N,N-Dimethylaniline → (2E)-3-(4-{[(benzyloxy)carbonyl]amino}phenyl)prop-2-enyl diazoacetate

HRID 1179486Notes

Reaction equation

HRID 1179486 reaction equation
C1(C)C=CC(S([NH:10][N:11]=[CH:12][C:13](Cl)=[O:14])(=O)=O)=CC=1.[OH:17][CH2:18]/[CH:19]=[CH:20]/[C:21]1[CH:26]=[CH:25][C:24]([NH:27][C:28](=[O:37])[O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[CH:23][CH:22]=1.CN(C)C1C=CC=CC=1.C(N(CC)CC)C>ClCCl>[N+:11](=[CH:12][C:13]([O:17][CH2:18]/[CH:19]=[CH:20]/[C:21]1[CH:26]=[CH:25][C:24]([NH:27][C:28]([O:29][CH2:30][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)=[O:37])=[CH:23][CH:22]=1)=[O:14])=[N-:10]

Participants

6

Reactant 4

HCID 949N,N-DimethylanilineHCID 8471TriethylamineHCID 57296158Glyoxylyl Chloride p-toluenesulfonylhydrazoneHCID 58978090benzyl 4-[(1E)-3-hydroxyprop-1-enyl]phenylcarbamate

Product 1

HCID 86619689(2E)-3-(4-{[(benzyloxy)carbonyl]amino}phenyl)prop-2-enyl diazoacetate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Glyoxylic acid chloride p-toluenesulfonylhydrazone (1.66 g, 6.35 mmol) was added to a suspension of benzyl 4-[(1E)-3-hydroxyprop-1-enyl]phenylcarbamate (1.0 g, 3.53 mmol) in dichloromethane (25 mL). The mixture was cooled to 0° C. and treated with N,N-dimethylaniline (0.8 mL, 6.35 mmol). After 0.5 h, triethylamine (2.5 mL, 17.6 mmol) was added and the mixture stirred 2 h at 0° C. and warmed to room temperature. The reaction mixture was then concentrated and water was added. The mixture was extracted with two portions of diethyl ether and the combined organic solutions washed with saturated NaHCO3, brine and dried (MgSO4), filtered and concentrated. Purification by silica gel column chromatography (gradient 0-25% EtOAc-hexane) provided the title compound.

Workup

  1. temperaturewarmed to room temperature
  2. concentrationThe reaction mixture was then concentrated
  3. additionwater was added
  4. extractionThe mixture was extracted with two portions of diethyl ether
  5. washthe combined organic solutions washed with saturated NaHCO3, brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by silica gel column chromatography (gradient 0-25% EtOAc-hexane)

Sources & evidence

ORD record
ord-8755f2912bf2400c8de5c9157b9396ab
Source dataset
uspto-grants-2007_10
Patent number
US07279494B2

Reaction notes

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