Triethylamine → HCID 86601558, compound

HRID 346871Notes

Reaction equation

HRID 346871 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][C:7]([C:8](Cl)=[O:9])=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH2:13]([O:20][C:21]([NH:23][C@@H:24]([CH2:29][S:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C@@H:25]([OH:28])[CH2:26]O)=[O:22])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(N(CC)CC)C.[CH3:44][S:45](Cl)(=[O:47])=[O:46]>O1CCCC1>[CH2:13]([O:20][C:21]([NH:23][C@@H:24]([CH2:29][S:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C@@H:25]([O:28][S:45]([CH3:44])(=[O:47])=[O:46])[CH2:26][O:9][CH2:8][C:7]1[CH:11]=[CH:12][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)=[O:22])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 85024-Nitrobenzoyl chlorideHCID 31297Methanesulfonyl chlorideHCID 10545614HCID 10545614, compound

Product 1

HCID 86601558HCID 86601558, compoundYield 61.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

p-Nitrobenzoyl chloride (20.8 g, 0.112 mol) was added at 3–10° C. to a 0° C. to 5° C. solution of (2R, 3R)-3-benzyloxycarbonylamino-4-phenylthio-1,2-butanediol 14 (39.0 g) and triethylamine (39.1 ml, 0.280 mol) in tetrahydrofuran (300 ml). The resulting mixture was stirred for one hour with ice-cooling. Methanesulfonyl chloride (10.4 ml, 0.135 mol) was added dropwise at 2–12° C. and the mixture was stirred with ice-cooling for one hour. Any insoluble matter was filtered off and washed with ethyl acetate. The filtrate and the washing were combined and concentrated under vacuum. The resulting residue was dissolved in ethyl acetate (300 ml) and washed successively with water (50 ml), a 0.5 M aqueous citric acid solution (50 ml), a saturated aqueous solution of sodium hydrogencarbonate (50 ml) and saturated brine (50 ml), dried over magnesium sulfate and concentrated under vacuum. The resulting residue was recrystallized from toluene (400 ml)/diisopropyl ether (300 ml) to give (2R, 3R)-3-benzyloxycarbonylamino-4-phenylthio-2-methanesulfonyloxy-1-(4-nitrobenzyloxy)butane (38.6 g, 51% yield from (2R, 3R)-3-benzyloxycarbonylamino-4-phenylthio-1,2-butanediol 14) as colorless crystals. 1H NMR (CDCl3, 300 MHz) δ 8.5–8.0 (m, 4H), 7.5–7.2 (m, 10H), 5.44 (ddd, J=6.9, 5.1, 2.3 Hz, 1H), 5.11 (s, 2H), 5.09 (brd d, 1H), 4.57 (dd, J=12.0, 6.9 Hz, 1H), 4.50 (dd, J=12.0, 5.1 Hz, 1H), 4.21 (m, 1H), 3.25 (dd, J=14.0, 6.2 Hz, 1H), 3.05 (s, 3H), 3.05 (dd, J=14.0, 8.2 Hz, 1H) IR (KBr): 3347, 1725, 1699, 1531, 1514, 1349, 1283, 1172, 1109, 1028, 925 cm−1, [α]D25: −14.0° (cl.01,CHCl3); Elemental Analysis (C26H26N2O9S2): Calculated: C, 54.35; H, 4.56; N, 4.88; Found: C, 54.49; H, 4.19; N, 4.75.

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred with ice-
  3. temperaturecooling for one hour
  4. filtrationAny insoluble matter was filtered off
  5. washwashed with ethyl acetate
  6. concentrationconcentrated under vacuum
  7. dissolutionThe resulting residue was dissolved in ethyl acetate (300 ml)
  8. washwashed successively with water (50 ml)
  9. dry with materiala 0.5 M aqueous citric acid solution (50 ml), a saturated aqueous solution of sodium hydrogencarbonate (50 ml) and saturated brine (50 ml), dried over magnesium sulfate
  10. concentrationconcentrated under vacuum
  11. customThe resulting residue was recrystallized from toluene (400 ml)/diisopropyl ether (300 ml)

Sources & evidence

ORD record
ord-bdb39d006b444408a868cc0f08156f14
Source dataset
uspto-grants-2007_02
Patent number
US07173059B2

Reaction notes

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