Water → 1-(2-methyl-[1,3]dioxolan-2-yl)propane-1,2-dione 1-(O-methyloxime) 2-oxime

HRID 2306152Notes

Reaction equation

HRID 2306152 reaction equation
[OH-:1].[Na+].O.S([O-])([O-])(=O)=O.O[NH3+:10].O[NH3+].[CH3:13][O:14]/[N:15]=[C:16](/[C:20]1([CH3:25])[O:24][CH2:23][CH2:22][O:21]1)\[C:17](=O)[CH3:18]>C(OC)(C)(C)C>[CH3:13][O:14][N:15]=[C:16]([C:20]1([CH3:25])[O:24][CH2:23][CH2:22][O:21]1)[C:17](=[N:10][OH:1])[CH3:18]

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium Hydroxide3×HCID 24846Hydroxylamine sulfate2×HCID 22967234(1E)-1-methoxyimino-1-(2-methyl-1,3-dioxolan-2-yl)propan-2-one

Product 1

HCID 1363835521-(2-methyl-[1,3]dioxolan-2-yl)propane-1,2-dione 1-(O-methyloxime) 2-oxime

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
50 °C

Procedure

24 g (0.03 mol) of 50% strength aqueous sodium hydroxide solution and 200 ml of water were initially charged at 25° C. and admixed a little at a time with a total of 25 g (0.0152 mol) of hydroxylammonium sulfate. 50 g (0.0267 mol) of the ketal (Example 2) were then added dropwise, and the reaction mixture was stirred at 50° C. (pH=7-8) for 9 hours. A pH of 5-6 was then set using aqueous sodium hydroxide solution, and the mixture was stirred at 50° C. for 48 hours. Another 25 g of hydroxylammonium sulfate and 24 g of 50% strength aqueous sodium hydroxide solution were then metered in, and the mixture was stirred at 50° C. for another 20 hours. 300 ml of methyl tert-butyl ether were then added. The solid which is insoluble in the two-phase mixture was filtered off, washed with a little hexane and dried. This gave 9 g of the title compound (phys. data of the E,E-isomers see Tab. 2). The organic phase of the two-phase mixture obtained as mother liquor was dried over sodium sulfate and subsequently concentrated on a rotary evaporator. This gave another 17.5 g of the title compound.

Workup

  1. stirringthe mixture was stirred at 50° C. for 48 hours
  2. stirringwas stirred at 50° C. for another 20 hours
  3. filtrationwas filtered off
  4. washwashed with a little hexane
  5. customdried
  6. customThe organic phase of the two-phase mixture obtained as mother liquor
  7. dry with materialwas dried over sodium sulfate
  8. concentrationsubsequently concentrated on a rotary evaporator

Sources & evidence

ORD record
ord-01736f72029c4e44a0cb72335530c32d
Source dataset
uspto-grants-2002_08
Patent number
US06441236B1

Reaction notes

Loading…