Chloromethyl Methyl Ether → (cis-3-Methoxymethoxymethylcyclohexyl)methanol

HRID 854658Notes

Reaction equation

HRID 854658 reaction equation
[OH:1][CH2:2][C@@H:3]1[CH2:8][CH2:7][CH2:6][C@H:5]([C:9]([O:11][CH3:12])=O)[CH2:4]1.[CH3:13][O:14]CCl.C(NC(C)C)(C)C.[NH4+].[Cl-]>ClCCl.O>[CH3:13][O:14][CH2:12][O:11][CH2:9][C@@H:5]1[CH2:6][CH2:7][CH2:8][C@H:3]([CH2:2][OH:1])[CH2:4]1

Participants

7

Reactant 4

HCID 7864Chloromethyl Methyl EtherHCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 57350257Methyl cis-3-hydroxymethylcyclohexanecarboxylate

Product 1

HCID 69243775(cis-3-Methoxymethoxymethylcyclohexyl)methanolYield 88.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

1.70 g of methyl cis-3-hydroxymethylcyclohexanecarboxylate are dissolved in 20 ml of dichloromethane, 1.60 g of methoxymethyl chloride and 2.60 g of diisopropylamine are added and the mixture is stirred at room temperature for 15 h. 50 ml of saturated NH4Cl solution and 50 ml of water are added to the solution, and the organic phase is separated off. The aqueous phase is extracted with dichloromethane and the combined organic phases are dried over magnesium sulfate and concentrated. This gives 2.0 g of methyl cis-3-methoxymethoxymethylcyclohexanecarboxylate as a yellow oil. This is dissolved in 50 ml of diethyl ether, 350 mg of LiAlH4 are added and the mixture is stirred at room temperature. After 2 h at 0° C., 5 ml of ethyl acetate, 40 ml of methyl tert-butyl ether and 3 g of MgSO4 are added. 15 ml of 10N KOH are then added dropwise. The suspension is stirred for 3 h and filtered through Celite and the filtrate is concentrated, which gives 1.65 g of (cis-3-methoxymethoxymethylcyclohexyl)methanol as a colorless oil.

Workup

  1. customthe organic phase is separated off
  2. extractionThe aqueous phase is extracted with dichloromethane
  3. dry with materialthe combined organic phases are dried over magnesium sulfate
  4. concentrationconcentrated
  5. dissolutionThis is dissolved in 50 ml of diethyl ether
  6. addition350 mg of LiAlH4 are added
  7. stirringthe mixture is stirred at room temperature
  8. waitAfter 2 h at 0° C.
  9. addition5 ml of ethyl acetate, 40 ml of methyl tert-butyl ether and 3 g of MgSO4 are added
  10. addition15 ml of 10N KOH are then added dropwise
  11. stirringThe suspension is stirred for 3 h
  12. filtrationfiltered through Celite
  13. concentrationthe filtrate is concentrated

Sources & evidence

ORD record
ord-c8a52700e3e14f6f853f6f4894ecf53e
Source dataset
uspto-grants-2007_08
Patent number
US07259177B2

Reaction notes

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