(0.100 g, 23 yield more than 3 measures). TLC Rf = 0.1 (25 EtOAc/hexanes); mp 111.6- 113.6 ; 1H NMR (500 MHz, CDCl3) eight.64 (d, J = 7.six Hz, 2H), 7.67 (d, J = 7.9 Hz, 1H), 7.49 (d, J = 6.0 Hz, 2H), 7.07 (d, J = 1.three Hz, 1H), 4.21 (qd, J = 7.0, two.five Hz, 1H), three.91 (s, 3H), 2.27-2.21 (m, 1H), 1.47 (d, J = 7.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) 156.5, 150.1, 148.five, 138.0, 132.two, 128.four, 121.7, 119.5, 109.0, 87.1, 70.0, 55.six, 25.three, 22.6; IR (neat cm-1) 3156, 3042, 2930, 2099, 1596, 1454, 1227, 1032, 810; HRMS (DART, M+ + H) m/z 238.1259 (calculated for C16H16NO, 238.1232). 3-Methoxy-4-(1-methyl-prop-2-ynyl)-biphenyl-4-ol (20). As outlined by the general process for homologation, methoxymethyl triphenylphosphonium chloride (four.71 g, 13.73 mmol) in dry THF (37 mL), NaOtBu (1.58 g, 16.5 mmol), and ketone 11 (1.S-Adenosyl-L-methionine (tosylate) 79 g, 5.49 mmol) in THF (7 mL) have been stirred at 0 . Following the basic workup, the mixture of enol ethers (1.77 g, five.00 mmol) in THF/H2O (9:1, 17 mL) was hydrolyzed making use of Hg(OAc)two (four.8 g, 14.97 mmol) at space temperature. Right after the basic extraction process, aldehyde (1.564 g, 4.65 mmol) in MeOH (20 mL), the Ohira-Bestmann reagent (1.60 g, 8.four mmol) dissolved (11 mL) in MeOH, and powdered K2CO3 (1.337 g, 9.7 mmol) had been stirred at 0 . Following the basic workup and flash chromatography (SiO2, 30 g, 15 EtOAc/hexanes), O-THP alkyne was obtained as a pale white strong (0.(-)-(S)-Equol 84 g). Deprotection of O-THP alkyne was carried out by dissolving the protected alkyne (0.84 g, two.5 mmol) in MeOH (150 mL) and cooled to 0 . p- Toluenesulfonic acid (0.951 g, two.five mmol) was added and the reaction permitted to warm to room temperature. The reaction was followed by TLC, diluted with water, neutralized with sat NaHCO3, and extracted with ether. The organic extracts have been washed with brine, dried over MgSO4, and filtered. The filtrate was concentrated and purified by flash column chromatography (SiO2, 30g, 15 EtOAc/ hexanes) to offer the terminal acetylene 20 as a white solid (0.PMID:23376608 61 g, 43 yield over 4 steps); TLC Rf = 0.three (25 EtOAc/hexanes); mp 90.2-91 ; 1H NMR (500 MHz, CDCl3) 7.57 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 8.six Hz, 2H), 7.11 (dd, J = 7.9, 1.7 Hz, 1H), 6.98 (d, J = 1.6 Hz, 1H), 6.88 (d, J = eight.6 Hz, 2H), four.18 (qd, J = 7.0, 2.4 Hz, 1H), three.88 (s, 3H), two.20 (d, J = 2.5 Hz, 1H), 1.45 (d, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) 156.5, 155.3, 141.0, 134.3, 129.7, 128.6, 128.2, 119.four, 115.eight, 109.3, 87.eight, 69.5, 55.7, 25.three, 22.9; IR (neat cm-1) 3334. 3300, 2938, 1606, 1494, 1218, 807, 633; HRMS (DART, M+ + H) m/ z 253.1224 (calculated for C17H17O2, 253.1229). 3-Methoxy-4-methyl-4-(1-methyl-prop-2-ynyl)-biphenyl (21). According to the common process for homologation, methoxymethyl triphenylphosphonium chloride (1.07 g, 3.12 mmol) in dry THF (9 mL), NaOtBu (0.37g, three.9 mmol), and ketone 12 (0.376 g, 1.56 mmol) in THF (three mL) were stirred at 0 . Following the common workup, the mixture of enol ethers (0.375 g, 1.39 mmol) in THF/H2O (9:1, 5 mL) was hydrolyzed using Hg(OAc)2 (1.30g, four.1 mmol) at space temperature. Following the basic extraction procedure, aldehyde (0.141 g 0.60 mmol) in MeOH (3 mL), the Ohira-Bestmann reagent (0.160 g, 0.83 mmol) dissolved in MeOH (1 mL), and powdered K2CO3 (0.161 g, 1.16 mmol) have been stirred at 0 . Following the basic workup and flash chromatography (SiO2, 6 g, 2 EtOAc/hexanes), alkyne 21 was obtained as a colorless oil (0.017 g, 5 yield over three steps); TLC Rf = 0.two (2 EtOAc/hexanes); 1H NMR (500 MHz, CDCl3) 7.60 (d, J = 7.8 Hz, 1H.
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