Naphthalene → 2-Ethyl-9-methyl-13-(3-phenylpropyl)-2,4,9,15-tetraazatricyclo[9.4.0.0^{3,8}]pentadeca-1(11),3,5,7,12,14-hexaen-10-one

HRID 724963Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 724963
[CH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[Li].BrCCCC1C=CC=CC=1.[CH2:22]([N:24]1[C:30]2[N:31]=[CH:32]C(I)=[CH:34][C:29]=2[C:28](=[O:36])[N:27]([CH3:37])[C:26]2[CH:38]=[CH:39][CH:40]=[N:41][C:25]1=2)[CH3:23]>O1CCCC1.[Cl-].[Zn+2].[Cl-].[Zn].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:22]([N:24]1[C:30]2[N:31]=[CH:32][C:6]([CH2:7][CH2:8][CH2:9][C:10]3[CH:1]=[CH:2][CH:3]=[CH:4][CH:5]=3)=[CH:34][C:29]=2[C:28](=[O:36])[N:27]([CH3:37])[C:26]2[CH:38]=[CH:39][CH:40]=[N:41][C:25]1=2)[CH3:23]

Komponenten

9

Edukt 4

HCID 931NaphthaleneHCID 12503(3-Bromopropyl)benzeneHCID 3028194LithiumHCID 10547779HCID 10547779, Verbindung

Produkt 1

HCID 4707262-Ethyl-9-methyl-13-(3-phenylpropyl)-2,4,9,15-tetraazatricyclo[9.4.0.0^{3,8}]pentadeca-1(11),3,5,7,12,14-hexaen-10-oneAusbeute 7,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23994ZincKatalysatorHCID 3007855ZincchlorideKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

A solution of naphthalene (0.65 g, 5.07 mmol) in 2 mL of tetrahydrofuran was added to lithium wire (35 mg, 5.04 mmol), and the mixture was stirred overnight at room temperature under argon. A solution of zinc chloride in tetrahydrofuran (0.5M, 5.25 mL, 2.63 mmol) was then added. After 20 min, 1-bromo-3-phenylpropane (0.18 mL, 1.15 mmol) was added, and the reaction mixture was stirred at room temperature for 4.5 hours. Unreacted zinc was allowed to settle, and the supernatant was added by cannula to a solution of 5,11-dihydro-11-ethyl-8-iodo-5-methyl-6H-dipyrido[3,2-b:2',3'-e][1,4]diazepin-6-one (0.22 g, 0.58 mmol) and tetrakis(triphenylphosphine)palladium(0) (70 mg, 0.06 mmol) in 3 mL of tetrahydrofuran. The reaction mixture was allowed to stir overnight at room temperature under argon. The reaction was quenched by the addition of saturated aqueous ammonium chloride, and the product was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride, dried over magnesium sulfate, and concentrated. Purification by flash chromatography, eluting with ethyl acetate/dichloromethane, and recrystallization from ethyl acetate/hexanes afforded 16 mg of the title compound as off-white crystals, m.p. 100°-102° C.

Aufarbeitung

  1. waitAfter 20 min
  2. stirringthe reaction mixture was stirred at room temperature for 4.5 hours
  3. stirringto stir overnight at room temperature under argon
  4. customThe reaction was quenched by the addition of saturated aqueous ammonium chloride
  5. extractionthe product was extracted with ethyl acetate
  6. washThe organic layer was washed with saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. customPurification by flash chromatography
  10. washeluting with ethyl acetate/dichloromethane, and recrystallization from ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-3280a3dd59c141bd8b22e869fc0d9c37
Quelldatensatz
uspto-grants-1998_01
Patentnummer
US05705499

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