Ammonium Chloride → N2-(3-Fluoro-4-methylphenyl)pyridine-2,3-diamine

HRID 2272691

反応式

HRID 2272691 の反応式
[F:1][C:2]1[CH:3]=[C:4]([NH:9][C:10]2[C:15]([N+:16]([O-])=O)=[CH:14][CH:13]=[CH:12][N:11]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].[Cl-].[NH4+]>O1CCCC1.O.[Zn]>[F:1][C:2]1[CH:3]=[C:4]([NH:9][C:10]2[C:15]([NH2:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[CH:5]=[CH:6][C:7]=1[CH3:8]

参加物

6

反応物 2

HCID 25517Ammonium ChlorideHCID 40676958N-(3-fluoro-4-methylphenyl)-3-nitro-2-pyridylamine

生成物 1

HCID 29067357N2-(3-Fluoro-4-methylphenyl)pyridine-2,3-diamine収率 110.9%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Zinc dust (14.3 g, 219 mmol) was added to a stirring mixture of N-(3-fluoro-4-methylphenyl)-3-nitropyridin-2-amine (C1) (6.78 g, 27.4 mmol) and ammonium chloride (11.7 g, 219 mmol) in tetrahydrofuran (55 mL) and water (55 mL), which caused the temperature of the mixture to rise to 45° C. The reaction mixture was stirred for 10 minutes, and then filtered through a pad of Celite, rinsing with ethyl acetate. The organic layer from the filtrate was further diluted with ethyl acetate, washed with aqueous ammonium chloride solution and with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. The filtrate was concentrated in vacuo to afford the product as a black solid (6.6 g), the bulk of which was taken directly to the following step. LCMS m/z 218.1 [M+H]+. 1H NMR (400 MHz, CDCl3), characteristic product peaks: δ 7.84 (dd, J=4.9, 1.6 Hz, 1H), 7.01 (dd, J=7.6, 1.6 Hz, 1H), 6.82 (br dd, J=8, 2 Hz, 1H), 6.77 (dd, J=7.6, 4.9 Hz, 1H), 2.20 (d, J=2 Hz, 3H).

後処理

  1. customto rise to 45° C
  2. filtrationfiltered through a pad of Celite
  3. washrinsing with ethyl acetate
  4. additionThe organic layer from the filtrate was further diluted with ethyl acetate
  5. washwashed with aqueous ammonium chloride solution and with saturated aqueous sodium chloride solution
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-45ced77ae4694299a580cf8281ae971c
出典データセット
uspto-grants-2015_09
特許番号
US09120788B2

関連ノート

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