Carbon tetrabromide → N-benzyloxy-3-(phenylthio)acrylimidoyl bromide

HRID 1960223Notes

Reaction equation

HRID 1960223 reaction equation
[CH2:1]([O:8][NH:9][C:10](=O)[CH:11]=[CH:12][S:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(Br)(Br)(Br)[Br:22].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(#N)C>[CH2:1]([O:8][N:9]=[C:10]([Br:22])[CH:11]=[CH:12][S:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 86617341N-benzyloxy-3-(phenylthio)acrylamide

Product 1

HCID 86617336N-benzyloxy-3-(phenylthio)acrylimidoyl bromideYield 90.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Pyridine (2.7 ml) was added to THF (80 ml) solution of 3-(phenylthio)acryloyl chloride (3.0 g) and hydrochloric acid salt of O-benzylhydroxylamine (2.6 g) under ice-cooling and stirred at the same temperature for one hour and at room temperature for three hours. The reaction mixture was concentrated under reduced pressure. Chloroform (150 ml) was added to the residue, washed successively with 1N hydrochloric acid, pure water and aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (hexane:ethyl acetate 2:1) to obtain N-benzyloxy-3-(phenylthio)acrylamide (3.5 g) as colorless oil. N-benzyloxy-3-(phenylthio)acrylamide (1.0 g) was dissolved to acetonitrile (70 ml), carbon tetrabromide (2.3 g) and triphenylphosphine (1.8 g) were added thereto under ice-cooling, then heat refluxing for four hours. The reaction mixture was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (hexane:ethyl acetate20:1) to obtain N-benzyloxy-3-(phenylthio)acrylimidoyl bromide (1.1 g) as light yellow oil.

Workup

  1. additionwere added
  2. temperatureunder ice-cooling
  3. temperatureheat
  4. temperaturerefluxing for four hours
  5. concentrationThe reaction mixture was concentrated under reduced pressure

Sources & evidence

ORD record
ord-f2cb0f85e67f449396ef7af8204f1212
Source dataset
uspto-grants-2013_04
Patent number
US08410316B2

Reaction notes

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