Benzylamine → HCID 58529366, compound

HRID 1972711Notes

Reaction equation

HRID 1972711 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH3:9])=[C:4]([N+:11]([O-])=O)[CH:3]=1.[CH2:14]([NH2:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C(OP(OCC)OCC)C.[OH-].[Na+]>C1(C)C=CC=CC=1.C(O)C.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[CH2:14]([N:21]1[C:8]([CH3:9])=[C:5]2[C:4]([CH:3]=[C:2]([Cl:1])[CH:7]=[CH:6]2)=[N:11]1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

8

Reactant 4

HCID 7504BenzylamineHCID 14798Sodium HydroxideHCID 31215Triethyl phosphiteHCID 126437961-(4-Chloro-2-nitrophenyl)ethan-1-one

Product 1

HCID 58529366HCID 58529366, compoundYield 62%

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 1-(4-chloro-2-nitrophenyl)ethanone (12.5 g, 63 mmol) and benzylamine (13.7 g, 125 mmol) in 200 mL toluene was treated with titanium(IV) isopropoxide (53.5 g, 188 mmol) and heated at 60° C. for 16 h. The solvent was removed in vacuo and the residue taken up in triethylphosphite (31 g, 187 mmol) and the mixture heated cautiously to 150° C. for 2 h. The reaction was cooled to rt and diluted with 30 mL absolute ethanol. 3 mL of 4N aq NaOH was added dropwise with vigorous stirring. After 5 min, the solids were filtered off and the solution diluted with 60 mL absolute ethanol and 60 mL 1N aq NaOH. After stirring overnight, the ethanol was removed in vacuo and the residue diluted with water. Filtration gave the desired product as a dark brown solid (9.86 g, 62%) 1H-NMR (DMSO): δ 7.72 (dd, 1H, J=9, 1 Hz), 7.61 (dd, 1H, J=2, 1 Hz), 7.23 to 7.36 (m, 3H), 7.15 to 7.20 (m, 2H), 6.96 (dd, 1H, J=9, 2 Hz), 5.60 (s, 2H), 2.58 (s, 1H); MS: LC/MS (+esi): m/z=275.1 [MH]+; LC/MS rt=3.51 min.

Workup

  1. customThe solvent was removed in vacuo
  2. temperaturethe mixture heated cautiously to 150° C. for 2 h
  3. temperatureThe reaction was cooled to rt
  4. filtrationthe solids were filtered off
  5. additionthe solution diluted with 60 mL absolute ethanol and 60 mL 1N aq NaOH
  6. customthe ethanol was removed in vacuo
  7. additionthe residue diluted with water
  8. filtrationFiltration

Sources & evidence

ORD record
ord-e95b1e9a37d64f2ba7c42c031ef9e688
Source dataset
uspto-grants-2013_04
Patent number
US08431695B2

Reaction notes

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