Bromoacetonitrile → HCID 86637602、化合物

HRID 1694371ノート

反応式

HRID 1694371 の反応式
[OH:1][C:2]1[C:9]([OH:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[H-].[Na+].[CH2:13]([O:15][C:16]([C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH2:24]Br)[N:19]=1)=[O:17])[CH3:14].Br[CH2:27][C:28]#[N:29].[NH4+].[Cl-]>CS(C)=O>[CH2:13]([O:15][C:16]([C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH2:24][O:10][C:9]2[CH:8]=[CH:7][CH:6]=[C:3]([CH:4]=[O:5])[C:2]=2[O:1][CH2:27][C:28]#[N:29])[N:19]=1)=[O:17])[CH3:14]

参加物

7

反応物 5

HCID 11534BromoacetonitrileHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 905792,3-DihydroxybenzaldehydeHCID 23033755Ethyl 6-(bromomethyl)picolinate

生成物 1

HCID 86637602HCID 86637602、化合物

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

実験手順

To 2,3-dihydroxybenzaldehyde (1 mmol) in dry DMSO (2.5 mL) is added NaH (60% suspension in oil, 2.5 mmol). After 10 minutes, 6-bromomethyl-pyridine-2-carboxylic acid ethyl ester (1 mmol) is added. After 1 hour, bromoacetonitrile (0.07 mL, 1 mmol) is introduced at ambient temperature and mixture is stirred for 16 hours. Saturated aqueous NH4Cl solution is used to quench the reaction and the mixture is extracted with EtOAc. After drying over sodium sulfate, solvent is removed. Purification of the mixture by preparative HPLC (20-70% MeCN/H2O) gives 6-(2-cyanomethoxy-3-formyl-phenoxymethyl)-pyridine-2-carboxylic acid ethyl ester. 1H NMR (400 MHz, CDCl3) δ 10.4 (s, 1H), 8.1 (d, J=7.7 Hz, 1H), 7.9 (t, J=7.9 Hz, 1H), 7.7 (d, J=8.2 Hz, 1H), 7.5 (dd, J=8.2, 2.4 Hz, 1H), 7.24 (m, 2H), 5.42 (s, 2H), 5.14 (s, 2H), 4.5 (q, J=7.2 Hz, 2H), 1.45 (t, J=7 Hz, 3H); LC/MS (ES+): 341.2 (M+1)+.

後処理

  1. waitAfter 1 hour
  2. customto quench
  3. customthe reaction
  4. extractionthe mixture is extracted with EtOAc
  5. dry with materialAfter drying over sodium sulfate, solvent
  6. customis removed
  7. customPurification of the mixture by preparative HPLC (20-70% MeCN/H2O)

出典と根拠

ORDレコード
ord-3799c70c8dc344b48c8943dcf21c5527
出典データセット
uspto-grants-2012_04
特許番号
US08158662B2

反応ノート

読み込み中…