Dimethyl Sulfoxide → HCID 53890318, compound

HRID 1742292Notes

Reaction equation

HRID 1742292 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]1([C:17]2[C:25]([CH:26]=[CH:27][C:28]([N:30]3[CH2:35][CH2:34][CH2:33][CH2:32][C@@H:31]3[CH2:36][CH2:37][OH:38])=[O:29])=[C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][N:19]3[N:18]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Cl-].[NH4+]>C(Cl)Cl.C(N(CC)CC)C>[C:11]1([C:17]2[C:25]([CH:26]=[CH:27][C:28]([N:30]3[CH2:35][CH2:34][CH2:33][CH2:32][C@@H:31]3[CH2:36][CH:37]=[O:38])=[O:29])=[C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][N:19]3[N:18]=2)[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 129453HCID 129453, compound

Product 1

HCID 53890318HCID 53890318, compoundYield 38.4%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolvent

Conditions

Temperature
-45 °C

Procedure

A solution of dimethyl sulfoxide (202 mg) in methylene chloride (1.0 ml) was added dropwise to a solution of oxalyl dichloride (247 mg) in methylene chloride (10 ml) over 5 minutes at -78° C. After 10 minutes, a solution of (2R)-1-[3-(2-phenylpyrazolo[1,5-a]pyridin-3-yl)acryloyl]-2-(2-hydroxyethyl)piperidine (trans isomer) (364 mg) in methylene chloride (3.4 mg) was added dropwise over 10 minutes at -78° C. The solution was stirred at -78° C. for 20 minutes and at -45° C. for 1 hour. Triethylamine (986 μl) was added to the solution and the mixture was stirred at -20°~0° C. for 20 minutes. Saturated ammonium chloride solution (20 ml) was added to the reaction mixture and the mixture was extracted with methylene chloride (10 ml×2). The combined extracts were washed with brine (10 ml), dried over magnesium sulfate and evaporated in vacuo. The crude material was purified by column chromatography on silica gel (10 g) with a mixture of methylene chloride and ethyl acetate (10:1) as an eluent to give (2R)-1-[3-(2-phenylpyrazolo-[1,5-a]pyridin-3-yl)acryloyl]-2-(formylmethyl)piperidine (trans isomer) (139.0 mg) as an oil.

Workup

  1. stirringthe mixture was stirred at -20°~0° C. for 20 minutes
  2. extractionthe mixture was extracted with methylene chloride (10 ml×2)
  3. washThe combined extracts were washed with brine (10 ml)
  4. dry with materialdried over magnesium sulfate
  5. customevaporated in vacuo
  6. customThe crude material was purified by column chromatography on silica gel (10 g) with a mixture of methylene chloride and ethyl acetate (10:1) as an eluent

Sources & evidence

ORD record
ord-0d1018eb05304acba574ba8584a20c80
Source dataset
uspto-grants-1994_08
Patent number
US05338743

Reaction notes

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