Triethylamine → HCID 86714028, compound

HRID 576310Notes

Reaction equation

HRID 576310 reaction equation
[Cl:1][C:2]1[C:3]([CH2:48][C:49]2[CH:54]=[CH:53][C:52]([O:55][CH2:56][CH3:57])=[CH:51][CH:50]=2)=[CH:4][C:5]([C@H:9]2[C@H:14]([O:15][CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C@@H:13]([O:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[C@H:12]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@@H:11]([CH2:39][O:40][CH2:41][C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=3)[O:10]2)=[C:6]([OH:8])[CH:7]=1.CCN(CC)CC.[Br:65]Br.[NH4+].[Cl-]>CC(O)=O>[Br:65][C:7]1[C:2]([Cl:1])=[C:3]([CH2:48][C:49]2[CH:50]=[CH:51][C:52]([O:55][CH2:56][CH3:57])=[CH:53][CH:54]=2)[CH:4]=[C:5]([C@H:9]2[C@H:14]([O:15][CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[C@@H:13]([O:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[C@H:12]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@@H:11]([CH2:39][O:40][CH2:41][C:42]3[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=3)[O:10]2)[C:6]=1[OH:8]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 24408BromineHCID 25517Ammonium ChlorideHCID 86714026HCID 86714026, compound

Product 1

HCID 86714028HCID 86714028, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of phenol 27 (0.98 g, 1.24 mmol) in AcOH (12 mL) were added Et3N (0.37 mL, 1.86 mmol) and bromine (77 μL, 1.50 mmol) at 0° C. The mixture was stirred at 0° C. for 5 min and at room temperature for 12 hours. The reaction mixture was cooled to 0° C. and aqueous saturated NH4Cl solution (30 mL) was added to the mixture. The mixture was extracted with EtOAc (100 mL). The organic layer was washed with H2O (50 mL×2), aqueous saturated NaHCO3 solution (100 mL), dried over anhydrous MgSO4, filtered and concentrated in vacuo. The crude 2-bromo-3-chloro-4-(4-ethoxybenzyl)-6-((2S,3S,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran-2-yl)phenol (28, 1.08 g) was carried on to the next step without further purification.

Workup

  1. temperatureThe reaction mixture was cooled to 0° C.
  2. extractionThe mixture was extracted with EtOAc (100 mL)
  3. washThe organic layer was washed with H2O (50 mL×2), aqueous saturated NaHCO3 solution (100 mL)
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude 2-bromo-3-chloro-4-(4-ethoxybenzyl)-6-((2S,3S,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)tetrahydro-2H-pyran-2-yl)phenol (28, 1.08 g) was carried on to the next step without further purification

Sources & evidence

ORD record
ord-2391111df4cf47d799b2ebc1fb53eb9b
Source dataset
uspto-grants-2015_05
Patent number
US09034921B2

Reaction notes

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