3-Chloro-2-chloromethyl-1-propene → (Allylthio)benzene

HRID 716676Notes

Reaction equation

HRID 716676 reaction equation
[Na].O[C:3]1[CH:8]=[CH:7][C:6]([SH:9])=[CH:5][CH:4]=1.C[O-].[Na+].Cl[CH2:14][C:15](CCl)=[CH2:16]>CO>[CH2:16]([S:9][C:6]1[CH:7]=[CH:8][CH:3]=[CH:4][CH:5]=1)[CH:15]=[CH2:14]

Participants

6

Reactant 4

HCID 158593-Chloro-2-chloromethyl-1-propeneHCID 2401474-MercaptophenolHCID 5360545SodiumHCID 10942334Sodium Methoxide

Product 1

HCID 79180(Allylthio)benzeneYield 173.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a 1 L flask at 0 C was added 160 mL of methanol. The solution was kept under 30 C as Na metal (5.10 g, 221.24 mmol) was added in small portions. After all the sodium had reacted, 4-hydroxythiophenol (25.0 g, 2.2 eq) was added to the solution of sodium methoxide. The solution was heated to reflux and 3-chloro-2-chloromethyl-1-propene (11.26 g, 1 eq) was added dropwise over 1 hour. The solution was allowed to reflux overnight. The solution was cooled to 25 C, filtered, and reduced in vacuo to remove the methanol. The crude material was taken up in 500 mL of water and extracted with ether (4×150 mL). The ether layer was washed with 1N HCl, water, brine, and dried over sodium sulfate. The organic layer was reduced in vacuo to a crude orange oil. The oil was purified by flash chromatography 90:10 hexanes/ethyl acetate to yield 23.52 g of a colorless oil. Yield 85.8%. 1H NMR (400 MHz, CDCl3, δ): 7.23 (m, 4H, Ar—H), 6.74 (m, 4H, Ar—H), 5.84 (s, 2H, Ar—OH), 4.70 (s, 2H, C═CH2), 3.57 (s, 4H, CH2); 13C NMR (400 MHz, CDCl3, δ): 155.3 (C1), 140.45 (C10), 138.6 (C5), 134.3 (C8), 132.7 (C4), 126.0 (C7), 116.5 (C3), 116.0 (C6), 40.63 (C11); MS (ESI, m/z): [M+Li]+ calcd for C16H16O2S2, 344.3; found, 344.3.

Workup

  1. additionwas added in small portions
  2. temperatureThe solution was heated
  3. temperatureto reflux
  4. temperatureto reflux overnight
  5. temperatureThe solution was cooled to 25 C
  6. filtrationfiltered
  7. customto remove the methanol
  8. extractionextracted with ether (4×150 mL)
  9. washThe ether layer was washed with 1N HCl, water, brine
  10. dry with materialdried over sodium sulfate
  11. customThe oil was purified by flash chromatography 90:10 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-224254f1a7f8407689ea8d6aa4c1cda2
Source dataset
uspto-grants-2015_11
Patent number
US09193682B2

Reaction notes

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