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

HRID 1912094노트

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HRID 1912094 반응식
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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-207a4ad4f13f4b58932d46edfaf1fd6b
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08604069B2

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