Diazomethane → 2-(2-Tetrahydrothienyl)-3-methoxy-5,5-dimethyl-2-cyclohexen-1-one

HRID 1156087Notes

Reaction equation

HRID 1156087 reaction equation
[N+](=C)=[N-].N(N[C:7](N)=O)=O.[OH-].[K+].[S:12]1[CH2:16][CH2:15][CH2:14][CH:13]1[C:17]1[C:18](=[O:26])[CH2:19][C:20]([CH3:25])([CH3:24])[CH2:21][C:22]=1[OH:23]>C(O)(=O)C.CCOCC>[S:12]1[CH2:16][CH2:15][CH2:14][CH:13]1[C:17]1[C:22](=[O:23])[CH2:21][C:20]([CH3:24])([CH3:25])[CH2:19][C:18]=1[O:26][CH3:7]

Participants

7

Reactant 4

HCID 9550Diazomethane2×HCID 14797Potassium HydroxideHCID 105035NitrosoureaHCID 123916482-(2-Tetrahydrothienyl)-3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one

Product 1

HCID 123916642-(2-Tetrahydrothienyl)-3-methoxy-5,5-dimethyl-2-cyclohexen-1-one

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 3283Diethyl EtherSolvent

Procedure

To 500 parts by volume of an ether solution of diazomethane prepared using 47 parts of N-nitroso urea and 140 parts by volume of a 40% aqueous solution of potassium hydroxide in a conventional manner, 17.7 parts of 2-(2-tetrahydrothienyl)-3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one was added little by little over a period of 20 minutes. After stirring for 15 hours at room temperature, the unreacted diazomethane was decomposed by the addition of 5 parts of acetic acid and washed with 1 N aqueous sodium hydroxide solution and then with a saturated aqueous sodium chloride solution followed by drying. After removing ether by distillation, the residue was passed through a column containing a silica gel using a solvent mixture of chloroform and benzene (1:3) as a spreading agent. Upon recrystallization of the raw product from a solvent mixture of benzene and n-hexane, 2-(2-tetrahydrothienyl)-3-methoxy-5,5-dimethyl-2-cyclohexen-1-one was obtained in the form of colorless scale-like crystals. The melting point was 111° to 112° C. The yield was 5.7 parts.

Workup

  1. additionwas added little by little over a period of 20 minutes
  2. washwashed with 1 N aqueous sodium hydroxide solution
  3. customby drying
  4. customAfter removing ether
  5. distillationby distillation
  6. additioncontaining a silica gel using
  7. additiona solvent mixture of chloroform and benzene (1:3) as a spreading agent
  8. customUpon recrystallization of the raw product
  9. additionfrom a solvent mixture of benzene and n-hexane

Sources & evidence

ORD record
ord-7776a77706874393a010dc527cce2e84
Source dataset
uspto-grants-1982_06
Patent number
US04334010

Reaction notes

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