1,2-Dibromoethane → N-[2-(2,2-dimethyl-4H-benzo[1,3]dioxin-6-yl)-2-hydroxyethyl]-N-benzyloxycarbonyl-6-(4-phenylbutoxy)hexylamine

HRID 1936217Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1936217
[CH3:1][C:2]1([CH3:13])[O:7][CH2:6][C:5]2[CH:8]=[C:9](Br)[CH:10]=[CH:11][C:4]=2[O:3]1.BrCCBr.[CH2:18]([O:25][C:26]([N:28]([CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][O:38][CH2:39][CH2:40][CH2:41][CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)[CH2:29][CH:30]=[O:31])=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[NH4+].[Cl-]>C1COCC1.CCOC(C)=O>[CH3:1][C:2]1([CH3:13])[O:7][CH2:6][C:5]2[CH:8]=[C:9]([CH:30]([OH:31])[CH2:29][N:28]([CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][O:38][CH2:39][CH2:40][CH2:41][CH2:42][C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[C:26]([O:25][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[O:27])[CH:10]=[CH:11][C:4]=2[O:3]1

Komponenten

7

Edukt 4

HCID 78391,2-DibromoethaneHCID 25517Ammonium ChlorideHCID 11235634Benzyl (2-oxoethyl)(6-(4-phenylbutoxy)hexyl)carbamateHCID 145203386-Bromo-2,2-dimethyl-4H-benzo[d][1,3]dioxine2×

Produkt 1

HCID 11467416N-[2-(2,2-dimethyl-4H-benzo[1,3]dioxin-6-yl)-2-hydroxyethyl]-N-benzyloxycarbonyl-6-(4-phenylbutoxy)hexylamineAusbeute 41 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel3×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

To 0.166 g (6.83 mmol) Mg in 1 ml THF is added dropwise a few drops of a solution comprising 1.51 g (6.21 mmol) 2,2-dimethyl-6-bromobenzo-1,3-dioxane in 20 ml THF and a catalytic amount of 1,2-dibromoethane. Once the reaction has started, the remaining 2,2-dimethyl-6-bromobenzo-1,3-dioxane solution was added while maintaining the temperature at 40° C. Upon completion of the addition (15 min), the reaction is allowed to stand a further 30 min at 40° C. The mixture is then cooled to −7° C. and a solution of 2.64 g (6.21 mmol) N-benzyloxycarbonyl-N-2-oxoethyl-6-(4-phenylbutoxy)hexylamine in 5 ml THF is added thereto. After allowing the reaction to stand at 0° C. for 1 hr, the temperature of the reaction mixture is allowed to increase to room temperature, 30 ml of a saturated NH4Cl solution is added and the mixture stirred for 15 min. Finally, 30 ml AcOEt is added, the EtOAc phase is separated, washed with 30 ml H2O, dried on anhydrous Na2SO4 concentrated to dryness and the residue purified by column chromatography on silica gel (gradient CH2Cl2 to CH2Cl2/EtOAc 4:1), to give 1.50 g (40.9%) N-[2-(2,2-dimethyl-4H-benzo[1,3]dioxin-6-yl)-2-hydroxyethyl]-N-benzyloxycarbonyl-6-(4-phenylbutoxy)hexylamine.

Aufarbeitung

  1. additionUpon completion of the addition (15 min)
  2. temperatureThe mixture is then cooled to −7° C.
  3. customthe reaction
  4. waitto stand at 0° C. for 1 hr
  5. temperatureto increase to room temperature
  6. customthe EtOAc phase is separated
  7. washwashed with 30 ml H2O
  8. dry with materialdried on anhydrous Na2SO4
  9. concentrationconcentrated to dryness
  10. customthe residue purified by column chromatography on silica gel (gradient CH2Cl2 to CH2Cl2/EtOAc 4:1)

Quellen und Nachweise

ORD-Eintrag
ord-f600047be60f4cc7b2e334aeb02f5357
Quelldatensatz
uspto-grants-2002_05
Patentnummer
US06388134B1

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