2-Bromopropane → Ethyl (1aR,5aR)-2-Isopropyl-1a,2,5,5a-tetrahydro-1H-2,3-diazacyclopropa[a]pentalene-4-carboxylate

HRID 1623894Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1623894
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[CH2:8][C@H:9]3[CH2:14][C@H:10]3[C:11]=2[NH:12][N:13]=1)=[O:5])[CH3:2].Br[CH:16]([CH3:18])[CH3:17]>CN(C=O)C.CCOC(C)=O>[CH:16]([N:12]1[C:11]2[C@@H:10]3[CH2:14][C@@H:9]3[CH2:8][C:7]=2[C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])=[N:13]1)([CH3:18])[CH3:17]

Komponenten

5

Edukt 2

HCID 63582-BromopropaneHCID 589068031H-Cyclopropa[4,5]cyclopenta[1,2]pyrazole-3-carboxylic acid, 4,4a,5,5a-tetrahydro-, ethyl ester, (4aR,5aR)-

Produkt 1

HCID 86669646Ethyl (1aR,5aR)-2-Isopropyl-1a,2,5,5a-tetrahydro-1H-2,3-diazacyclopropa[a]pentalene-4-carboxylateAusbeute 59,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

(1aR,5aR)-1a,2,5,5a-Tetrahydro-1H-2,3-diazacyclopropa[a]pentalene-4-carboxylic acid ethyl ester (0.100 g, 0.520 mmol) (from Example 1.4, Step A) was dissolved in anhydrous DMF (5.20 mL). CsCO3 (0.678 g, 2.081 mmol) was added to give a suspension which was stirred at 25° C. for several minutes. 2-Bromopropane (0.098 mL, 1.041 mmol) was added dropwise at 25° C. After stirring for 4 h, the reaction was diluted with EtOAc (50 mL), washed with water (2×10 mL), brine, and dried over MgSO4. The solvent was evaporated under reduced pressure. The oil residue was purified by silica gel column chromatography to give the title compound as an oil (0.073 g). LCMS m/z=235.3 [M+H]+; 1H NMR (400 MHz, CDCl3) ppm 0.29-0.35 (m, 1H), 1.12 (td, J=8.02, 4.93 Hz, 1H), 1.34 (t, J=7.20 Hz, 3H), 1.46 (dd, J=15.16, 6.57 Hz, 6H), 2.04-2.12 (m, 1H), 2.16-2.24 (m, 1H), 2.74-2.82 (m, 1H), 2.90-2.99 (m, 1H), 4.27 (q, J=7.07 Hz, 2H), 5.31-5.43 (m, 1H).

Aufarbeitung

  1. customto give a suspension which
  2. stirringAfter stirring for 4 h
  3. washwashed with water (2×10 mL), brine
  4. dry with materialdried over MgSO4
  5. customThe solvent was evaporated under reduced pressure
  6. customThe oil residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-dcf780a0001648eebbeeeca345f00492
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08778950B2

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