Methanol → HCID 13928469, compound

HRID 1862189Notes

Reaction equation

HRID 1862189 reaction equation
[CH3:1][S-:2].[Na+].CO.[CH:6]([CH:8](Cl)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[CH2:7].C(OCC)C>O1CCCC1>[CH:6]([CH:8]([S:2][CH3:1])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[CH2:7]

Participants

6

Reactant 4

HCID 887MethanolHCID 3283Diethyl EtherHCID 4378561Sodium methanethiolate2×HCID 11768772Benzene, 1-(chloromethyl)-3(or 4)-ethenyl-2×

Product 1

HCID 13928469HCID 13928469, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Sodium methanethiolate (24.67 g, 0.35 mol) was combined with methanol (250 ml) in a 1 liter round bottomed flask outfitted with an addition funnel and a nitrogen inlet. Vinylbenzyl chloride (41.0 ml, 60:40 mixture of p- and o-isomers, 0.29 mol) in tetrahydrofuran (100 ml) was added via addition funnel over 30 minutes. The reaction mixture grew slightly warm and a milky suspension resulted. This was allowed to stir at room temperature for 20 hours at which point only a small amount of vinylbenzyl chloride was still evident by thin layer chromatography (2:1 hexanes/CH2Cl2 eluent). Another portion of sodium methanethiolate was added (5.25 g, 7.49×10−2 mol) and after ten minutes, the reaction had proceeded to completion by thin layer chromatography. Diethyl ether (400 ml) was added and the resulting mixture was extracted twice with 600 ml of water and once with 600 ml of brine. The resulting organic extracts were dried over magnesium sulfate, a small amount (about 1 mg) of 3-t-butyl-4-hydroxy-5-methyl phenyl sulfide was added, and the solvents were stripped by rotary evaporation to afford a yellowish oil. Purification by vacuum distillation through a long Vigreux column yielded 43.35 g (91%) of the pure product as a clear liquid.

Workup

  1. customoutfitted with an addition funnel and a nitrogen inlet
  2. temperatureThe reaction mixture grew slightly warm
  3. customa milky suspension resulted
  4. waitafter ten minutes
  5. extractionthe resulting mixture was extracted twice with 600 ml of water and once with 600 ml of brine
  6. dry with materialThe resulting organic extracts were dried over magnesium sulfate
  7. additiona small amount (about 1 mg) of 3-t-butyl-4-hydroxy-5-methyl phenyl sulfide was added
  8. customthe solvents were stripped by rotary evaporation
  9. customto afford a yellowish oil
  10. customPurification
  11. distillationby vacuum distillation through a long Vigreux column

Sources & evidence

ORD record
ord-ac2d3b3ea79640968799932df0a32659
Source dataset
uspto-grants-2003_03
Patent number
US06537730B1

Reaction notes

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