Chlorotrimethylsilane → HCID 67353158, compound

HRID 2369233Notes

Reaction equation

HRID 2369233 reaction equation
[F:1][C:2]1[CH:20]=[C:19]2[C:5]([CH2:6][C:7]3[C:15]4[CH:14]=[CH:13][C:12]([O:16][CH3:17])=[CH:11][C:10]=4[N:9]([CH3:18])[C:8]=32)=[CH:4][CH:3]=1.[Li]CCCC.[CH3:26][Si:27](Cl)([CH3:29])[CH3:28]>CCOCC>[F:1][C:2]1[CH:20]=[C:19]2[C:5]([CH:6]([Si:27]([CH3:29])([CH3:28])[CH3:26])[C:7]3[C:15]4[CH:14]=[CH:13][C:12]([O:16][CH3:17])=[CH:11][C:10]=4[N:9]([CH3:18])[C:8]=32)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 67351679HCID 67351679, compoundHCID 178418339Butyllithium

Product 1

HCID 67353158HCID 67353158, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

A round bottom flask containing 56 (201 mg, 0.75 mmol) in dry ether (6 mL) was immersed in a 25° C. water bath. n-BuLi (1.5 M in THF, 602 μL, 0.90 mmol) was added via syringe pump over one hour, generating an orange solution. Following addition of base, the reaction mixture was stirred at 25° C. for an additional 1.5 hours and then cooled to −78° C. TMSCl (200 μL, 1.58 mmol) was added rapidly via syringe, and the reaction mixture was stirred an additional 5 minutes at −78° C., then warmed to room temperature over 3.5 hours. The reaction was subsequently diluted with ether, filtered, and concentrated in vacuo. Crude product was purified by flash column chromatography (20:1 hexanes-ethyl acetate) to yield 57 as a solid in 62% yield (159 mg, 0.47 mmol). 1H NMR (600 MHz, CDCl3): δ 7.54 (d, 1H, J=8.4 Hz), 7.39-7.41 (dd, 1H, J=8.4, 4.8 Hz), 7.33-7.35 (dd, 1H, J=9, 2.4 Hz), 6.83-6.89 (m, 3H), 3.98 (s, 3H), 3.93 (s, 3H), −0.02 (s, 9H). 13C NMR (150 MHz, CDCl3): δ 61.4 (d, J=238.5 Hz), 156.2, 144.5 (d, J=2.0), 143.0, 141.5 (d, J=3 Hz), 134.8 (d, J=9.5 Hz), 125.4, 124.79 (d, J=9.15 Hz), 120.9, 118.0, 109.4 (d, J=22.8 Hz), 108.6, 103.9 (d, J=24.3 Hz), 93.5, 5.6, 36.3, 31.0, −2.5; 19F NMR (CD3CD, 376 MHz): δ −117.6 (m); FTIR: cm−1 2952, 1608, 1523, 1372, 1223, 1163, 1107, 1042, 939, 841.

Workup

  1. customwas immersed in a 25° C.
  2. additionaddition of base
  3. temperaturecooled to −78° C
  4. stirringthe reaction mixture was stirred an additional 5 minutes at −78° C.
  5. temperaturewarmed to room temperature over 3.5 hours
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customCrude product was purified by flash column chromatography (20:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-44250054a3414a82ac5ceeb1d90fae50
Source dataset
uspto-grants-2014_04
Patent number
US08703936B2

Reaction notes

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