* 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.
With dmap; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper(I) triflate; 5-[(2S)-pyrrolidine-2-yl]-1H-tetrazole In acetonitrile at 25℃; for 1 h;
General procedure: A round-bottom flask was charged with alcohol (2 mmol), CuOTf (0.1 mmol, 0.05 equiv) (S)-5-(pyrrolidin-2-yl)-1H-tetrazole (0.1 mmol, 0.05 equiv), TEMPO (0.1 mmol, 0.05 equiv), DMAP (0.15 mmol, 0.075 equiv) and CH3CN (5 ml). The reaction mixture was stirred at 25 °C open to air until the completion of the reaction, as monitored by TLC. After completion, CH3CN was evaporated under vacuum. The residue was then diluted with CH2Cl2 (5 ml) and filtered through a plug of silica gel to afford the desired product.
86%
With C35H28Cl2N5PRu; potassium <i>tert</i>-butylate In toluene at 50℃; for 6 h;
General procedure: using the complex 1 as catalyst in presence of a base following a general procedure. In a round-bottom flask, 1 mmol of substrate, 0.005mmol of catalyst (3.6mg) and 0.010 mmol of tBuOK (1.1mg) were mixed in 10mL toluene. The reaction mixture was heated at 50°C in aerobic condition with continuous stirring for 6h and then the solvent was evaporated with a rotary evaporator under reduced pressure. The crude product, thus obtained, was purified on preparative silica gel GF-254 TLC plate using ethyl acetate: hexane (1:10) solvent mixture as eluent. The oxidized products were characterized by NMR spectroscopy (See Figs. S4–S32).
80%
With 1-hydroxy-1H-1,2,3-benziodoxathiole 1,3,3-trioxide; Oxone; cetyltrimethylammonim bromide In water at 20℃; for 2 h; Green chemistry
General procedure: The alcohol (2 mmol) was added to a solution of IBS (0.02 mmol, 0.01 eq), oxone (2.2 mmol, 1.1 equiv.) and 3 wtpercent CTAB solution (5 mL). The mixture was stirred at room temperature. The reaction was monitored by TLC. After completion, the solution was extracted with CH2Cl2 (3 × 10 mL). The combined organic phase was then filtered through a pad of silica gel and evaporated under vacuum to afford the desired product.
Reference：
[1] Chemical Communications, 2003, # 6, p. 758 - 759
[2] Inorganic Chemistry, 2016, vol. 55, # 12, p. 6114 - 6123
[3] Inorganic Chemistry, 2017, vol. 56, # 22, p. 14084 - 14100
[4] Tetrahedron, 2014, vol. 70, # 52, p. 9791 - 9796
[5] Chemistry - A European Journal, 2016, vol. 22, # 26, p. 8814 - 8822
[6] Journal of Organic Chemistry, 2017, vol. 82, # 14, p. 7165 - 7175
[7] Inorganica Chimica Acta, 2019, vol. 484, p. 160 - 166
[8] Journal of Materials Chemistry, 2007, vol. 17, # 29, p. 3030 - 3036
[9] Journal of Chemical Research, 2014, vol. 38, # 7, p. 427 - 431
[10] Inorganic Chemistry, 2018, vol. 57, # 19, p. 11995 - 12009
[11] ACS Catalysis, 2018, vol. 8, # 6, p. 5425 - 5430
[12] Tetrahedron Letters, 2002, vol. 43, # 40, p. 7179 - 7183
[13] Journal of the American Chemical Society, 2014, vol. 136, # 21, p. 7543 - 7546
[14] Angewandte Chemie - International Edition, 2018, vol. 57, # 21, p. 6077 - 6081[15] Angew. Chem., 2018, vol. 130, p. 6185 - 6189,5
[16] Inorganic Chemistry, 2018, vol. 57, # 12, p. 6816 - 6824
2
[ 129-00-0 ]
[ 4885-02-3 ]
[ 3029-19-4 ]
Yield
Reaction Conditions
Operation in experiment
96%
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 2.5 h;
To a stirred CH2Cl2 (90 mL) solution of pyrene (2.022 g, 10 mmol) was added Cl2CHOCH3 (1.2 mL, 13 mmol) at 0 °C. To the solution was slowly added TiCl4 (2.0 mL, 18 mmol). The color of solution turned from yellow to purplish red. The mixture was stirred at 0 °C for 1 h and at room temperature for 1.5 h. The solution was poured into cold water (100 mL), and stirred until the color turned from purplish red to yellow. The mixture was extracted with CH2Cl2 (50 mL x 2). The combined organic layers were washed with brine (50 mL), separated, dried over MgSO4, filtered, and concentrated in vacuo to give 1-formylpyrene (2.24 g, 96percent yield). Yellow solid; 1H NMR (400 Mz, CDCl3) d 8.08-8.13 (m, 2H), 8.23-8.36 (m, 5H), 8.47 (d, J = 8.0 Hz, 1H), 9.45 (d, J = 9.6 Hz, 1H), 10.80 (s, 1H) ppm. To a stirred CH2Cl2 (20 mL) solution of 1-formylpyrene (0.46 g, 2 mmol) was added m-CPBA (0.68 g, 3 mmol), and the resulting solution was stirred at reflux for 24 h, then concentrated in vacuo. To the residue was added THF (5 mL), MeOH (5 mL), and 25percent KOH aq (0.6 mL), giving a mixture that was stirred at room temperature for 4 h, then concentrated in vacuo. The residue was dissolved in 2percent KOH aq (10 mL). The solution was extracted with CH2Cl2 (10 mL x 2). The combined organic layers were washed with ice-cooled HCl aq (pH = 2), separated, dried over MgSO4, filtered, and concentrated in vacuo, giving as residue that was subjected to silica gel column chromatography (eluent; CHCl3, Rf = 0.3) to give 1-hydroxypyrene (3, 0.223 g, 50percent yield). Gray solid; 1H NMR (400 Mz, CDCl3) d 5.70 (brs, 1H), 7.48 (d, J = 6.4 Hz, 1H), 7.91 (d, J = 8.8 Hz, 1H), 7.96-7.99 (m, 2H), 8.03-8.07 (m, 2H), 8.10-8.13 (m, 2H), 8.35 (d, J = 7.6 Hz, 1H).
Reference：
[1] Tetrahedron Letters, 2017, vol. 58, # 46, p. 4377 - 4380
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1993, # 24, p. 3127 - 3138
[3] Organic Preparations and Procedures International, 1997, vol. 29, # 3, p. 321 - 330
[4] Journal of the American Chemical Society, 2008, vol. 130, p. 12846 - 12847
[5] ACS Catalysis, 2016, vol. 6, # 11, p. 7398 - 7408
3
[ 129-00-0 ]
[ 39828-35-8 ]
[ 3029-19-4 ]
[ 273736-52-0 ]
Yield
Reaction Conditions
Operation in experiment
86%
With hydrogenchloride In dichloromethane
1-(2,4-Dimethoxybenzoyl)pyrene (2a) Pyrene (10,1 g; 0.05 mol) and 2,4-dimethoxybenzoyl chloride (10 g; 0.05 mol) were dissolved in 400 ml of anhydrous methylene chloride. Anhydrous aluminium chloride (6.6 g; 0.05 mol) was added to the reaction mixture in small portions over 1 h at 0° C. with intense stirring. The reaction mixture was stirred for another 2 h at 0° C., 2 h at rt and then poured onto a mixture of ice and HCl (500 ml) and transferred into a separating funnel. The organic layer was washed with water (1*500 ml), saturated NaHCO3 (2*500 ml) and saturated NaCl (1*500 ml). The organic fraction was evaporated and recrystallized from toluene to give pyrenylketone as white solid (15.7 g; 86percent). Found: C, 82.09; H, 4.81. C25H18O3 (MW 366.41) requires C, 81.95; H, 4.95percent. 1H-NMR (CDCl3, d): 8.65-6.45 (m, 12 H, arom.), 3.91 (s, 3H, OCH3), 3.55 (s, 3H, OCH3). Mass-spectrum, MALDI-TOF: 388.89 (MI+Na; 15), 366.89 (100), 203.82 (40). Calculated exact mass for C25H18O3: 366.12559; found 366.12617 [1.6 ppm error].
