4-Methylmorpholine → HCID 25187105, compound

HRID 750527Notes

Reaction equation

HRID 750527 reaction equation
[C:1]([O:5][C:6]([O:8][C:9]1[CH:10]=[C:11]([CH:15]=[CH:16][C:17]=1[N+:18]([O-:20])=[O:19])[C:12](O)=[O:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].CN1CCOCC1.C(OC(Cl)=O)C(C)C.[BH4-].[Na+]>C1COCC1.CO.CCOC(C)=O>[C:6](=[O:7])([O:8][C:9]1[CH:10]=[C:11]([CH2:12][OH:13])[CH:15]=[CH:16][C:17]=1[N+:18]([O-:20])=[O:19])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 79724-MethylmorpholineHCID 62365Isobutyl chloroformateHCID 4311764Sodium borohydrideHCID 21874666HCID 21874666, compound

Product 1

HCID 25187105HCID 25187105, compoundYield 86%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-(tert-butoxycarbonyloxy)-4-nitrobenzoic acid (2.26 g, 8 mmol) and N-methylmorpholine (1.85 mL, 16.8 mmol) in THF (20 mL) at 0° C., was treated with isobutylchloroformate (1.09 mL, 8.4 mmol) and stirred for 1 h. The reaction mixture was added to a cooled (−78° C.) solution of NaBH4 (605 mg, 16 mmol) in MeOH (16 mL) and stirred at room temperature for 1 h. The reaction mixture was diluted with EtOAc (20 mL), washed with saturated NaHCO3 (10 mL) and 10% citric acid solution (10 mL), dried (MgSO4) and concentrated in vacuo to give tert-butyl (5-hydroxymethyl-2-nitrophenyl) carbonate (1.36 g, 86%) as a cream solid. This material was brominated directly using Method AB to give the title compound (961 mg, 58%) as a yellow oil: NMR δH (400 MHz, CDCl3) 8.09 (1H, d, J 8.4 Hz), 7.41 (1H, dd, J 8.4, 2.0 Hz), 7.34 (1H, d, J 2.0 Hz), 4.47 (2H, s) and 1.58 (9H, s).

Workup

  1. additionThe reaction mixture was added to
  2. stirringstirred at room temperature for 1 h
  3. washwashed with saturated NaHCO3 (10 mL) and 10% citric acid solution (10 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-c91ee4e8f5994f90ab23c3e1f326a37f
Source dataset
uspto-grants-2008_07
Patent number
US07405219B2

Reaction notes

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