Triethylamine → 1-(3,4-Dichlorophenyl)-2-pyridin-4-yl-ethane-1,2-dione

HRID 1768315Notes

Reaction equation

HRID 1768315 reaction equation
C(Cl)(=O)C(Cl)=O.[Cl:7][C:8]1[CH:9]=[C:10]([CH:15]([OH:24])[CH:16]([C:18]2[CH:23]=[CH:22][N:21]=[CH:20][CH:19]=2)[OH:17])[CH:11]=[CH:12][C:13]=1[Cl:14].C(N(CC)CC)C>ClCCl.CS(C)=O>[Cl:7][C:8]1[CH:9]=[C:10]([C:15](=[O:24])[C:16]([C:18]2[CH:19]=[CH:20][N:21]=[CH:22][CH:23]=2)=[O:17])[CH:11]=[CH:12][C:13]=1[Cl:14]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 221854501-(3,4-Dichlorophenyl)-2-pyridin-4-yl-ethane-1,2-diol

Product 1

HCID 154548601-(3,4-Dichlorophenyl)-2-pyridin-4-yl-ethane-1,2-dioneYield 85.3%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

Dimethylsulfoxide (37 ml, 0.53 mol) was dissolved in dichloromethane (250 ml) and cooled to −78° C. Oxalyl chloride (34.5 ml, 0.40 mol) was added dropwise and the solution stirred for 20 min. A solution of the product of Step 1 (34 g, 0.12 mol) in dimethylsulfoxide (40 ml) and dichloromethane (200 ml) was added dropwise at −78° C., and the solution stirred for 30 minutes. Triethylamine (104 ml, 0.74 mol) was added dropwise and the solution became floculent such that overhead stirring became necessary. The solution was allowed to stir at room temperature over 2 hours then was poured on to ice/saturated sodium bicarbonate solution. The aqueous layer was separated, and re-extracted with dichloromethane. The combined organic phases were concentrated under reduced pressure to a green-yellow solid. The solid was redissolved in dichloromethane and washed with water and brine, dried (MgSO4) and evaporated to a solid. The crude solid was purified by silica gel chromatography eluting with dichloromethane, to afford the title compound (28.66 g, 85%) as a yellow solid; MS(-ve ion) m/e 279/281/283 [M−H]−.

Workup

  1. stirringthe solution stirred for 30 minutes
  2. stirringstirring
  3. stirringto stir at room temperature over 2 hours
  4. additionthen was poured on to ice/saturated sodium bicarbonate solution
  5. customThe aqueous layer was separated
  6. extractionre-extracted with dichloromethane
  7. concentrationThe combined organic phases were concentrated under reduced pressure to a green-yellow solid
  8. dissolutionThe solid was redissolved in dichloromethane
  9. washwashed with water and brine
  10. dry with materialdried (MgSO4)
  11. customevaporated to a solid
  12. customThe crude solid was purified by silica gel chromatography
  13. washeluting with dichloromethane

Sources & evidence

ORD record
ord-c6be4e8f5384414c9b4daa90d49c94a9
Source dataset
uspto-grants-2007_06
Patent number
US07235658B2

Reaction notes

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