Reference：
[1] Patent: US2003/175742, 2003, A1,
4
[ 24463-15-8 ]
[ 16640-68-9 ]
[ 3029-19-4 ]
[ 103698-30-2 ]
Reference：
[1] Angewandte Chemie - International Edition, 2002, vol. 41, # 24, p. 4740 - 4743
5
[ 129-00-0 ]
[ 68-12-2 ]
[ 3029-19-4 ]
Reference：
[1] Journal of the Indian Chemical Society, 2008, vol. 85, # 9, p. 959 - 961
[2] Dyes and Pigments, 2011, vol. 89, # 3, p. 199 - 211
[3] Frontiers of Chemistry in China, 2010, vol. 5, # 2, p. 193 - 199
[4] New Journal of Chemistry, 2018, vol. 42, # 22, p. 18297 - 18304
6
[ 24463-15-8 ]
[ 16640-68-9 ]
[ 3029-19-4 ]
[ 74833-81-1 ]
Reference：
[1] European Journal of Organic Chemistry, 2006, # 19, p. 4367 - 4378
7
[ 1714-29-0 ]
[ 68-12-2 ]
[ 3029-19-4 ]
Reference：
[1] Organic Syntheses, 2016, vol. 93, p. 100 - 114
[2] Russian Chemical Bulletin, 2014, vol. 63, # 6, p. 1312 - 1316[3] Izv. Akad. Nauk, Ser. Khim., 2014, # 6, p. 1312 - 1316,5
8
[ 2381-21-7 ]
[ 3029-19-4 ]
Reference：
[1] Journal of Organic Chemistry, 1983, vol. 48, # 5, p. 749 - 751
9
[ 164461-18-1 ]
[ 298-12-4 ]
[ 3029-19-4 ]
Reference：
[1] Angewandte Chemie - International Edition, 2017, vol. 56, # 28, p. 8201 - 8205[2] Angew. Chem., 2017, vol. 129, # 28, p. 8313 - 8317,5
10
[ 129-00-0 ]
[ 93-61-8 ]
[ 3029-19-4 ]
Reference：
[1] Chemistry - A European Journal, 2009, vol. 15, # 47, p. 12941 - 12944
[2] Chemistry - A European Journal, 2010, vol. 16, # 30, p. 9154 - 9163
[3] Justus Liebigs Annalen der Chemie, 1937, vol. 531, p. 1,35, 107
11
[ 93265-41-9 ]
[ 3029-19-4 ]
Reference：
[1] Journal of the American Chemical Society, 1986, vol. 108, # 15, p. 4498 - 4504
[2] Journal of the American Chemical Society, 1986, vol. 108, # 15, p. 4498 - 4504
[3] Journal of the American Chemical Society, 1986, vol. 108, # 15, p. 4498 - 4504
Reference：
[1] Journal of Physical Chemistry, 1985, vol. 89, # 4, p. 670 - 673
35
[ 129-00-0 ]
[ 95-50-1 ]
[ 93-61-8 ]
[ 10025-87-3 ]
[ 3029-19-4 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1937, vol. 531, p. 1,35, 107
36
[ 67-56-1 ]
[ 220196-58-7 ]
[ 3029-19-4 ]
[ 24463-15-8 ]
[ 91385-15-8 ]
Reference：
[1] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 10, p. 1927 - 1932
37
[ 67-56-1 ]
[ 220196-58-7 ]
[ 142-08-5 ]
[ 822-89-9 ]
[ 3029-19-4 ]
[ 91385-15-8 ]
Reference：
[1] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 10, p. 1927 - 1932
38
[ 3029-19-4 ]
[ 24463-15-8 ]
Yield
Reaction Conditions
Operation in experiment
88%
With sodium tetrahydroborate In tetrahydrofuran; methanol
Pyrene-aldehyde (1 g, 4.3 mmol) anddry tetrahydrofuran (20 mL) were placed in a round bottom flask.Sodium borohydride (165 mg, 4.3 mmol) was added in small portions,together with small portions of methanol to help the solubilization(total volume of added methanol = 10 mL). An orangesolution was obtained. The reaction was quenched with a 2percent concentratedhydrochloric acid solution. The solvent was removedunder reduced pressure. The white powder obtained was dissolvedin dichloromethane, washed with water and the organic phase wasdried with magnesium sulphate. The solvent was removed underreduce pressure. The resulting solid was subjected to silica gel columnchromatography (eluent = dichloromethane). Yield = 88percent.1H NMR (300 MHz, CDCl3, 300 K): d (ppm) = 1.87 (s, 1H); 5.39 (s,2H); 7.9–8.4 (m, 9H). 13C NMR {1H} (75 MHz, CDCl3, 300 K): d(ppm) = 6403; 123.15; 124.87; 124.93; 125.13; 125.42; 125.45;126.14; 126.19; 127.54; 127.63; 128.07; 128.97; 130.95; 131.42;131.44; 133.94. ESI-MS: m/z = 254.97 [M+Na]+, 214.99 [MOH]+(Calcd. for C17H12O:: 232.09 (exact mass); 232.28 (FW)). UV–Vis(DCM): kmax (nm) = 314; 327; 344.
81%
With sodium tetrahydroborate In methanol at 0 - 20℃;
1-pyrenecarboxaldehyde (0.35 g, 1.50 mmol) was dissolved in15 mL methanol, and NaBH4 (0.08 g, 2.10 mmol) was added slowly into the reaction mixture at 0 °C for 30 min. After stirring at room temperature overnight, 20 mL 5percent HCl was added in the reaction to quench the excess NaBH4, and the solution changed to milk-white suspension. The organic solvent was removed and then the solid was extracted with ethyl acetate (3 × 15 mL). The organic fractions were washed with saturated NaHCO3 aqueous solution. The collected organic solution was dried with sodium sulfate and was concentrated to give compound 8 in an 81percent yield. 1H NMR (400MHz, CDCl3) δ 8.30–7.96 (m, 9 H, Ar–H),5.33 (s, 2 H, CH2). TOF-MS: m/z 231.1[M–H]−.
75%
With sodium tetrahydroborate In tetrahydrofuran; ethanol at 0 - 20℃; for 5 h;
To a solution of pyrene aldehyde 13 (1.0 g, 4.34 mmol) in THF/Ethanol (10 mL: 30 mL) at 0 °C, NaBH4 (0.83 g, 21.71 mmol) was slowly added in five portions. The reaction mixture was slowly raised to rt and stirred for 5 h. It was then poured into ice-water (100 mL) containing 10 mL of Conc. HCl. The reaction mixture was extracted with CHCl3 (3 x 25 mL). The combined organic layer was washed with water and dried (Na2SO4). Removal of solvent under reduced pressure afforded pyrenyl methanol 15 (0.76 g, 75percent) as a pale yellow solid. mp 124-125 °C (Lit. 123-124 °C); 1H-NMR (300 MHz, CDCl3): δ 8.24 (d, J = 9.3 Hz, 1 H, ArH), 8.13 (t, J = 7.5 Hz, 2 H, ArH), 8.06-8.01 (m, 2 H, ArH), 7.99-7.918 (m, 4 H, ArH), 5.28 (s, 2 H, OCH2), 2.03 (s, 1 H, OH) ppm. 13C-NMR (75 MHz, CDCl3): δ 133.7 (C), 131.2 (2C), 131.1 (C), 130.7 (C), 128.7 (C), 127.8 (C-H), 127.4 (C-H), 127.3 (C-H), 125.9 (C-H), 125.9 (2C-H), 125.2 (C-H), 125.2 (C-H), 124.6 (C), 122.9 (C-H), 63.7 (Ar-CH2) ppm.
54 %Chromat.
With sodium hydroxide In isopropyl alcohol at 82℃; for 2 h;
General procedure: In a typical procedure, a 5 mg (0.77 molpercent) of RuO2/MWCNT and 80 mg (2 mmol) of NaOH were stirred with 5 mL of i-PrOH taken in an ace pressure tube equipped with a stirring bar. Then the substrate (1 mmol) was added to the stirring solution and then the mixture was heated at 82°C. The completion of the reaction was monitored by GC. After the reaction, the catalyst was separated out from the reaction mixture by simple centrifugation and the products and unconverted reactants were analyzed by GC without any purification. Selectivity of the product for each reaction was alsocalculated. Finally, the separated RuO2/MWCNT was washed well with diethyl ether followed by drying in an oven at 60°C for 5 h and it was reused for the subsequent transfer hydrogenation of carbonyl compounds to investigate the reusability of the RuO2/MWCNT.
