تفاعل #480136

ord-19f122d7136f4c22aeb42268e863abde

معادلة التفاعل

O=C([O-])[O-].[Cs+].[Cs+]
cesium carbonate
O[C@H](CN(Cc1cccc(OC(F)(F)F)c1)c1cccc(Br)c1)C(F)(F)F
(2R)-3-[[(3-bromophenyl)][[3-(trifluoromethoxy)phenyl]methyl]amino]-1,1,1-trifluoro-2-propanol
O=C(O)c1cccc2ccccc12
1-naphthoic acid
Cc1cc(O)ccc1F
4-fluoro-3-methylphenol
O=C([O-])[O-].[Cs+].[Cs+]
cesium carbonate
Cc1cc(Oc2cccc(N(Cc3cccc(OC(F)(F)F)c3)C[C@@H](O)C(F)(F)F)c2)ccc1F
(2R)-3-[[3-(4-fluoro-3-methylphenoxy)phenyl][[3-(trifluoromethoxy)phenyl]methyl]amino]-1,1,1-trifluoro-2-propanol
المردود 23.0%

ظروف التفاعل

درجة الحرارة
105°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    أخرىto the reaction three different times
  2. 2
    درجة الحرارةThe reaction was cooled to room temperature
  3. 3
    ترشيحfiltered through celite
  4. 4
    أخرىthe solvent was evaporated
  5. 5
    أخرىThe residue was purified by reverse phase HPLC
  6. 6
    غسيلeluting with 35% to 90% acetonitrile in water

الإجراء التجريبي

A suspension of 4-fluoro-3-methylphenol (98.0 μL, 0.88 mmol) and cesium carbonate (319.5 mg, 0.98 mmol) in 1 mL of N,N-dimethylacetamide was preheated at 60° C. for 5 minutes. To this solution was added 4 mL of a stock solution containing (2R)-3-[[(3-bromophenyl)][[3-(trifluoromethoxy)phenyl]methyl]amino]-1,1,1-trifluoro-2-propanol (200 mg, 0.437 mmol) from EX-33B, 1-naphthoic acid (164 mg, 0.95 mmol), copper(I) trifluoromethansulfonate benzene complex (21.8 mg, 0.0434 mmol), 4 Å sieves (105 mg), and 4 mL of toluene. The reaction mixture was stirred at 105° C. for 3 weeks and 2 days. During that time, additional cesium carbonate and catalyst were added (a spatula tip of each) to the reaction three different times. The reaction was cooled to room temperature, filtered through celite, and the solvent was evaporated. The residue was purified by reverse phase HPLC eluting with 35% to 90% acetonitrile in water to afford 50.5 mg (23%) of the desired (2R)-3-[[3-(4-fluoro-3-methylphenoxy)phenyl][[3-(trifluoromethoxy)phenyl]methyl]amino]-1,1,1-trifluoro-2-propanol product as an orange oil. HRMS calcd. for C24H20F7NO3: 504.1410 [M+H]+, found: 504.1389. 1H NMR (acetone-d6) δ 7.44 (t, 1H), 7.24 (d, 1H), 7.08-7.21 (m, 3H), 6.98 (t, 1H), 6.75-6.85 (m, 1H), 6.68-6.74 (m, 1H), 6.53 (d, 1H), 6.21-6.34 (m, 2H), 4.79 (t, 2H), 4.46-4.53 (m, 1H), 3.95 (dd, 1H), 2.61-2.72 (m, 1H), 2.20 (s, 3H).

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US06803388B2uspto-grants-2004_10