Methanol → HCID 86751609, compound

HRID 2293884Notes

Reaction equation

HRID 2293884 reaction equation
[N:1]([C@H:4]([C@H:34]([O:50][C:51](=[O:58])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1)/[CH:35]=[CH:36]/[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[CH2:5][O:6][C@@H:7]1[O:23][C@H:22]([CH2:24][O:25][CH2:26][C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[C@H:12]([O:13][CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@H:10]([OH:11])[C@H:8]1[OH:9])=[N+]=[N-].[C:59](Cl)(=[O:66])[C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1.[CH3:68][OH:69]>N1C=CC=CC=1.C(Cl)Cl>[C:51]([O:50][C@H:34](/[CH:35]=[CH:36]/[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[C@@H:4]([NH:1][C:68](=[O:69])[CH2:46][CH2:45][CH2:44][CH2:43][CH2:42][CH2:41][CH2:40][CH2:39][CH2:38][CH2:37][CH2:36][CH2:35][CH2:34][CH2:4][CH3:5])[CH2:5][O:6][C@@H:7]1[O:23][C@H:22]([CH2:24][O:25][CH2:26][C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[C@H:12]([O:13][CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@H:10]([O:11][C:59](=[O:66])[C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[C@H:8]1[OH:9])(=[O:58])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 7412Benzoyl chlorideHCID 86751610HCID 86751610, compound

Product 1

HCID 86751609HCID 86751609, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 21875418Pyridine methylene chlorideSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of (2S,3R,4E)-2-azido-3-benzoyloxy-1-(4,6-di-O-tert-butyloxycarbonylmethyl-β-D-galactopyranosyloxy)-4-octadecene described in Example 15-A (1.34 g 1.63 mmol) in a mixture of pyridine/methylene chloride (1:1, 70 mL) was treated with benzoyl chloride (210 μL, 1.81 mmol) at -78° C. The mixture was stirred at -78° C. for 1 hour, then methanol (10 mL) was added and the resulting mixture was stirred at 22° C. for 20 more hours. The solvents were evaporated and the residue was dissolved in ethyl acetate (200 mL). This solution was washed with water (4×75 mL), saturated aqueous sodium bicarbonate (2×100 mL) and brine (2×100 mL), dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography (150 g, 5 to 50 % ethyl acetate/hexane) and gave the title compound (0.275 g, 20%), along with the starting material (0.839 g, 63%), the 2-benzoate (0.124 g, 8%) and the bis-benzoate (0.030 g, 2%).

Workup

  1. stirringthe resulting mixture was stirred at 22° C. for 20 more hours
  2. customThe solvents were evaporated
  3. dissolutionthe residue was dissolved in ethyl acetate (200 mL)
  4. washThis solution was washed with water (4×75 mL), saturated aqueous sodium bicarbonate (2×100 mL) and brine (2×100 mL)
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel chromatography (150 g, 5 to 50 % ethyl acetate/hexane)

Sources & evidence

ORD record
ord-74bd5cffa2a24e6eaac2faf8b9f355bd
Source dataset
uspto-grants-1997_11
Patent number
US05686426

Reaction notes

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