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Sodium Hydroxide → HCID 178488125, Verbindung

HRID 1944986
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1944986
Cl.O[CH2:3][C:4]1[C:9]([CH3:10])=[C:8]([O:11][CH3:12])[C:7]([CH3:13])=[CH:6][N:5]=1.S(Cl)(Cl)=O.[SH:18][C:19]1[NH:20][C:21]2[CH:27]=[C:26]([O:28][CH3:29])[CH:25]=[CH:24][C:22]=2[N:23]=1.[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl.O>[CH3:29][O:28][C:26]1[CH:25]=[CH:24][C:22]2[NH:23][C:19]([S:18][CH2:3][C:4]3[C:9]([CH3:10])=[C:8]([O:11][CH3:12])[C:7]([CH3:13])=[CH:6][N:5]=3)=[N:20][C:21]=2[CH:27]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 14798Sodium HydroxideHCID 24386Thionyl ChlorideHCID 184590773,5-Dimethyl-4-methoxy-2-pyridineHCID 178488032HCID 178488032, Verbindung

Produkt 1

HCID 178488125HCID 178488125, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 74236
Tetrabutylammonium Bromide
Katalysator
HCID 962WaterLösungsmittel
HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
17.5 °C

Versuchsvorschrift

2-hydroxymethyl-3,5-dimethyl-4-methoxy pyridine hydrochloride (300 g) was charged to dichloromethane (1770 ml) and cooled to 15-20° C. Thionyl chloride (240 g) was added slowly at 15 to 20° C. and the contents were stirred at 25 to 30° C. for 1 hour. After reaction completion, water (300 ml) was added at 15 to 20° C. and allowed to attain 25 to 30° C. To this reaction mass 2-mercapto-5-methoxy benzimidazole (252 g) and tetrabutyl ammonium bromide (6 g) was added, and the pH of the reaction mass was adjusted to 10.0 to 10.5 at 5 to 15° C. using 30% sodium hydroxide solution and stirred for 2 hours at 15 to 20° C. maintaining pH 10.0-10.5. After reaction completion the dichloromethane layer was separated and the aqueous layer was extracted with dichloromethane (370 ml×2). The dichloromethane layer was then washed with water until the pH of the aqueous layer was 7.0 to 7.5, dried over sodium sulphate and partially concentrated at temperature below 50° C. under vacuum. Ethyl acetate (240 ml) was added and stripped off to remove traces of dichloromethane, further ethyl acetate (800 ml) was added and heated to 50 to 60° C., cooled to room temperature, chilled to 10 to −5° C. and maintained for 1 hour. The product was then filtered, washed with chilled ethyl acetate (200 ml). The product was then dried at 30 to 35° C. to yield 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl)thio]-1H benzimidazole form II (392 g, 80.6% yield).

Aufarbeitung

  1. additionwas added at 15 to 20° C.
  2. customto attain 25 to 30° C
  3. customwas adjusted to 10.0 to 10.5 at 5 to 15° C.
  4. stirringstirred for 2 hours at 15 to 20° C.
  5. temperaturemaintaining pH 10.0-10.5
  6. customwas separated
  7. extractionthe aqueous layer was extracted with dichloromethane (370 ml×2)
  8. washThe dichloromethane layer was then washed with water until the pH of the aqueous layer
  9. dry with materialdried over sodium sulphate
  10. concentrationpartially concentrated at temperature below 50° C. under vacuum
  11. additionEthyl acetate (240 ml) was added
  12. customto remove traces of dichloromethane, further ethyl acetate (800 ml)
  13. additionwas added
  14. temperatureheated to 50 to 60° C.
  15. temperaturecooled to room temperature
  16. temperaturechilled to 10 to −5° C.
  17. temperaturemaintained for 1 hour
  18. filtrationThe product was then filtered
  19. washwashed with chilled ethyl acetate (200 ml)
  20. customThe product was then dried at 30 to 35° C.

Quellen und Nachweise

ORD-Eintrag
ord-e4c5069e659d4d00895345092b6fee18
Quelldatensatz
uspto-grants-2013_03
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08394963B2

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