Reference：
[1] Molecules, 2011, vol. 16, # 8, p. 6950 - 6968
[2] Journal of the American Chemical Society, [3] Journal of the American Chemical Society, 2008, vol. 130, p. 12846 - 12847
[4] Analytical Chemistry, 2018, vol. 90, # 2, p. 1402 - 1407
[5] Journal of Physical Chemistry A, 2003, vol. 107, # 40, p. 8363 - 8370
[6] Inorganic Chemistry, 2017, vol. 56, # 22, p. 13715 - 13731
[7] Chemistry - A European Journal, 2010, vol. 16, # 30, p. 9154 - 9163
[8] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 2, p. 413 - 420
[9] Journal of Medicinal Chemistry, 1990, vol. 33, # 9, p. 2385 - 2393
[10] Organic Preparations and Procedures International, 1998, vol. 30, # 2, p. 203 - 210
[11] Chemical Communications, 2013, vol. 49, # 5, p. 478 - 480
[12] Tetrahedron Letters, 1991, vol. 32, # 44, p. 6347 - 6350
[13] Journal of the Chemical Society, Faraday Transactions, 1993, vol. 89, # 6, p. 891 - 904
[14] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2016, vol. 159, p. 209 - 218
[15] Journal of the American Chemical Society, 2012, vol. 134, # 46, p. 18883 - 18885
[16] Synthetic Communications, 2016, vol. 46, # 22, p. 1810 - 1819
[17] Bulletin of the Chemical Society of Japan, 1990, vol. 63, # 10, p. 2881 - 2890
[18] Journal of the American Chemical Society, 1941, vol. 63, p. 2494,2496
[19] Journal of the American Chemical Society, 1941, vol. 63, p. 2494,2496
[20] Journal of the Chemical Society, 1965, p. 5920 - 5926
[21] Helvetica Chimica Acta, 1955, vol. 38, p. 2009,2020
[22] Journal of Organic Chemistry, 1997, vol. 62, # 17, p. 5804 - 5810
[23] Journal fuer Praktische Chemie (Leipzig), 1958, vol. <4> 6, p. 80
[24] Bulletin de la Societe Chimique de France, 1954, p. 615,617
[25] Bulletin of the Chemical Society of Japan, 1973, vol. 46, p. 358 - 363
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[27] Nucleosides and Nucleotides, 1996, vol. 15, # 5, p. 1029 - 1039
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[29] Chemistry - A European Journal, 2007, vol. 13, # 11, p. 3169 - 3176
[30] Tetrahedron Letters, 1987, vol. 28, # 6, p. 679 - 682
[31] Organic Letters, 2009, vol. 11, # 19, p. 4294 - 4297
[32] Organic Letters, 2010, vol. 12, # 18, p. 4014 - 4017
[33] Chemical Communications, 2012, vol. 48, # 38, p. 4567 - 4569
[34] Tetrahedron, 2013, vol. 69, # 23, p. 4536 - 4540
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[38] Chemical Science, 2015, vol. 6, # 8, p. 4978 - 4985
[39] Dalton Transactions, 2018, vol. 47, # 7, p. 2352 - 2359
[40] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2018, vol. 204, p. 425 - 431
[41] Tetrahedron Letters, 2019, vol. 60, # 1, p. 59 - 62
With sodium tetrahydroborate; In tetrahydrofuran; methanol;
Pyrene-aldehyde (1 g, 4.3 mmol) anddry tetrahydrofuran (20 mL) were placed in a round bottom flask.Sodium borohydride (165 mg, 4.3 mmol) was added in small portions,together with small portions of methanol to help the solubilization(total volume of added methanol = 10 mL). An orangesolution was obtained. The reaction was quenched with a 2% concentratedhydrochloric acid solution. The solvent was removedunder reduced pressure. The white powder obtained was dissolvedin dichloromethane, washed with water and the organic phase wasdried with magnesium sulphate. The solvent was removed underreduce pressure. The resulting solid was subjected to silica gel columnchromatography (eluent = dichloromethane). Yield = 88%.1H NMR (300 MHz, CDCl3, 300 K): d (ppm) = 1.87 (s, 1H); 5.39 (s,2H); 7.9-8.4 (m, 9H). 13C NMR {1H} (75 MHz, CDCl3, 300 K): d(ppm) = 6403; 123.15; 124.87; 124.93; 125.13; 125.42; 125.45;126.14; 126.19; 127.54; 127.63; 128.07; 128.97; 130.95; 131.42;131.44; 133.94. ESI-MS: m/z = 254.97 [M+Na]+, 214.99 [MOH]+(Calcd. for C17H12O:: 232.09 (exact mass); 232.28 (FW)). UV-Vis(DCM): kmax (nm) = 314; 327; 344.
81%
With sodium tetrahydroborate; In methanol; at 0 - 20℃;
1-pyrenecarboxaldehyde (0.35 g, 1.50 mmol) was dissolved in15 mL methanol, and NaBH4 (0.08 g, 2.10 mmol) was added slowly into the reaction mixture at 0 C for 30 min. After stirring at room temperature overnight, 20 mL 5% HCl was added in the reaction to quench the excess NaBH4, and the solution changed to milk-white suspension. The organic solvent was removed and then the solid was extracted with ethyl acetate (3 × 15 mL). The organic fractions were washed with saturated NaHCO3 aqueous solution. The collected organic solution was dried with sodium sulfate and was concentrated to give compound 8 in an 81% yield. 1H NMR (400MHz, CDCl3) delta 8.30-7.96 (m, 9 H, Ar-H),5.33 (s, 2 H, CH2). TOF-MS: m/z 231.1[M-H]-.
75%
With sodium tetrahydroborate; In tetrahydrofuran; ethanol; at 0 - 20℃; for 5.0h;
To a solution of pyrene aldehyde 13 (1.0 g, 4.34 mmol) in THF/Ethanol (10 mL: 30 mL) at 0 C, NaBH4 (0.83 g, 21.71 mmol) was slowly added in five portions. The reaction mixture was slowly raised to rt and stirred for 5 h. It was then poured into ice-water (100 mL) containing 10 mL of Conc. HCl. The reaction mixture was extracted with CHCl3 (3 x 25 mL). The combined organic layer was washed with water and dried (Na2SO4). Removal of solvent under reduced pressure afforded pyrenyl methanol 15 (0.76 g, 75%) as a pale yellow solid. mp 124-125 C (Lit. 123-124 C); 1H-NMR (300 MHz, CDCl3): delta 8.24 (d, J = 9.3 Hz, 1 H, ArH), 8.13 (t, J = 7.5 Hz, 2 H, ArH), 8.06-8.01 (m, 2 H, ArH), 7.99-7.918 (m, 4 H, ArH), 5.28 (s, 2 H, OCH2), 2.03 (s, 1 H, OH) ppm. 13C-NMR (75 MHz, CDCl3): delta 133.7 (C), 131.2 (2C), 131.1 (C), 130.7 (C), 128.7 (C), 127.8 (C-H), 127.4 (C-H), 127.3 (C-H), 125.9 (C-H), 125.9 (2C-H), 125.2 (C-H), 125.2 (C-H), 124.6 (C), 122.9 (C-H), 63.7 (Ar-CH2) ppm.
With sodium tetrahydroborate;
The intermediate 2 was synthesized by the reduction of aldehyde group of 1-pyrenecarboxaldehyde into hydroxyl group using NaBH4 and the esterification of 1-pyrenemethanol with 2-carboxyethyl disulfide. 1-Pyrenecarboxaldehyde (2 g, 8.7 mmol) was dissolved in 50 mL of CH3OH and NaBH4 (3 g, 79.2 mmol) was added to the solution, rendering the solvent turn from yellow to colorless. The mixture was stirred for 3 h at room temperature. After the removal of solvent by rotary evaporation, 100 mL of water was added to the flask. Then CH2Cl2 was used to extract the product for three times, and the resulting solution was dried over anhydrous MgSO4, and evaporated to get the crude product of 1-pyrenemethanol.
54%Chromat.
With sodium hydroxide; In isopropyl alcohol; at 82℃; for 2.0h;
General procedure: In a typical procedure, a 5 mg (0.77 mol%) of RuO2/MWCNT and 80 mg (2 mmol) of NaOH were stirred with 5 mL of i-PrOH taken in an ace pressure tube equipped with a stirring bar. Then the substrate (1 mmol) was added to the stirring solution and then the mixture was heated at 82C. The completion of the reaction was monitored by GC. After the reaction, the catalyst was separated out from the reaction mixture by simple centrifugation and the products and unconverted reactants were analyzed by GC without any purification. Selectivity of the product for each reaction was alsocalculated. Finally, the separated RuO2/MWCNT was washed well with diethyl ether followed by drying in an oven at 60C for 5 h and it was reused for the subsequent transfer hydrogenation of carbonyl compounds to investigate the reusability of the RuO2/MWCNT.
