Hydrochloric Acid → HCID 178420267, Verbindung

HRID 263808Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 263808
[C:1]1([C:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:8][CH2:9][OH:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O[C:24]1[CH:29]=[CH:28][C:27]([CH2:30][CH2:31][C:32]#[N:33])=[CH:26][CH:25]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.C[Al](C)C.[N:69]([Si](C)(C)C)=[N+:70]=[N-:71].Cl>C1COCC1.C1(C)C=CC=CC=1.CCOC(C)=O>[C:17]1([C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH2:8][CH2:9][O:10][C:24]2[CH:29]=[CH:28][C:27]([CH2:30][CH2:31][C:32]3[NH:33][N:71]=[N:70][N:69]=3)=[CH:26][CH:25]=2)[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Komponenten

11

Edukt 7

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 78378AzidotrimethylsilaneHCID 870793-(p-Hydroxyphenyl)propiononitrileHCID 2986573,3,3-Triphenylpropan-1-olHCID 5462977Diethyl azodicarboxylateHCID 16682925Trimethylaluminum

Produkt 1

HCID 178420267HCID 178420267, VerbindungAusbeute 30 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 1140TolueneLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To 3,3,3-triphenylpropanol (8.70 mmol), 3-(4-hydroxyphenyl)propionitrile (9.40 mmol) and triphenylphosphine (2.42 g, 9.23 mmol) in dry THF (25 mL) under a nitrogen atmosphere at room temperature, was added dropwise DEAD (1.50 mL, 9.52 mmol) in dry THF (20 mL) over approximately 30 minutes. The reaction was heated to reflux overnight. After cooling, the THF was evaporated and the residue chromatographed on a silica column, with 15-20% EtOAc/hexanes. White solid, mp=98°-100° C. (ether), 60% yield. 1H NMR δ 7.18-7.35 (m, 15H), 7.06 (d, J=8.6 Hz, 2H), 6.67 (d, J=8.6 Hz, 2H), 3.72 (t, J=7.8 Hz, 2H), 3.13 (t, J=7.8 Hz, 2H), 2.85 (t, J=7.3 Hz, 2H), 2.54 (t, J=7.3 Hz, 2H). IR 2243, 1540 cm-1. MS 418 (MH+), 243. Anal. calcd. for C30H27NO: C, 86.30; H, 6.52; N, 3.35. Found: C, 86.07; H, 6.39; N, 3.24. To a solution of trimethyl aluminum (1M in hexanes, 0.57 mL), in toluene (3 mL) at ~2° C., was added azidotrimethylsilane (0.569 mmol). A solution of nitrile (0.474 mmol) in toluene (2 mL) was slowly added. The reaction was stirred at 80° C. for 72 h. The cooled (0° C.) reaction was added dropwise to HCl (6M, 10 mL) and EtOAc (10 mL). The resulting mixture was extracted with EtOAc (2×50 mL). The combined organic layers were dried (MgSO4), filtered and evaporated. The crude material was triturated with dichloromethane to remove unreacted starting nitrile leaving behind the title compound as a hydrate, a white solid (mp=193°-195° C., 30% yield). 1H NMR (DMSO-d6) δ 7.19-7.35 (m, 15H), 7.02 (d, J=8.5 Hz, 2H), 6.58 (d, J=8.5 Hz, 2H), 3.60 (t, J=7.4 Hz, 2H), 3.04-3.12 (m, 4H), 2.91 (t, J=7.6 Hz, 2H). IR 3300-3450 (br), 1586, 1511 cm-1. MS 461 (MH+), 243. Anal. calcd. for C30H28N4O.0.25H2O: C, 77.48; H, 6.18; N, 12.05. Found: C, 77.18; H, 5.96; N, 11.71.

Aufarbeitung

  1. temperatureThe reaction was heated
  2. temperatureto reflux overnight
  3. temperatureAfter cooling
  4. customthe THF was evaporated
  5. customthe residue chromatographed on a silica column, with 15-20% EtOAc/hexanes
  6. temperatureThe cooled
  7. custom(0° C.) reaction
  8. extractionThe resulting mixture was extracted with EtOAc (2×50 mL)
  9. dry with materialThe combined organic layers were dried (MgSO4)
  10. filtrationfiltered
  11. customevaporated
  12. customThe crude material was triturated with dichloromethane
  13. customto remove unreacted

Quellen und Nachweise

ORD-Eintrag
ord-5962dd71f1304d1a81e7f98f0a9ff223
Quelldatensatz
uspto-grants-1997_07
Patentnummer
US05643950

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