Sulfuric Acid → HCID 15511354, compound

HRID 1420480Notes

Reaction equation

HRID 1420480 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 15511357HCID 15511357, compound2×

Product 1

HCID 15511354HCID 15511354, compoundYield 770%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

PDC oxidation of 10-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyloxy)-n-decanol. Under an atmosphere of nitrogen, pyridinium dichromate (400 mg, 1.036 mmol) was added to a dry methylene chloride solution (10 mL) of 10-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyloxy)-n-decanol (450 mg, 0.646 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 15 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 345 mg (0.497 mmol, 770%) of 10-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyloxy)-n-decanal as a clear oil. Rf =0.50 (silica gel, 300 ethyl acetate in hexanes); 1H NMR (CDCl3, 300 MHz) δ: 9.76 (dt, J=5.1, 1.5 Hz, 1H), 7.31 (m, 20H), 4.93 (d, J=6.6 Hz, 1H), 4.91 (d, J=2.4 Hz, 1H), 4.78 (d, J=2.1 Hz, 1H), 4.72 (d, J=12.0 Hz, 1H), 4.67 (m, 2H), 4.57 (dd, J=12.0, 10.8 Hz, 2H), 4.09 (t, J=6.9 Hz, 1H), 4.03 (d, J=9.3 Hz, 1H), 3.96 (dd, J=12.0, 2.7 Hz, 1H), 3.82 (m, 3H), 3.68 (m, 1H), 3.40 (dt, J=9.6, 6.6, Hz, 2H), 2.41 (dt, J=7.2, 1.8 Hz, 2H), 1.64 (m, 4H), 1.32 (m, 12H); MS (FAB+): 717.1 ((M+Na)+, 33), 701.1 ((M+Li)+, 100), 671.1 (8), 615.1 (7), 455.1 (12), 439.1 (10), 423.1 (20), 243.1 (10), 181.1 (17), 160.0 (20).

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-91f0234cba3945f4a9b9ca8a4c4b1be1
Source dataset
uspto-grants-2000_06
Patent number
US06071532

Reaction notes

Loading…