Diethyl Ether → Methyl 3-azido-6'-methoxy-6-(4-methoxyphenyl)-2,3'-bipyridine-4-carboxylate

HRID 2410686ノート

反応式

HRID 2410686 の反応式
[NH2:1][C:2]1[C:3]([C:20]2[CH:21]=[N:22][C:23]([O:26][CH3:27])=[CH:24][CH:25]=2)=[N:4][C:5]([C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=2)=[CH:6][C:7]=1[C:8]([O:10][CH3:11])=[O:9].N([O-])=O.[Na+].[N-:32]=[N+:33]=[N-].[Na+].C(OCC)C>FC(F)(F)C(O)=O>[N:1]([C:2]1[C:3]([C:20]2[CH:21]=[N:22][C:23]([O:26][CH3:27])=[CH:24][CH:25]=2)=[N:4][C:5]([C:12]2[CH:13]=[CH:14][C:15]([O:18][CH3:19])=[CH:16][CH:17]=2)=[CH:6][C:7]=1[C:8]([O:10][CH3:11])=[O:9])=[N+:32]=[N-:33]

参加物

6

反応物 4

HCID 3283Diethyl EtherHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 66604594Methyl 3-amino-6'-methoxy-6-(4-methoxyphenyl)-2,3'-bipyridine-4-carboxylate

生成物 1

HCID 86663008Methyl 3-azido-6'-methoxy-6-(4-methoxyphenyl)-2,3'-bipyridine-4-carboxylate収率 95%

試薬・触媒・溶媒 1

HCID 6422Trifluoroacetic acid溶媒

実験手順

Methyl 3-amino-6′-methoxy-6-(4-methoxyphenyl)-2,3′-bipyridine-4-carboxylate (120 mg, 0.33 mmol) was dissolved in trifluoroacetic acid (1.6 mL) and the solution was cooled in an ice bath. Sodium nitrite (45 mg, 0.66 mmol) was added with stirring to give a dark red suspension. After 30 min, sodium azide (214 mg, 3.3 mmol) was added followed immediately by diethyl ether (1.6 mL). This was stirred in the ice bath for 30 min. and then partially concentrated on the rotary evaporator. The residue was partitioned between ethyl acetate and sufficient saturated aqueous sodium bicarbonate solution (gas evolution) to neutralize the mixture. The organic phase was separated, washed with brine, dried with sodium sulfate, and the solvent removed to leave methyl 3-azido-6′-methoxy-6-(4-methoxyphenyl)-2,3′-bipyridine-4-carboxylate (122 mg, 95% yield) as a yellow solid. MS (ESI) m/z 392.1 (M+H). 1H NMR (CDCl3) δ ppm 8.74 (1H, d, J=2.52 Hz), 8.13 (1H, dd, J=8.69, 2.39 Hz), 8.01 (2H, d, J=9.07 Hz), 7.98 (1H, s), 6.97 (2H, d, J=8.81 Hz), 6.85 (1H, d, J=8.81 Hz), 4.03 (3H, s), 4.01 (4H, s), 3.85 (3H, s).

後処理

  1. temperaturethe solution was cooled in an ice bath
  2. customto give a dark red suspension
  3. concentrationpartially concentrated on the rotary evaporator
  4. customThe residue was partitioned between ethyl acetate and sufficient saturated aqueous sodium bicarbonate solution (gas evolution)
  5. customThe organic phase was separated
  6. washwashed with brine
  7. dry with materialdried with sodium sulfate
  8. customthe solvent removed

出典と根拠

ORDレコード
ord-240ca224d2614425b0e6c3a884d2f6cb
出典データセット
uspto-grants-2014_08
特許番号
US08815840B2

反応ノート

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