Dimethyl Sulfoxide → HCID 131722684, compound

HRID 2301172Notes

Reaction equation

HRID 2301172 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C@@H:13]1[C@@H:17]([C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[CH:19]=2)[CH2:16][N:15]([C@H:25]([C@@H:36]([CH3:39])[CH2:37][CH3:38])[C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[O:27])[CH2:14]1.C(N(CC)CC)C>C(Cl)Cl.CCOCC>[CH:12]([C@@H:13]1[C@@H:17]([C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[CH:19]=2)[CH2:16][N:15]([C@H:25]([C@@H:36]([CH3:39])[CH2:37][CH3:38])[C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[O:27])[CH2:14]1)=[O:11]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 131722685HCID 131722685, compound

Product 1

HCID 131722684HCID 131722684, compoundYield 79.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent4×

Procedure

After cooling 0.605 g (4.767 mmole) oxalyl chloride in 30 mL DCM in a dry ice acetone bath under nitrogen, 0.748 g (9.569 mmole) DMSO in 5 mL DCM was added over 5 minutes. After stirring for 15 minutes, a solution of the alcohol (1.587 g, 3.987 mmole) from Step C above in 30 mL DCM was added over 20 minutes. After an additional 20 minutes, a solution of 2.017 g (19.935 mmole) triethylamine in 5 mL DCM was added over 5 minutes. The cooling bath was allowed to warm up overnight. The reaction mixture was transferred into a separatory funnel with ether and was washed with 1 N NaOH, water, and saturated brine. The organic layer was dried over sodium sulfate and concentrated to give 1.63 g crude product. FC on silica gel (5˜40% ethyl acetate in hexanes) gave 1.257 g title compound as a colorless oil. Rf: 0.44 (20% ethyl acetate in hexanes). 1H NMR (500 MHz) δ 9.64 (d, J=2.1 Hz, 1H), 7.33˜7.41 (m, 5H), 7.24˜7.27 (m, 1H), 6.90˜6.98 (m, 3H), 5.21 (AB d, J=12.2 Hz, 1H), 5.18 (AB d, J=12.2 Hz, 1H), 3.54˜3.58 (m, 1H), 3.26˜3.29 (m, 1H), 3.14˜3.22 (m, 3H), 2.89˜2.93 (m, 1H), 2.68˜2.71 (m, 1H), 1.86˜1.93 (m, 1H), 1.39˜1.47 (m, 1H), 1.04˜1.15 (m, 1H), 0.99 (d, J=6.7 Hz, 3H), 0.91 (t, J=7.5 Hz, 3H). Some starting material was also recovered (0.298 g). Rf: 0.13 (20% ethyl acetate in hexanes).

Workup

  1. waitAfter an additional 20 minutes
  2. temperatureto warm up overnight
  3. washwas washed with 1 N NaOH, water, and saturated brine
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. concentrationconcentrated
  6. customto give 1.63 g crude product

Sources & evidence

ORD record
ord-3ce2411c0275443d826c5fde7b18d274
Source dataset
uspto-grants-2002_12
Patent number
US06498161B1

Reaction notes

Loading…