1-Bromopropane → Dicyclopentadiene

HRID 1196445Notes

Reaction equation

HRID 1196445 reaction equation
[CH:1]1[CH2:5][CH:4]=[CH:3][CH:2]=1.[CH:6]1[CH2:10][CH:9]=[CH:8][CH:7]=1.C1C(O)=CC=C(C)C=1.C(C(Cl)C1C=CC=CC=1)=C.C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C.[OH-].[K+].C(Br)CC>CN1CCCC1=O.CO.C1(C)C=CC=CC=1>[CH2:2]1[CH:1]2[CH:8]3[CH:7]=[CH:6][CH:10]([CH:5]2[CH:4]=[CH:3]1)[CH2:9]3

Participants

9

Reactant 5

HCID 78401-BromopropaneHCID 14797Potassium Hydroxide2×HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 11768772Benzene, 1-(chloromethyl)-3(or 4)-ethenyl-HCID 66623677HCID 66623677, compound

Product 1

HCID 6492Dicyclopentadiene

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 1140TolueneSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
60 °C

Procedure

318.5 grams of the para-cresol icyclopentadiene (PCDP) from above was dissolved in 1100 mL of N-methylpyrrolidinone (NMP) in a 2000 mL 3-neck round bottom flask equipped with mechanical stirrer, addition funnel, condenser, thermometer, nitrogen purge and Therm-O-Watch. To this reaction mixture was added 195.0 g (1.278 moles) of vinylbenzylchloride (60/40 para/meta isomer ratio) and 0.30 g of 2,6-di-tert-butyl-p-cresol (BHT). The reaction mixture was heated to 60° C. and 84.05 g (1.498 moles) of potassium hydroxide in 200 mL of methanol was added dropwise over a 3 hour interval. The reaction was maintained at 60° C. for 16 hrs with stirring under a nitrogen purge. To this reaction mixture was added 49.88 g (0.406 moles) of n-propylbromide, and then 24.43 g (0.435 moles) of potassium hydroxide in 125 mL of methanol added over a 2 hour interval. The reaction was maintained at 60° C. for 4 hours and then allowed to cool to room temperature. The reaction mixture was then transferred to a separatory funnel, and 1.5 Liters of toluene added and then washed once with 4 Liters of water and twice with saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated under vacuum, yielding a red resinous product; Mn=700, Mw=1600, dispersity of 2.3.

Workup

  1. customequipped with mechanical stirrer, addition funnel, condenser
  2. customthermometer, nitrogen purge
  3. temperatureThe reaction was maintained at 60° C. for 16 hrs
  4. custompurge
  5. temperatureThe reaction was maintained at 60° C. for 4 hours
  6. temperatureto cool to room temperature
  7. customThe reaction mixture was then transferred to a separatory funnel
  8. washwashed once with 4 Liters of water and twice with saturated sodium chloride solution
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under vacuum
  12. customyielding a red resinous product

Sources & evidence

ORD record
ord-5a1909285f574866aeabc4454beacf96
Source dataset
uspto-grants-1992_05
Patent number
US05114741

Reaction notes

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