With sodium tetrahydroborate; In methanol; at 0 - 20℃; for 5.0h;Reflux;
1-Pyrenecarboxaldehyde (1e) was purchased from Sigma-Aldrichand used as received. 1d (pyren-1-ylmethanol), 1c (1-(bromomethyl)pyrene) and 1b (diethyl (pyren-1-ylmethyl)phosphonate) were synthesizedfollowing previous reports with some modifications [14,16-22]. Briefly, the procedure to synthesize 1b is as follows: 1e (230 mg, 1.0 mmol) was poured into anhydrous methanol (40 ml)resulting into a suspension and to this excess of NaBH4 (380 mg,10.0 mmol) was added in portions at 0 C. The mixture was stirred for1 h at room temperature and then refluxed for 4 h. The mixture wascooled and saturated aq. NH4Cl was added to get a white precipitate. Itwas extracted with dichloromethane (5 × 10 ml) and dried with anhydrousNa2SO4. The solvent was evaporated to obtain a pale yellowcoloured solid 1d. Thus obtained 1d (186 mg, 0.8 mmol) was takeninto dry THF (4 ml) forming a suspension and PBr3 (0.114 ml,1.2 mmol) and was added to the mixture. The mixture was stirred for1 h at room temperature. The residue was filtered and washed withEt2O to give the desired product 1c. The mixture of 1c (147 mg,0.5 mmol) and an excess amount of triethyl phosphite (2 ml) wastaken in CHCl3 (10 ml) and refluxed overnight in inert atmosphere.The mixture was settled down to room temperature and the excesstriethyl phosphite was evaporated under reduced pressure. The crudeproduct was purified by column chromatography using 1-10% methanol/dichloromethane to give white coloured 1b. An excess amount ofNaH (43 mg, 1.8 mmol, 6 equiv.) was added gradually to a solution ofphosphonate derivative 1b (106 mg, 0.3 mmol) in dry THF (30 ml)and the mixture was stirred for 1 h at room temperature. To this,terephthalaldehyde (41mg, 0.3mmol)was added at once. Themixturewas stirred overnight in dark at room temperature. 10 ml of distilledwater was added upon completion of the reaction to destroy excessNaH present in the solution. The solvents were evaporated using a rotaryevaporator (procured fromCitizen) and the crude product was purifiedby column chromatography using 10-60% of hexane/dichloromethane mixture as eluent. The solvents were evaporated toobtain the orange-yellow coloured 1a ((E)-4-(2-(pyren-1-yl)vinyl)benzaldehyde). The mixture of 1a (33.2 mg, 0.1 mmol) and 3-ethyl-2-methylbenzothiazolium iodide (43 mg, 0.14 mmol) was dissolved inmethanol (20 ml). An excess amount of NaOMe (~10 equiv.) wasadded to the mixture and refluxed overnight. The initial yellowsolutionturned intowine-red coloured solution at the end of reflux. Themixturewas cooled to room temperature and methanol was evaporated. Thewhole process has been represented by Scheme 2. The crude productwaswashedwith distilledwater, dried and purified by column chromatographyusing 1-10% methanol/dichloromethane mixture as eluent toobtain the red-brown coloured 1 (3-ethyl-2-((Z)-4-((E)-2-(pyren-1-yl)vinyl)styryl)benzo[d]thiazol-3-ium) (Scheme 1). 1H NMR (400 MHz,DMSO d6): delta (ppm) 8.857 (d, 1H, J = 9.92 Hz), 8.655 (d, 1H, J =16.04 Hz), 8.592 (d, 1H, J = 8.40 Hz), 8.460 (d, 1H, J = 8.4 Hz),8.368-8.286 (m, 6H), 8.221 (s, 2H), 8.183 (d, 2H, J = 8.4Hz),8.123-8.089 (m, 4 H), 7.900 (t, 1H, J = 7.26 Hz), 7.814 (t, 1H, J =8.02 Hz), 7.704 (d, 1H, J = 16.04 Hz), 5.013 (q, 2H, J=7.12 Hz), 1.514(t, 3H, J = 7.26 Hz), ESI-MS (m/z): calculated - 492.18, found - 493.19[M + H]+.
With trichlorophosphate at 100℃; for 6h; Inert atmosphere;
70%
With trichlorophosphate at 20 - 100℃; for 6h; Inert atmosphere;
With 1,2-dichloro-benzene; trichlorophosphate at 90 - 95℃; Behandeln des Reaktionsprodukts mit Wasser;
Stage #1: N-methyl-N-phenylformamide With trichlorophosphate In 1,2-dichloro-benzene at 20℃; for 0.25h; Inert atmosphere;
Stage #2: pyrene In 1,2-dichloro-benzene at 85℃; for 18h; Inert atmosphere;
18 Synthesis of 1-formylpyrene:
To 250 mL of a three-necked flask containing N-methylformanilide (11 g, 54.4 mmol) and freshly distilled o-dichlorobenzene (20 mL) was added dropwise phosphorus oxychloride (11.0 g, 71.7 mmol). The mixture was stirred at room temperature for 15 min under nitrogen. Pyrene was added (8.8g, 44mmol), stirred under a nitrogen atmosphere was heated 85 18h. A concentrated solution of sodium acetate (50 g) was added and stirring was continued for 2 h. Extract three times with dichloromethane, wash three times with water, dry the organic phase, and concentrate the solution by evaporation. After standing overnight, a brownish yellow solid product was isolated.
With potassium permanganate; In water; acetone; at 80℃; for 3h;
First weighed 2.09g(About 0.0091 mol) pyrene Formaldehyde was placed in a round bottom flask,After adding 20.0ml of acetone dissolved.To a round bottom flask was added KMnO4 5.0g,Continue to add 15.0ml of deionized water to dissolve,Stir well.The round bottom flask was placed in an oil bath at 80 heating 3h,After the reaction is completed,Cool and filter.A sufficient amount of sodium carbonate was added to the filtrate until the filtrate had a pH of 8.5,And washed three times with CH 2 Cl 2 to remove unreacted starting material.Liquid separation,Take water solution.With dilute hydrochloric acid solution pH is adjusted to about 2.0,At this time a large number of precipitation precipitation,Filtered to give a precipitate.1.8 g was obtained after vacuum drying the precipitate(About 0.0073 mol)Pyrene formic acid,The yield is 80.39%.
62.6%
With potassium permanganate; water; In acetone; at 80℃; for 3h;
To a solution of 1-pyrenecarboxaldehyde (1.5 g, 6.5 mmol) in dryacetone (20.0 mL), potassium permanganate (4.0 g) dissolved indistilled water (20.0 mL) was added. The resulting mixture was refluxedat 80 C for 3 h, under the monitoring of thin-layer chromatography(TLC). Thereafter, the mixture was cooled to room temperature andfiltered. The filtrate was then adjusted to a pH of ~8.5 with sodiumcarbonate solution, and washed with dichloromethane three times toremove unreacted raw material. The aqueous solution was adjusted a pHof ~2.0 with dilute hydrochloric acid, and solid precipitate appeared.The precipitate was collected and vacuum-dried to obtain light yellowsolids (1.0 g, 62.6%).
Stage #1: 5-hydroxypentylamine; pyrene-1-aldehyde With toluene-4-sulfonic acid In toluene for 66h; Reflux;
Stage #2: With sodium tetrahydroborate In ethanol; toluene at 20℃; for 18h;
Alternative synthesis of 3
Pyrene carboxaldehyde 1 (1.15 g, 5.0 mmol), 5-amino-1-pentanol (660 mg, 6.40 mmol) and p-TsOH (23 mg) were dissolved in toluene and the mixture was refluxed for 18 h. Water was removed by adapting a Dean Stark trap. An additional portion of 5-amino-1-pentanol (500 mg, 4.8 mmol) was then added. Further heating under the same conditions for a 48 h period, revealed the corresponding imine as an elongated spot by CCD (EtOAc). The solution was cooled at room temperature and EtOH (25 mL) and NaBH4 (378 mg, 10 mmol) were added. The reaction proceeded for 18 h. 1 M Hydrochloric acid solution was added until pH 5. After evaporation of the sample, the residue was extracted with CH2Cl2. Final purification by silica gel column chromatography by elution with CHCl3:MeOH (9:1) → (7:3) was achieved, to obtain 4 (1.11 g, 70% yield). 1H-RMN (200 MHz, CD3OD): δ 8.39-8.01 (m, 9H, H-aromatic), 4.73 (t, 2H, CH2Ar), 3.56 (t, J = 6.2 Hz, CH2OH), 3.04 (m, 2H, CH2NH), 1.81-1.39 (m, 6H, 3 × CH2); 13C RMN (50.3 MHz, CD3OD): 132.6, 129.6, 129.2, 129.1, 128.3, 127.4, 126.8, 126.6, 126.0, 123.4 (C-aromatic), 62.5 (CH2OH), 50.2, 49.8 (CH2NHCH2), 33.1, 28.3, 24.4.
With C144H148N4Ni8O42S8*C4H12N(1+)*Cl(1-) In chloroform at 20℃; for 48h;
82%
With 4,5,6,7-tetrachloro-2′,4′,5′,7′-tetraiodofluorescein disodium salt In lithium hydroxide monohydrate at 20℃; for 0.75h; Irradiation;
61%
With aluminum(III) oxide In dichloromethane at 20℃; for 24h;
Typical procedure for the synthesis of malononitrile derivatives
General procedure: Into a solution of malononitrile (8.00 mmol) in methylene chloride(20 mL), aluminum trioxide (800 mg) and the appropriate aldehyde(4.00 mmol) were added. The reaction mixture was stirred at roomtemperature for 24 h. After this time, the crude product was purifiedusing column chromatography (SiO2, CH2Cl2). All compounds wereprepared according to the method described in our previous paper [24].
47%
With N-(3-trifluoromethylphenylcarbamoyl)chitosan In dimethyl sulfoxide at 20℃; for 216h;
7 2.8. General procedure for Knoevenagel condensation
General procedure: To a solution of the aryl aldehyde (1 equiv.) in DMSO (1.5 mL), malononitrile (or ethyl cyanoacetate) (1.1 equiv.) and chitosan beads or ureydil chitosan derivative 1 disks (10-15 units) were added. The heterogeneous mixture was allowed to stand at room temperature until the reaction was completed monitoring by TLC(1:2 or 1:4 EtOAc-hexane). Then, the reaction was diluted with CH2Cl2(3 mL) and the chitosan beads, or compound 1 disks, fil-tered off. The resulting solution was concentrated, treated with H2O(2.5 mL) and extracted with EtOAc (4 × 10 mL). The organic layers were successively washed with H2O (3 × 15 mL) and brine, then dried (Na2SO4) and concentrated to give the desired product.
