Triethylamine → 2-(Chloromethyl)-4-methoxy-1-nitrobenzene

HRID 362779Notes

Reaction equation

HRID 362779 reaction equation
CS([Cl:5])(=O)=O.CCN(CC)CC.[CH3:13][O:14][C:15]1[CH:16]=[CH:17][C:18]([N+:23]([O-:25])=[O:24])=[C:19]([CH:22]=1)[CH2:20]O>C(Cl)Cl>[CH3:13][O:14][C:15]1[CH:16]=[CH:17][C:18]([N+:23]([O-:25])=[O:24])=[C:19]([CH:22]=1)[CH2:20][Cl:5]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 53405061(5-Methoxy-2-nitrophenyl)methanol

Product 1

HCID 108457632-(Chloromethyl)-4-methoxy-1-nitrobenzeneYield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

MsCl (1.9 mL, 24 mmol) was added to Et3N (4.5 mL, 32 mmol) and 5-methoxy-2-nitrobenzyl alcohol (1.48 g, 8.1 mmol) in CH2Cl2 (80 mL) and the ni-xture kept at reflux for 12 h. The solution was cooled, washed with dilute HCl (2N, 2×50 mL), dried (Na2SO4), concentrated, and filtered through a short column of silica (eluting with 9:1 petroleum ether:EtOAc) to give 5-methoxy-2-nitrobenzyl chloride as a yellow liquid (1.55 g, 95%). 1H N (CDCl3) δ 8.17 (d, J=9.1 Hz, 1 H, H-3), 7.20 (d, J=2.8Hz, 1 H, H-6), 6.93 (dd, J=9.1, 2.8 Hz, 1 H, H-4), 5.03 (s, 2 H, ArCH2Cl), 3.93 (s, 3 H, ArOCH3); 13C NMR (CDCl3) δ 163.7 (C-2), 140.7, 135.5, 128.2, 116.5, 113.7 (C-1,3,4,5,6), 56.1 (OCH3), 43.7 (CH2Cl); MS (EI) m/z 201 [70%, M+ (35Cl)], 184 (100%), 166 (60%, M - Cl), 156 (50%), 106 (70%); HRMS (EI) Calcd. for C8H8ClNO3 203.0163 (35Cl). Found 203.0165.

Workup

  1. temperatureat reflux for 12 h
  2. temperatureThe solution was cooled
  3. washwashed with dilute HCl (2N, 2×50 mL)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. filtrationfiltered through a short column of silica (eluting with 9:1 petroleum ether:EtOAc)

Sources & evidence

ORD record
ord-ba8082c1dc77487292648e3440a08eaf
Source dataset
uspto-grants-1999_02
Patent number
US05872129

Reaction notes

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