Sulfuric Acid → 1-(4-Nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine

HRID 1015517Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1015517
[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](C(O)=O)([CH2:13]4)[CH2:11]3)=[CH:6][CH:5]=1)([O-:3])=[O:2].OS(O)(=O)=O.[N-:27]=[N+]=[N-].[Na+]>C(Cl)(Cl)Cl.O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([C:10]23[CH2:18][CH:14]4[CH2:15][CH:16]([CH2:17]2)[C:12]([NH2:27])([CH2:13]4)[CH2:11]3)=[CH:8][CH:9]=1)([O-:3])=[O:2]

Komponenten

6

Edukt 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 670178551-(4-Nitrophenyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid

Produkt 1

HCID 593749781-(4-Nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amineAusbeute 74 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6212ChloroformLösungsmittel

Reaktionsbedingungen

Temperatur
45 °C

Versuchsvorschrift

To the stirred solution of 1-(4-nitrophenyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid (3.0 g, 10.45 mmol) obtained in step II, in CHCl3 (21 mL) was added conc. H2SO4 (4.2 mL, 78.9 mmol) then solid NaN3 was added in portions, so that the temperature of the reaction did not rise above 40° C. The reaction mixture was warmed to 45° C. and after stirring for 2 h it was cooled again to ice bath temperature, diluted with water and extracted with EtOAc. The aqueous layer was basified with 50% NaOH solution and extracted with CHCl3. The combined organic layer was washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain 1-(4-nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine as an off-white solid (2.0 g) in 74% yield. M.R: 201.0-205.9° C. m/z (M+1) 259; IR cm−1 3435, 2941, 1643, 1596, 1518, 1400, 1349, 1013, 750. 1H NMR (CDCl3) 300 MHz δ 8.14 (d, J=8.8 Hz, 2H), 7.39 (d, J=8.8 Hz, 2H), 3.70-3.60 (d (br), 2H), 2.62-2.50 (m, 2H), 2.38-2.23 (m, 3H), 2.15-2.0 (m, 3H), 1.95-1.60 (m, 4H).

Aufarbeitung

  1. customdid not rise above 40° C
  2. temperaturewas cooled again to ice bath temperature
  3. extractionextracted with EtOAc
  4. extractionextracted with CHCl3
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. customthe solvent was removed under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-e4f5912861f542e695a8739a2944371e
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07985759B2

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