Formaldehyde → 1,1-Dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamate

HRID 1014389ノート

反応式

HRID 1014389 の反応式
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([O:16][CH3:17])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:7]=1.[CH2:18]=O.C[O-].[Na+].[BH4-].[Na+]>CO.C(OCC)(=O)C.C(=O)(O)[O-].[Na+]>[CH3:18][NH:1][C:2]1[CH:3]=[CH:4][C:5]([O:16][CH3:17])=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:13])[CH3:14])[CH:7]=1

参加物

8

反応物 4

HCID 712FormaldehydeHCID 4311764Sodium borohydrideHCID 10942334Sodium MethoxideHCID 22344747tert-butyl N-(5-amino-2-methoxyphenyl)carbamate

生成物 1

HCID 594418351,1-Dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamate収率 104.7%

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 8857Ethyl Acetate溶媒HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
50 °C

実験手順

A suspension of 1,1-dimethylethyl [5-amino-2-(methyloxy)phenyl]carbamate (1.94 g, 8.14 mmol), paraformaldehyde (1.222 g, 40.7 mmol), and sodium methoxide (2.199 g, 40.7 mmol) in methanol (50 ml) was maintained at 50° C. for 16 hours, cooled, sodium borohydride (0.924 g, 24.42 mmol) was added portionwise, and the solution was re-heated to 50° C. and maintained for an additional 24 hours. The solution was cooled, diluted with ethyl acetate, saturated sodium bicarbonate, and the organic layer was dried over sodium sulfated, filtered, taken to a residue under reduced pressure, and purified by column chromatography to afford 1,1-dimethylethyl [5-(methylamino)-2-(methyloxy)phenyl]carbamate (2.15 g, 8.52 mmol, quant. Yield) as a pale yellow oil. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.58 (s, 1 H), 7.10 (d, J=1.6 Hz, 1 H), 6.76 (d, J=8.8 Hz, 1 H), 6.14 (dd, J=8.7, 2.7 Hz, 1H), 5.07-5.31 (m, 1 H), 3.61-3.74 (m, 3 H), 2.60 (d, J=4.4 Hz, 3 H), 1.44 (s, 9 H).

後処理

  1. temperaturecooled
  2. temperaturethe solution was re-heated to 50° C.
  3. temperaturemaintained for an additional 24 hours
  4. temperatureThe solution was cooled
  5. dry with materialthe organic layer was dried over sodium
  6. filtrationfiltered
  7. custompurified by column chromatography

出典と根拠

ORDレコード
ord-86ff43889252450e9139978a77ad0a01
出典データセット
uspto-grants-2011_07
特許番号
US07981903B2

反応ノート

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