4-Methylmorpholine → Methyl 2-amino-4-(hydroxymethyl)benzoate

HRID 1894092Notes

Reaction equation

HRID 1894092 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]([C:12]([O-])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].CN1CCOCC1.[BH4-].[Na+].[OH-].[Na+]>COCCOC.O>[CH3:7][O:6][C:4](=[O:5])[C:3]1[CH:8]=[CH:9][C:10]([CH2:12][OH:13])=[CH:11][C:2]=1[NH2:1]

Participants

7

Reactant 4

HCID 79724-MethylmorpholineHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 21924002HCID 21924002, compound

Product 1

HCID 602338Methyl 2-amino-4-(hydroxymethyl)benzoateYield 86.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
-15 °C

Procedure

To a solution of 1-methyl 2-aminoterephthalate (10.0 g, 51.2 mmol) and NMM (5.75 mL, 1 equiv) in DME (90 mL) at −15° C. was added dropwise IBCl (6.7 mL, 1 equiv). The mixture was stirred at this temperature for 15 min. The salt was removed by filtration and the solution was cooled down to −15° C. A solution of NaBH4 (3.06 g, 1.5 equiv) in water (30 mL) was added carefully dropwise. At the end of the addition, water (100 mL) was added and the mixture was stirred at r.t. for 15 min. Aq NaOH (2N, 50 mL) was added and the aqueous phase was extracted twice with AcOEt. The organic phase were combined and dried (Na2SO4). The solution was concentrated in vacuo to afford a white solid (8.0 g, 86%) (ES-MS: m/z 182.1 [M+H]+, rt 3.50 min)

Workup

  1. customThe salt was removed by filtration
  2. additionwas added
  3. stirringthe mixture was stirred at r.t. for 15 min
  4. extractionthe aqueous phase was extracted twice with AcOEt
  5. dry with materialdried (Na2SO4)
  6. concentrationThe solution was concentrated in vacuo

Sources & evidence

ORD record
ord-07a27a50090342c19f568dad5af8cc1e
Source dataset
uspto-grants-2013_08
Patent number
US08513268B2

Reaction notes

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