2-BROMO-6-(BROMOMETHYL)NAPHTHALENE

169 g of (6-bromo-2-naphthyl) methanol and 1250 g of chloroform were placed in a reacting flask. phosphorus tribromide was dissolved in 180 ml of chloroform and slowly dropped into the reacting flask at room temperature in a nitrogen atmosphere to compose a mixture. The mixture was stirred for one-hour, and a white solid was precipitated after the mixture become transparent. Then, 750 ml of methanol was added to the mixture. After cold bathing and filtering, the solid obtained was further mixed with 750 ml of methanol solution again and stirred for 10 min. The solid was obtained by filtering the methanol solution and dried at 100° C. 110 g of (6-bromo-2bromomethyl) naphthalene was obtained (yield: 48.6percent; purity: 99.2percent). Third Act: Synthesization of Compound A, 2-[4-(N, N-diphenylamino)styryl]-6-bromo-naphthalenePreparation of starting material 2-bromo-6-(bromomethyl)naphthalene (1d) To a solution of (6-bromonaphthalen-2-yl)methanol (1.19 g, 5 mmol) in anhydrous EtKHMDS (0.5M in toluene, 12.0mL, 6.0mmol) was added dropwise to a stirred-78C solution of ethyl 4-methylvalerate (1.00mL, 6.0mmol) in anhydrous THF (10mL). The mixture was stirred at-78C for 30min before 55 (900mg, 3.0mmol) in THF (10mL) was added. After complete addition, the mixture was allowed to warm to room temperature and stirred overnight. The reaction was then quenched with water (20mL) and extracted with diethyl ether (2×30mL). The organic extracts were combined, washed with aqueous 2M HCl (10mL), water (10mL), brine (10mL), dried over MgSO4 and concentrated in vacuo. The resultant residue was dissolved in ethyl acetate and passed through a short silica plug (10cm). After concentration in vacuo the crude bromide (58) was dissolved in a mixture of anhydrous methanol (3mL) and DMF (9mL). Triethylamine (0.92mL, 6.6mmol) was added and the solution subsequently de-gassed. A flask containing Pd(OAc)2 (67mg, 0.3mmol) and DPPP (136mg, 0.33mmol) was briefly evacuated and backfilled with carbon monoxide three times. The de-gassed bromide solution was then added and the resultant mixture heated at 80C for 24h. The reaction was then quenched with water (20mL) and extracted with ethyl acetate (30mL). The organic phase was washed with aqueous 2M HCl (10mL), water (10mL), brine (10mL), dried over MgSO4 and concentrated in vacuo. The resultant residue was purified by flash chromatography (10% EtOAc in hexane) to afford 59 as a colourless oil (690mg, 67% over two steps); 1H NMR (400MHz, CDCl3) delta 8.56 (s, 1H, ArH), 8.03 (d, J=8.6Hz, 1H, ArH), 7.86 (d, J=8.6Hz, 1H, ArH), 7.80 (d, J=8.6Hz, 1H, ArH), 7.64 (s, 1H, ArH), 7.37 (d, J=8.6Hz, 1H, ArH), 4.01-3.98 (m, 2H, -CH(CO2CH2CH3)), 3.97 (s, 3H, -CO2CH3), 3.07 (dd, J=13.5 & 8.8Hz, 1H, ArCH2-), 2.98-2.80 (m, 2H, ArCH2CH-), 1.74-1.67 (m, 1H, -CH2CH(CH3)2), 1.65-1.55 (m, 1H, -CH2CH(CH3)2), 1.36-1.30 (m, 1H, -CH2CH(CH3)2), 1.05 (t, J=7.1Hz, 3H, -CH(CO2CH2CH3)), 0.91-0.89 (m, 6H, -CH(CH3)2); 13C NMR (100MHz, CDCl3) delta 175.6, 167.3, 139.8, 135.6, 131.2, 130.8, 129.3, 128.2, 127.7, 127.1, 126.9, 125.3, 60.1, 52.2, 45.6, 41.6, 39.3, 26.1, 23.0, 22.0, 14.1; HRMS-ESI calcd for C21H26O4 [M+ H]+ 243.1831; found 243.1832.To a stirring suspension of 60% NaH (1.2g, 30.0mmol) in anhydrous DMF (150mL) was added 2-methylpropan-1-ol (5.5mL, 60.0mmol). The mixture was stirred at room temperature for 4h before 55 (3.0g, 10.0mmol) was added. After complete addition, the reaction was stirred at room temperature for 3h before being quenched with water (50mL) and extracted with hexane (100mL). The organic layer was separated, dried over Na2SO4 and concentrated in vacuo. The resultant residue was purified by flash chromatography (2% EtOAc in hexane) to afford 56 as a colourless oil (2.7g, 92%); 1H NMR (400MHz, CDCl3) delta 7.99 (d, J=2.0Hz, 1H, ArH), 7.75 (s, 1H, ArH), 7.73 (d, J=8.8Hz, 1H, ArH), 7.69 (d, J=8.8Hz, 1H, ArH), 7.54 (dd, J=8.8 & 2.0Hz, 1H, ArH), 7.49 (dd, J=8.8 & 1.6Hz, 1H, ArH), 4.65 (s, 2H, ArCH2-), 3.29 (d, J=7.8Hz, 2H, -CH2CH(CH3)2), 2.00-1.90 (m, 1H, -CH2CH(CH3)2), 0.97 (d, J=6.4Hz, 6H, -CH2CH(CH3)2); 13C NMR (100MHz, CDCl3) delta 137.0, 133.9, 131.7, 129.7, 129.5, 129.4, 127.1, 126.7, 126.0, 119.6, 72.8, 28.56, 22.7, 19.4.

Molecular Weight:299.99
XLogP3:4.4
Rotatable Bond Count:1
Exact Mass:299.89723
Monoisotopic Mass:297.89928
Heavy Atom Count:13
Complexity:170
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes