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Hydrochloric Acid → HCID 86622859, Verbindung

HRID 1013124
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1013124
ClC1C=CC2CCN(C(=O)C(F)(F)F)CCC=2C=1OS(C(F)(F)F)(=O)=O.CC1(CCCN)OCCO1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[Cl:89][C:90]1[CH:106]=[CH:105][C:93]2[CH2:94][CH2:95][N:96]([C:99](=[O:104])[C:100]([F:103])([F:102])[F:101])[CH2:97][CH2:98][C:92]=2[C:91]=1[NH:107][CH2:108][CH2:109][CH2:110][C:111]1([CH3:116])OCCO1.Cl.C([BH3-])#N.[Na+]>C1(C)C=CC=CC=1.CCOC(C)=O.C(Cl)Cl.C(OCC)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CO>[Cl:89][C:90]1[CH:106]=[CH:105][C:93]2[CH2:94][CH2:95][N:96]([C:99](=[O:104])[C:100]([F:101])([F:103])[F:102])[CH2:97][CH2:98][C:92]=2[C:91]=1[N:107]1[CH2:108][CH2:109][CH2:110][CH:111]1[CH3:116]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

14

Edukt 7

HCID 313Hydrochloric AcidHCID 10796Cesium carbonateHCID 5600073-(2-Methyl-1,3-dioxolan-2-yl)-1-propanamineHCID 634876Binap, (A+-)-HCID 5003444Sodium cyanoborohydrideHCID 574477477-Chloro-3-(2,2,2-trifluoroacetyl)-6-trifluoromethylsulfonyloxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine
HCID 866228607-chloro-3-(2,2,2-trifluoroacetyl)-6-[3-(2-methyl[1,3]dioxolan-2-yl)-propylamino]-2,3,4,5-tetrahydro-1H-benzo[d]azepine

Produkt 1

HCID 86622859HCID 86622859, VerbindungAusbeute 81,3 %

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 887MethanolLösungsmittelHCID 1140TolueneLösungsmittelHCID 3283Diethyl EtherLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

Place 7-chloro-3-(2,2,2-trifluoroacetyl)-6-trifluoromethanesulfonyloxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (prepared essentially as described in Preparation 1) (3 g, 7.08 mmol) in toluene (60 mL) with 3-(2-methyl-[1,3]dioxolan-2-yl)-propylamine (prepared essentially as described in Preparation 38) (3.08 g, 21.24 mmol), tris(dibenzylideneacetone)dipalladium (1.3 g, 1.42 mmol), racemic 2,2′-bis(diphenylphosphino)-1,1′-binapthyl (1.77 g, 2.84 mmol), and cesium carbonate (3.3 g, 9.91 mmol) and heat for 16 h at 95° C. in a sealed tube. Cool the reaction to RT, dilute with EtOAc (600 mL) and filter. Concentrate the filtrate and purify (silica gel chromatography, eluting with 10:90 to 25:75 EtOAc:hexanes) to give the crude product as an orange oil (1.72 g). Dissolve 7-chloro-3-(2,2,2-trifluoroacetyl)-6-[3-(2-methyl[1,3]dioxolan-2-yl)-propylamino]-2,3,4,5-tetrahydro-1H-benzo[d]azepine (1.72 g, 4.09 mmol) in DCM (20 mL) and add methanol (2 mL) and 2 N HCl in diethyl ether (20 mL) and stir at RT for 3 h. Concentrate and dissolve the residue in acetic acid (30 mL) and add sodium cyanoborohydride (1.28 g, 20.43 mmol). Stir the reaction at RT for 0.5 h then concentrate to remove the acetic acid. Dissolve the residue in DCM (200 mL) and extract with saturated aqueous sodium bicarbonate solution (400 mL), Extract the aqueous layer with DCM (100 mL) and combine the organic fractions, dry (sodium sulfate), concentrate and purify (silica gel chromatography, eluting with 10:90 EtOAc:hexanes) to give the title compound as a foam (1.2 g, 81%).

Aufarbeitung

  1. customprepared essentially
  2. temperatureCool
  3. customthe reaction to RT
  4. filtrationfilter
  5. concentrationConcentrate the filtrate
  6. custompurify
  7. wash(silica gel chromatography, eluting with 10:90 to 25:75 EtOAc:hexanes)
  8. customto give the crude product as an orange oil (1.72 g)
  9. concentrationConcentrate
  10. dissolutiondissolve the residue in acetic acid (30 mL)
  11. stirringStir
  12. customthe reaction at RT for 0.5 h
  13. concentrationthen concentrate
  14. customto remove the acetic acid
  15. dissolutionDissolve the residue in DCM (200 mL)
  16. extractionextract with saturated aqueous sodium bicarbonate solution (400 mL)
  17. extractionExtract the aqueous layer with DCM (100 mL)
  18. dry with materialdry (sodium sulfate)
  19. concentrationconcentrate
  20. custompurify
  21. wash(silica gel chromatography, eluting with 10:90 EtOAc:hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-c22474ca54ec40f59dfcd8a782ea4786
Quelldatensatz
uspto-grants-2011_07
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07981882B2

Notizen zur Reaktion

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