Dimethyl Sulfoxide → HCID 18999056, compound

HRID 2260801Notes

Reaction equation

HRID 2260801 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[N+:11]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[CH:20]([C:22]1[C:27]([Br:28])=[CH:26][N:25]=[C:24]([O:29][CH3:30])[CH:23]=1)[OH:21])([O-:13])=[O:12].C(N(CC)CC)C>ClCCl>[N+:11]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[C:20]([C:22]1[C:27]([Br:28])=[CH:26][N:25]=[C:24]([O:29][CH3:30])[CH:23]=1)=[O:21])([O-:13])=[O:12]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 18999057HCID 18999057, compound

Product 1

HCID 18999056HCID 18999056, compoundYield 96.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-75 °C

Procedure

Anhydrous dimethylsulphoxide (1.2 ml) in anhydrous dichloromethane (20 ml) was added dropwise to a stirred, cooled (-75° C.) solution of oxalyl chloride (0.7 ml) in anhydrous dichloromethane (100 ml) under a nitrogen atmosphere. After 5 minutes a solution of (2-nitrophenyl)-(5-bromo-2-methoxypyridin-4-yl)methanol (2.5 g) in anhydrous dichloromethane (70 ml) was added dropwise keeping the temperature of the reaction mixture below -72° C. After a further 15 minutes triethylamine (5.3 ml) was added dropwise and the reaction mixture stirred at -75° C. for 10 minutes then the cooling bath was removed and the mixture allowed to warm to room temperature. Water (50 ml) was added, the organic layer separated, washed with water then dried (sodium sulphate) and evaporated to dryness. The product was dissolved in dichloromethane, treated with activated charcoal, filtered, evaporated to dryness, then recrystallised from dichloromethane/petroleum ether (60-80) to afford the title compound as a pale yellow solid (2.4 g). mp 128°-131° C. Rf =0.9 in 10% diethyl ether/dichloromethane on silica plates; 1 H NMR (360 MHz, CDCl3) δ 3.91 (3H, s), 6.69 (1H, s), 7.59 (1H, dd, J=1.5 and 7 Hz), 7.74 (1H, dt, J=1.5 and 7 Hz), 7.79 (1H, ddd, J=1.5 and 7 Hz), 8.13 (1H, dd, J=1.5 and 7 Hz), 8.38 (1H, s); IR (KBr) 1705 and 1695 cm-1.

Workup

  1. customthe temperature of the reaction mixture below -72° C
  2. customthe cooling bath was removed
  3. temperatureto warm to room temperature
  4. additionWater (50 ml) was added
  5. customthe organic layer separated
  6. washwashed with water
  7. dry with materialthen dried (sodium sulphate)
  8. customevaporated to dryness
  9. dissolutionThe product was dissolved in dichloromethane
  10. additiontreated with activated charcoal
  11. filtrationfiltered
  12. customevaporated to dryness
  13. customrecrystallised from dichloromethane/petroleum ether (60-80)

Sources & evidence

ORD record
ord-0f72d36ab07545ae9e4a9e710840d31c
Source dataset
uspto-grants-1995_12
Patent number
US05478933

Reaction notes

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