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

HRID 1912094ノート

反応式

HRID 1912094 の反応式
Br[C:2](Br)=[CH:3][CH:4]1[CH2:7][CH:6]([CH2:8][CH:9]([CH2:12][CH3:13])[CH2:10][CH3:11])[CH2:5]1.C([Li])CCC.[Si:20]([O:37][CH2:38][CH2:39][CH:40]([C:49](=[O:54])NCOC)[CH2:41][C:42]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[O:43])([C:33]([CH3:36])([CH3:35])[CH3:34])([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Cl-].[NH4+]>O1CCCC1>[Si:20]([O:37][CH2:38][CH2:39][CH:40]([C:49](=[O:54])[C:2]#[C:3][CH:4]1[CH2:7][CH:6]([CH2:8][CH:9]([CH2:12][CH3:13])[CH2:10][CH3:11])[CH2:5]1)[CH2:41][C:42]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[O:43])([C:33]([CH3:34])([CH3:36])[CH3:35])([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

参加物

6

反応物 4

HCID 25517Ammonium ChlorideHCID 71114767tert-Butyl 5-(tert-butyldiphenylsilanyloxy)-3-methoxymethylcarbamoylvalerateHCID 866750521-(2,2-Dibromovinyl)-3-(2-ethylbutyl)cyclobutaneHCID 178418339Butyllithium

生成物 1

HCID 71127334tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-[3-(2-ethylbutyl)cyclobutyl]-4-oxo-5-hexynoate収率 75.8%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

1-(2,2-Dibromovinyl)-3-(2-ethylbutyl)cyclobutane (9.78 g) and tetrahydrofuran (100 mL) were mixed. To the mixture was added dropwise n-butyllithium (1.65 M in hexane) (39 mL) at −78° C. The mixture was stirred under ambient temperature. To the mixture was added dropwise a solution of tert-butyl 5-(tert-butyldiphenylsilanyloxy)-3-methoxymethylcarbamoylvalerate (10.6 g) in tetrahydrofuran (30 mL) at ice temperature. After stirring at ice temperature for 2 hr., saturated aqueous ammonium chloride (150 mL) was added to the reaction mixture. The mixture was extracted with ethyl acetate (150 mL, 100 mL). The combined organic layer was washed with water (75 mL) and brine (75 mL, 50 mL), then dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo. The resultant residue was purified by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/40→1/30→1/20) to give the title compound (9.70 g).

後処理

  1. stirringAfter stirring at ice temperature for 2 hr
  2. extractionThe mixture was extracted with ethyl acetate (150 mL, 100 mL)
  3. washThe combined organic layer was washed with water (75 mL) and brine (75 mL, 50 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationThe sodium sulfate was filtered off
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe resultant residue was purified by silica gel column chromatography (Eluent: ethyl acetate/hexane=1/40→1/30→1/20)

出典と根拠

ORDレコード
ord-207a4ad4f13f4b58932d46edfaf1fd6b
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…