1,2-Dimethoxyethane → 1-Azabicyclo(2.2.2)octane-3-carbonitrile

HRID 976288

反応式

HRID 976288 の反応式
CC(C)([O-])C.[K+].C(COC)OC.[N:13]12[CH2:20][CH2:19][CH:16]([CH2:17][CH2:18]1)[C:15](=O)[CH2:14]2.S([CH2:32][N:33]=C=O)(C1C=CC(C)=CC=1)(=O)=O>C(O)C>[C:32]([CH:15]1[CH:16]2[CH2:19][CH2:20][N:13]([CH2:18][CH2:17]2)[CH2:14]1)#[N:33]

参加物

6

反応物 4

HCID 80711,2-Dimethoxyethane2 回HCID 195073-QuinuclidinoneHCID 117890781-Isocyanatomethanesulfonyl-4-methylbenzeneHCID 23665647Potassium tert-butoxide

生成物 1

HCID 1428651-Azabicyclo(2.2.2)octane-3-carbonitrile収率 74.5%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒2 回

実験手順

A solution of potassium tert-butoxide (18.27 ml) in 1:1 (v/v) mixture of dimethoxyethane and ethanol (100 ml) was added slowly to a stirred mixture of 3-quinuclidinone (8.14 g), tosylmethylisocyanate (16.53 g) in dry ethanol (6.5 ml), and dry dimethoxyethane (228 ml) under an atmosphere of argon whilst maintaining the temperature below 10° C. The reaction mixture was allowed to warm to ambient temperature and stirred at this temperature for 30 minutes. The reaction mixture was then stirred at 40° C. for 3 hours. The reaction mixture was cooled, filtered and the filtrate evaporated. The residue was purified by flash column chromatography on alumina (Brockmann Grade I) using a 2:98 (v/v) mixture of methanol/ethyl acetate as eluant to give 3-cyanoquinuclidine (6.6 g), microanalysis, found: C, 67.6; H, 8.5; N, 18.7%; C8H12N2 requires: C, 70.6; H, 8.8; N, 20.6%; NMR (CDCl3): 1.4-1.7 (3H, m), 1.85-2.0 (1H, m) 2.0-2.1 (1H, m) and 2.6-3.4 (7H, m); m/z 137 (M+H).

後処理

  1. temperaturewhilst maintaining the temperature below 10° C
  2. stirringThe reaction mixture was then stirred at 40° C. for 3 hours
  3. temperatureThe reaction mixture was cooled
  4. filtrationfiltered
  5. customthe filtrate evaporated
  6. customThe residue was purified by flash column chromatography on alumina (Brockmann Grade I)
  7. additiona 2:98 (v/v) mixture of methanol/ethyl acetate as eluant

出典と根拠

ORDレコード
ord-674cbd93d49343d395987c36d51fabd6
出典データセット
uspto-grants-1997_03
特許番号
US05612352

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