Hydrochloric Acid → HCID 86654065, compound

HRID 511549

Reaction equation

HRID 511549 reaction equation
[N+:1]([C:4]1[C:9]([O:10][CH3:11])=[CH:8][CH:7]=[CH:6][N:5]=1)([O-])=O.Cl[CH2:13][P:14](=[O:21])([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17].C(O[Na])(C)(C)C.Cl>CS(C)=O>[NH2:1][C:4]1[N:5]=[CH:6][C:7]([CH2:13][P:14](=[O:21])([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17])=[CH:8][C:9]=1[O:10][CH3:11]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 76633Phosphonic acid, P-(chloromethyl)-, diethyl esterHCID 5560633-Methoxy-2-nitropyridineHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 86654065HCID 86654065, compoundYield 19.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

A solution of 2-nitro-3-methoxypyridine (300 mg, 1.95 mmol) and diethyl chloromethylphosphonate (363 mg, 1.95 mmol) in DMSO (4 mL) was added dropwise to vigorously stirred solution of t-BuONa (0.561 g, 5.84 mmol) in DMSO (4 mL) at room temperature. The reaction mixture turned to deep orange immediately. Stirring was continued for 30 min, then the mixture was poured into 1 M HCl (aq) (10 mL). The product was extracted into ether (3×30 mL), dried over MgSO4, concentrated, and purified by silica gel chromatography (3% MeOH in DCM) to afford 102.6 mg of diethyl [(6-amino-5-methoxypyridin-3-yl)methyl]phosphonate (yield: 17%). 1H NMR (CD3OD, 400 MHz): δ=1.30 (t, J=6.8 Hz, 6 H), 3.45 (d, J=22.4 Hz, 2 H), 4.00 (s, 3 H), 4.09-4.17 (m, 4 H), 7.79 (t, J=2.4 Hz, 1 H), 7.97 (t, J=2.4 Hz, 1 H). MS (ES+): m/z 305.07 [MH+]. HPLC: tR=1.17 min (UPLC TOF, polar—3 min).

Workup

  1. extractionThe product was extracted into ether (3×30 mL)
  2. dry with materialdried over MgSO4
  3. concentrationconcentrated
  4. custompurified by silica gel chromatography (3% MeOH in DCM)

Sources & evidence

ORD record
ord-b094019293b348d7992af49170ca0d9c
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Linked notes

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