Nitric Acid → (R)-3-methyl-4-nitroxy-2-(2-propynyl)-2-cyclopenten-1-one

HRID 1583499Notes

Reaction equation

HRID 1583499 reaction equation
[N+:1]([O-:4])([OH:3])=[O:2].C(OC(=O)C)(=O)C.O[C@@H:13]1[CH2:17][C:16](=[O:18])[C:15]([CH2:19][C:20]#[CH:21])=[C:14]1[CH3:22]>C(Cl)(Cl)Cl>[CH3:22][C:14]1[C@H:13]([O:2][N+:1]([O-:4])=[O:3])[CH2:17][C:16](=[O:18])[C:15]=1[CH2:19][C:20]#[CH:21]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic AnhydrideHCID 11116226(R)-4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopenten-1-one

Product 1

HCID 13387529(R)-3-methyl-4-nitroxy-2-(2-propynyl)-2-cyclopenten-1-oneYield 97%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Into a mixed solution of 8 g of fuming nitric acid and 24 g of acetic anhydride, kept at a temperature of -5° to 10° C., was added dropwise 6 g of (R)-4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopenten-1-one ([α]D23 ; -19.5° (C=1.36, in chloroform), (R)-isomer/(S)-isomer=96.7/3.3). Then, the mixture was stirred for 30 minutes at the same temperature. Thereafter, the reaction mixture was poured into 200 ml of ice water, and then subjected to a toluene extraction. The toluene layer was separated and washed with an aqueous 5% sodium hydrogencarbonate solution and then with water. The extract was dried over anhydrous magnesium sulfate and, then, concentrated to give 7.56 g of crude (R)-3-methyl-4-nitroxy-2-(2-propynyl)-2-cyclopenten-1-one.

Workup

  1. customkept at a temperature of -5° to 10° C.
  2. extractionsubjected to a toluene extraction
  3. customThe toluene layer was separated
  4. washwashed with an aqueous 5% sodium hydrogencarbonate solution
  5. dry with materialThe extract was dried over anhydrous magnesium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-c820d7fce1214156a5f9fd7fae3ae70b
Source dataset
uspto-grants-1985_11
Patent number
US04552703

Reaction notes

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