11%
With [Zn4(dmf)(ur)2(ndc)4]; calcium(II) chloride In 1,4-dioxane at 25℃; for 24h; Inert atmosphere; Schlenk technique;
Reaction between 4-biphenylaldehyde and malononitrile.
Test. 1-Pyrenaldehyde (0.230 g, 1.00 mmol) and malononitrile (0.132 g, 2.00 mmol) were dissolved in dioxane (2.5 mL). Anhydrous CaCl2 (101 mg) was added to the reaction mixture to remove water traces, and 10 mol.% urotropine (0.014 g, 0.1 mmol) was then added. Samples were taken every 30 min. Study of the catalytic activity of [Zn4(dmf)(ur)2(ndc)4]. 1-Pyrenaldehyde (0.230 g, 1.00 mmol) and malononitrile (0.132 g,2.00 mmol) were dissolved in dioxane (2.5 mL). Anhydrous CaCl2 (101 mg) was added to the reaction mixture to remove watertraces, and 10 mol.% [Zn4(dmf)(ur)2(ndc)4] (148 mg, 0.1 mmol)was then added. Samples were taken 9.5 and 25 h after the reaction onset.
With piperidine
With piperazinyl polystyrene
With piperidine In chloroform Heating;
With ammonium acetate; glacial acetic acid
With piperidine In ethanol
1.1-1 [Preparation Example 1-1] 2-((pyrene-3-yl) methylene) malononitrile
With ethanol as a solvent, piperidine (onedrop) and malononitrile (1 equivalent) were added to pyrenecarboxaldehyde andthe reaction started being in a progress while changing a yellow solution intoorange. After recrystallizing it, its purity was tested. Purity analysis (HPLC Area% at 395 nm):99.2%.The mass spectrum of 2- ((pyrene -3 -yl)methylene) malononitrile, which was produced, shows in Figure 1.
With triethylamine In ethanol at 20℃; for 0.5h;
Two component synthesis of benzannulated tetrahydroindolizines without isolation of intermediate products (method D).
General procedure: A flask equipped with a magnetic stirrer and reflux condenser was charged with ethanol (6 mL), then aromatic aldehyde (3.0 mmol), malononitrile (3 mmol), and triethylamine (3.3 mmol) were successively added with stirring. The reaction mixture was kept for 30 min at room temperature. A solution of isoquinoline or quinoline (3.0 mmol) and chloroacetone (3.0 mmol) in ethanol (1 mL) was prepared in a separate flask. The reaction mixture was carefully refluxed with stirring for 15 min, cooled, and added to the first reaction mixture. After stirring for 3.5 h at room temperature, the reaction mixture was workedup as described in method A.
With zinc oxide nanoparticles In methanol at 25℃; for 0.25h;
2.2.1 Procedure for Knoevenagel Condensation
General procedure: In a typical reaction, a mixture of malononitrile (0.1mmol)and aldehyde (0.1mmol) was taken along with the catalyst in 1ml of solvent. The resulting mixture was stirred atroom temperature for the respective period of time. After the completion of reaction, the solvent was evaporated under vacuum and then the product was extracted in dichloromethane.The progress of the reaction was monitored by 1H NMR spectroscopy.
With C28H24O5OsP(1+)*C24H20B(1-); oxygen; potassium carbonate; In 1,2-dichloro-ethane; at 80℃; under 1125.11 Torr; for 12.0h;
To a 50 mL reaction tube with a screw cap and a magnetic stir bar, add 1-hydroxypyrene(0.3 mmol), potassium carbonate (0.6 mmol), I-1 (5 mol%),1,2-dichloroethane (1.5 mL). Pass oxygen into the reaction solution,The oxygen pressure was maintained at 0.15 MPa; heated at 80 C for 12 hours; after the reaction was completed, the reaction solution was cooled to room temperature and separated through a 200-300 mesh silica gel column. Petroleum ether:Dichloromethane = 2: 1 is the eluent. The organic solvent is removed under reduced pressure to obtain 1-acetaldehyde.The product was a yellow solid with a yield of 98%
93%
With dmap; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper(I) triflate; 5-[(2S)-pyrrolidine-2-yl]-1H-tetrazole; In acetonitrile; at 25℃; for 1.0h;Catalytic behavior;
General procedure: A round-bottom flask was charged with alcohol (2 mmol), CuOTf (0.1 mmol, 0.05 equiv) (S)-5-(pyrrolidin-2-yl)-1H-tetrazole (0.1 mmol, 0.05 equiv), TEMPO (0.1 mmol, 0.05 equiv), DMAP (0.15 mmol, 0.075 equiv) and CH3CN (5 ml). The reaction mixture was stirred at 25 C open to air until the completion of the reaction, as monitored by TLC. After completion, CH3CN was evaporated under vacuum. The residue was then diluted with CH2Cl2 (5 ml) and filtered through a plug of silica gel to afford the desired product.
86%
With C35H28Cl2N5PRu; potassium tert-butylate; In toluene; at 50℃; for 6.0h;
General procedure: using the complex 1 as catalyst in presence of a base following a general procedure. In a round-bottom flask, 1 mmol of substrate, 0.005mmol of catalyst (3.6mg) and 0.010 mmol of tBuOK (1.1mg) were mixed in 10mL toluene. The reaction mixture was heated at 50C in aerobic condition with continuous stirring for 6h and then the solvent was evaporated with a rotary evaporator under reduced pressure. The crude product, thus obtained, was purified on preparative silica gel GF-254 TLC plate using ethyl acetate: hexane (1:10) solvent mixture as eluent. The oxidized products were characterized by NMR spectroscopy (See Figs. S4-S32).
80%
With 1-hydroxy-1H-1,2,3-benziodoxathiole 1,3,3-trioxide; Oxone; cetyltrimethylammonim bromide; In water; at 20℃; for 2.0h;Green chemistry;
General procedure: The alcohol (2 mmol) was added to a solution of IBS (0.02 mmol, 0.01 eq), oxone (2.2 mmol, 1.1 equiv.) and 3 wt% CTAB solution (5 mL). The mixture was stirred at room temperature. The reaction was monitored by TLC. After completion, the solution was extracted with CH2Cl2 (3 × 10 mL). The combined organic phase was then filtered through a pad of silica gel and evaporated under vacuum to afford the desired product.
Stage #1: 2-acetylpyridine; pyrene-1-aldehyde With potassium hydroxide In ethanol; water at 20℃; for 2h;
Stage #2: With ammonium hydroxide In ethanol; water at 78℃; for 24h;
1.1 1) Synthesis of compound 1-1a:
Weigh the compound 1-pyrene formaldehyde (626.5mg, 2.72mmol) in a 100ml dry reaction flask,And dissolve with 25ml of 95% ethanol solution,Then weigh 2-acetylpyridine (660mg, 2mmol) and 580mg potassium hydroxide into the above system,The system was stirred at room temperature for 2 hours,The color of the solution is a clear yellow solution.Then measure 8ml of 28-33% ammonia solution and slowly add it to the above system.And heated to reflux for 24h at 78.During the reaction, TLC detection was performed every 8 hours until the reaction was complete.After the reaction is completed, wait for the system to cool to room temperature,Suction filtration with a Buchner funnel to obtain a yellow-green crude product,Then recrystallize with ethanol,The result is a clean yellow-green solid,Namely, compound 1-1a (846 mg, 72%).
64%
With ammonium hydroxide; potassium hydroxide Reflux;
59.18%
With ammonium hydroxide; sodium hydroxide In ethanol at 85℃; for 24h;
1.S2 S2.2-acetylpyridine reacts with pyrene-1-formaldehyde to generate tpy-py ligand
Heat a mixture of pyrene-1-carbaldehyde (2.3027g, 10mmol), 2-acetylpyridine (2.4228g, 20mmol), ammonia (35mL) and sodium hydroxide (1.1g) in ethanol (75mL) to 85°C, The reaction was refluxed for 24 hours, and the resulting orange body was recrystallized in ethanol. The powder was collected by vacuum filtration and dried in vacuum to obtain an ocher powdered solid tpy-py (2.5654 g) with a yield of 59.18%.
