تفاعل #2122499

ord-4a5cb7caa99746bfb61f14b73d2a214b

معادلة التفاعل

Ic1ccc(OCC2CC3C=CC2C3)cc1
8
Ic1ccc(OCC2CC3C=CC2C3)cc1
5-[[(p-iodophenyl)oxy]methyl]bicyclo[2.2.1]hept-2-ene
C[Si](C)(C)P(c1ccccc1)c1ccccc1
diphenyl(trimethylsilyl)phosphine
CCCCC
pentane
C1=CC2CC1CC2COc1ccc(P(c2ccccc2)c2ccccc2)cc1
compound
المردود 14.7%
C1=CC2CC1CC2COc1ccc(P(c2ccccc2)c2ccccc2)cc1
[p-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)phenyl]diphenylphosphine
المردود 14.7%

المذيبات

ظروف التفاعل

درجة الحرارة
70°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    أخرىevacuated
  2. 2
    أخرىpurged with nitrogen three times
  3. 3
    درجة الحرارةcooled to room temperature
  4. 4
    أخرىthe solvent evaporated under reduced pressure
  5. 5
    أخرىThe residue was chromatographed on a column of silica gel using first hexane
  6. 6
    أخرى9:1 hexane ethyl acetate as eluent to collect the product
  7. 7
    أخرىAfter evaporation of the solvent
  8. 8
    workup.ADDITIONthe product 9 (10 g), a mixture of endo and exo isomers
  9. 9
    أخرىwas obtained as white gummy material

الإجراء التجريبي

Bis(acetonitrile)dichloropalladium(II) (1 mmol) was placed in a Schlenk flask, stoppered with a septum and evacuated and purged with nitrogen three times. To this flask was then added a solution of 8 (0.038 mol) in 100 mL of anhydrous toluene and 9.6 g of diphenyl(trimethylsilyl)phosphine. The resulting deep purple solution was heated at 70° C. overnight, then cooled to room temperature and the solvent evaporated under reduced pressure. The residue was chromatographed on a column of silica gel using first hexane and then 9:1 hexane ethyl acetate as eluent to collect the product. After evaporation of the solvent, the product 9 (10 g), a mixture of endo and exo isomers, was obtained as white gummy material. Addition of 50 mL of hot pentane to this compound resulted in the separation of white crystalline compound (2.1 g). 1H NMR (500 MHz, 25° C., CDCl3): δ (endo isomer, ˜85%) 7.30 (m, 12H, Ar—H), 6.88 (m, 2H, Ar—H), 6.18 (m, 1H, olefinic), 5.98 (m, 1H, olefinic), 3.72 (m, 1H, nor-CH2), 3.57 (m 1H, nor-CH2), 3.04 (br s 1H), 2.88 (br s, 1H), 2.53 (m, 1H), 1.92 (m, 1H), 1.51 (d, |J|=8.0 Hz), 1.32 (d, |J|=8.2 Hz, 1H), 0.65 (m, 1H); (exo isomer, partial) 6.92 (m, 2H, Ar—H), 4.05 (m, 1H), 3.88 (m, 1H). 31P {1H} NMR (200 MHz, 25° C., CDCl3): δ −6.57

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US08574680B2uspto-grants-2013_11