Ethyl chloroformate → Methyl-(6-thiomorpholin-4-yl-4-o-tolyl-pyridin-3-yl)-amine

HRID 22646Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 22646
[N:1]1([C:7]2[N:12]=[CH:11][C:10]([NH2:13])=[C:9]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[CH3:20])[CH:8]=2)[CH2:6][CH2:5][S:4][CH2:3][CH2:2]1.[C:21](=O)([O-])[O-].[K+].[K+].ClC(OCC)=O.[H-].COCCO[Al+]OCCOC.[Na+].[H-].[OH-].[Na+]>O1CCCC1.C1(C)C=CC=CC=1>[CH3:21][NH:13][C:10]1[CH:11]=[N:12][C:7]([N:1]2[CH2:6][CH2:5][S:4][CH2:3][CH2:2]2)=[CH:8][C:9]=1[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[CH3:20]

Komponenten

8

Edukt 5

HCID 10928Ethyl chloroformateHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydrideHCID 225914486-Thiomorpholin-4-yl-4-o-tolyl-pyridin-3-ylamine

Produkt 1

HCID 22591450Methyl-(6-thiomorpholin-4-yl-4-o-tolyl-pyridin-3-yl)-amineAusbeute 92 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1140TolueneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 2.46 g (8.6 mmol) 6-thiomorpholin-4-yl-4-o-tolyl-pyridin-3-ylamine in 38 ml tetrahydrofuran were added 2.38 g (17 mmol) potassium carbonate (dissolved in 25 ml water) and 1.03 g (9.5 mmol) ethyl cloroformate. The reaction mixture was stirred for 1 h at room temperature and evaporated to remove tetrahydrofuran. The aqueous layer was extracted twice with 50-ml portions of dichloromethane and the organic layer was dried (sodium sulfate) and evaporated in vacuo. The residual oil was dissolved in 30 ml tetrahydrofuran and 7.4 ml (2.6 mmol) 3.5 M sodium bis(2-methoxyethoxy)aluminum hydride solution in toluene were added within 30 min. The reaction mixture was stirred at 50° C. overnight. After cooling to 0° C., 7.5 ml 1 N sodium hydroxide solution were added dropwise. Tetrahydrofuran was removed in vacuo and 10 ml of water were added. The aqueous layer was extracted twice with 20-ml portions of dichloromethane and the combined organic layers were dried (sodium sulfate), evaporated and purified by flash chromatography to give 2.37 g (92%) of the title compound as a yellow solid.

Aufarbeitung

  1. customevaporated
  2. customto remove tetrahydrofuran
  3. extractionThe aqueous layer was extracted twice with 50-ml portions of dichloromethane
  4. dry with materialthe organic layer was dried (sodium sulfate)
  5. customevaporated in vacuo
  6. dissolutionThe residual oil was dissolved in 30 ml tetrahydrofuran
  7. stirringThe reaction mixture was stirred at 50° C. overnight
  8. temperatureAfter cooling to 0° C.
  9. customTetrahydrofuran was removed in vacuo and 10 ml of water
  10. additionwere added
  11. extractionThe aqueous layer was extracted twice with 20-ml portions of dichloromethane
  12. dry with materialthe combined organic layers were dried (sodium sulfate)
  13. customevaporated
  14. custompurified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-2c54b39b4c354d18a0467494dcfa5c8a
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06849624B2

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