Bromoacetonitrile → HCID 86637602, compound

HRID 1694371Notes

Reaction equation

HRID 1694371 reaction equation
[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]

Participants

7

Reactant 5

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

Product 1

HCID 86637602HCID 86637602, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

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)+.

Workup

  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)

Sources & evidence

ORD record
ord-3799c70c8dc344b48c8943dcf21c5527
Source dataset
uspto-grants-2012_04
Patent number
US08158662B2

Reaction notes

Loading…