Dimethyl Sulfoxide → HCID 13357470, compound

HRID 1381505Notes

Reaction equation

HRID 1381505 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[OH:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:17]2[C:22]=1[CH:21]=[CH:20][NH:19][CH:18]=2.C(N(CC)CC)C>C(Cl)Cl>[CH:18]1[C:17]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12](=[O:11])[C:22]=2[CH:21]=[CH:20][N:19]=1

Participants

6

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 21276159HCID 21276159, compound

Product 1

HCID 13357470HCID 13357470, compoundYield 93.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-70 °C

Procedure

Dimethylsulfoxide (9.37 g, 0.12 mole) was added dropwise to a stirred solution of oxalyl chloride (7.61 g, 0.060 mole) in methylene chloride (120 ml) maintained at betweeen -70° C. to -60° C. The mixture was stirred for 10 minutes at -70° C., then a solution of 5-hydroxycyclohepta[ 1,2-c]pyridine (10.00 g, 0.061 mole) and additional dimethylsulfoxide (12 ml) in methylene chloride (~115 ml) was added rapidly (~10 minutes) while maintaining the temperature of the reaction mixture at -70° C. After stirring for an additional 30 minutes at -75° C. to 60° C., a solid precipitate was present. Triethylamine (37.026 g, 0.366 mole) was added rapidly at -70° C. and the resulting yellow reaction mixture was stirred at -70° C. for ~10 minutes, then allowed to warm to room temperature. After about 48 hours at room temperature the reaction mixture was quenched with water (600 ml), the organic phase separated, then extracted with water (2X, 500 ml), aqueous sodium bicarbonate (5%, 2X, 500 ml), and brine. After drying, the organic layer was filtered through celite and concentrated by solvent evaporation to give 9.00 g of a brown oil. Distillation (90°-120° C., 0.03 mm) gave the desired product as a yellow liquid (07.41 g, 75%). The analytical sample was prepared by chromatography of ~0.1 g on a 20×20 cm preparative tlc plate eluting with a mixture of 35% ethanol - 65% methylene chloride.

Workup

  1. temperaturemaintained at betweeen -70° C. to -60° C
  2. temperaturewhile maintaining the temperature of the reaction mixture at -70° C
  3. stirringAfter stirring for an additional 30 minutes at -75° C. to 60° C.
  4. stirringthe resulting yellow reaction mixture was stirred at -70° C. for ~10 minutes
  5. temperatureto warm to room temperature
  6. customAfter about 48 hours at room temperature the reaction mixture was quenched with water (600 ml)
  7. customthe organic phase separated
  8. extractionextracted with water (2X, 500 ml), aqueous sodium bicarbonate (5%, 2X, 500 ml), and brine
  9. customAfter drying
  10. filtrationthe organic layer was filtered through celite and
  11. concentrationconcentrated by solvent evaporation

Sources & evidence

ORD record
ord-8ef1ffae906c4f349162ecf2ce21004c
Source dataset
uspto-grants-1989_02
Patent number
US04803210

Reaction notes

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