Allyl bromide → Carbamic acid, N-(4-chloro-3-pyridinyl)-N-2-propen-1-yl-, 1,1-dimethylethyl ester

HRID 2382099Notes

Reaction equation

HRID 2382099 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:9]=[N:10][CH:11]=[CH:12][C:13]=1[Cl:14])([CH3:4])([CH3:3])[CH3:2].[CH2:16](Br)[CH:17]=[CH2:18].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[C:1]([O:5][C:6](=[O:15])[N:7]([CH2:18][CH:17]=[CH2:16])[C:8]1[CH:9]=[N:10][CH:11]=[CH:12][C:13]=1[Cl:14])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 10796Cesium carbonateHCID 51063702tert-Butyl (4-chloropyridin-3-yl)carbamate

Product 1

HCID 68554147Carbamic acid, N-(4-chloro-3-pyridinyl)-N-2-propen-1-yl-, 1,1-dimethylethyl esterYield 71%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of (4-chloro-pyridin-3-yl)-carbamic acid tert-butyl ester (6.78 g, 29.7 mmol), allyl bromide (5.1 g, 40.8 mmol) and cesium carbonate (20.1 g, 61.8 mmol) in DMF (200 mL) is heated at 60° C. for 1 h. The reaction is quenched with water, extracted with EtOAc. The organic layer is dried (Na2SO4), filtered and concentrated. The residue is purified by silica gel column chromatography eluting with 0-40% EtOAc in heptane to afford allyl-(4-chloro-pyridin-3-yl)-carbamic acid tert-butyl ester (5.66 g, 71%). MS: 269 (M+H); 1H NMR (300 MHz, CDCl3): δ 8.42(d, 1H), 7.40 (d, 1H), 5.80-5.98 (m, 1H), 4.35-4.51 (m, 1H), 3.90-4.07 (m, 1H).

Workup

  1. customThe reaction is quenched with water
  2. extractionextracted with EtOAc
  3. dry with materialThe organic layer is dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue is purified by silica gel column chromatography
  7. washeluting with 0-40% EtOAc in heptane

Sources & evidence

ORD record
ord-618597ec7f774aef8c137a286428f8c2
Source dataset
uspto-grants-2012_09
Patent number
US08258130B2

Reaction notes

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