Acetone → Methyl 4-cyano-5-(isopropylamino)-2-methylbenzoate

HRID 906160ノート

反応式

HRID 906160 の反応式
[NH2:1][C:2]1[C:3]([C:13]#[N:14])=[CH:4][C:5]([CH3:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].FC(F)(F)C(O)=O.[CH3:22][C:23]([CH3:25])=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl>[C:13]([C:3]1[C:2]([NH:1][CH:23]([CH3:25])[CH3:22])=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:12])[CH:4]=1)#[N:14]

参加物

6

反応物 4

HCID 180AcetoneHCID 6422Trifluoroacetic acidHCID 5049666Sodium triacetoxyborohydrideHCID 67402842Methyl 5-amino-4-cyano-2-methylbenzoate

生成物 1

HCID 67403235Methyl 4-cyano-5-(isopropylamino)-2-methylbenzoate収率 76.2%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒

実験手順

Methyl 5-amino-4-cyano-2-methylbenzoate (synthesized in reagent preparation 41, step 4) (240 mg, 1.26 mmol) was dissolved in 1,2-dichloroethane (7 mL) and was treated with trifluoroacetic acid (0.6 mL, 7.57 mmol), acetone (0.28 mL, 3.79 mmol), and sodium triacetoxyborohydride (802 mg, 3.78 mmol) at 45° C. for 20 min. The reaction mixture was cooled to ambient temperature and quenched with saturated aqueous sodium bicarbonate and was partitioned with dichloromethane. The aqueous portion was extracted with dichloromethane. The combined organic portion was washed with brine, dried over sodium sulfate, then filtered and concentrated to afford a yellow oil which was purified by column chromatography (silica gel, 10% dichloromethane in hexanes) to afford methyl 4-cyano-5-(isopropylamino)-2-methylbenzoate (224 mg, 0.96 mmol, 76% yield) as a pale yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.25 (s, 1H), 7.16 (s, 1H), 4.28 (d, 1H), 3.91 (s, 3H), 3.77-3.74 (m, 1H), 2.40 (s, 3H), 1.27 (s, 3H), 1.26 (s, 3H); MS (EI) for C14H16N2O2: 233 (MH+).

後処理

  1. customquenched with saturated aqueous sodium bicarbonate
  2. customwas partitioned with dichloromethane
  3. extractionThe aqueous portion was extracted with dichloromethane
  4. washThe combined organic portion was washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto afford a yellow oil which
  9. customwas purified by column chromatography (silica gel, 10% dichloromethane in hexanes)

出典と根拠

ORDレコード
ord-5e85a1eb39394eaf884e270ed6ec4d7a
出典データセット
uspto-grants-2011_09
特許番号
US08012956B2

反応ノート

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