Acetonitrile → HCID 178432738, Verbindung

HRID 1672216Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1672216
[ClH:1].[CH3:2][N:3]([CH3:15])[CH2:4][CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([NH2:14])[C:10]([CH3:13])=[N:11][CH:12]=1.C(#N)C.Cl.[Cl:20][C:21]([NH2:23])=[NH:22]>C(O)(=O)C>[ClH:20].[ClH:1].[ClH:20].[CH3:15][N:3]([CH3:2])[CH2:4][CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([NH:14][C:21]([NH2:23])=[NH:22])[C:10]([CH3:13])=[N:11][CH:12]=1

Komponenten

5

Edukt 3

HCID 6342AcetonitrileHCID 3084509Chloroformamidinium chlorideHCID 67336892HCID 67336892, Verbindung

Produkt 1

HCID 178432738HCID 178432738, VerbindungAusbeute 136,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel2×

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A 1 L, three-neck, round-bottom flask equipped with an overhead stirrer, a reflux condenser, an N2 inlet tube, and a temperature probe was charged with 5-(3-(dimethylamino)propyl)-2-methylpyridin-3-amine hydrochloride (25 g, 0.109 mol). Acetonitrile (275 mL, 11 vol) was added to it followed by acetic acid (25 mL, 1 vol). The initial suspension turned into a clear solution after the addition of acetic acid. Chloroformamidine hydrochloride (15.6 g, 0.136 mol, 1.25 equiv) was added to the solution resulting in a suspension. The reaction was heated at 40° C. for 30 min and at 50° C. for another 30 min. Then the temperature was raised to 60° C. and the reaction was continued at this temperature. After 1-2 h at 60° C., the reaction mixture became turbid and after 3-4 h, solid started separating out. The reaction was continued at 60° C. for 20 h and was judged complete by LC-MS analysis. The reaction was cooled to ambient temperature and the solid was collected by filtration (N2 flow was used during the filtration). The filter cake was washed with acetonitrile (50 mL, 2 vol). The solid was dried under high vacuum overnight to obtain N-{5-[3-(Dimethylamino)propyl]-2-methylpyridin-3-yl}guanidine trihydrochloride (32.1 g, 85% recovery) as a light brown solid. Elemental analysis Calcd: C, 41.81; H, 7.02; Cl, 30.85; N, 20.32. Found: C, 41.09; H, 6.72; Cl, 31.51; N, 20.47; 1H NMR (500 MHz, D2O) δ ppm: 8.57 (s, 1H), 8.45 (s, 1H), 3.22-3.19 (m, 2H), 2.90 (t, 2H, J=10 Hz), 2.86 (s, 6H), 2.69 (s, 3H), 2.15-2.07 (m, 2H); ESI-MS m/z 236 (M+H, 100%).

Aufarbeitung

  1. customA 1 L, three-neck, round-bottom flask equipped with an overhead stirrer, a reflux condenser, an N2 inlet tube
  2. customresulting in a suspension
  3. temperatureThen the temperature was raised to 60° C.
  4. waitafter 3-4 h
  5. customsolid started separating out
  6. waitThe reaction was continued at 60° C. for 20 h
  7. temperatureThe reaction was cooled to ambient temperature
  8. filtrationthe solid was collected by filtration (N2 flow
  9. filtrationwas used during the filtration)
  10. washThe filter cake was washed with acetonitrile (50 mL, 2 vol)
  11. customThe solid was dried under high vacuum overnight

Quellen und Nachweise

ORD-Eintrag
ord-45678a1eae2e4e18bbf28ff4ed927b33
Quelldatensatz
uspto-grants-2011_08
Patentnummer
US07998952B2

Notizen zur Reaktion

Wird geladen…