Chlorotrimethylsilane → HCID 86762369, compound

HRID 2369236Notes

Reaction equation

HRID 2369236 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: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

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 58403371HCID 58403371, compoundHCID 178418339Butyllithium

Product 1

HCID 86762369HCID 86762369, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

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.

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-f407100cb1344ef08cba862591b37b92
Source dataset
uspto-grants-2014_04
Patent number
US08703936B2

Reaction notes

Loading…