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Hydrochloric Acid → HCID 118377797, Verbindung

HRID 1055503
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1055503
[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
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 5

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

Produkt 1

HCID 118377797HCID 118377797, Verbindung
Ausbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-3a3fa362845248ab8b9e6dd1c4fe8def
Quelldatensatz
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09394329B2

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