Chlorotrimethylsilane → HCID 58403396, compound

HRID 1897549Notes

Reaction equation

HRID 1897549 reaction equation
[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: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[CH:5]2[Si:27]([CH3:29])([CH3:28])[CH3:26]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 58403371HCID 58403371, compoundHCID 178418339Butyllithium

Product 1

HCID 58403396HCID 58403396, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

A round bottom flask containing 48b (1.11g, 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=289.5 117.2 (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.

Workup

  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

Sources & evidence

ORD record
ord-da3710f596fa433fbd6c333ccdf4a545
Source dataset
uspto-grants-2013_08
Patent number
US08519122B2

Reaction notes

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