((1,1-Dimethyl-2-propynyl)oxy)trimethylsilane → 2-Methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrile

HRID 1425870

반응식

HRID 1425870 반응식
[CH3:1][Si:2]([CH3:10])([CH3:9])[O:3][C:4]([CH3:8])([C:6]#[CH:7])[CH3:5].[Li]CCCC.[C:16]([C:18]1[CH:19]=[C:20]([CH:27]=[CH:28][C:29]=1[O:30][CH3:31])[C:21](N(OC)C)=[O:22])#[N:17]>C1COCC1>[CH3:31][O:30][C:29]1[CH:28]=[CH:27][C:20]([C:21](=[O:22])[C:7]#[C:6][C:4]([CH3:8])([O:3][Si:2]([CH3:10])([CH3:9])[CH3:1])[CH3:5])=[CH:19][C:18]=1[C:16]#[N:17]

참가 물질

5

반응물 3

HCID 87344((1,1-Dimethyl-2-propynyl)oxy)trimethylsilaneHCID 593547633-cyano-N,4-dimethoxy-N-methylbenzamideHCID 178418339Butyllithium

생성물 1

HCID 593548212-Methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrile수율 56%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-78 °C

실험 절차

To a −78° C. stirred solution of trimethyl(2-methylbut-3-yn-2-yloxy)silane (1.9 g, 12.501 mmol) in dry THF (25 mL), n-BuLi (2.80 mL, 4.50 mmol, 1.6 M in hexane) was added dropwise over 10 minutes under an inert atmosphere. The reaction was stirred for 30 min at −78° C., and then a solution of 3-cyano-N,4-dimethoxy-N-methylbenzamide (1.10 g, 5.01 mmol) in dry THF (10 mL) was added to reaction mixture and stirring was continued for an additional 3 h at −78° C. The reaction mixture was quenched with a saturated NH4Cl solution and extracted with EtOAc (2×50 mL). The combined organic layers were washed with water (20 mL) and brine (20 mL), dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude product. The crude material was purified via silica gel column chromatography eluting with 5% EtOAc in hexanes to afford 2-methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrile (0.8 g, 56%) as a pale yellow oil.

후처리

  1. additionwas added dropwise over 10 minutes under an inert atmosphere
  2. stirringstirring
  3. waitwas continued for an additional 3 h at −78° C
  4. customThe reaction mixture was quenched with a saturated NH4Cl solution
  5. extractionextracted with EtOAc (2×50 mL)
  6. washThe combined organic layers were washed with water (20 mL) and brine (20 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto obtain the crude product
  11. customThe crude material was purified via silica gel column chromatography
  12. washeluting with 5% EtOAc in hexanes

출처 및 근거

ORD 기록
ord-6427279982f54fa1addb21f06a5a3c4b
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08933074B2

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