Ethylenediamine → N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamine

HRID 1861070Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1861070
[CH3:1][N:2]([C:10]1[CH:18]=[C:17]2[C:13]([C:14]([CH:27]=[CH:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)=[N:15][N:16]2COCC[Si](C)(C)C)=[CH:12][CH:11]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([NH2:9])[CH:4]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1COCC1.C(N)CN>>[CH3:1][N:2]([C:10]1[CH:18]=[C:17]2[C:13]([C:14]([CH:27]=[CH:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)=[N:15][NH:16]2)=[CH:12][CH:11]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([NH2:9])[CH:4]=1

Komponenten

5

Edukt 4

HCID 3301EthylenediamineHCID 8028TetrahydrofuranHCID 2724141Tetrabutylammonium FluorideHCID 69369951HCID 69369951, Verbindung

Produkt 1

HCID 69370903N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamineAusbeute 70,5 %

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To N-methyl-N-{3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-yl}-benzene-1,3-diamine (237 mg, 0.5 mmol) was added 1M TBAF in THF (10.1 mL, 10.1 mmol), followed by ethylenediamine (0.34 mL, 5.04 mmol, 10 equiv). The resulting mixture was heated to 70° C. for 5 h. The reaction was then quenched with saturated NaHCO3 (10 mL) and extracted 3×35 mL EtOAc. The pooled EtOAc phase was washed 5×20 mL H2O, then brine (20 mL), dried with Na2SO4, decanted and concentrated under reduced pressure to a foam. The crude material was purified by silica gel chromatography (9:1 dichloromethane/ethyl acetate) to give N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamine as a foam (120 mg, 70% yield). Rf sm 0.73, Rf p 0.27 (dichloromethane:ethylacetate 7:3); 13C NMR (75 MHz, CDCl3) δ 150.3, 148.8, 147.5, 147.5, 143.9, 143.4, 137.5, 131.1, 130.3, 129.3, 128.9, 128.2, 127.9, 126.7, 121.0, 120.5, 117.0, 116.0, 112.6, 109.8, 109.0, 98.3, 40.7; LCMS (ESI) [M+H]/z Calc'd 341, Found 341. Anal. Calc'd: C, 77.62; H, 5.92; N, 16.46. Found: C, 76.16; H, 5.88; N, 15.95.

Aufarbeitung

  1. customThe reaction was then quenched with saturated NaHCO3 (10 mL)
  2. extractionextracted 3×35 mL EtOAc
  3. washThe pooled EtOAc phase was washed 5×20 mL H2O
  4. dry with materialbrine (20 mL), dried with Na2SO4
  5. customdecanted
  6. concentrationconcentrated under reduced pressure to a foam
  7. customThe crude material was purified by silica gel chromatography (9:1 dichloromethane/ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-ac236768194d484b9fa98c44bbc10d95
Quelldatensatz
uspto-grants-2003_03
Patentnummer
US06531491B1

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