Epichlorohydrin → HCID 58044386, Verbindung

HRID 2368026Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2368026
ClC1C(Cl)=CC(O)=C(OC)C=1.C(C1OC1)Cl.C([O-])([O-])=O.[K+].[K+].[F:23][C:24]([F:42])([F:41])[C:25]1[CH:30]=[CH:29][C:28]([C:31]2[CH:32]=[CH:33][C:34]3[N:35]([C:37](=[O:40])[NH:38][N:39]=3)[CH:36]=2)=[CH:27][CH:26]=1.[Cl:43][C:44]1[C:54]([Cl:55])=[CH:53][C:47]([O:48][CH2:49][CH:50]2[CH2:52][O:51]2)=[C:46]([O:56][CH3:57])[CH:45]=1>CN(C=O)C.O>[Cl:43][C:44]1[C:54]([Cl:55])=[CH:53][C:47]([O:48][CH2:49][CH:50]([OH:51])[CH2:52][N:38]2[C:37](=[O:40])[N:35]3[CH:36]=[C:31]([C:28]4[CH:29]=[CH:30][C:25]([C:24]([F:23])([F:41])[F:42])=[CH:26][CH:27]=4)[CH:32]=[CH:33][C:34]3=[N:39]2)=[C:46]([O:56][CH3:57])[CH:45]=1

Komponenten

8

Edukt 5

HCID 7835EpichlorohydrinHCID 11430Potassium Carbonate2×HCID 171604,5-DichloroguaiacolHCID 58044490HCID 58044490, VerbindungHCID 58044663HCID 58044663, Verbindung

Produkt 1

HCID 58044386HCID 58044386, VerbindungAusbeute 27,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

4,5-dichloro-2-methoxyphenol (200.0 mg, 1.036 mmol), epichlorohydrin (958.6 mg, 10.36 mmol, 10 equiv.) and K2CO3 (1.43 g, 10.36 mmol, 10 equiv.) were placed in a 50 mL round bottomed flask under a nitrogen atmosphere. To the flask were added DMF (3 mL) at ambient temperature. The mixture was heated at 70° C. for 16 hour. To the mixture was added water (30 mL). And then the whole was extracted with EtOAc (30 mL×3). Combined organic layers were washed with brine and dried over Na2SO4. The solvent was removed under a reduced pressure. Crude product (2-((4,5-dichloro-2-methoxyphenoxy)methyl)oxirane, 248.7 mg, 0.998 mmol, 96.4%) was used for the subsequent step without further purification. 6-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[4,3-a]pyridin-3(2H)-one (47.2 mg, 0.169 mmol), 2-((4,5-dichloro-2-methoxyphenoxy)methyl)oxirane (50.5 mg, 0.2028 mmol, 1.2 equiv.) and K2CO3 (46.8 mg, 0.339 mmol, 2.0 equiv.) were placed in a 50 mL round bottomed flask under a nitrogen atmosphere. To the flask were added DMF (3 mL) at ambient temperature. The mixture was heated at 80° C. for 1 hour. The mixture was filtered through Celite and the filtrate was injected to preparative HPLC to give compound 198 as a colorless oil (24.3 mg, 0.0460 mmol, 27.2%). LCMS (EI: 70 eV) 552 (M++2+Na), 551 (M++1+Na), 550 (M++Na), 530 (M++2), 529 (M++1), 528 (M+).

Aufarbeitung

  1. extractionAnd then the whole was extracted with EtOAc (30 mL×3)
  2. washCombined organic layers were washed with brine
  3. dry with materialdried over Na2SO4
  4. customThe solvent was removed under a reduced pressure
  5. temperatureThe mixture was heated at 80° C. for 1 hour
  6. filtrationThe mixture was filtered through Celite

Quellen und Nachweise

ORD-Eintrag
ord-f2a74d02e21a4a45841f62054837a3ab
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08703759B2

Notizen zur Reaktion

Wird geladen…