Hexamethyldisilazane → 2-[4-(1-Methylpiperidin-4-ylidene)-4,10-dihydro-9-oxa-3-thiabenzo[f]azulen-6-yl]propionic acid hydrochloride

HRID 389022

반응식

HRID 389022 반응식
C[Si](C)(C)N[Si](C)(C)C.C([Li])CCC.CCCCCC.[C:21]([O:25]C(C)(C)C)(=[O:24])[CH2:22][CH3:23].CC(C1C=CC=C(C(C)C)C=1N1C=[N+](C2C(C(C)C)=CC=CC=2C(C)C)CC1)C.[Cl-:59].Br[C:61]1[CH:62]=[CH:63][C:64]2[O:73][CH2:72][C:71]3[CH:70]=[CH:69][S:68][C:67]=3[C:66](=[C:74]3[CH2:79][CH2:78][N:77]([CH3:80])[CH2:76][CH2:75]3)[C:65]=2[CH:81]=1.Cl.O1CCOCC1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].O.C1(C)C=CC=CC=1>[ClH:59].[CH3:80][N:77]1[CH2:78][CH2:79][C:74](=[C:66]2[C:65]3[CH:81]=[C:61]([CH:22]([CH3:23])[C:21]([OH:25])=[O:24])[CH:62]=[CH:63][C:64]=3[O:73][CH2:72][C:71]3[CH:70]=[CH:69][S:68][C:67]2=3)[CH2:75][CH2:76]1

참가 물질

10

반응물 6

HCID 13838HexamethyldisilazaneHCID 88561tert-Butyl propionateHCID 27349181,3-Bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazol-3-ium chlorideHCID 204431481,4-Dioxane hydrochlorideHCID 684907724-(6-Bromo-10H-9-oxa-3-thiabenzo[f]azulen-4-ylidene)-1-methylpiperidineHCID 178418244HCID 178418244, 화합물

생성물 1

HCID 684884562-[4-(1-Methylpiperidin-4-ylidene)-4,10-dihydro-9-oxa-3-thiabenzo[f]azulen-6-yl]propionic acid hydrochloride수율 461.9%

시약·촉매·용매 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium촉매HCID 962Water용매HCID 1140Toluene용매

실험 절차

Hexamethyldisilazane (5.0 mL, 31.2 mmol) was ice-cooled in an argon atmosphere, and a 1.6 mol/L butyllithium-hexane solution (19.5 mL, 31.2 mmol) was added dropwise thereto. After stirring the mixture for 30 minutes, t-butyl propionate (2.1 g, 16.1 mmol) was added dropwise to the solution, and stirred for 30 minutes. Further, Pd(dba)2 (0.45 g, 0.8 mmol) and N,N′-(2,6-diisopropylphenyl)dihydroimidazolium chloride (0.34 g, 0.8 mmol) were added thereto, the mixture was stirred for 10 minutes, and a toluene (25 mL) solution of 4-(6-bromo-10H-9-oxa-3-thiabenzo[f]azulen-4-ylidene)-1-methylpiperidine (3.0 g, 8.0 mmol) was then added dropwise thereto. The mixture was stirred overnight at room temperature, water was then added to the reaction mixture, and the product was extracted with ethyl acetate. The solvents in the organic layer were distilled off under a reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate). The purified compound was dissolved in dioxane (10 mL), a 4 mol/L hydrogen chloride-dioxane solution (12.5 mL, 50 mmol) was added to the solution, and the mixture was stirred overnight. The solvents were distilled off under a reduced pressure, and the precipitated crystals were collected by filtration, to give 1.5 g (69%) of the captioned compound.

후처리

  1. temperaturecooled in an argon atmosphere
  2. stirringstirred for 30 minutes
  3. stirringthe mixture was stirred for 10 minutes
  4. stirringThe mixture was stirred overnight at room temperature
  5. extractionthe product was extracted with ethyl acetate
  6. distillationThe solvents in the organic layer were distilled off under a reduced pressure
  7. customthe residue was purified by silica gel column chromatography (hexane-ethyl acetate)
  8. dissolutionThe purified compound was dissolved in dioxane (10 mL)
  9. stirringthe mixture was stirred overnight
  10. distillationThe solvents were distilled off under a reduced pressure
  11. filtrationthe precipitated crystals were collected by filtration

출처 및 근거

ORD 기록
ord-8f6c830543e3480a82bca019922a2442
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08377967B2

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