Hydrochloric Acid → HCID 118377797, compound

HRID 1055503Notes

Reaction equation

HRID 1055503 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:46]=[CH:45][C:44]([O:47][CH2:48][CH3:49])=[CH:43][CH:42]=4)[CH:34]=3)[O:32][C@@:10]1([CH2:50][OH:51])[CH2:11][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O)[O-:53].[Na+].[Br-].[K+].Cl[O-].[Na+].Cl>O1CCCC1>[CH2:1]([O:8][C@H:9]1[C@H:15]([O:16][CH2:17][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:42]=[CH:43][C:44]([O:47][CH2:48][CH3:49])=[CH:45][CH:46]=4)[CH:34]=3)[O:32][C@@:10]1([C:50]([OH:53])=[O:51])[CH2:11][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 67153941HCID 67153941, compound

Product 1

HCID 118377797HCID 118377797, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of [(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 1j (0.36 g, 0.51 mmol, obtained from the synthetic method described in step 9 of example 1) in tetrahydrofuran (7 mL) were added saturated aqueous sodium bicarbonate (7.4 mL), potassium bromide (12 mg, 0.10 mmol) and 2,2,6,6-tetramethylpiperidinooxy (8 mg, 0.05 mmol) in turn at 0° C., and then sodium hypochlorite (6.7 mL, available chlorine ≧5.5%) was added dropwise over a period of 10 min. The mixture was stirred at 0° C. for 2 hours and acidified with aqueous HCl(1N) till pH becomes 4. The resulting mixture was extracted with ethyl acetate (10 mL×2). The combined organic layers were washed with saturated aqueous sodium chloride (10 mL), dried over anhydrous sodium sulfate and concentrated in vacuo to give the title compound 2a (0.38 g, 100%) as yellow oil. The crude product was used in next step without further purification. The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, DMSO-d6) δ (ppm): 13.92 (s, 1H), 7.52 (s, 1H), 7.45 (dd, 2H), 7.30 (dd, 10H), 7.19 (t, 3H), 7.05 (d, 2H), 6.82 (d, 2H), 6.75 (d, 2H), 4.75 (m, 3H), 4.68 (d, 1H), 4.36 (d, 1H), 4.29 (d, 1H), 4.09 (d, 1H), 4.02 (m, 3H), 3.93 (m, 2H), 3.89-3.82 (m, 2H), 3.76 (d, 1H), 1.28 (t, 3H).

Workup

  1. extractionThe resulting mixture was extracted with ethyl acetate (10 mL×2)
  2. washThe combined organic layers were washed with saturated aqueous sodium chloride (10 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3a3fa362845248ab8b9e6dd1c4fe8def
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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