HCID 131732062, compound → (R)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl (1S)-camphanate

HRID 1057238Notes

Reaction equation

HRID 1057238 reaction equation
[C@:1]12([CH3:30])[C:7]([CH3:9])([CH3:8])[CH:4]([CH2:5][CH2:6]1)[CH2:3][CH:2]2[C:10]([O:12][CH:13]([C:18]1[CH:23]=[C:22]([O:24][CH3:25])[C:21]([I:26])=[CH:20][C:19]=1[N+:27]([O-:29])=[O:28])[C:14]([CH3:17])([CH3:16])[CH3:15])=[O:11]>C(O)C>[C@:1]12([CH3:30])[C:7]([CH3:8])([CH3:9])[CH:4]([CH2:5][CH2:6]1)[CH2:3][CH:2]2[C:10]([O:12][C@@H:13]([C:18]1[CH:23]=[C:22]([O:24][CH3:25])[C:21]([I:26])=[CH:20][C:19]=1[N+:27]([O-:29])=[O:28])[C:14]([CH3:15])([CH3:16])[CH3:17])=[O:11]

Participants

3

Reactant 1

HCID 131732062HCID 131732062, compound

Product 1

HCID 131732063(R)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl (1S)-camphanateYield 51%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

(R/S)-1-(4-Iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl(1S)-camphanate (3.4 g) was dissolved in boiling ethanol (150 ml), the solution was kept in a warm oil bath and slowly cooled to room temperature and stood overnight. Needle crystals were formed gradually and collected by filtration to yield pure single diastereomer (R)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl(1S)-camphanate (870 mg, 51%). The remaining mother liquor was concentrated in vacuo, and the residue was dissolved again in boiling ethanol (150 ml), and the solution was quickly cooled to room temperature and needle crystals were formed within two hours. The crystals were collected by filtration to yield pure single diastereomer (S)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl(1S)-camphanate. The crystallization process was repeated twice to yield additional pure (S)-diastereomer (total 1.07 g, 63%). 1H NMR (400 MHz, CDCl3) for (R)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1-propyl(1S)-camphanate: δ 8.48 (s, 1H, Ph-H), 6.94 (s, 1H, Ph-H), 6.84 (s, 1H, Ph-CH), 3.93 (s, 3H, OCH3), 2.42 (m, 1H, CH), 2.11 (m, 1H, CH), 1.92 (m, 1H, CH2), 1.75 (m, 1H, CH2), 1.11 (s, 3H, CH3), 1.05 (s, 3H, CH3), 0.97 (s, 9H, C(CH3)3), 0.86 (s, 3H, CH3). 1H NMR (400 MHz, CDCl3) for (S)-1-(4-iodo-5-methoxy-2-nitrophenyl)-2,2-dimethyl-1 propyl(1S)-camphanate: δ 8.48 (s, 1H, Ph-H), 6.95 (s, 1H, Ph-H), 6.80 (s, 1H, Ph-CH), 3.96 (s, 3H, OCH3), 2.37 (m, 1H, CH), 1.92 (m, 2H, CH2), 1.66 (m, 1H, CH), 1.14 (s, 3H, CH3), 1.07 (s, 3H, CH3), 1.06 (s, 3H, CH3), 0.98 (s, 9H, C(CH3)3).

Workup

  1. customthe solution was kept in a warm oil bath
  2. customNeedle crystals were formed gradually
  3. filtrationcollected by filtration

Sources & evidence

ORD record
ord-1c5c03004f0b4dfc979769b936877a29
Source dataset
uspto-grants-2016_07
Patent number
US09399798B2

Reaction notes

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