تفاعل #69952

ord-f69b0b8d89b34c5cb08116bccd469b1f

معادلة التفاعل

COB(OC)OC
trimethyl borate
O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
[Li][CH2]CCC
butyl lithium
CCCCCC
hexane
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
Clc1ccc(I)cc1
4-chloro-iodobenzene
CCc1sc(Br)cc1Br
3,5-dibromo-2-ethyl-thiophene
CCc1sc(-c2ccc(Cl)cc2)cc1Br
3-bromo-5-(4-chlorophenyl)-2-ethyl-thiophene
المردود 75.0%

المذيبات

ظروف التفاعل

درجة الحرارة
-78°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    workup.STIRRINGThe reaction is stirred at −78° C. for 30 minutes
  2. 2
    درجة الحرارةto warm to room temperature
  3. 3
    workup.STIRRINGstirred for a further 60 minutes
  4. 4
    درجة الحرارةthe reaction is heated
  5. 5
    درجة الحرارةto reflux for 3 hours
  6. 6
    أخرىThe cooled reaction mixture
  7. 7
    أخرىis partitioned between ether (250 ml) and water (300 ml)
  8. 8
    أخرىThe organic layer is separated
  9. 9
    تجفيفdried over magnesium sulphate
  10. 10
    ترشيحfiltered
  11. 11
    أخرىevaporated under reduced pressure
  12. 12
    أخرىThe residue is therefore purified by flash chromatography on silica gel

الإجراء التجريبي

To a solution of 3,5-dibromo-2-ethyl-thiophene (3.28 g, 12.15 mmol) in diethyl ether (50 ml) at −78° C. under N2 is added, slowly, 2.5M butyl lithium in hexane solution (4.86 ml, 12.15 mmol) over 10 minutes and the reaction stirred at −78° C. for a further 30 minutes. The reaction is then cooled to −78° C. before the dropwise addition of trimethyl borate (1.64 ml, 14.6 mmol) over 5 minutes. The reaction is stirred at −78° C. for 30 minutes, then allowed to warm to room temperature and stirred for a further 60 minutes. Palladium acetate (68 mg, 0.3 mmol), triphenylphosphine (314 mg, 1.2 mmol) and 4-chloro-iodobenzene (4.9 g, 12.15 mmol) is then added to the reaction, followed by THF (50 ml) and 1N sodium carbonate solution (20 ml) and the reaction is heated to reflux for 3 hours. The cooled reaction mixture is partitioned between ether (250 ml) and water (300 ml). The organic layer is separated, dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue is therefore purified by flash chromatography on silica gel to give 3-bromo-5-(4-chlorophenyl)-2-ethyl-thiophene as a white solid (2.75 g).

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US08530667B2uspto-grants-2013_09