Hydrochloric Acid → 1-(1-Trimethylsilylpropyl)-4-chlorobenzene

HRID 1197724Notes

Reaction equation

HRID 1197724 reaction equation
Cl[CH2:2][Si:3]([CH3:6])([CH3:5])[CH3:4].[Mg].[CH2:8](I)[CH3:9].C1(C)C(S(OCC[C:23]2[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=2)(=O)=O)=CC=CC=1.ClC1C=CC(CCO)=CC=1.C1(C)C(S(Cl)(=O)=O)=CC=CC=1.Cl>C(OCC)C.O1CCCC1>[CH3:4][Si:3]([CH3:6])([CH3:5])[CH:2]([C:23]1[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=1)[CH2:8][CH3:9]

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 6340IodoethaneHCID 8623o-Toluenesulfonyl chlorideHCID 74647p-Chlorophenethylic alcoholHCID 75361Silane, (chloromethyl)trimethyl-HCID 5462224MagnesiumHCID 867456882-(4-Chlorophenyl)ethyl toluenesulfonate

Product 1

HCID 199721521-(1-Trimethylsilylpropyl)-4-chlorobenzeneYield 75.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

12.3 g (0.1 mol) of commercially available chloromethyltrimethylsilane were dissolved in 100 ml of diethyl ether, and this solution was added dropwise over the course of one hour with stirring at 20° C. and under a protective gas to a mixture of 3 g of magnesium turnings, an initiating amount of 2 ml of the above mixture and a trace of ethyl iodide after the reaction had commenced. When the addition was complete, the mixture was refluxed for a further 30 minutes, then cooled and decanted from the excess magnesium. The solution obtained was added dropwise over the course of 30 minutes with stirring at 20°-30° C. to a solution of 22.7 g (0.1 mol) of 2-(4-chlorophenyl)ethyl toluenesulfonate (obtainable from commercially available 2-(4-chlorophenyl)ethanol by customary reaction with toluenesulfonyl chloride) in 100 ml of tetrahydrofuran. When the addition was complete, 100 ml of the solvent mixture were removed by distillation and replaced by 50 ml of tetrahydrofuran. The mixture was heated at an internal temperature of 60° C. for 60 minutes, during which a precipitate of magnesium tosylate formed. After cooling, the mixture was poured onto ice and acidified using a little hydrochloric acid, and the aqueous phase was extracted twice with tert.butyl methyl ether. The combined organic phases were washed with NaCl solution, dried and evaporated. Fractional distillation of the residue at 16 hPa and 115°-118° C. gave 17.1 g (75.4% of theory) of 1-(1-trimethylsilylpropyl)-4-chlorobenzene.

Workup

  1. additionthis solution was added dropwise over the course of one hour
  2. additionWhen the addition
  3. temperaturethe mixture was refluxed for a further 30 minutes
  4. temperaturecooled
  5. customdecanted from the excess magnesium
  6. customThe solution obtained
  7. additionwas added dropwise over the course of 30 minutes
  8. additionWhen the addition
  9. custom100 ml of the solvent mixture were removed by distillation
  10. customformed
  11. temperatureAfter cooling
  12. additionthe mixture was poured onto ice
  13. extractionthe aqueous phase was extracted twice with tert.butyl methyl ether
  14. washThe combined organic phases were washed with NaCl solution
  15. customdried
  16. customevaporated
  17. distillationFractional distillation of the residue at 16 hPa and 115°-118° C.

Sources & evidence

ORD record
ord-6adefb2c7edc4364af6e0d1d4fdb1c98
Source dataset
uspto-grants-1994_01
Patent number
US05277838

Reaction notes

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