Boron trifluoride etherate → HCID 14652263, compound

HRID 2352492Notes

Reaction equation

HRID 2352492 reaction equation
[CH:1](=O)[CH2:2][CH2:3][C:4]#[CH:5].[CH2:7]([SH:11])[CH2:8][CH2:9][SH:10].B(F)(F)F.CCOCC>C(Cl)Cl>[CH2:2]([CH:1]1[S:11][CH2:7][CH2:8][CH2:9][S:10]1)[CH2:3][C:4]#[CH:5]

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 80131,3-PropanedithiolHCID 11804674HCID 11804674, compound

Product 1

HCID 14652263HCID 14652263, compoundYield 62.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of pent-4-ynal (6.99 g, 85.1 mmol) dissolved in methylene chloride (85 mL) was added 1,3-propanedithiol (8.54 mL, 85.1 mmol). The solution was stirred at room temperature for 1 hour and then cooled to -20° C. Boron trifluoride etherate (10.46 mL, 85.1 mmol) was added and, after warming to room temperature, the solution was stirred for 16 hours. The solution was washed with water (2×20 mL) and the aqueous extract was washed with additional methylene chloride (2×40 mL). The combined organic extracts were washed with 10% potassium hydroxide solution (4×30 mL) and the aqueous extract was washed with additional methylene chloride (2×40 mL). The combined organic extracts were washed with 10% potassium hydroxide solution (4×30 mL) and the aqueous extract was back-extracted with methylene chloride (2×40 mL). The combined organic extracts were washed with brine (2×40 mL) and dried (K2CO3). The solvent was removed by rotary evaporation to afford 9.14 g (62%) of 2-(but-3-ynyl)-1,3-dithiane as a pale yellow oil. 1H NMR (CDCl3)δ: 4.2 (t, 1H), 3.1-2.8 (m, 4H), 2.6-2.4 (m, 1H), 2.3-2.0 (m, 6H); IR (neat): 3286, 2908, 1421, 1272, 907 cm-1 ; GC retention time=3.11 min (88% area); TLC (silica gel, 90% hexane: 10% ethyl acetate) Rf=0.74.

Workup

  1. temperaturecooled to -20° C
  2. temperatureafter warming to room temperature
  3. stirringthe solution was stirred for 16 hours
  4. washThe solution was washed with water (2×20 mL)
  5. extractionthe aqueous extract
  6. washwas washed with additional methylene chloride (2×40 mL)
  7. washThe combined organic extracts were washed with 10% potassium hydroxide solution (4×30 mL)
  8. extractionthe aqueous extract
  9. washwas washed with additional methylene chloride (2×40 mL)
  10. washThe combined organic extracts were washed with 10% potassium hydroxide solution (4×30 mL)
  11. extractionthe aqueous extract
  12. extractionwas back-extracted with methylene chloride (2×40 mL)
  13. washThe combined organic extracts were washed with brine (2×40 mL)
  14. dry with materialdried (K2CO3)
  15. customThe solvent was removed by rotary evaporation

Sources & evidence

ORD record
ord-f0b85ff6b6f7437dbe0c74cafd86933e
Source dataset
uspto-grants-1989_10
Patent number
US04877779

Reaction notes

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