2,4,6-Trimethylpyridine → 2-octadecyl-7-(2,3,4,6-tetra-O-acetyl beta-D-galactopyranosyloxy)-3H-phenoxazin-3-one

HRID 4880Notes

Reaction equation

HRID 4880 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]2[C:13](=[CH:14][CH:15]=1)[N:12]=[C:11]1[C:6](=[CH:7][C:8](=[O:34])[C:9]([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[CH:10]1)[O:5]2.CC1C=C(C)N=C(C)C=1.[CH3:44][C:45]([O:47][CH2:48][CH:49]1[O:54][C@H:53](Br)[CH:52]([O:56][C:57]([CH3:59])=[O:58])[C@@H:51]([O:60][C:61]([CH3:63])=[O:62])[C@H:50]1[O:64][C:65]([CH3:67])=[O:66])=[O:46]>ClCCl.C(=O)([O-])[O-].[Ag+2]>[CH2:16]([C:9]1[C:8](=[O:34])[CH:7]=[C:6]2[C:11](=[N:12][C:13]3[C:4]([O:5]2)=[CH:3][C:2]([O:1][C@@H:53]2[O:54][C@H:49]([CH2:48][O:47][C:45](=[O:46])[CH3:44])[C@H:50]([O:64][C:65](=[O:66])[CH3:67])[C@H:51]([O:60][C:61](=[O:62])[CH3:63])[C@H:52]2[O:56][C:57](=[O:58])[CH3:59])=[CH:15][CH:14]=3)[CH:10]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33]

Participants

6

Reactant 3

HCID 79532,4,6-TrimethylpyridineHCID 24802013Acetobromo-a-D-galactoseHCID 178418639HCID 178418639, compound

Product 1

HCID 228467472-octadecyl-7-(2,3,4,6-tetra-O-acetyl beta-D-galactopyranosyloxy)-3H-phenoxazin-3-one

Reagents, catalysts & solvents 2

HCID 178418647HCID 178418647, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 7-hydroxy-2-octadecyl-3H-phenoxazine-3-one ("octadecylresorufin) (220 mg, 0.47 mmole), powdered, activated 4Å molecular sieves (0.5 g), sym-collidine (125 μL, 0.95 mmole), and silver carbonate (155 mg, 0.56 mmole) in dry dichloromethane (20 mL) is allowed to stir at room temperature, under an atmosphere of dry nitrogen gas, in the dark for 1 hour. To this mixture is added 1-bromo-2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside (389 mg, 0.95 mmole), slowly with stirring, and the resulting heterogenous solution allowed to stir as above for 72 hours. After this time the reaction mixture is filtered through a pad of diatomaceous earth. The precipitate is washed with chloroform (5×10 mL) and the combined organic filtrates are extracted with 1M aqueous HCl (1×75 mL), saturated aqueous sodium bicarbonate solution (1×75 mL), 1M sodium thiosulfate (1×75 mL), and water (1×75 mL). The organic layer is dried over anhydrous sodium sulfate, filtered, evaporated under reduced pressure, and dried in vacuo to an orange-brown powder (440 mg). An analytical sample of the title compound can be isolated by preparative t.l.c. (20×20 cm SiO2 plate; eluent=9:1 chloroform:ethylacetate) with the bright-orange product eluting at the highest Rf (0.44), (50 mg from 200 mg applied).

Workup

  1. stirringslowly with stirring
  2. stirringto stir as above for 72 hours
  3. filtrationAfter this time the reaction mixture is filtered through a pad of diatomaceous earth
  4. washThe precipitate is washed with chloroform (5×10 mL)
  5. extractionthe combined organic filtrates are extracted with 1M aqueous HCl (1×75 mL), saturated aqueous sodium bicarbonate solution (1×75 mL), 1M sodium thiosulfate (1×75 mL), and water (1×75 mL)
  6. dry with materialThe organic layer is dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. dry with materialdried in vacuo to an orange-brown powder (440 mg)

Sources & evidence

ORD record
ord-524d531152204c2e8e6ceed8643f94a1
Source dataset
uspto-grants-1993_09
Patent number
US05242805

Reaction notes

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