HCID 59189444, compound → HCID 86639078, compound

HRID 1686863Notes

Reaction equation

HRID 1686863 reaction equation
[C@:1]12([CH3:13])[C:7]([CH3:9])([CH3:8])[CH:4]([CH2:5][CH2:6]1)[CH2:3][CH:2]2[C:10](Cl)=[O:11].[I:14][C:15]1[CH:20]=[CH:19][C:18]([CH:21]([OH:25])[CH:22]([CH3:24])[CH3:23])=[C:17]([N+:26]([O-:28])=[O:27])[CH:16]=1>CN(C1C=CN=CC=1)C.ClCCl>[C@:1]12([CH3:13])[C:7]([CH3:9])([CH3:8])[CH:4]([CH2:5][CH2:6]1)[CH2:3][CH:2]2[C:10]([O:25][C@@H:21]([C:18]1[CH:19]=[CH:20][C:15]([I:14])=[CH:16][C:17]=1[N+:26]([O-:28])=[O:27])[CH:22]([CH3:24])[CH3:23])=[O:11]

Participants

5

Reactant 2

HCID 59189444HCID 59189444, compoundHCID 71432218(1s)-Camphanoyl chloride

Product 1

HCID 86639078HCID 86639078, compoundYield 65%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

Under a nitrogen atmosphere (1S)-camphanic acid chloride (0.89 g, 4.09 mmol) was added to a solution of (RS)-1-(4-Iodo-2-nitrophenyl)-2-methyl-1-propanol (1.10 g, 3.41 mmol) and DMAP (0.50 g, 4.09 mmol) in anhydrous dichloromethane (30 mL). The mixture was stirred for 1.5 hours at room temperature and then concentrated in vacuo. The residue was purified by silica gel column chromatography to (RS)-1-(4-Iodo-2-nitrophenyl)-2-methyl-1-propyl (1S)-camphanates (1.44 g, 84%, 1:1 mixture of diastereomers) as a solid, which was dissolved in boiling methanol (70 mL) and left at room temperature overnight. Crystals formed were filtered to yield pure (R)-1-(4-iodo-2-nitrophenyl)-2-methyl-1-propyl (1S)-camphanate (0.465 g, 65%). The mother liquor was evaporated, and the residue was dissolved in boiling isopropanol (40 mL) and left at room temperature overnight. Crystals formed were filtered and recrystallized from boiling isopropanol (20 mL) to yield pure (S)-1-(4-iodo-2-nitrophenyl)-2-methyl-1-propyl (1S)-camphanate (0.288 g, 40%). 1H NMR (400 MHz, CDCl3) for (R,S)-camphanate: δ 8.30 (d, 1H, J=1.8 Hz, Ph-H), 7.92 (dd, 1H, J=1.8 and 8.3 Hz, Ph-H), 7.56 (d, 1H, J=8.3 Hz, Ph-H), 6.27 (d, 1H, J=6.8 Hz, Ph-CH), 2.40 (m, 1H), 2.23 (m, 1H), 2.06 (m, 1H), 1.92 (m, 1H), 1.72 (m, 1H), 1.11 (s, 3H, CH3), 1.03 (d, J=6.8 Hz, 3H, CH3), 1.02 (s, 1H, CH3), 0.98 (d, J=6.8 Hz, 3H, CH3), 0.82 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3) for (R,S)-camphanate: δ 178.21 (C), 166.92 (C), 148.67 (C), 142.07 (CH), 134.80 (C), 133.34 (CH), 129.73 (CH), 92.59 (C), 90.75 (C), 76.07 (CH), 54.79 (C), 54.34 (C), 33.27 (CH), 31.03 (CH2), 28.88 (CH2), 19.07 (CH3), 17.40 (CH3), 16.70 (CH3), 16.66 (CH3), 9.61 (CH3).

Workup

  1. concentrationconcentrated in vacuo
  2. customThe residue was purified by silica gel column chromatography to (RS)-1-(4-Iodo-2-nitrophenyl)-2-methyl-1-propyl (1S)-camphanates (1.44 g, 84%, 1:1 mixture of diastereomers) as a solid, which
  3. dissolutionwas dissolved
  4. waitleft at room temperature overnight
  5. customCrystals formed
  6. filtrationwere filtered

Sources & evidence

ORD record
ord-53dc768b789545bf9acdcb4375ec0b1e
Source dataset
uspto-grants-2012_04
Patent number
US08148503B2

Reaction notes

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