N,N,N',N'-Tetramethylethylenediamine → HCID 178447945、化合物

HRID 1198326

反応式

HRID 1198326 の反応式
[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH2:15][CH2:14][CH:13]([CH2:16][CH2:17][C@H:18]3[CH2:23][CH2:22][C@H:21]([CH2:24][CH2:25][CH3:26])[CH2:20][CH2:19]3)[CH2:12][CH:11]=2)=[C:6]([F:27])[C:5]=1[F:28])[CH3:2].C([Li])CCC.C(OC1C=CC=C(F)C=1F)C.CN(C)CCN(C)C.C([C@H]1CC[C@H](CCC2CCC(=O)CC2)CC1)CC.[Cl-].[NH4+]>CCCCCC.O1CCCC1>[CH2:24]([C@H:21]1[CH2:22][CH2:23][C@H:18]([CH2:17][CH2:16][C:13]2[CH:14]=[CH:15][C:10]([C:7]3[CH:8]=[CH:9][C:4]([O:3][CH2:1][CH3:2])=[C:5]([F:28])[C:6]=3[F:27])=[CH:11][CH:12]=2)[CH2:19][CH2:20]1)[CH2:25][CH3:26]

参加物

9

反応物 6

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 25517Ammonium ChlorideHCID 27829281-Ethoxy-2,3-DifluorobenzeneHCID 178418339ButyllithiumHCID 178447946HCID 178447946、化合物HCID 178447952HCID 178447952、化合物

生成物 1

HCID 178447945HCID 178447945、化合物

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

反応条件

温度
-70 °C

実験手順

0.2 mol of 1-(4-ethoxy-2,3-difluorophenyl)-4-(trans-4-n-propylcyclohexylethyl)-cyclohex-1-ene (obtainable as follows: 131 ml of a 1.6N solution of butyllithium in n-hexane are added dropwise to a solution of 0.2 mol of ethoxy-2,3-difluorobenzene and 0.2 mol of tetramethylethylenediamine in 400 ml of tetrahydrofuran at -70° C., with exclusion of moisture and under a nitrogen atmosphere. The mixture is then stirred at -70° C. for 4 hours and 0.11 mol of 4-(trans-4-n-propylcyclohexylethyl)-cyclohexanone in 100 ml of THF are subsequently slowly added. The reaction mixture is allowed to warm slowly to room temperature and is hydrolysed with 1.5 l of a saturated ammonium chloride solution. The mixture is extracted with ether and the ether phase is washed several times with water, dried and evaporated. The residue is taken up in 700 ml of ethanol, 70 ml of concentrated HCl are added and the mixture is boiled under reflux for 3 hours. 1.5 l of water are then added and the mixture is extracted with methyl tert.-butyl ether. The ether phase is washed neutral, dried and evaporated and the residue is recrystallized. The product (has a mp. of 73° and a cp. of 139°) and 50 g of DDQ are boiled under reflux in 250 ml of toluene for one hour. After cooling, the reaction mixture is filtered with toluene over silica gel, the filtrate is evaporated and the residue is purified by chromatography. 1-(trans-4-Propylcyclohexyl)-2-(4'-ethoxy-2',3'-difluorobiphenyl-4-yl)-ethane is obtained, C 64° N 144° I.

後処理

  1. temperatureto warm slowly to room temperature
  2. extractionThe mixture is extracted with ether
  3. washthe ether phase is washed several times with water
  4. customdried
  5. customevaporated
  6. addition70 ml of concentrated HCl are added
  7. temperatureunder reflux for 3 hours
  8. addition1.5 l of water are then added
  9. extractionthe mixture is extracted with methyl tert.-butyl ether
  10. washThe ether phase is washed neutral
  11. customdried
  12. customevaporated
  13. customthe residue is recrystallized
  14. customof 139°
  15. temperatureunder reflux in 250 ml of toluene for one hour
  16. temperatureAfter cooling
  17. filtrationthe reaction mixture is filtered with toluene over silica gel
  18. customthe filtrate is evaporated
  19. customthe residue is purified by chromatography

出典と根拠

ORDレコード
ord-0fcd9389dcbf49a383abafc93c7a6144
出典データセット
uspto-grants-1994_01
特許番号
US05279764

関連ノート

読み込み中…