Triphenylphosphine → Ethyl 3-(chloromethyl)-5-(dimethylamino)benzoate

HRID 2368874Notes

Reaction equation

HRID 2368874 reaction equation
[CH3:1][N:2]([CH3:16])[C:3]1[CH:4]=[C:5]([CH:11]=[C:12]([CH2:14]O)[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C(=O)N([Cl:43])C(=O)C1>C(Cl)Cl>[Cl:43][CH2:14][C:12]1[CH:11]=[C:5]([CH:4]=[C:3]([N:2]([CH3:16])[CH3:1])[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 31398ChlorosuccinimideHCID 68335184Ethyl 3-(dimethylamino)-5-(hydroxymethyl)benzoate

Product 1

HCID 68335175Ethyl 3-(chloromethyl)-5-(dimethylamino)benzoateYield 96%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of Compound 2 (3.45 g, 15.452 mmol) and PPh3 (6.14 g, 23.17 mmol) in 70 mL of DCM was added NCS (3.19 g, 23.178 mmol) at 0° C. The reaction mixture was stirred for 1.5 hours. After removal of solvent under reduced pressure, the residue was dissolved in Et2O. The solution was washed with brine and dried with MgSO4. The solution was filtered and concentrated. The residue was subjected to chromatography over silica gel (Hexanes/EtOAc=9.5/0.5) to give Compound 3 (3.585 g, 96%). 1H-NMR (500 MHz, CDCl3) δ 7.38 (s, 1H), 7.35 (s, 1H), 6.89 (s, 1H), 4.57 (s, 2H), 4.37 (q, J=7.1 Hz, 2H), 3.00 (s, 6H), 1.39 (t, J=7.1 Hz, 3H); 13C-NMR (125 MHz, CDCl3) δ 166.73, 150.63, 138.35, 131.59, 117.31, 116.20, 113.22, 60.95, 46.40, 40.43, 14.31; ESI-MS: m/z (MH+): 242.0942 (calc'd), 242.0944 (found).

Workup

  1. customAfter removal of solvent under reduced pressure
  2. dissolutionthe residue was dissolved in Et2O
  3. washThe solution was washed with brine
  4. dry with materialdried with MgSO4
  5. filtrationThe solution was filtered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-64a0cd2b68f24191bab7483321b13776
Source dataset
uspto-grants-2014_04
Patent number
US08703815B2

Reaction notes

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