Dimethyl Sulfoxide → 6-cyano-3,4-dihydro-2,2-dimethyl-4(2-oxocyclopentyl)-2H-1,4-benzoxazine

HRID 37120Notes

Reaction equation

HRID 37120 reaction equation
CS(C)=O.[C:5]([C:7]1[CH:8]=[CH:9][C:10]2[O:15][C:14]([CH3:17])([CH3:16])[CH2:13][N:12]([CH:18]3[CH2:22][CH2:21][CH2:20][CH:19]3[OH:23])[C:11]=2[CH:24]=1)#[N:6].C(N(CC)CC)C>C(Cl)Cl.C(Cl)(=O)C(Cl)=O.O>[C:5]([C:7]1[CH:8]=[CH:9][C:10]2[O:15][C:14]([CH3:17])([CH3:16])[CH2:13][N:12]([CH:18]3[CH2:22][CH2:21][CH2:20][C:19]3=[O:23])[C:11]=2[CH:24]=1)#[N:6]

Participants

7

Reactant 3

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 199345646-cyano-3,4-dihydro-2,2-dimethyl-4-(2-hydroxycyclopentan-1-yl)-2H-1,4-benzoxazine

Product 1

HCID 106834746-cyano-3,4-dihydro-2,2-dimethyl-4(2-oxocyclopentyl)-2H-1,4-benzoxazineYield 52.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×HCID 65578Oxalyl chlorideSolvent

Procedure

In 5 ml of methylene chloride was dissolved 0.2 ml of oxalyl chloride and at a constant temperature between -50° C. and -60° C., a solution prepared by dissolving 0.34 ml of dimethyl sulfoxide in 1 ml of methylene chloride was added dropwise. The mixture was stirred for 2 minutes, after which a solution of 0.54 g of 6-cyano-3,4-dihydro-2,2-dimethyl-4-(2-hydroxycyclopentan-1-yl)-2H-1,4-benzoxazine in 2 ml of methylene chloride was added dropwise. The mixture was further stirred for 15 minutes and 0.7 ml of triethylamine was added. The mixture was stirred for an additional 5 minutes, after which it was allowed to return to room temperature. The reaction mixture was diluted with 10 ml of water and extracted with methylene chloride. The extract was washed with aqueous sodium chloride solution and dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was recovered by filtration, washed with ethanol and recrystallized from ethyl acetate to give 0.28 g of 6-cyano-3,4-dihydro-2,2-dimethyl-4(2-oxocyclopentyl)-2H-1,4-benzoxazine.

Workup

  1. customat a constant temperature between -50° C. and -60° C., a solution prepared
  2. additionwas added dropwise
  3. stirringThe mixture was further stirred for 15 minutes
  4. stirringThe mixture was stirred for an additional 5 minutes
  5. customto return to room temperature
  6. extractionextracted with methylene chloride
  7. washThe extract was washed with aqueous sodium chloride solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationthe solvent was distilled off under reduced pressure
  10. filtrationThe residue was recovered by filtration
  11. washwashed with ethanol
  12. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-6ae0e0ccde2c4fd48a16193d6a52ab20
Source dataset
uspto-grants-1995_05
Patent number
US05420126

Reaction notes

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