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3-Bromopyridine → 1-(2-Chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-(3-pyridyl)piperidin-4-ol

HRID 1490176
ノート
印刷プレビュー

反応式

HRID 1490176 の反応式
C([Li])CCC.Br[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1.[Cl:13][C:14]1[CH:27]=[CH:26][C:25]2[CH:24]3[CH2:28][C:17]([CH2:29][N:30]4[CH2:35][CH2:34][C:33](=[O:36])[CH2:32][CH2:31]4)([C:18]4[C:23]3=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:16]=2[CH:15]=1>O1CCCC1>[Cl:13][C:14]1[CH:27]=[CH:26][C:25]2[CH:24]3[CH2:28][C:17]([CH2:29][N:30]4[CH2:31][CH2:32][C:33]([C:7]5[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=5)([OH:36])[CH2:34][CH2:35]4)([C:18]4[C:23]3=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:16]=2[CH:15]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 122863-BromopyridineHCID 214806221-(2-Chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-piperidinoneHCID 178418339Butyllithium

生成物 1

HCID 214805851-(2-Chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-(3-pyridyl)piperidin-4-ol収率 81%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-75 °C

実験手順

To a cooled solution (-90° C.) of n-butyllithium (2.5M in hexane, 2.40 mL, 6.0 mmol, 1.5 eq) in tetrahydrofuran (40 mL) under nitrogen was added freshly distilled 3-bromopyridine (0.540 mL, 5.6 mmol, 1.4 eq). The metal-halogen exchange reaction was warmed to -75° C. and maintained for 1.5 h. During that time a dark green solution evolved with the appearance of fine particulate. A solution of 1-(2-chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-piperidinone (1.35 g, 4.0 mmol) in tetrahydrofuran (10 mL) was then added dropwise with considerable lightening of the solution color to a deep yellow. The reaction was warmed to room temperature over 1 h and quenched with water (50 mL). The aqueous phase was extracted with ethyl acetate (3×60 mL). Combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and reduced to an oil. The reaction mixture was purified by flash chromatography over silica gel (80 mL, eluent: ethyl acetate) to yield 1.35 g (81%) of the title compound as a white solid. TLC analysis (Rf 0.20, ethyl acetate). 1H NMR (D6 -DMSO, 300 MHz) 8.69 (br s, 1H), 8.41 (d, J=4.5 Hz, 1H), 7.83 (dt, J=8.0 Hz, 1H), 7.29 (m, 5H), 6.95 (m, 3H), 5.05 (s, 1H), 4.35 (s, 1H), 3.41 (m, 2H), 3.34 (s, 1H), 2.75 (m, 4H), 1.92 (m, 2H), 1.62 (m, 2H) MS (CI, CH4) m/z 417 (M+1,100), 419 (36), 445 (M+29,15), 399 (15) The free base was dissolved in diethyl ether containing a small amount of methylene chloride, acidified with ethereal HCl, and the hydrochloride salt suspension was diluted with additional ether. The salt was filtered, washed with fresh ether and dried in vacuo (50° C., 13 pascal, 18 h) to yield a white solid, mp 225°-228° C. (dec).

後処理

  1. temperaturemaintained for 1.5 h
  2. temperatureThe reaction was warmed to room temperature over 1 h
  3. customquenched with water (50 mL)
  4. extractionThe aqueous phase was extracted with ethyl acetate (3×60 mL)
  5. dry with materialCombined organic extracts were dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customThe reaction mixture was purified by flash chromatography over silica gel (80 mL, eluent: ethyl acetate)

出典と根拠

ORDレコード
ord-75869803a2094c36bea1df3c6bdeca90
出典データセット
uspto-grants-1997_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05681840

反応ノート

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