4-Methylmorpholine → 4-Nitrophenyl 1,3-thiazol-5-ylmethyl carbonate

HRID 1861155Notes

Reaction equation

HRID 1861155 reaction equation
[OH:1][CH2:2][C:3]1[S:7][CH:6]=[N:5][CH:4]=1.CN1CCOCC1.Cl[C:16]([O:18][C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1)=[O:17]>C(Cl)Cl.C(Cl)(Cl)Cl>[CH:23]1[C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=[C:19]([O:18][C:16]([O:1][CH2:2][C:3]2[S:7][CH:6]=[N:5][CH:4]=2)=[O:17])[CH:24]=1

Participants

6

Reactant 3

HCID 79724-MethylmorpholineHCID 821294-Nitrophenyl chloroformateHCID 27632165-Thiazolylmethanol

Product 1

HCID 98821474-Nitrophenyl 1,3-thiazol-5-ylmethyl carbonateYield 78%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 3.11 g (27 mmol) of 5-(hydroxymethyl)thiazole and excess N-methyl morpholine in 100 ml of methylene chloride was cooled to 0° C. and treated with 8.2 g (41 mmol) of 4-nitrophenyl chloroformate. After being stirred for 1 h, the reaction mixture was diluted with CHCl3, washed successively with 1 N HCl, saturated aqueous NaHCO3, and saturated brine, dried over NaSO4, and concentrated in vacuo. The residue was purified by silica gel chromatography (SiO2, 1-2% MeOH/CHCl3, Rf=0.5 in 4% MeOH/CHCl3) to yield 5.9 g (78%) of the desired compound as a yellow solid. NMR (CDCl3) δ 5.53 (s, 2 H), 7.39 (dt, J=9, 3 Hz, 2 H), 8.01 (s, 1 H), 8.29 (dt, J=9, 3 Hz, 2 H), 8.90 (s, 1 H). Mass spectrum: (M+H)+=281.

Workup

  1. washwashed successively with 1 N HCl, saturated aqueous NaHCO3, and saturated brine
  2. dry with materialdried over NaSO4
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by silica gel chromatography (SiO2, 1-2% MeOH/CHCl3, Rf=0.5 in 4% MeOH/CHCl3)

Sources & evidence

ORD record
ord-276a29540ea94cc8b7fe1d71c2a5b26b
Source dataset
uspto-grants-2003_03
Patent number
US06531610B1

Reaction notes

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