Sulfuric Acid → HCID 53880642, compound

HRID 565163Notes

Reaction equation

HRID 565163 reaction equation
C1C=C[NH+]=CC=1.C1C=C[NH+]=CC=1.[O-][Cr](O[Cr]([O-])(=O)=O)(=O)=O.[CH2:22]([O:29][C@@H:30]1[C@@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@@H:34]([O:44][CH2:45][C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@@H:33]([CH2:52][O:53][CH2:54][C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[O:32][C@H:31]1[O:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][OH:72])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C(Cl)Cl.S(=O)(=O)(O)O>C(O)C>[CH2:22]([O:29][C@@H:30]1[C@@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@@H:34]([O:44][CH2:45][C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=2)[C@@H:33]([CH2:52][O:53][CH2:54][C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[O:32][C@H:31]1[O:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH:71]=[O:72])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 6344DichloromethaneHCID 2724130Cornforth reagent2×HCID 54436511HCID 54436511, compound2×

Product 1

HCID 53880642HCID 53880642, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

(i) PDC oxidation of 10-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyloxy)-n-decanol. Under an atmosphere of nitrogen, pyridinium dichromate (460 mg, 1.222 mmol) was added to a dry methylene chloride solution (10 mL) of 10-(2,3,4,6-tetra-O-benzyl-β-D-galactopyrano-syloxy)-n-decanol (570 mg, 0.818 mmol). The resulting brown slurry was stirred at room temperature under nitrogen. TLC analysis (visualization by UV and char with 10% sulfuric acid in ethanol) of the reaction mixture indicated complete consumption of the starting material and the formation of a new compound after 20 h. The reaction mixture was treated with ether (10 mL), filtered through silica gel and Celite with an ether wash (25 mL) and concentrated to an off-white oil. Chromatographic purification (silica gel, 20% ethyl acetate in hexanes) afforded 374 mg (0.539 mmol, 66%) of 10-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyloxy)-n-decanal as a clear oil. Rf=0.61 (silica gel, 30% ethyl acetate in hexanes); 1H NMR (CDCl3, 300 MHz) δ: 9.77 (t, J=1.5 Hz, 1H), 7.30 (m, 20H), 4.97 (dd, J=12.0, 2.7 Hz, 2H), 4.78 (d, J=11.1 Hz, 1H), 4.77 (d, J=4.5 Hz, 1H), 4.65 (d, J=12 Hz, 1H), 4.46 (d, J=4.2 Hz, 2H), 4.38 (d, J=7.8 Hz, 1H), 3.95 (m, 1H), 3.84 (dt, J=10.2, 1.8 Hz, 1H), 3.50 (m, 6H), 2.40 (dt, J=7.5, 1.8 Hz, 2H), 1.65 (m, 6H), 1.30 (m, 10 H); MS (FAB+): 701.0 ((M+Li)+, 100), 455.1 (4), 181.1 (19), 160.0 (8).

Workup

  1. customconsumption of the starting material
  2. additionThe reaction mixture was treated with ether (10 mL)
  3. filtrationfiltered through silica gel and Celite with an ether
  4. washwash (25 mL)
  5. concentrationconcentrated to an off-white oil
  6. customChromatographic purification (silica gel, 20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-aeaf625b106e4c05ae70b2331130f724
Source dataset
uspto-grants-2001_01
Patent number
US06171614B2

Reaction notes

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