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Benzyl chloroformate → Benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1h)-yl]carbamate

HRID 1015518
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1015518
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]23[CH2:18][CH:14]4[CH2:15][CH:16]([CH2:17]2)[C:12]([NH2:19])([CH2:13]4)[CH2:11]3)=[CH:6][CH:5]=1)([O-:3])=[O:2].C([O-])([O-])=O.[K+].[K+].[CH2:26]([O:33][C:34](Cl)=[O:35])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1.O>[CH2:26]([O:33][C:34](=[O:35])[NH:19][C:12]12[CH2:13][CH:14]3[CH2:18][C:10]([C:7]4[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=4)([CH2:17][CH:16]1[CH2:15]3)[CH2:11]2)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 10387Benzyl chloroformateHCID 11430Potassium CarbonateHCID 593749781-(4-Nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine

Produkt 1

HCID 131729071Benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1h)-yl]carbamateAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962Water
Lösungsmittel
HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a stirred mixture of 1-(4-nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine (2.0 g, 8.0 mmol) obtained in step III, K2CO3 (3.5 g, 24 mmol) in THF (80 mL), cooled to ice-bath temperature was added benzylchloroformate (50% w/v in Toluene, 2.2 mL, 12 mmol). After stirring the reaction mixture at r.t for 2 h, it was diluted with water and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1H)-yl]carbamate as an off-white solid (2.1 g) in 70% yield. M.R: 104.1-105.9° C.; m/z (M+1) 393; IR cm−1 3440, 2952, 1714, 1518, 1349, 1216, 757; 1H NMR (CDCl3) 300 MHz δ 8.12 (d, J=8.8 Hz, 2H), 7.50-7.27 (m, 7H), 5.20-5.0 (s (br), 2H), 2.65-2.55 (m, 1H), 2.50-1.55 (m, 11H). 13C NMR (CDCl3) 75 MHz δ 155.1, 154.2, 146.1, 136.4, 131.1, 128.5 (2C), 128.1 (2C), 126.6 (2C), 123.4 (2C), 66.3, 64.4, 49.248.0, 47.5, 43.8, 42.1, 40.8, 37.0.

Aufarbeitung

  1. temperaturecooled to ice-bath temperature
  2. extractionextracted with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. customthe solvent was removed under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-5ab5f44f251b42bb8ccc6c5993cd6806
Quelldatensatz
uspto-grants-2011_07
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07985759B2

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