46.98%
Stage #1: 2-acetylpyridine; pyrene-1-aldehyde With potassium hydroxide In ethanol at 20℃; for 0.166667h;
Stage #2: With ammonium hydroxide In ethanol at 34℃; for 24h;
44%
Stage #1: 2-acetylpyridine; pyrene-1-aldehyde With sodium hydroxide In ethanol at 20℃;
Stage #2: With ammonium acetate In ethanol for 4h; Heating; Further stages.;
Stage #1: 2-acetylpyridine; pyrene-1-aldehyde With ammonium acetate In acetonitrile at 180℃; for 3h;
Stage #2: With sodium hydroxide In water at 120℃; for 2h;
Stage #1: 2-acetylpyridine; pyrene-1-aldehyde With sodium hydroxide
Stage #2: With ammonium acetate In ethanol Reflux;
With ammonium hydroxide; sodium hydroxide In ethanol at 35℃; for 24h;
1,4-bis(triphenylphosphoniomethyl)-2,5-dioctyloxybenzene dibromide[ No CAS ]
[ 945529-35-1 ]
Yield
Reaction Conditions
Operation in experiment
20%
Stage #1: pyrene-1-aldehyde; 2,2’-bipyridine-5-carbaldehyde; 1,4-bis(triphenylphosphoniomethyl)-2,5-dioctyloxybenzene dibromide With sodium hydride In tetrahydrofuran at 30℃; for 40h;
Stage #2: With iodine In dichloromethane at 20℃; Further stages.;
1-(2,4-Dimethoxybenzoyl)pyrene (2a)
1-(2,4-Dimethoxybenzoyl)pyrene (2a) Pyrene (10,1 g; 0.05 mol) and 2,4-dimethoxybenzoyl chloride (10 g; 0.05 mol) were dissolved in 400 ml of anhydrous methylene chloride. Anhydrous aluminium chloride (6.6 g; 0.05 mol) was added to the reaction mixture in small portions over 1 h at 0° C. with intense stirring. The reaction mixture was stirred for another 2 h at 0° C., 2 h at rt and then poured onto a mixture of ice and HCl (500 ml) and transferred into a separating funnel. The organic layer was washed with water (1*500 ml), saturated NaHCO3 (2*500 ml) and saturated NaCl (1*500 ml). The organic fraction was evaporated and recrystallized from toluene to give pyrenylketone as white solid (15.7 g; 86%). Found: C, 82.09; H, 4.81. C25H18O3 (MW 366.41) requires C, 81.95; H, 4.95%. 1H-NMR (CDCl3, d): 8.65-6.45 (m, 12 H, arom.), 3.91 (s, 3H, OCH3), 3.55 (s, 3H, OCH3). Mass-spectrum, MALDI-TOF: 388.89 (MI+Na; 15), 366.89 (100), 203.82 (40). Calculated exact mass for C25H18O3: 366.12559; found 366.12617 [1.6 ppm error].
Stage #1: pyrene-1-aldehyde; bis[(2-pyridyl)methyl]amine In methanol at 60℃; for 0.25h; Microwave irradiation;
Stage #2: With sodium cyanoborohydride In methanol at 60℃; for 0.5h; Microwave irradiation;
Synthesis of 1-[bis(pyridine-2-ylmethyl)amino]methylpyrene (L)
Pyrenecarboxaldehyde (1 mmol) and DPA (1 mmol) wereplaced in a round-bottomed flask followed by MeOH(5 mL), and the resulting mixture was irradiated at 300 W for 15 min at 60 C. NaBH3CN (1.2 mmol) was then addedto the reaction, and the resulting mixture was irradiated at300 Wfor 30 min at 60 C. The mixture was then cooled toambient temperature and partitioned between a saturatedaqueous solution of sodium carbonate and CH2Cl2. Theorganic phase was collected and the aqueous phases washedwith CH2Cl2. The combined organic layers were washedsequentially with water and brine, and then dried overMgSO4. The solvent was then removed in vacuo to give thecrude product as a residue, which was washed with a smallamount of MeOH before being recrystallized from a 1:1(v:v) mixture of THF and EtOAc to give the desired ligandas a white powder. The isolated yield was 0.36 g (87 %).mp 178-180 C. 1H NMR (400 MHz, CDCl3) d: 3.92(s, 4H), 4.38 (s, 2H), 7.09-7.26 (m, 2H), 7.47-7.52 (t, 2H,J = 9.0 Hz), 7.57-7.61 (m, 2H), 7.96-8.00 (m, 3H),8.04-8.08 (t, 1H, J = 7.2, Hz), 8.10 (d, 2H, J = 1.9, Hz),8.13-8.17 (dd, 2H, J = 16.6, 7.1 Hz), 8.35-8.37 (d, 1H,J = 9.3 Hz), 8.52-8.53 (d, 2H, J = 7.6 Hz). 13C NMR(100 MHz, CDCl3) d: 156.05, 145.37, 145.31, 133.15,133.0, 132.87, 129.01, 127.74, 127.30, 126.32, 124.75,123.91, 123.50, 122.33, 121.46, 120.97, 119.84, 118.52,57.00, 56.97, 53.67. HRMS (ESI-MS) calcd. for C29H23N3[M?H]?: 414.1970, found m/z: 414.1956. Anal. calcd. forC29H23N3: C 84.23 %, H 5.61 %, N 10.16 %, found: C84.18 %, H 5.70 %, N 10.05 %. FT-IR (cm-1) 3448, 3046,2966, 2898, 2868, 1717, 1613, 1514, 1485, 1427, 1302,1265, 1118, 787. UV-Vis (DMSO:CD3CN = 1:1-v/v,1.0 9 10-5 mol/L, kmax/nm): 267, 278, 330, 347; Km(DMSO:CD3CN = 1:1-v/v, 1.0 9 10-5 mol/L, X-1 -mol-1 cm2): 4.93. A single crystal for analysis by XRD wasobtained via the vapor diffusion of diethyl ether into aconcentrated acetonitrile and HClO4 solution of the compoundover 15 days at room temperature.
81%
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; Molecular sieve;
1.14 Example 1.14: Compound 14
[00229] To a solution of 1-Pyrenealdehyde (200 mg, 0.87 mmol) in 4.35 mL DCE, Di- (2-picolyl)amine (DPA) (137.4 μ, 0.87 mmol) was added along with sodium triacetoxyborohydride (553.2 mg, 2.61 mmol). To this reaction mixture, 4 A molecular sieves were added. The mixture was left to stir at rt overnight. This was then passed through a column packed with Amberlite IRN-78. This was purified by flash chromatography with Titanic/DCM (1 :1 ) to give 1 -(pyren-1-yl)-A/,/V-bis(pyridin-2- ylmethyl)methanamine (compound 14) (291 mg, 81 %); mp 108-1 12 °C; 1H NMR (400 MHz, CDCI3) δ 8.53 (d, J = 4.7 Hz, 2H), 8.40 (d, J = 9.3 Hz, 1 H), 8.20-8.06 (m, 5H), 8.05-7.97 (m, 3H), 7.61 (t, J = 7.6 Hz, 2H), 7.49 (d, J = 7.8 Hz, 2H), 7.12 (t, J = 6.3 Hz, 2H), 4.47 (s, 2H), 3.99 (s, 4H); 3C NMR (100 MHz, CDCI3) δ 148.5, 136.5, 131 .1 , 130.73, 130.67, 129.8, 128.3, 127.3, 127.1 , 127.0, 125.7, 124.90, 124.86, 124.6, 124.4, 123.9, 123.4, 122.0, 77.1 , 60.1 , 57.0; LRMS (ESI+) m/z calc'd for C29H2 N3 [M + H]+ 414.20, found 414.24; HRMS (ESI+) m/z calc'd for C29H24N3 [M + H]+ 414.1970, found 414.1981 ; rpHPLC tR: condition (A) 13.531 min., condition (B) 19.731 min., purity 98.8% and 97.5% respectively.
30%
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane for 5h; Inert atmosphere;
30%
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 8h; Inert atmosphere;
2.2. Synthesis of Receptor 1
A solution of sodium tris(acetoxy)borohydride (0.552 g, 3.25mmol)in 10 mL of 1,2-dichloroethane, dipicolylamine (0.400 g, 2.5mmol) andpyrenecarboxaldehyde (0.464 g, 2.52 mmol) were added stepwise. Thereaction mixturewas stirred at roomtemperature under nitrogen atmospherefor 8 h. Completion of reaction was monitored by TLC (usingCHCl3:MeOH, 9:1). The reaction mixture was then quenched with saturatedsodium hydrogen carbonate solution which was then extractedthree timeswith ethyl acetate. The organic phasewas dried over sodiumsulphate, and the solvent was removed under reduced pressure with arotary evaporator. The product was purified by column chromatography(eluted with CHCl3:MeOH, 9:1) (yield 0.240 g, 30%). m.p. 178-180 °C Anal. calcd. for C29H23N3: C, 84.23; H, 5.61; N, 10.16, Found:C,84.05; H, 5.41; N, 10.35; UV-vis (MeOH) λ/nm (ε mol-1 cm-1) 266(18200), 276 (33300), 300 (4800), 313 (1200), 327 (28100), 343(41700); 1H NMR (300 MHz, CDCl3, TMS) δ 8.52 (d, 2H, J = 4.9 Hz),8.36 (d,1H, J = 9.3 Hz), 8.17-7.96 (m, 8H), 7.6 (t, 2H, J = 7.2 Hz), 7.48(d, 2H, J = 7.8 Hz), 7.17-7.05 (m, 2H), 4.38 (s,2H, CH2), 3.9 (s, 4H,2CH2); 13C NMR (100 MHz, CDCl3) δ 159.57, 148.83, 136.31, 132.53,131.24, 130.80, 130.71, 129.81, 128.23, 127.38, 127.05, 126.97, 125.79,124.94, 124.89, 124.70, 124.44, 124.06, 123.30, 121.97, 60.48, 57.14;FT-IR (ATR, cm-1): 3051, 2916, 2814, 1589, 1470, 1428, 1128, 980,845, 762, 706; HRMS (ESI-MS) m/z: [M + H]+ calcd. For C29H23N3:414.20, found 414.19.
