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

HRID 1180123Notes

Reaction equation

HRID 1180123 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 1N 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, 2H), 7.39 (dt, J=9, 3 Hz, 2H), 8.01 (s, 1H), 8.29 (dt, J=9, 3 Hz, 2H), 8.90 (s, 1H). Mass spectrum: (M+H)+=281.

Workup

  1. washwashed successively with 1N 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-e61ec72ccffd4e818a203975608a74b9
Source dataset
uspto-grants-2007_10
Patent number
US07279582B2

Reaction notes

Loading…