Dimethyl Sulfoxide → HCID 70067124, compound

HRID 2395404Notes

Reaction equation

HRID 2395404 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[CH:11]12[CH2:17][CH:14]([CH2:15][CH2:16]1)[CH2:13][CH:12]2[O:18][C:19]1[CH:20]=[C:21]([CH:27](O)[CH:28]2[C:33](=[O:34])[N:32]([CH2:35][C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)[C:31]3[CH:42]=[CH:43][CH:44]=[CH:45][C:30]=3[S:29]2)[CH:22]=[CH:23][C:24]=1[O:25][CH3:26].C(N(CC)CC)C>C(Cl)Cl.ClCl.C(OCC)(=O)C>[CH:11]12[CH2:17][CH:14]([CH2:15][CH2:16]1)[CH2:13][CH:12]2[O:18][C:19]1[CH:20]=[C:21]([CH:27]=[C:28]2[C:33](=[O:34])[N:32]([CH2:35][C:36]3[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=3)[C:31]3[CH:42]=[CH:43][CH:44]=[CH:45][C:30]=3[S:29]2)[CH:22]=[CH:23][C:24]=1[O:25][CH3:26]

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 18971764HCID 18971764, compound

Product 1

HCID 70067124HCID 70067124, compoundYield 100.4%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolventHCID 24526ChlorineSolvent

Conditions

Temperature
-60 °C

Procedure

To a stirred solution of (87 μl, 1.24 mmol, 2.0 eq) dry dimethylsulfoxide in 3 ml of dry CH2Cl2 at -65° C. was added (0.46 ml, 0.927 mmol, 1.5 eq) of 2.0M oxalyl chloride in CH2 Cl2. The mixture was stirred at ca. -60° C. for 15 minutes, then a solution of (310 mg, 0.618 mmol, 1.0 eq) 2-[[3-(bicyclo[2.2.1]hept-2-yloxy)-4-methoxyphenyl]hydroxy-methyl]-4-(phenylmethyl)-2H-1,4-benzothiazin-3(4H)-one in 10 ml dry CH2Cl2 was added dropwise at -65° C. The mixture was allowed to warm to -30° C. over 1 hour, then cooled to -78° C. and (0.43 ml, 3.09 mmol, 5.0 eq) triethylamine was added to the mixture. The mixture was stirred at room temperature for 1 hour then diluted with 400 ml ethyl acetate, washed twice with H2O, once with brine, dried over MgSO4, and concentrated to give 0.3 g of an oil. Silica gel chromatography eluting with 10% ethyl acetate-hexane gave 120 mg of a yellow oil, which was recrystallized from ether-hexane to yield 55 mg, 18%, of a yellow solid. M.P.: 135°-137° C. Elemental Analysis Calc'd for C30H29NO3S: Calc'd: C, 74.51; H, 6.04; N, 2.90. Found: C, 74.53; H, 5.48; N, 2.88.

Workup

  1. temperatureto warm to -30° C. over 1 hour
  2. temperaturecooled to -78° C.
  3. stirringThe mixture was stirred at room temperature for 1 hour
  4. washwashed twice with H2O, once with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-b9b7570c454e4b1190c0379c7bc801a0
Source dataset
uspto-grants-1998_09
Patent number
US05814651

Reaction notes

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