* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Tetrahedron Letters, 2000, vol. 41, # 16, p. 2987 - 2990
[2] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2012, vol. 90, p. 85 - 92
[3] Chemical Communications, 2013, vol. 49, # 97, p. 11430 - 11432
[4] Justus Liebigs Annalen der Chemie, 1903, vol. 327, p. 86
[5] Gazzetta Chimica Italiana, 1923, vol. 53, p. 503[6] Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1923, vol. <5> 32 I, p. 344
[7] Journal of Molecular Structure, 2017, vol. 1143, p. 344 - 354
With ethyl bromide; diethyl ether; magnesium weiteres Reagens: Toluol;
Stage #1: 5-bromoacenaphthene With n-butyllithium In tetrahydrofuran at -78℃; for 0.333333h; Inert atmosphere; Schlenk technique;
Stage #2: carbon dioxide In tetrahydrofuran at -78 - 20℃; Inert atmosphere; Schlenk technique;
Stage #1: 5-bromoacenaphthene With n-butyllithium In diethyl ether; hexane; toluene at -70 - -10℃; for 2h;
Stage #2: With Triisopropyl borate In diethyl ether; hexane; toluene at -70℃;
Stage #3: With hydrogenchloride; water In diethyl ether; hexane; toluene
9.A 1,2-dihydro-5-acenaphthylenylboronic acid
EXAMPLE 9A 1,2-dihydro-5-acenaphthylenylboronic acid The desired product was prepared by substituting 5-bromo-1,2-dihydroacenaphthylene for 3-bromo-1,1'-biphenyl in Example 6A. MS (DCI/NH3) m/z 216 (M+NH4)+; 1H NMR (300 MHz, CD3OD) δ 7.55 (dd, 2H), 7.45 (t, 1H), 7.25 (dd, 2H), 3.4 (s, 4H).
5-(acenaphth-5-yl)-2,3,7,8,12,13,17,18-octaethylporphyrin[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
26%
Stage #1: 5-bromoacenaphthene With n-butyllithium In diethyl ether; hexane at -60 - 20℃; Inert atmosphere;
Stage #2: 2,3,7,8,12,13,17,18-octaethyl-porphyrin In tetrahydrofuran; diethyl ether; hexane at -20℃; for 1h; Inert atmosphere; Further stages;
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 12h;Inert atmosphere;
5-bromo-1,2-dihydroacenaphthylene (100 mmol, 23.3 g) was added to a 1000 mL 2-necked round bottom flask,2-Boronobenzoic acid (100 mmol, 16.6 g), Pd (PPh3) 4 (3.0 mmol, 3.45 g) and K2CO3 (200 mmol, 27.7 g)Add 100 mL of water with tedrahydrofuran, fill with nitrogen, and stir at 80 C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature and extracted with dichloromethane. Then, the organic solvent layerAfter the water is removed, the solvent is removed by drying under reduced pressure. The obtained reaction productRecrystallization using ethanol gave 22.7 g of Sub 1-1 as a white solid. (Yield: 83%).
Stage #1: 5-bromoacenaphthene With tert.-butyl lithium In tetrahydrofuran at -78℃; for 2h; Inert atmosphere;
Stage #2: Triisopropyl borate In tetrahydrofuran at -78 - 20℃; Inert atmosphere;
Stage #3: With hydrogenchloride; water In tetrahydrofuran
With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 100℃; Inert atmosphere;
7 Synthesis of intermediate compound 7-2
Dissolve 10mmol of compound 1-1, 10mmol of compound 7-1, 0.1mmol of palladium catalyst Pd(dba)2, 0.2mmol of TTBP and 30mmol of sodium tert-butoxide in toluene solvent, stir at 100°C for 6h in a nitrogen atmosphere, and cool The solvent was removed by rotary evaporation, extracted and washed with water to separate the liquid, and the organic phase was separated by column chromatography to obtain 7.96 mmol of intermediate compound 7-2.Among them, the yield of intermediate compound 7-2 was 79.6%,
With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 100℃; Inert atmosphere;
8 Synthesis of intermediate compound 8-2
Dissolve 10mmol of compound 1-1, 10mmol of compound 8-1, 0.1mmol of palladium catalyst Pd(dba)2, 0.2mmol of TTBP and 30mmol of sodium tert-butoxide in toluene solvent, stir at 100°C for 6h in a nitrogen atmosphere, and cool The solvent was removed by rotary evaporation, extracted and washed with water to separate the liquid, and the organic phase was separated by column chromatography to obtain 7.32 mmol of intermediate compound 8-2.Among them, the yield of intermediate compound 8-2 was 73.2%,
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 100℃; Inert atmosphere;
1; 6; 7; 16 Synthesis of Intermediates 1-3:
Intermediates 1-1 (10mmol), 1-2 (10mmol) were dissolved in a mixed solvent of 1,4-dioxane and water (21/2ml), and Pd(PPh3)4(0.1) and Potassium carbonate (30 mmol).Under nitrogen atmosphere, stir at 100°C for 6h.After cooling, most of the solvent was removed by rotary evaporation, and then extracted and washed with water to separate the liquids. The organic phase was column chromatographed and recrystallized to obtain intermediate 1-3 with a molar weight of 7.18 mmol and a yield of 71.8%.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
