Bromoacetonitrile → HCID 86637602, Verbindung

HRID 1694371Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1694371
[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]

Komponenten

7

Edukt 5

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

Produkt 1

HCID 86637602HCID 86637602, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel

Versuchsvorschrift

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)+.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-3799c70c8dc344b48c8943dcf21c5527
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08158662B2

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