2-Amino-2-methyl-1,3-propanediol → 5,5-dimethyl-1-pyrroline N-oxide

HRID 1817925Notes

Reaction equation

HRID 1817925 reaction equation
CC(N)(CO)CO.O=O.CCO[C:13]([C:15]1([CH3:21])[N+:19]([O-:20])=[CH:18][CH2:17][CH2:16]1)=O.[CH3:22][CH2:23][O:24][P:25]([O:34][CH2:35][CH3:36])([C:27]1([CH3:33])[N+:31]([O-:32])=[CH:30][CH2:29][CH2:28]1)=[O:26].O=O.CC(N)(CO)CO>>[CH3:13][C:15]1([CH3:21])[N+:19]([O-:20])=[CH:18][CH2:17][CH2:16]1.[CH3:22][CH2:23][O:24][P:25]([O:34][CH2:35][CH3:36])([C:27]1([CH3:33])[N+:31]([O-:32])=[CH:30][CH2:29][CH2:28]1)=[O:26]

Participants

6

Reactant 4

HCID 15312-Amino-2-methyl-1,3-propanediol2×HCID 121684955-ethoxycarbonyl-5-methyl-1-pyrroline N-oxideHCID 131727652Ampo O2HCID 131727653Depmpo O2

Product 2

HCID 17745,5-dimethyl-1-pyrroline N-oxideHCID 1196065-(Diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide

Procedure

The nitrone 5-carbamoyl-5-methyl-1-pyrroline N-oxide (AMPO) was successfully synthesized and characterized. Spin trapping by AMPO of hydroxyl, superoxide, C-centered, sulfite, and tert-butoxyl radicals has been demonstrated for the first time by electron paramagnetic resonance (EPR) spectroscopy. Resulting spin adducts for each of these radicals gave unique spectral profiles. Rate of superoxide radical trapping was obtained by competitive trapping by AMPO versus DEPMPO and gave kAMPO=38 M−1 s−1 (based on kDEPMPO=58 M−1 s−1) comparable to that of EMPO kEMPO=44 M−1 s−1. The half-life of AMPO-O2 adduct is about t1/2˜10 minutes similar to that observed from EMPO but significantly shorter than that of DEPMPO-O2 adduct t1/2˜16 minutes. Theoretical analyses using density functional theory calculations at the B3LYP/6-31=G**/B3LYP6-31G* level were performed on AMPO and its corresponding suproxide product. Calculations predicted the presence of intramolecular H-bonding in both AMPO and its superoxide adduct, and these interactions were further confirmed by an X-ray structure (in the case of AMPO) of a novel and the amido nitrone compound 2-amino-5-carbamoyl-5-methyl-1-pyrroline N-oxide (NH2-AMPO). The thermodynamic quantities for superoxide radical trapping by various nitrones have been found to predict favorable formation of certain isomers. The measured partition coefficient in an n-octanol/buffer system of AMPO gave a comparable value to those of DMPO and DEPMPO. This study demonstrates the suitability of AMPO nitrone as spin trap to study radical production in aqueous systems.

Workup

  1. custom2˜10 minutes
  2. custom2˜16 minutes
  3. customThe measured partition coefficient in an n-octanol/buffer system of AMPO

Sources & evidence

ORD record
ord-0da2e3e964474ac0a0955a46dabebc2a
Source dataset
uspto-grants-2009_10
Patent number
US07598400B2

Reaction notes

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