Ammonium Chloride → tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-oxo-5-hexynoate

HRID 1912051ノート

反応式

HRID 1912051 の反応式
Br[C:2](Br)=[CH:3][CH:4]1[CH2:7][CH:6]([CH2:8][CH:9]([CH3:11])[CH3:10])[CH2:5]1.C([Li])CCC.[Si:18]([O:35][CH2:36][CH2:37][CH:38]([C:47](=[O:52])NCOC)[CH2:39][C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])([C:31]([CH3:34])([CH3:33])[CH3:32])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[Cl-].[NH4+]>O1CCCC1.O>[Si:18]([O:35][CH2:36][CH2:37][CH:38]([C:47](=[O:52])[C:2]#[C:3][CH:4]1[CH2:7][CH:6]([CH2:8][CH:9]([CH3:11])[CH3:10])[CH2:5]1)[CH2:39][C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])([C:31]([CH3:32])([CH3:34])[CH3:33])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

参加物

7

反応物 4

HCID 25517Ammonium ChlorideHCID 71114767tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-methoxymethylcarbamoylvalerateHCID 866750331-(2,2-Dibromovinyl)-3-isobutylcyclobutaneHCID 178418339Butyllithium

生成物 1

HCID 71127321tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-oxo-5-hexynoate収率 96.7%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

1-(2,2-Dibromovinyl)-3-isobutylcyclobutane (40 g) and tetrahydrofuran (280 mL) were mixed. To the mixture was added n-butyllithium (2.66 M in hexane) (104 mL) dropwise at −78° C. The mixture was stirred at ice temperature and a solution of tert-butyl 5-(tert-butyldiphenylsilanyloxy)-3-methoxymethylcarbamoylvalerate (54 g) in tetrahydrofuran (100 mL) was added dropwise to the mixture. After stirring at ice temperature for 1 hr, saturated aqueous ammonium chloride (180 mL) and water (100 mL) were added to the reaction mixture. The mixture was extracted with ethyl acetate (600 mL), washed with saturated aqueous ammonium chloride (180 mL and 400 mL) and dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo. After an addition of silica gel (90 g) and ethyl acetate/hexane=1/20 (600 mL) into the resultant residue, the mixture was stirred at RT for 1 hr. The silica gel was filtered off and the filtrate was concentrated in vacuo to give the title compound (60.09 g) as a crude product.

後処理

  1. stirringAfter stirring at ice temperature for 1 hr
  2. extractionThe mixture was extracted with ethyl acetate (600 mL)
  3. washwashed with saturated aqueous ammonium chloride (180 mL and 400 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationThe sodium sulfate was filtered off
  6. concentrationthe filtrate was concentrated in vacuo
  7. additionAfter an addition of silica gel (90 g) and ethyl acetate/hexane=1/20 (600 mL) into the resultant residue
  8. stirringthe mixture was stirred at RT for 1 hr
  9. filtrationThe silica gel was filtered off
  10. concentrationthe filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-7573f9e280e54c9db91176c4719b9e58
出典データセット
uspto-grants-2013_12
特許番号
US08604069B2

反応ノート

読み込み中…