Thiophenol → 2-(p-Nitrophenylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

HRID 653326Notes

Reaction equation

HRID 653326 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([SH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[H-].[Na+].[C:13]([O:16][C@@H:17]1[C@@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@@H:25]([O:31][C:32](=[O:34])[CH3:33])[C@@H:24]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:23][C@H:18]1[O:19][CH2:20][CH2:21]Br)(=[O:15])[CH3:14].C1(S)C=CC=CC=1>CN(C)C=O.CCOCC.C(OCC)(=O)C.C(CC(C)(C)C)(C)C>[C:13]([O:16][C@@H:17]1[C@@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@@H:25]([O:31][C:32](=[O:34])[CH3:33])[C@@H:24]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:23][C@H:18]1[O:19][CH2:20][CH2:21][S:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)(=[O:15])[CH3:14]

Participants

8

Reactant 4

HCID 7969ThiophenolHCID 158094-NitrobenzenethiolHCID 24758Sodium hydrideHCID 105757262-bromoethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

Product 1

HCID 545191362-(p-Nitrophenylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×HCID 18516502EtOAc isooctaneSolvent

Procedure

p-Nitrothiophenol (50 mg; 0.32 mmol) was added to a suspension of sodium hydride (oil-free; 11 mg; 0.46 mmol) in dimethylformamide (3 ml) at room temperature and with stirring. 2-Bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (1) (110 mg; 0.24 mmol) in dimethylformamide (3 ml) was added during 10 min to the thiophenol solution and the reaction mixture was stirred for another 75 min (TLC: SiO2, ethyl acetate:isooctane 1:1). The reaction mixture was poured into ice-cold water (20 ml) and ether (40 ml). The aqueous phase was extracted further with ether (40 ml) and the combined organic phases were washed with cold water (20 ml) and dried (sodium sulfate). Evaporation and chromatography (SiO2, ethyl acetate:isooctane 1:1) gave the title compound (25) as a light yellow oil. Yield: 80 mg (62%). [α]D23 -15.2° (c 1.1; CDCl3); 1H-NMR (CDCl3, TMS) δ 8.14, 7.36 (ABq, 4H, JAB =9.2 Hz, aromatic H), 5.40 (dd, 1H, J4,5 =1.0 Hz, H4), 5.22 (dd, 1H, J2,3 =10.5 Hz, H2), 5.01 (dd, 1H, J3,4 =3.4 Hz, H3), 4.52 (d, 1H, J1,2 =7.8 Hz, H1), 3.25 (t, 2H, J=6.5 Hz, S--CH2), 2.17, 2.05, 2.04, 1.99 (s, 3H each, CH3CO) ppm. 13C-NMR (CDCl3, TMS) δ 170.4, 170.2, 170.1, l69.4 (CO), 146.6, 145.3, 126.5, 124.1 (aromatic C), 101.4 (Cl), 70.9, 70.8, 68.5, 66.9 (C2-C5), 67.9 (CH2 --O) 61.2 (C6), 31.8 (S--CH2), 20.8, 20.7, 20.6 (CH3CO) ppm.

Workup

  1. extractionThe aqueous phase was extracted further with ether (40 ml)
  2. washthe combined organic phases were washed with cold water (20 ml)
  3. dry with materialdried (sodium sulfate)
  4. customEvaporation and chromatography (SiO2, ethyl acetate:isooctane 1:1)

Sources & evidence

ORD record
ord-a75a6a942fdb47e286f909a18d51a4b0
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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