Chlorotrimethylsilane → HCID 86762369, 화합물

HRID 2369236노트

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HRID 2369236 반응식
[F:1][C:2]1[CH:3]=[C:4]2[C:18](=[CH:19][CH:20]=1)[C:7]1[N:8]([CH3:17])[C:9]3[CH:10]=[C:11]([CH3:16])[CH:12]=[C:13]([CH3:15])[C:14]=3[C:6]=1[CH2:5]2.[Li]CCCC.[CH3:26][Si:27](Cl)([CH3:29])[CH3:28]>CCOCC>[F:1][C:2]1[CH:3]=[C:4]2[C:18]([CH:7]([Si:27]([CH3:29])([CH3:28])[CH3:26])[C:6]3[C:14]4[C:13]([CH3:15])=[CH:12][C:11]([CH3:16])=[CH:10][C:9]=4[N:8]([CH3:17])[C:5]=32)=[CH:19][CH:20]=1

참가 물질

5

반응물 3

HCID 6397ChlorotrimethylsilaneHCID 58403371HCID 58403371, 화합물HCID 178418339Butyllithium

생성물 1

HCID 86762369HCID 86762369, 화합물수율 78%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매2회

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온도
25 °C

실험 절차

A round bottom flask containing 48b (1.11 g, 4.17 mmol) in dry ether (27 mL) was immersed in a 25° C. water bath. n-BuLi (1.5 M in THF, 3.33 mL, 5.00 mmol) was added via syringe pump over one hour, generating a brown solution. Following addition of base, the reaction mixture was stirred at 25° C. for an additional 30 minutes and then cooled to −78° C. TMSCl (1.11 mL, 8.76 mmol) was added rapidly via syringe and the solution was subsequently warmed to room temperature. The reaction was diluted with ether, filtered, and concentrated in vacuo. Crude product was purified by flash column chromatography (20:1 hexanes-ethyl acetate followed by a second column 40:1 to 26:1 hexanes—ethyl acetate) to yield 49b as an orange solid in 78% yield (1.09 g, 3.24 mmol). 1H NMR (400 MHz, CDCl3): δ 7.57-7.60 (dd, 1H, J=8.4, 5.2 Hz), 7.19-7.22 (dd, 1H, J=9.6, 2.4 Hz), 7.00-7.04 (m, 2H), 6.78 (s, 1H), 4.01 (s, 3H), 3.97 (s, 1H), 2.61 (s, 3H), 2.49 (s, 3H), −0.15 (s, 9H); 13C NMR (150 MHz, CDCl3): δ 159.7 (d, J=289.5 Hz), 152.2 (d, J=10.1 Hz), 142.1, 141.2, 131.17, 129.4, 129.0, 122.7, 121.9, 121.7, 117.2 (d, J=10.5 Hz), 111.7 (d, J=27.9 Hz), 111.6 (d, J=29.7 Hz), 107.0, 38.2, 31.0, 21.8, 20.1, −2.2; 19F NMR (CD3CD, 376 MHz): δ −118.6 (m) FTIR: cm−1 2952, 1583, 1445, 1357, 1248, 1198, 1037, 838. EI-HRMS: Calcd. for C21H24FNSi+ [M]+: 337.1662. found 337.1664.

후처리

  1. customwas immersed in a 25° C.
  2. additionaddition of base
  3. temperaturecooled to −78° C
  4. temperaturethe solution was subsequently warmed to room temperature
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customCrude product was purified by flash column chromatography (20:1 hexanes-ethyl acetate

출처 및 근거

ORD 기록
ord-f407100cb1344ef08cba862591b37b92
출처 데이터셋
uspto-grants-2014_04
특허 번호
US08703936B2

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