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

HRID 1015517ノート

反応式

HRID 1015517 の反応式
[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]

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6212Chloroform溶媒

反応条件

温度
45 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-e4f5912861f542e695a8739a2944371e
出典データセット
uspto-grants-2011_07
特許番号
US07985759B2

反応ノート

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