Methanesulfonic Acid → (E)-1,2,3,9-Tetrahydro-9-methyl-3-[(5-methyl-1H-imidazol-4-yl)methylene]-4H-carbazol-4-one methanesulphonate

HRID 621204

Reaktionsgleichung

Reaktionsgleichung von HRID 621204
C([N-:4][CH:5](C)C)(C)C.[Li+].[CH2:9]([Li])[CH2:10][CH2:11][CH3:12].C([NH:17]C(C)C)(C)C.[CH3:21][N:22]1[C:34]2[CH2:33][CH2:32][CH2:31][C:30](=[O:35])[C:29]=2[C:28]2[C:23]1=[CH:24][CH:25]=[CH:26][CH:27]=2.[CH3:36][S:37]([OH:40])(=[O:39])=[O:38]>CCCCCC.C1COCC1.C(O)(=O)C>[CH3:36][S:37]([OH:40])(=[O:39])=[O:38].[CH3:21][N:22]1[C:34]2[CH2:33][CH2:32]/[C:31](=[CH:9]\[C:10]3[N:17]=[CH:5][NH:4][C:11]=3[CH3:12])/[C:30](=[O:35])[C:29]=2[C:28]2[C:23]1=[CH:24][CH:25]=[CH:26][CH:27]=2

Komponenten

9

Edukt 5

HCID 6395Methanesulfonic AcidHCID 7912DiisopropylamineHCID 5988759-Methyl-1,2,3,9-tetrahydro-4H-carbazol-4-oneHCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Produkt 1

HCID 14233888(E)-1,2,3,9-Tetrahydro-9-methyl-3-[(5-methyl-1H-imidazol-4-yl)methylene]-4H-carbazol-4-one methanesulphonate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

Lithium diisopropylamide (from n-butyllithium, 1.55M in hexane; (57.3 ml) and diisopropylamine (11.64 ml) in THF (45 ml) was added dropwise over 15 min. at -5° under nitrogen to a stirred suspension of 1,2,3,9-tetrahydro-9-methyl-4H-carbazol-4-one (15 g) in THF (510 ml). After 45 min., Intermediate 2 (26.5 g) was added in one portion and the resultant solution was stirred at -5° to +5° for 1.75 h. The solution was treated with acetic acid at below 20° and stirred for 1 h. Methanesulphonic acid (34 ml) was added and the mixture was stirred and heated under reflux for 16 h. The resultant suspension was cooled to 5°, stirred at below 5° for 1 h and the solid was filtered off. The product was washed with THF (2×50 ml) and dried in vacuo at 50° to give a solid (28.5 g) which was recrystallised from methanol to give the title compound (17 g), m.p. 264.5°-267°.

Aufarbeitung

  1. stirringthe mixture was stirred
  2. temperatureheated
  3. temperatureunder reflux for 16 h
  4. stirringstirred at below 5° for 1 h
  5. filtrationthe solid was filtered off
  6. washThe product was washed with THF (2×50 ml)
  7. customdried in vacuo at 50°

Quellen und Nachweise

ORD-Eintrag
ord-4322a0ef7d564d7eb768ee64818e6324
Quelldatensatz
uspto-grants-1989_04
Patentnummer
US04822881

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