Hydrochloric Acid → Diethyl[(6-amino-5-methoxypyridin-3-yl)methyl]phosphonate

HRID 511549

반응식

HRID 511549 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

HCID 86654065Diethyl[(6-amino-5-methoxypyridin-3-yl)methyl]phosphonate수율 19.2%

시약·촉매·용매 1

HCID 679Dimethyl Sulfoxide용매2회

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-b094019293b348d7992af49170ca0d9c
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09096624B2

연결된 노트

불러오는 중…