N,N,N',N'-Tetramethylethylenediamine → HCID 20339675、化合物

HRID 1395433ノート

反応式

HRID 1395433 の反応式
[C:1]1([CH:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:8][CH:9]2[CH2:14][CH:13]3[CH2:15][CH2:16][N:10]2[CH2:11][CH2:12]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CN(C)CCN(C)C.C([Li])CCC.[C:36]1(=[O:41])[CH2:40][CH2:39][CH2:38][CH2:37]1>CCCCCC.C1CCCCC1>[N:10]12[CH2:16][CH2:15][CH:13]([CH2:12][CH2:11]1)[CH2:14][CH:9]2[CH2:8][C:7]([C:36]1([OH:41])[CH2:40][CH2:39][CH2:38][CH2:37]1)([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

参加物

7

反応物 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8452CyclopentanoneHCID 20339673HCID 20339673、化合物HCID 178418339Butyllithium

生成物 1

HCID 20339675HCID 20339675、化合物

試薬・触媒・溶媒 2

HCID 8058Hexane溶媒HCID 8078Cyclohexane溶媒

実験手順

A solution of 20.4 parts 2-(2,2-diphenylethyl)-1-azabicyclo[2.2.2]octane, 10.5 parts by volume of N,N,N',N'-tetramethylethylenediamine, 48 parts by volume of a 1.6 M solution of butyllithium in hexane in 500 parts by volume of cyclohexane is heated to reflux while being stirred for 1.2 hours under nitrogen. The reaction mixture is cooled to 10 and 6.8 parts by volume of cyclopentanone is added during 5 minutes. It is washed four times with water and one time with saturated sodium chloride solution, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The residual solid is triturated with 40 parts diethyl ether and filtered. The filtrate is evaporated under reduced pressure to give residual solid and oil. This residue is put on a 25 mm volume of Woelm silica gel and eluted with a mixed solvent of ethanol, concentrated ammonia and toluene (ratio 2:0.25:98) under a pressure to maintain a flow rate of 8 ml per minute. The desired fraction is evaporated under reduced pressure giving residual oil which solidifies. The solid is washed with n-pentane and recrystallized from diethylether giving the product as a white solid: (XI) 1-[2-(1-azabicyclo [2.2.2]octan-2-yl)-1,1-diphenylethyl]cyclopentanol m.p. 178°-179.5°, MW 376. The hydrochloride of this compound is crystallized from a mixed solvent of isopropanol and diethyl ether: 1-[2-(1-azabicyclo[2.2.2]octan-2-yl)-1,1-diphenylethyl] cyclopentanol hydrochloride (XVII); m.p. 247°-249°; MW 412.

後処理

  1. temperatureto reflux
  2. additionis added during 5 minutes
  3. washIt is washed four times with water and one time with saturated sodium chloride solution
  4. dry with materialdried over anhydrous sodium sulfate
  5. customevaporated under reduced pressure
  6. customThe residual solid is triturated with 40 parts diethyl ether
  7. filtrationfiltered
  8. customThe filtrate is evaporated under reduced pressure
  9. customto give residual solid and oil
  10. washeluted with a mixed solvent of ethanol, concentrated ammonia and toluene (ratio 2:0.25:98) under a pressure
  11. temperatureto maintain a flow rate of 8 ml per minute
  12. customThe desired fraction is evaporated under reduced pressure
  13. customgiving residual oil which
  14. washThe solid is washed with n-pentane
  15. customrecrystallized from diethylether giving the product as a white solid
  16. customThe hydrochloride of this compound is crystallized from a mixed solvent of isopropanol and diethyl ether

出典と根拠

ORDレコード
ord-7c9386dfc1bb4678a76c464f0c8dafda
出典データセット
uspto-grants-1980_05
特許番号
US04203989

反応ノート

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