Dimethyl Sulfoxide → HCID 23657705, compound

HRID 2220587Notes

Reaction equation

HRID 2220587 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][CH2:13][CH2:14][C:15]1[O:16][C:17]2[CH:23]=[CH:22][C:21]([C:24]([O:26][CH3:27])=[O:25])=[CH:20][C:18]=2[CH:19]=1.C(N(CC)CC)C>C(Cl)Cl.O>[CH:12]([CH2:13][CH2:14][C:15]1[O:16][C:17]2[CH:23]=[CH:22][C:21]([C:24]([O:26][CH3:27])=[O:25])=[CH:20][C:18]=2[CH:19]=1)=[O:11]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 69286085HCID 69286085, compound

Product 1

HCID 23657705HCID 23657705, compoundYield 91.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-70 °C

Procedure

Oxalyl chloride (2 M solution in CH2Cl2, 40 mL, 80 mmol) was placed under Ar into a reaction flask, equipped with addition funnel, inlet thermometer and drying tube charged with Drierite, and cooled to −70° C. A mixture of DMSO (12.2 mL, 171.2 mmol) and dry CH2Cl2 (30 mL) was added dropwise. After 30 min a solution of 95 (14.3 g, 61 mmol) in CH2Cl2 was slowly added and the mixture was stirred at −70° C. for 60 min. After that time triethylamine (45.2 mL, 405 mmol) was added dropwise at −60° C. The mixture was allowed to warm to room temperature, water (100 mL) was added carefully and the stirring continued for 10 min. Organic layer was separated and the aqueous layer was extracted with CH2Cl2 (2×75 mL). Combined organic were washed with 2 M HCl (30 mL), dried over Na2SO4 and concentrated. Column chromatography (SiO2, EtOAc/hexanes, 5/1) followed by recrystalliztion (EtOAc/hexanes, 1/3) afforded 97 as light yellow crystals (12.93 g, 91%): mp. 48-49° C. 1H NMR (DMSO-d6) δ9.70 (s, 1H), 8.20 (s, 1H), 7.87 (d, J=8.2 Hz, 1H), 7.62 (d, J=8.2 Hz, 1H), 6.75 (s, 1H), 3.87 (s, 3H), 3.07 (m, 2H), 2.96 (m, 2H). Anal. (C13H12O4.0.1H2O) C, H.

Workup

  1. customequipped with addition funnel, inlet
  2. customdrying tube
  3. additioncharged with Drierite
  4. additionwas added dropwise
  5. temperatureto warm to room temperature
  6. waitthe stirring continued for 10 min
  7. customOrganic layer was separated
  8. extractionthe aqueous layer was extracted with CH2Cl2 (2×75 mL)
  9. washCombined organic were washed with 2 M HCl (30 mL)
  10. dry with materialdried over Na2SO4
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-ceac97c0eedc44c99e7521c691a3b580
Source dataset
uspto-grants-2008_08
Patent number
US07417158B2

Reaction notes

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