Diisopropylamine → HCID 14230330、化合物

HRID 359045ノート

反応式

HRID 359045 の反応式
[CH:1]([NH:4][CH:5]([CH3:7])[CH3:6])([CH3:3])[CH3:2].C([Li:12])CCC.CCCCCC.[Br:19][C:20]1[CH:21]=[C:22]([CH:29]=[CH:30][CH:31]=1)[CH2:23][N:24]1[CH:28]=[CH:27][N:26]=[CH:25]1.[CH3:32][C:33]([CH3:39])([CH2:36][CH:37]=[CH2:38])[CH:34]=[O:35].C(OC(C)C)(C)C.CCCCCC>O1CCCC1.O>[CH:1]([N-:4][CH:5]([CH3:7])[CH3:6])([CH3:3])[CH3:2].[Li+:12].[Br:19][C:20]1[CH:21]=[C:22]([CH:23]([N:24]2[CH:28]=[CH:27][N:26]=[CH:25]2)[CH:34]([OH:35])[C:33]([CH3:39])([CH3:32])[CH2:36][CH:37]=[CH2:38])[CH:29]=[CH:30][CH:31]=1

参加物

9

反応物 5

HCID 7912DiisopropylamineHCID 796362,2-Dimethylpent-4-enalHCID 102203371-(3-Bromobenzyl)-1H-imidazoleHCID 21881879Diisopropylether hexaneHCID 178418244HCID 178418244、化合物

生成物 2

HCID 2724682Lithium diisopropylamideHCID 14230330HCID 14230330、化合物収率 74.4%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-70 °C

実験手順

A solution of lithium diisopropylamide was prepared in 40 ml of absolute tetrahydrofuran (THF) at -30° C. starting from 2.06 g (20.4 mmol) of diisopropylamine and 13.4 ml of 1.5 molar n-butyllithium/hexane solution (20 mmol). A solution of 4.75 g (20 mmol) of 1-(3-bromobenzyl)imidazole in 25 ml of absolute THF was added dropwise to this solution at -70° C. to -78° C., the mixture was stirred at about -70° C. for a further 30 minutes, a solution of 3.22 g of 70% purity (20 mmol) 2,2-dimethyl-4-pentenaldehyde in 30 ml of absolute THF was subsequently added dropwise at about -70° C., and the mixture was stirred at about -70° C. for a further 20 minutes and allowed to warm to room temperature over about 2.5 hours 300 ml of water were subsequently added dropwise at 0° C.-5° C., and the mixture was stirred for 1 hour with ice cooling. After separating the phases, the aqueous solution was extracted repeatedly with ether. The combined organic solutions were further worked up as described in Example 1. The extract residue (7.3 g) was chromatographed by elution with CH2Cl2 and CH2Cl2 /C2H5OH mixtures with an increase in C2H5OH content (to a maximum of 2% by volume) on a silica gel S/CH2Cl2 column (φ 2.8 cm, height 48 cm). After elution of 2.0 g preliminary fractions, 5.2 g of product were eluted in which the compound desired was greatly concentrated. From these 5.2 g, 3.05 g (φ 43.6% yield) of pure 1-(3-bromophenyl)-3,3-dimethyl-1-(1-imidazolyl)-5-hexen-2-ol of melting point 126° C. were obtained by crystallization from diisopropyl ether/hexane 2:1.

後処理

  1. stirringthe mixture was stirred at about -70° C. for a further 20 minutes
  2. additionwere subsequently added dropwise at 0° C.-5° C.
  3. stirringthe mixture was stirred for 1 hour with ice cooling
  4. customAfter separating the phases
  5. extractionthe aqueous solution was extracted repeatedly with ether
  6. customThe extract residue (7.3 g) was chromatographed by elution with CH2Cl2 and CH2Cl2 /C2H5OH
  7. temperaturean increase in C2H5OH content (to a maximum of 2% by volume) on a silica gel S/CH2Cl2 column (φ 2.8 cm, height 48 cm)
  8. washAfter elution of 2.0 g preliminary fractions, 5.2 g of product
  9. washwere eluted in which the compound
  10. concentrationdesired was greatly concentrated

出典と根拠

ORDレコード
ord-d4855c3047e641aa833ec1235ece1a7a
出典データセット
uspto-grants-1991_03
特許番号
US04999352

反応ノート

読み込み中…