Dimethyl Sulfoxide → HCID 19698672, compound

HRID 1078625Notes

Reaction equation

HRID 1078625 reaction equation
[C:1](Cl)(=O)[C:2](Cl)=O.CS(C)=O.[CH:11]1[C:24]2[C:23]3([CH2:26][N:27]4[CH2:32][CH2:31][CH:30]([CH2:33][OH:34])[CH2:29][CH2:28]4)[CH2:25][CH:16]([C:17]4[C:22]3=[CH:21][CH:20]=[CH:19][CH:18]=4)[C:15]=2[CH:14]=[CH:13][CH:12]=1.[CH2:35]([N:37](CC)[CH2:38]C)[CH3:36].[OH-].[Na+]>ClCCl>[CH:21]1[C:22]2[C:23]3([CH2:26][N:27]4[CH2:32][CH2:31][CH:30]([CH:33]([C:36]5[CH:35]=[N:37][CH:38]=[CH:1][CH:2]=5)[OH:34])[CH2:29][CH2:28]4)[CH2:25][CH:16]([C:15]4[C:24]3=[CH:11][CH:12]=[CH:13][CH:14]=4)[C:17]=2[CH:18]=[CH:19][CH:20]=1

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 65578Oxalyl chlorideHCID 196986601-(9,10-Dihydro-9,10-methanoanthracen-9-ylmethyl)4-piperidinemethanol

Product 1

HCID 19698672HCID 19698672, compoundYield 79.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-60 °C

Procedure

A solution of oxalyl chloride (3.86 g, 30.4 mmol) in dichloromethane (100 mL) was cooled to -60° C. and treated dropwise with dimethylsulfoxide (2.49 g, 31.89 mmol), resulting in vigorous gas evolution. The resulting mixture was stirred at -60° C. for 15 min, then was treated dropwise with a solution of 1-(9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)4-piperidinemethanol (6.47 g, 20.25 mmol) in dichloromethane (30 mL). This mixture was stirred at -60° C. for 1 h, then was treated with triethylamine (6.15 g, 60.75 mmol). The reaction was allowed to warm to room temperature, then was poured into 10% aqueous sodium hydroxide (50 mL) and extracted with chloroform (3×75 mL). The organic extracts were washed sequentially with 1N aqueous sodium hydroxide (50 mL) and brine (50 mL), combined, dried (K2CO3), filtered and evaporated to leave a tan solid. Trituration with hexane (50 mL) followed by filtration gave the title compound (5.09 g, 16.05 mmol, 79%) as a tan solid. 1H NMR (d6-DMSO): δ 9.57 (s, 1H, CHO), 7.28 (m, 2H), 7.17 (m, 2H), 6.91 (m, 4H), 4.30 (s, 1H, H-C(10)), 3.34 (s, 2H, CH2N), 2.86 (m, 2H, eq-H-C(2')), 2.45 (s, 2H, H-C(11)), 2.29 (m, 3H, ax-H-C(2'), H-C(4')), 1.76 (m, 2H, eq-H-C(3')), 1.45 (m, 2H, ax-H-C(3')).

Workup

  1. customresulting in vigorous gas evolution
  2. stirringThis mixture was stirred at -60° C. for 1 h
  3. temperatureto warm to room temperature
  4. extractionextracted with chloroform (3×75 mL)
  5. washThe organic extracts were washed sequentially with 1N aqueous sodium hydroxide (50 mL) and brine (50 mL)
  6. dry with materialdried (K2CO3)
  7. filtrationfiltered
  8. customevaporated
  9. customto leave a tan solid
  10. filtrationTrituration with hexane (50 mL) followed by filtration

Sources & evidence

ORD record
ord-f282523663814a748f60ba723a83bfda
Source dataset
uspto-grants-1996_08
Patent number
US05550136

Reaction notes

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