous portion extracted with MTBE twice. The combined organic portion was dried over sodium sulfate and concentrated to afford a crude oil. Column purification afforded the title compound as viscous oil (5.30 g, quantitative yield). LC/MS, ESI-MS(+): 357.1, RT: 1.38 (Condition E).

Workup

  1. temperatureThe mixture was heated to 80 C
  2. customquenched with a saturated solution of sodium bicarbonate
  3. washThe organic portion was washed with saturated sodium bicarbonate
  4. extractionthe aqueous portion extracted with MTBE twice
  5. dry with materialThe combined organic portion was dried over sodium sulfate
  6. concentrationconcentrated
  7. customto afford a crude oil
  8. customColumn purification

Sources & evidence

ORD record
ord-6972e56f9d5140af8bbf0c975eceb7b6
Source dataset
uspto-grants-2015_03
Patent number
US08993619B2

Reaction notes

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