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

HRID 1948121

反応式

HRID 1948121 の反応式
[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>[CH2:16]([O:15][P:14]([CH2:13][C:7]1[CH:6]=[N:5][C:4]([NH2:1])=[C:9]([O:10][CH3:11])[CH:8]=1)(=[O:21])[O:18][CH2:19][CH3:20])[CH3:17]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒2 回

実験手順

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, 6H), 3.45 (d, J=22.4 Hz, 2H), 4.00 (s, 3H), 4.09-4.17 (m, 4H), 7.79 (t, J=2.4 Hz, 1H), 7.97 (t, J=2.4 Hz, 1H). MS (ES+): m/z 305.07 [MH+]. HPLC: tR=1.17 min (UPLC TOF, polar—3 min).

後処理

  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)

出典と根拠

ORDレコード
ord-38df4a388e804322a0c06b393ec59d54
出典データセット
uspto-grants-2013_03
特許番号
US08399433B2

関連ノート

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