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

HRID 1015517노트

반응식

HRID 1015517 반응식
[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]

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 6212Chloroform용매

반응 조건

온도
45 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-e4f5912861f542e695a8739a2944371e
출처 데이터셋
uspto-grants-2011_07
특허 번호
US07985759B2

반응 노트

불러오는 중…