Ammonia → HCID 178508628, Verbindung

HRID 493819Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 493819
[NH3:1].Cl[C:3]1[C:4]2[C:11]([I:12])=[CH:10][N:9]([C@@H:13]3[CH2:16][C@H:15]([CH2:17][OH:18])[CH2:14]3)[C:5]=2[N:6]=[CH:7][N:8]=1.C(=O)=O.CC(C)=O>O1CCOCC1.CC(O)C>[NH2:1][C:3]1[C:4]2[C:11]([I:12])=[CH:10][N:9]([C@@H:13]3[CH2:16][C@H:15]([CH2:17][OH:18])[CH2:14]3)[C:5]=2[N:6]=[CH:7][N:8]=1

Komponenten

6

Edukt 3

HCID 222AmmoniaHCID 18522661Acetone cardiceHCID 178521037HCID 178521037, Verbindung

Produkt 1

HCID 178508628HCID 178508628, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3776IsopropanolLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

Gaseous ammonia (from a lecture bottle) was bubbled into a suspension of cis-[3-(4-chloro-5-iodopyrrolo[2,3-d]pyrimidin-7-yl)-cyclobutyl]-methanol (406.8 mg, 1.12 mmol) in dioxane (10 mL) and iPrOH (10 mL) in a Parr bomb, cooled by dry ice/acetone, for 5 min, then the vessel was sealed and heated to 90° C. overnight. LC/MS after 17 h indicated incomplete conversion. More ammonia was bubbled into the mixture, and heating to 90° C. was continued. After 1 d, conversion was complete. The solvents were evaporated, water was added to the residue, and the pale yellow solid was filtered off and dried in vacuo to give the title compound as a pale yellow solid. The compound was used in the next step without further purification. The aqueous filtrate was extracted with CH2Cl2 (3×20 mL), the combined extracts were dried over MgSO4, filtered and concentrated to give a yellow oil that slowly solidified. Purification by HPLC gave analytically pure material. 1H NMR (CDCl3, 400 MHz): δ=2.40-2.57 (m, 4H), 2.57-2.66 (m, 2H), 3.73 (d, J=4.4 Hz, 2H), 5.03 (quint, J=8.4 Hz, 1H), 5.62 (brs, 2H), 7.21 (s, 1H), 8.26 (s, 1H). 13C NMR (DMSO-d6, 100.6 MHz, DEPT135): δ=29.96 (+), 32.70 (2C, −), 44.42 (+), 50.25 (Cquart), 64.16 (−), 102.98 (Cquart), 126.94 (+), 149.41 (Cquart), 151.72 (+), 157.13 (Cquart). MS (ES+): m/z 345.0 (100) [MH+]. HPLC: tR=1.7 min (OpenLynx, polar—5 min). C11H131IN4O.2/3 H2O: C, calc. 37.10; found 36.92;H, calc. 4.06; found 3.88; N, calc. 15.73; found 16.07.

Aufarbeitung

  1. customthe vessel was sealed
  2. customMore ammonia was bubbled into the mixture
  3. temperatureheating to 90° C.
  4. waitAfter 1 d
  5. customThe solvents were evaporated
  6. additionwater was added to the residue
  7. filtrationthe pale yellow solid was filtered off
  8. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-6054f1270a524939857dff9e0171b847
Quelldatensatz
uspto-grants-2009_05
Patentnummer
US07534797B2

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