Hydrochloric Acid → N-allyl-3-trimethylsilylpropiolic amide

HRID 1596700

반응식

HRID 1596700 반응식
[CH3:1][Si:2]([C:5]#[C:6][Si](C)(C)C)([CH3:4])[CH3:3].[CH2:11]([N:14]=[C:15]=[O:16])[CH:12]=[CH2:13].[Cl-].[Al+3].[Cl-].[Cl-].CS(O)(=O)=O.Cl.C(=O)(O)[O-].[Na+]>O1CCOCC1.[Ti](Cl)(Cl)(Cl)Cl.[Cl-].[Zn+2].[Cl-].O.ClCCl.ClC1C=CC=CC=1Cl.ClCCCl>[CH2:11]([NH:14][C:15](=[O:16])[C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH:12]=[CH2:13]

참가 물질

14

반응물 6

HCID 313Hydrochloric AcidHCID 6395Methanesulfonic Acid3회HCID 15123Allyl isocyanateHCID 84564Bis(trimethylsilyl)acetylene2회HCID 516892Sodium BicarbonateHCID 6451240Aluminum(III) Chloride

생성물 1

HCID 11217610N-allyl-3-trimethylsilylpropiolic amide

시약·촉매·용매 7

HCID 24193Titanium Tetrachloride촉매HCID 3007855Zincchloride촉매HCID 111,2-Dichloroethane용매HCID 962Water용매HCID 6344Dichloromethane용매HCID 72391,2-Dichlorobenzene용매HCID 312751,4-Dioxane용매

실험 절차

A solution of bis(trimethylsilyl)acetylene and allyl isocyanate in dry solvent is treated with an excess (at least 2 molar equivalents) of an acid catalyst. The preferred acid catalysts include aluminum chloride, ferric chloride and methanesulfonic acid; the most preferred acid catalyst is methanesulfonic acid. Acid catalysts which have been found not to work include: titanium tetrachloride, zinc chloride (in diethyl ether), Amberlyst 15 and Dowex 50 ion exchange resins, and gaseous hydrochloric acid in dioxane. 1,2-dichloroethane and o-dichlorobenzene are preferred solvents, the most preferred solvent is dichloromethane. The concentration of bis(trimethylsilyl) acetylene in the above reaction is preferred to be 1 molar or lower. The reaction is monitored by gas chromatography, and when product formation is complete the mixture is poured into water or saturated sodium bicarbonate and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over sodium sulfate, filtered and evaporated to give an oil. When methanesulfonic acid is used as the catalyst, the oil may be used without further purification. When aluminum chloride is used as the catalyst, the oil is distilled under vacuum in a Kugelrohr apparatus (from about 100 to about 130° C. at from about 0.5 to about 1.0 Torr) to give the N-allyl-3-trimethylsilylpropiolic amide.

후처리

  1. extractionextracted with ethyl acetate
  2. washThe organic phase is washed with water and brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customto give an oil
  7. customthe oil may be used without further purification
  8. distillationthe oil is distilled under vacuum in a Kugelrohr apparatus (from about 100 to about 130° C. at from about 0.5 to about 1.0 Torr)

출처 및 근거

ORD 기록
ord-d6e8806be392498f9df8a9cf9dba973c
출처 데이터셋
uspto-grants-2001_09
특허 번호
US06291513B1

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