Cesium carbonate → Tert-butyl 4-(4-methoxycarbonylphenyl)-1,4-diazepane-1-carboxylate

HRID 16760

Reaktionsgleichung

Reaktionsgleichung von HRID 16760
I[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.[N:12]1([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:18][CH2:17][CH2:16][NH:15][CH2:14][CH2:13]1.C(=O)([O-])[O-].[Cs+].[Cs+].C(C1CCCCC1=O)(=O)C>CN(C=O)C.[Cu](I)I>[CH3:9][O:8][C:6]([C:5]1[CH:10]=[CH:11][C:2]([N:15]2[CH2:16][CH2:17][CH2:18][N:12]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:13][CH2:14]2)=[CH:3][CH:4]=1)=[O:7]

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 134002-AcetylcyclohexanoneHCID 69273Methyl 4-iodobenzoateHCID 2756058Tert-butyl 1,4-diazepane-1-carboxylate

Produkt 1

HCID 57362684Tert-butyl 4-(4-methoxycarbonylphenyl)-1,4-diazepane-1-carboxylateAusbeute 13,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 83717Copper iodideKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

Methyl 4-iodobenzoate (1.00 g, 3.82 mmol, 1.0 eq) was dissolved in DMF and tert-butyl 1,4-diazepane-1-carboxylate (765 mg, 3.82 mmol, 1.0 eq), caesium carbonate (2.49 g, 7.63 mmol, 2.0 eq), 2-acetylcyclohexanone (101 μl, 0.76 mmol, 0.20 eq [20 mol %]) and copper iodide (37 mg, 0.19 mmol, 0.05 eq [5 mol %]) were added. The reaction mixture was stirred at 90° C. under nitrogen for 7 h. The reaction mixture was evaporated, dissolved in DCM (50 ml), washed with water (20 ml), saturated ammonium chloride solution (20 ml), dried over MgSO4, filtered and evaporated. The crude product was purified by silica column chromatography, eluting with 0-1% MeOH in DCM. The product containing fractions were combined, evaporated and dried in vacuo to give tert-butyl 4-(4-methoxycarbonylphenyl)-1,4-diazepane-1-carboxylate (168 mg, 13%) as a yellow oil.

Aufarbeitung

  1. customThe reaction mixture was evaporated
  2. dissolutiondissolved in DCM (50 ml)
  3. washwashed with water (20 ml), saturated ammonium chloride solution (20 ml)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude product was purified by silica column chromatography
  8. washeluting with 0-1% MeOH in DCM
  9. additionThe product containing fractions
  10. customevaporated
  11. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-bf580b2f31564622a5397ead6f2f9ef0
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07737149B2

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