Iodine → HCID 22884191, compound

HRID 1598379Notes

Reaction equation

HRID 1598379 reaction equation
[F:1][C:2]1[CH:22]=[CH:21][C:5]([CH2:6][N:7]([CH2:13][CH:14]([OH:20])[CH2:15][CH2:16][CH2:17][CH:18]=[CH2:19])[C:8](=[O:12])[O:9][CH2:10][CH3:11])=[CH:4][CH:3]=1.[I:23]I.C(OCC)(=O)C.C1C=CC=CC=1>C(Cl)Cl>[CH2:10]([O:9][C:8]([N:7]([CH2:13][C@H:14]1[O:20][C@@H:18]([CH2:19][I:23])[CH2:17][CH2:16][CH2:15]1)[CH2:6][C:5]1[CH:21]=[CH:22][C:2]([F:1])=[CH:3][CH:4]=1)=[O:12])[CH3:11].[CH2:10]([O:9][C:8]([N:7]([CH2:13][C@@H:14]1[O:20][C@@H:18]([CH2:19][I:23])[CH2:17][CH2:16][CH2:15]1)[CH2:6][C:5]1[CH:21]=[CH:22][C:2]([F:1])=[CH:3][CH:4]=1)=[O:12])[CH3:11]

Participants

6

Reactant 3

HCID 807IodineHCID 18933349HCID 18933349, compoundHCID 21583983Benzene ethyl acetate

Product 2

HCID 22884191HCID 22884191, compoundYield 51%HCID 22884194HCID 22884194, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of ethyl N-(p-fluorobenzyl)-N-(2-hydroxy-6-heptenyl)carbamate (1.0 g, 2.5 mmol) in methylene chloride (15 ml) was added iodine (1.26 g, 4.95 mmol) and the mixture was stirred at room temperature for 15 hours and then heated under reflux for further 7 hours. The reaction mixture was diluted with methylene chloride (50 ml) and washed successively with saturated aqueous sodium hydrogen carbonate (50 ml), 10% aqueous sodium thiosulfate (50 ml×2), saturated aqueous sodium hydrogen carbonate (50 ml) and saturated aqueous sodium chloride (50 ml), dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was chromatographed using silica gel column to give cis-6-[N-ethoxycarbonyl-N-(p-fluorobenzyl)aminomethyl]-2-iodomethyltetrahydropyrane (560 mg, yield 51%) and trans-6-[N-ethoxycarbonyl-N-(p-fluorobenzyl)aminomethyl]-2-iodomethyltetrahydropyrane (190 mg, yield 17%) from the fraction from ethyl acetate-benzene (1/30).

Workup

  1. temperatureheated
  2. temperatureunder reflux for further 7 hours
  3. washwashed successively with saturated aqueous sodium hydrogen carbonate (50 ml), 10% aqueous sodium thiosulfate (50 ml×2), saturated aqueous sodium hydrogen carbonate (50 ml) and saturated aqueous sodium chloride (50 ml)
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customThe residue was chromatographed

Sources & evidence

ORD record
ord-eb22ddd56ed44293a992cf13bedbe46f
Source dataset
uspto-grants-1998_04
Patent number
US05736550

Reaction notes

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