4-Toluenesulfonyl chloride → HCID 178481313, Verbindung

HRID 2362479Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2362479
C(OC([C@H:8]1[NH:13][C:12]([CH3:18])([C:14]([NH:16][NH2:17])=[O:15])[CH2:11][C:10](=[O:19])[N:9]1[CH3:20])=O)(C)(C)C.CC[N:23](CC)CC.[C:28]([C:30]1[CH:31]=[C:32]([CH:36]=[CH:37][CH:38]=1)[C:33](Cl)=O)#[N:29].S(Cl)(C1C=CC(C)=CC=1)(=O)=O>C(Cl)Cl.CN(C1C=CN=CC=1)C>[NH:23]=[C:8]1[NH:13][C@@:12]([C:14]2[O:15][C:33]([C:32]3[CH:31]=[C:30]([CH:38]=[CH:37][CH:36]=3)[C:28]#[N:29])=[N:17][N:16]=2)([CH3:18])[CH2:11][C:10](=[O:19])[N:9]1[CH3:20]

Komponenten

7

Edukt 4

HCID 73974-Toluenesulfonyl chlorideHCID 8471Triethylamine2×HCID 3084833-Cyanobenzoyl chlorideHCID 67303828(S)-2-(tert-butoxycarbonyl)-1,4-dimethyl-6-oxo-hexahydropyrimidine-4-carbohydrazide

Produkt 1

HCID 178481313HCID 178481313, VerbindungAusbeute 16,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6344DichloromethaneLösungsmittel4×

Versuchsvorschrift

To a solution of (S)-2-(tert-butoxycarbonyl)-1,4-dimethyl-6-oxo-hexahydropyrimidine-4-carbohydrazide (CY1; R6=Me, 0.037 g, 0.12 mmol) in DCM (0.3 mL) at 0° C. was added Et3N (0.035 mL, 0.24 mmol, 2 eq) followed by 3-cyanobenzoyl chloride (0.027 g, 0.16 mmol, 1.3 eq). The mixture was stirred at RT for 6 h. The mixture was diluted with DCM (20 mL), washed with H2O (10 mL) and saturated brine (10 mL), and concentrated in vacuo. The residue was then treated with TsCl (0.035 g, 0.18 mmol, 1.5 eq), Et3N (0.046 mL, 0.31 mmol, 2.6 eq), and DMAP (0.002 g, 0.016 mmol, 0.13 eq) in DCM (0.25 mL) at RT for 16 h. The mixture was diluted with DCM (20 mL), washed with H2O (10 mL) and saturated brine (10 mL), and concentrated in vacuo. The residue was treated with 30% TFA/DCM (1 mL) at RT for 1 h. The mixture was concentrated in vacuo and the residue was purified on reverse phase HPLC (B) to give 0.006 g (12%) of 3-(5-((S)-2-imino-1,4-dimethyl-6-oxo-hexahydropyrimidin-4-yl)-1,3,4-oxadiazol-2-yl)benzonitrile as a white solid (CZ1; R6=Me). 1HNMR (CD3OD, 300 MHz): 8.49 (m, 2H), 8.12 (d, 1H), 7.92 (t, 1H), 3.75 (m, 2H), 3.36 (s, 3H), 1.82 (s, 3H). MS (ESI): MH+=311.2, HPLC (A) Rt=4.175 min.

Aufarbeitung

  1. washwashed with H2O (10 mL) and saturated brine (10 mL)
  2. concentrationconcentrated in vacuo
  3. washwashed with H2O (10 mL) and saturated brine (10 mL)
  4. concentrationconcentrated in vacuo
  5. additionThe residue was treated with 30% TFA/DCM (1 mL) at RT for 1 h
  6. concentrationThe mixture was concentrated in vacuo
  7. customthe residue was purified on reverse phase HPLC (B)

Quellen und Nachweise

ORD-Eintrag
ord-f5c2b1873cc94ed7b4a2dfb6ed72d30d
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08691831B2

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