Benzyl Alcohol → Benzyl [1-(4-nitrobenzyl)but-3-enyl]carbamate

HRID 1738918Notes

Reaction equation

HRID 1738918 reaction equation
C([N:3]([CH2:6]C)CC)C.[CH2:8]([OH:15])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[N-]=[N+]=[N-].C1([O:25]P(=O)(O)OC2C=CC=CC=2)C=CC=CC=1.[N+:36]([C:39]1[CH:53]=[CH:52][C:42]([CH2:43][CH:44]([CH2:49][CH:50]=[CH2:51])CC(O)=O)=[CH:41][CH:40]=1)([O-:38])=[O:37].[N+](C1C=CC(CC(CC=C)C(O)=O)=CC=1)([O-])=O.ClC1C=CC(CC(CC=C)C(O)=O)=CC=1>C1(C)C=CC=CC=1>[CH2:8]([O:15][C:6](=[O:25])[NH:3][CH:44]([CH2:43][C:42]1[CH:41]=[CH:40][C:39]([N+:36]([O-:38])=[O:37])=[CH:53][CH:52]=1)[CH2:49][CH:50]=[CH2:51])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

8

Reactant 6

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 211410742-(4-Chloro-benzyl)-pent-4-enoic acidHCID 218395522-(4-Nitro-benzyl)-pent-4-enecarboxylic acidHCID 224570092-(4-Nitrobenzyl)pent-4-enoic acidHCID 66782931Phosphoric acid diphenylester azide

Product 1

HCID 53992691Benzyl [1-(4-nitrobenzyl)but-3-enyl]carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In the presence of triethylamine (5.6 ml, 40.0 mmol) and benzyl alcohol (5.18 g, 48.0 mmol) in toluene, 11.55 g (42.0 mmol) of phosphoric acid diphenyl ester azide are added at 50° C. to 2-(4-nitro-benzyl)-pent-4-enecarboxylic acid [2-(4-nitro-benzyl)-pent-4-enoic acid is prepared analogously to 2-(4-chloro-benzyl)-pent-4-enoic acid, see J. Med. Chem, 1968, 11(3), 5341 (9.3 g, 40.0 mmol). After 20 minutes the temperature is increased slowly and the mixture is then maintained under reflux for 3 hours. After cooling, the reaction mixture is washed twice with 1 N sodium hydroxide solution, twice with 1 N hydrochloric acid and twice with brine, dried over sodium sulfate and concentrated by evaporation using a rotary evaporator. After crystallisation of the crude product from toluene/hexane, the title compound is obtained in the form of white crystals. M.p.: 94-95° C. TLC: ethyl acetate/hexane (1:3) Rf =0.22.

Workup

  1. temperatureAfter 20 minutes the temperature is increased slowly
  2. temperaturethe mixture is then maintained
  3. temperatureunder reflux for 3 hours
  4. temperatureAfter cooling
  5. washthe reaction mixture is washed twice with 1 N sodium hydroxide solution, twice with 1 N hydrochloric acid and twice with brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated by evaporation
  8. customa rotary evaporator
  9. customAfter crystallisation of the crude product from toluene/hexane

Sources & evidence

ORD record
ord-3fe160750a404d9f96f513dd5ad4afd9
Source dataset
uspto-grants-1999_10
Patent number
US05965562

Reaction notes

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