With sodium methylate; In methanol; toluene; at 25℃; for 10h;
To an ice-cold solution of pyrene-1-carboxaldehyde (53, 1.15 g, 5 mmol) and diethyl (2-oxopropyl)phosphonate (1.44 mL, 7.5 mmol) in PhMe (2.5 mL), a 2 M solution of MeONa in MeOH (3.75 mL, 7.5 mmol) was added dropwise over 30 min. The resulting reaction mixture was stirred at ambient temperature for 10 h and then diluted with EtOAc. The organic phase was washed twice with H2O, dried over Na2SO4 and evaporated to dryness. The oily residue was subjected to FCC, using as eluant the solvent system E, to afford pure methyl ketone 54.
With (R)-3,3'-bis(2,4,6-triisopropylphenyl)binol phosphoric acid In cyclohexane at 10℃; for 12h; Inert atmosphere; Molecular sieve; optical yield given as %ee; enantioselective reaction;
With potassium ethoxide In ethanol; dichloromethane at 5℃; for 72h; Inert atmosphere;
15 mL of dry ethanol then 25 mL of a solution of potassium ethanolate at 24% by weight in ethanol are added to a solution of 1-pyrenecarboxaldehyde (3.2 g, 14 mmol) and pregnenolone (4 g, 12.64 mmol) in 30 mL of dry CH2Cl2, and the solution is stirred for 72 h at +5° C. 200 mL of water is added and the organic products are extracted with CH2Cl2 (3x100 mL). The combined organic extracts are rinsed with salt water, dried over sodium sulphate, filtered and evaporated. Purification by flash chromatography on silica G60 (0.040-0.063 mm), elution with ethyl acetate in CH2Cl2 (2/98) then with ethyl acetate in CH2Cl2 (15/85) produce 6.12 g (91%) of compound 1 in the form of a brilliant yellow solid; mp: 153° C.; TLC (CH2Cl2/AcOEt 15:85) Rf 0.5; IR (KBr, cm-1) 3300m, 2932s, 1676m, 1590s, 1436w, 1370w, 1352w, 1315w, 1234w, 1192w, 1102m, 1052m, 973w, 848s, 709w; 1H NMR (CDCl3) δ 0.59 (s, 3H), 0.87 (s, 3H), 0.70-2.38 (m, 22H), 2.73 (t, J=8.7 Hz, 1H), 3.42 (sept, J=4.8 Hz, 1H) 3.55 (t, J=9 Hz, 2H), 5.24 (d, J=4.8 Hz, 1H), 6.87 (d, J=15.6 Hz, 1H), 7.87-8.17 (m, 8H), 8.36 (d, J=9.3 Hz, 1H), 8.58 (d, J=15.6 Hz, 1H), 13C NMR (CDCl3) δ 200.2, 140.8, 138.0, 132.7, 131.3, 130.7, 130.2, 128.7, 128.6, 128.5, 127.3, 126.3, 126.0, 125.8, 125.0, 124.9, 124.6, 124.0, 122.5, 121.4, 71.7, 62.5, 57.1, 53.5, 50.0, 45.1, 42.3, 39.2, 37.3, 36.5, 32.0, 31.8, 31.6, 24.7, 22.8, 21.1, 19.4, 13.5; MS (CI, NH3) m/z 529 (100, [M +H]+).
With sodium acetate; In dichloromethane; at 0 - 20℃;
To a solution of sodium acetate (0.29 g, 3.0 mmol) in dichloromethane (30 mL), cooled at 0 C, was added the salicylhydroxylamine hydrochloride 2 (500 mg, 3.6 mmol) and successively, dropwise, the corresponding 1-pyrenylcarboxaldehyde 4 (0.69 g, 3,0 mmol). The reaction mixture was then stirred for 1 h at 0 C and then at room temperature overnight. After this time, organic solvent was removed under reduced pressure and the obtained solid was purified by silica gel flash-chromatography (MeOH/CHCl3 5:95) to give the pure nitrone 5 that was re-crystallized from ethyl acetate/cycloexane. Z/E ratio = 88:1. Yield 92%; yellow solid, mp 198-202 C. Z-isomer 1H NMR (500 MHz, CDCl3:CD3OD 1:1, 27 C, TMS): delta = 5.33 (s, 2H, CH2), 6.90-8.18 (m, 12H), 8.52 (s, 1H, HCN), 9.51 (d, J = 7.8 Hz, 1H, H9). 13C NMR (125 MHz, CDCl3:CD3OD 1:1, 27 C, CD3OD): delta = 67.84, 116.99, 120.77, 121.09, 122.40, 125.23, 125.37, 126.90, 127.19, 128.00, 128.10, 129.04, 129.93, 130.65, 131.69, 132.14, 132.55, 158.40. Anal. Calcd for C24H17NO2: C, 82.03; H, 4.88; N, 3.99. Found: C, 82.25; H, 4.87; N, 3.99.
In methanol at 85℃; for 0.333333h; Microwave irradiation; Sealed tube;
Syntheses of phenol Schiff bases ligands, (LH3 and LH4)
General procedure: A solution of pyrene-1-carboxaldehyde (0.46 g, 2mmol)inmethanol (~7 ml) and 2-aminobenzoic acid (0.28 g, 2mmol) were mixed together. The resulting suspension was stirred in a microwave reactor in a sealed vesselat 85 °C for 10 min (~2 atm). It was cooled to room temperature and heated again at 85 °C for 10 min. Then the resulting solution was stirred at room temperature for ~5 min. A yellow solid separated which was filtered and washed with ice-cold methanol followed by diethyl ether. Recrystallization from chloroform afforded yellow crystalline solid of2-(pyren-1-ylmethyleneamino)benzoic acid, LH3.Yield: 0.57 g (81%)
1,3-dimethyl-2-(1-pyrenyl)benzimidazoline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
With acetic acid; In dichloromethane; for 6h;Molecular sieve; Inert atmosphere; Cooling with ice;
General procedure: DMBIH 1a,7a 1b,8b, and 1g,8c are known compounds. 1c, 1d, 1e,and 1f were prepared by using modified literature procedures.6a,8b,c,10g A typical procedure for preparation of 1b is describedbelow. To a CH2Cl2 (10 mL) containing N,N0-dimethyl-o-phenylenediamine(DMPDA) (1.38 g, 10.1 mmol) with molecular sieves 4A(ca. 10g) under N2 seated in ice-water bath was slowly added 1-naphthoaldehyde (1.42 mL, 10.5 mmol) in CH2Cl2 (20 mL). Afteraddition of acetic acid (0.23 mL, 4.0 mmol), the resulting mixture was stirred for 6 h in an ice-water bath and then molecular sieveswere removed by filtration. The residue obtained after concentrationof the filtrate in vacuo was subjected to column chromatography(benzene with 1% triethylamine) to give 1b (1.85 g, 6.8 mmol,67%). In a similar fashion, 1c (1.61 g, 5.9 mmol, 71%) from DMPDA(1.12 g, 8.2 mmol) and 1e (1.30 g, 4.0 mmol, 50%) from DMPDA(1.09 g, 8.0 mmol) were prepared. 1d (1.74 g, 5.0 mmol, 61%) fromDMPDA (1.12 g, 8.2 mmol) was rinsed with MeOH after columnseparation. While 1b, 1c, and 1e were crystallized from dimethoxyethaneand EtOH, 1d was crystallized from CH2Cl2 and MeOHbefore using for the photoreactions. 1f (595 mg, 2.1 mmol, 49%)from DMPDA (584 mg, 4.3 mmol) was obtained by rinsing the solidwith EtOH after column chromatography (EtOAc/benzene1/6with 1% triethylamine), and then used for the photoreaction.
(E)-1,1-bis(methylthio)-5-(pyren-1-yl)penta-1,4-dien-3-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84%
With sodium hydroxide In ethanol at 0 - 20℃; for 1.5h;
General procedure for the synthesis of 1,1-bis(methylthio)-5-arylpenta-1,4-dien-3-one (2a-y)
General procedure: To a solution of 4,4-bis(methylthio)but-3-en-2-one (1mol) in ethanol (10 ml) were added NaOH (1.5mol) and aryl aldehyde (1.1 mol) under constant stirring. After the starting material was consumed as indicated by TLC, the reaction mixture was poured into ice water and the resulting solid was filtered, washed well with water (20 ml). The solid material obtained was crystallized from ethanol to furnish 81-99% of 1,1-bis(methylthio)-5-arylpenta-1,4-dien-3-one as a yellow solid.
