Dimethyl Sulfoxide → Di-tert-butyl (2-oxopropane-1,3-diyl)dicarbamate

HRID 1624352Notes

Reaction equation

HRID 1624352 reaction equation
CS(C)=O.C(=O)=O.CC(C)=O.C(Cl)(=O)C(Cl)=O.[C:18]([O:22][C:23](=[O:37])[NH:24][CH2:25][CH:26]([OH:36])[CH2:27][NH:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])([CH3:21])([CH3:20])[CH3:19].C(N(CC)CC)C>C(Cl)Cl.O>[C:18]([O:22][C:23](=[O:37])[NH:24][CH2:25][C:26](=[O:36])[CH2:27][NH:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])([CH3:21])([CH3:19])[CH3:20]

Participants

8

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 375632tert-butyl N-{3-[(tert-butoxycarbonyl)amino]-2-hydroxypropyl}carbamateHCID 18522661Acetone cardice

Product 1

HCID 15704320Di-tert-butyl (2-oxopropane-1,3-diyl)dicarbamateYield 88.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

To a solution of dimethyl sulfoxide (25.2 ml, 0.36 mol) in methylene chloride (357 ml) at −78° C. (dry ice/acetone) was added a solution of oxalyl chloride (20 ml, 0.23 mol) in methylene chloride (115 ml). The reaction mixture was stirred at −78° C. for 30 min under an atmosphere of N2 then a solution of (3-tert-Butoxycarbonylamino-2-hydroxy-propyl)-carbamic acid tert-butyl ester (31.9 g, 0.11 mol) in methylene chloride (300 ml) and triethylamine (75 ml, 0.54 mol) were added. The reaction was stirred for 16 hours, allowing the reaction to warm up to room temperature. The mixture was diluted with water (800 ml) and extracted with methylene chloride (2×300 ml). The combined organic extracts were dried (Na2SO4), filtered, and concentrated in vacuo to afford a yellowish oil. Purification via column chromatography on silica gel (ethyl acetate:hexane, 3:7, v/v) afforded the product as a white solid (28 g, 88%). 1H NMR (CDCl3) δ 1.44 (s, 18H), 4.04 (m, 4H), 5.19 (s, 1H).

Workup

  1. stirringThe reaction was stirred for 16 hours
  2. customthe reaction
  3. temperatureto warm up to room temperature
  4. extractionextracted with methylene chloride (2×300 ml)
  5. dry with materialThe combined organic extracts were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto afford a yellowish oil
  9. customPurification via column chromatography on silica gel (ethyl acetate:hexane, 3:7, v/v)

Sources & evidence

ORD record
ord-2a1402df2ace47a6a6fe1b0bce8cf482
Source dataset
uspto-grants-2014_07
Patent number
US08778967B2

Reaction notes

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