Diethyl Ether → 4-(Ethynyloxy)-1,1'-biphenyl

Temperatur

-78 °C

To a two-necked, round-bottomed flask (100 mL) equipped with a nitrogen inlet adapter and rubber septum was added the vinyl ether 2 (2.0 g, 7.6 mmol, 1 eq), anhydrous diethyl ether (30 mL), and TMEDA (23 mmol, 3.3 mL, 3 eq), and then cooled at −78° C. 2.5 M n-Butyllithium (9.0 mL, 23 mmol, 3 eq) was then added drop-wise to the reaction mixture for over 5 min. The reaction mixture was then maintained at −78 C for 1 h and at −40° C. for 40 min, and then cooled to −78° C. while 10% ethanol in pentane (10 mL) was added drop-wise. After 10 min, the reaction mixture was then diluted with n-pentane (20 mL) and the washed with saturated solution of ammonium chloride (25 mL). The organic phase was later washed twice with water (20 mL) and then finally with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated to give brown oil. The oil was purified by column chromatography with hexane as the eluent to yield 3 as dark brown oil (0.84 g, 70%) that later crystallized out as brown amorphous solid: mp 48-49° C. The compound was placed in a round bottom flask and was flushed with nitrogen and kept at −78° C. to avoid the decomposition if it was not to be used immediately. 1H NMR (300 MHz, CDCl3): 7.64-7.52 (m, 4H, HAr), 7.48-7.41 (m, 2H, HAr), 7.40-7.34 (m, 3H, HAr), 2.13 (s, 1H, ≡—H) ppm; 13C NMR (75 MHz, CDCl3): 155.0, 140.1, 138.0, 128.9, 128.4, 127.4, 127.0, 115.4, 84.5, 33.5 ppm; IR (cm−1): 3317 (≡C—H), 3029, 2927, 2174 (C≡C), 1606, 1512, 1484, 1208, 1166, 1062, 1008, 941, 838, 641, 548, 450; HRMS (ESI) Calculated for C14H10 [M−H]− 193.0654. Found 193.0651; Elemental analysis Calculated. for C14H10O.0.13H2O: C, 85.54; H, 5.26. found: C, 85.54; H, 5.38.

1. customTo a two-necked, round-bottomed flask (100 mL) equipped with a nitrogen inlet adapter
2. temperatureThe reaction mixture was then maintained at −78 C for 1 h and at −40° C. for 40 min
3. additionwas added drop-wise
4. washthe washed with saturated solution of ammonium chloride (25 mL)
5. washThe organic phase was later washed twice with water (20 mL)
6. dry with materialfinally with brine (20 mL), dried over anhydrous sodium sulfate
7. filtrationfiltered
8. concentrationconcentrated
9. customto give brown oil
10. customThe oil was purified by column chromatography with hexane as the eluent

ORD-Eintrag

ord-f0eccc755fae44e683d4c8d9497cb7b6

Quelldatensatz

uspto-grants-2016_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09393306B2