Methylamine → 2-Methoxy-5-(methylaminocarbonyl)phenylboronic acid

HRID 1478239Notes

Reaction equation

HRID 1478239 reaction equation
[B:1]([C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[C:7](O)=[O:8])([OH:3])[OH:2].CN.[CH3:17][N:18](C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CN1CCOCC1>CN(C=O)C>[CH3:14][O:13][C:12]1[CH:11]=[CH:10][C:6]([C:7](=[O:8])[NH:18][CH3:17])=[CH:5][C:4]=1[B:1]([OH:3])[OH:2]

Participants

6

Reactant 4

HCID 6329MethylamineHCID 79724-MethylmorpholineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 426145415-Carboxy-2-methoxybenzeneboronic acid

Product 1

HCID 574973242-Methoxy-5-(methylaminocarbonyl)phenylboronic acidYield 56.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

3-Borono-4-methoxybenzoic acid (2.5 g, 12.50 mmol) was dissolved in DMF (6 ml) and 12.50 ml methylamine (2 M solution in THF, 25 mmol) was added followed by HATU (4.75 mg, 12.5 mmol) and NMM (1.375, 12.50 mmol). The reaction mixture was stirred at RT for 20 hours and concentrated. The crude material was added to 50 ml water and extracted 3 times with EtOAc. The combined organic phases were dried (Na2SO4), filtered and concentrated. The crude material was triturated in EtOAc and filtered. The residue was purified by chromatography (Silicagel, CH2Cl2/MeOH 95:5) to give 1.92 g (7.11 mmol, 56.9% yield) of the title compound as a colorless solid. LCMS: (M+H)=210; tR=0.50 min (LC-MS 1). TLC: Rf=0.27 (CH2Cl2/MeOH 95:5). HPLC: tR=3.76 min (HPLC 3). 1H-NMR (d6-DMSO, 600.13 MHz) δ ppm 8.29 (bs, 1H), 8.03 (s, 1H), 7.87 (d, 1H), 7.85 (s, 2H) 7.02 (d, 1H), 3.84 (s, 3H), 2.75 (d, 3H).

Workup

  1. concentrationconcentrated
  2. additionThe crude material was added to 50 ml water
  3. extractionextracted 3 times with EtOAc
  4. dry with materialThe combined organic phases were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was triturated in EtOAc
  8. filtrationfiltered
  9. customThe residue was purified by chromatography (Silicagel, CH2Cl2/MeOH 95:5)

Sources & evidence

ORD record
ord-87687641b35449b98adf98e5ebec1704
Source dataset
uspto-grants-2016_08
Patent number
US09403827B2

Reaction notes

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