Thionyl Chloride → HCID 19698672、化合物

HRID 1609110ノート

反応式

HRID 1609110 の反応式
[CH:1]1[C:14]2[C:13]3([C:16](O)=O)[CH2:15][CH:6]([C:7]4[C:12]3=[CH:11][CH:10]=[CH:9][CH:8]=4)[C:5]=2[CH:4]=[CH:3][CH:2]=1.S(Cl)(Cl)=O.[NH:23]1[CH2:33][CH2:32][CH:26]([C:27]([O:29]CC)=O)[CH2:25][CH2:24]1>C1(C)C=CC=CC=1.CN(C)C=O>[CH:1]1[C:14]2[C:13]3([CH2:16][N:23]4[CH2:24][CH2:25][CH:26]([CH:27]([C:25]5[CH:24]=[N:23][CH:33]=[CH:32][CH:26]=5)[OH:29])[CH2:32][CH2:33]4)[CH2:15][CH:6]([C:7]4[C:12]3=[CH:11][CH:10]=[CH:9][CH:8]=4)[C:5]=2[CH:4]=[CH:3][CH:2]=1

参加物

6

反応物 3

HCID 24386Thionyl ChlorideHCID 70770Ethyl 4-piperidinecarboxylateHCID 125071199,10-Dihydro-9,10-methano-9-anthracenecarboxylic acid

生成物 1

HCID 19698672HCID 19698672、化合物収率 92.2%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 1140Toluene溶媒2 回

実験手順

A solution of 9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid (21.8 g, 92.4 mmol) in toluene (160 mL) was treated with thionyl chloride (11.7 g, 99 mmol) and N,N-dimethylformamide (0.1 g). The resulting solution was heated to reflux temperature for 2 h, then was cooled to room temperature. The mixture was then treated dropwise with a solution of ethyl isonipecotate (31.1 g, 198 mmol) in toluene (20 mL), using an ice/water bath to keep the reaction temperature <35° C. Upon complete addition, the mixture was stirred for 1 h at room temperature, then was washed sequentially with 10% hydrochloric acid (40 mL), water (40 mL), 1N aqueous sodium hydroxide (40 mL), water (40 mL) and brine (40 mL). The aqueous washes were extracted with toluene (100 mL). The organic extracts were combined, dried (MgSO4), filtered and concentrated to afford the title compound (33.0 g, 85.2 mmol, 92%) as an off-white solid. 1H NMR (d6-DMSO): δ7.33-7.14 (m, 4H), 6.99 (m, 4H), 4.54 (br, 1H), 4.38 (s, 1H, H--C(10)), 4.09 (q, J=6.5 Hz, 2H, CH2CH3), 3.8 (br, 1H), 3.0-2.5 (br, 6H), 2.05-1.45 (br, 5H), 1.19 (t, J=6.5 Hz, 3H, CH2CH3).

後処理

  1. temperatureThe resulting solution was heated
  2. temperatureto reflux temperature for 2 h
  3. customthe reaction temperature <35° C
  4. additionUpon complete addition
  5. washwas washed sequentially with 10% hydrochloric acid (40 mL), water (40 mL), 1N aqueous sodium hydroxide (40 mL), water (40 mL) and brine (40 mL)
  6. extractionThe aqueous washes were extracted with toluene (100 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-529d71a71a3d43b7a1c5ff19a477e310
出典データセット
uspto-grants-1995_03
特許番号
US05399568

反応ノート

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