Stage #1: pyrene-1-aldehyde With N-Bromosuccinimide In N,N-dimethyl-formamide for 3h; Reflux;
Stage #2: With toluene-4-sulfonic acid In methanol; chloroform for 2h; Reflux;
Stage #3: N,N-dimethyl-formamide Overall yield = 28 %; Further stages;
(Z)-3-(4-methoxyphenyl)-5-[(pyren-8-yl)methylene]-2-thioxoimidazolidin-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With sodium acetate In acetic acid for 3h; Reflux;
Synthesis of (Z)-3-(4-Methoxyphenyl)-5-[(pyren-8-yl)methylene]-2-thioxoimidazolidin-4-one (1)
To a mixture of 3-(4-methoxyphenyl)-2-thioxoimidazolidin-4-one (10 mmol), anhydrous AcONa (30 mmol) and glacial acetic acid (10 mL) was added pyrene-1-carbaldehyde (10 mmol). The reaction mixture was refluxed for 3 h, cooled to room temperature and poured into ice cold water. The formed precipitate was collected by filtration and recrystallized from AcOH to give the title compound 1. Yield 65%, mp 236-238 °C. IR spectrum, ν, cm-1: 3217 (NH), 1748 (C=O), 1613 (C=N). 1H NMR spectrum (DMSO-d6), δ, ppm: 3.81 s (3H, OCH3), 6.95 d, 7.23 d (4H, Ar-H), 7.63-8.34 m (10H, Py-H + =CH), 11.97 s (1H, 1NH exchangeable with D2O). 13C NMR spectrum (DMSO-d6), δ, ppm: 55.28, 107.80, 115.67, 117.17, 123.55, 124.69, 124.76, 125.55, 125.63, 125.80, 126.64, 126.89, 128.10, 128.29, 128.39, 131.22, 131.27, 136.43, 154.90, 165.08, 179.54. MS (EI, 70 eV): m/z (%) = 434 (46) [M]+. Found, %: C 74.51; H 4.05; N 6.32. C27H18N2O2S. Calculated, %: C 74.63; H 4.18; N 6.45.
(E)-3-(pyren-1-yl)-2-(thiophen-2-yl)acrylonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58.1%
With potassium <i>tert</i>-butylate In methanol at 20 - 65℃; for 12h;
4.1 2.4.1 Synthesis of (E)-3-(pyren-1-yl)-2-(thiophen-2-yl)acrylonitrile (2)
Freshly distilled methanol (30 mL) was taken in a 100 mL single neck round bottom flask. The compound 1 (pyrene-1-carbaldehyde) (0.5 g, 1 eq) and thiophene-2-acetonitrile (0.375 g, 1.4 eq) were added to the methanol. A catalytic amount of potassium tert-butoxide was added into this mixture at room temperature. Then the reaction mixture was stirred for 12 h at 65 °C. It was monitored by TLC. A bright yellow solid was filtered after 12 h. It was recrystallized in dichloromethane and methanol to give the product 0.423 g (yield = 58.1%). 1H NMR (500 MHz, CDCl3, ppm): δ 8.63 (d, 1H, J = 10 Hz), 8.42 (s, 1H), 8.24-8.05 (m, 8H), 7.52 (s, 1H), 7.40 (s, 1H), 7.15 (s, 1H). 13C NMR (CDCl3, ppm): δ 140.11, 139.47, 137.54, 134.75, 132.79, 132.36, 131.25, 130.90, 130.48, 129.75, 129.00, 128.49, 127.93, 127.39, 126.25, 124.97, 124.54, 123.34, 122.39, 118.76, 117.15, 112.05, 108.79. IR (KBr, cm-1): 2219. Chemical Formula: C23H13NS Molecular Weight: 335.42, Found: 335.12.
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; for 24h;Reflux; Inert atmosphere;
A mixture of 1-formylpyrene (see preparation of 4, 0.69 g,3.0 mmol) and m-CPBA (1.04 g, 6.0 mmol) in CH2Cl2 (50 mL) wasstirred at reflux for 24 h under an argon atmosphere. To the solutionwere added THF (5 mL), MeOH (10 mL), and 25 % KOH aq (0.6 mL),and the resulting solution was stirred at room temperature for 3 h. Thesolution was concentrated in vacuo to give a black residue. The residuewas extracted with CH2Cl2 (100 mL) and sat. NaCl aq (50 mL). Theorganic layer was separated, dried over Na2SO4, filtered, and concentratedin vacuo, giving a residue that was subjected to silica gelcolumn chromatography (eluent: CHCl3) to give 1-hydroxypyrene(0.36 g, 55 % yield, pink solid). Lit [96].A mixture of 1-hydroxypyrene (0.17 g, 0.77 mmol), NaOH (0.5 g,5.0 mmol), Me2SO4 (0.26 g, 2.1 mmol) in H2O (15 mL) and THF (10 mL)was stirred at room temperature for 12 h. The mixture was extractedwith AcOEt (100 mL) and then Et2O (100 mL). The combined organiclayers were washed with sat. NaCl aq (50 mL), dried over Na2SO4, filtered,and concentrated in vacuo, giving a residue that was subjected tosilica gel column chromatography (eluent: CHCl3) to give 1-methoxypyrene(0.080 g, 45 % yield, brown solid). Lit [97].To a stirred nitrobenzene (120 mL) solution of 1-methoxypyrene(0.46 g, 2.0 mmol) was added dropwise nitrobenzene (40 mL) solutionof Br2 (0.4 mL, 7.2 mmol), and the resulting solution was stirred at 80 Cfor 12 h. After cooling to room temperature, conc. NaOH aq (10 mL)was added to quench excess Br2. The formed solid was washed withCHCl3 (100 mL) and collected by filtration to give 1,3,6-tribromo-8-methoxypyrene (0.85 g, 91 % yield, yellow solid).A mixture of 1,3,6-tribromo-8-methoxypyrene (0.93 g, 2.0 mmol),trimethylsilylacetylene (0.844 g, 8.6 mmol), PdCl2(PPh3)2 (0.071 g,0.10 mmol), CuI (0.033 g, 0.17 mmol), and PPh3 (0.068 g, 0.26 mmol)in THF (30 mL) and i-Pr2NH (25 mL) was stirred at 80 C for 12 h underan argon atmosphere. The resulting mixture was concentrated in vacuo,giving a residue that was subjected to silica gel column chromatography(eluent: hexane) followed by recycling preparative HPLC (GPC, eluent:CHCl3) to give 1-methoxy-3,6,8-tris(trimethylsilylethynyl)pyrene 0.24 g, 23 % yield). Yellow solid; mp 288 C; 1H NMR (400 MHz, CDCl3)8 0.37 (s, 9 H), 0.38 (s, 9 H), 0.40 (s, 9 H), 4.18 (s, 3 H), 7.66 (s, 1 H),8.27 (s, 1 H), 8.42 (d, J =9.3 Hz, 1 H), 8.48 (d, J =9.3 Hz, 1 H), 8.52 (d,J =9.3 Hz, 1 H), 8.53 (d, J =9.3 Hz, 1 H) ppm; 13C NMR (100 MHz,CDCl3) 8 0.0, 0.0, 0.0, 56.2, 100.3, 101.0, 103.0, 103.0, 103.5, 111.8,111.8, 116.8, 117.0, 119.2, 121.1, 122.5, 123.8, 123.9, 124.7, 125.0,126.6, 127.0, 132.5, 132.5, 134.3, 134.3, 153.5 ppm; IR (KBr) 887,1119, 1250, 2152, 2360, 2959 cm-1; MS (CI) m/z (relative intensity,%)=75 (100), 245 (12), 448 (14), 520 (M+, 85); HRMS (EI) calcd forC32H36OSi3: 520.1316, found: 520.2074.
50%
To a stirred CH2Cl2 (90 mL) solution of pyrene (2.022 g, 10 mmol) was added Cl2CHOCH3 (1.2 mL, 13 mmol) at 0 C. To the solution was slowly added TiCl4 (2.0 mL, 18 mmol). The color of solution turned from yellow to purplish red. The mixture was stirred at 0 C for 1 h and at room temperature for 1.5 h. The solution was poured into cold water (100 mL), and stirred until the color turned from purplish red to yellow. The mixture was extracted with CH2Cl2 (50 mL x 2). The combined organic layers were washed with brine (50 mL), separated, dried over MgSO4, filtered, and concentrated in vacuo to give 1-formylpyrene (2.24 g, 96% yield). Yellow solid; 1H NMR (400 Mz, CDCl3) d 8.08-8.13 (m, 2H), 8.23-8.36 (m, 5H), 8.47 (d, J = 8.0 Hz, 1H), 9.45 (d, J = 9.6 Hz, 1H), 10.80 (s, 1H) ppm. To a stirred CH2Cl2 (20 mL) solution of 1-formylpyrene (0.46 g, 2 mmol) was added m-CPBA (0.68 g, 3 mmol), and the resulting solution was stirred at reflux for 24 h, then concentrated in vacuo. To the residue was added THF (5 mL), MeOH (5 mL), and 25% KOH aq (0.6 mL), giving a mixture that was stirred at room temperature for 4 h, then concentrated in vacuo. The residue was dissolved in 2% KOH aq (10 mL). The solution was extracted with CH2Cl2 (10 mL x 2). The combined organic layers were washed with ice-cooled HCl aq (pH = 2), separated, dried over MgSO4, filtered, and concentrated in vacuo, giving as residue that was subjected to silica gel column chromatography (eluent; CHCl3, Rf = 0.3) to give 1-hydroxypyrene (3, 0.223 g, 50% yield). Gray solid; 1H NMR (400 Mz, CDCl3) d 5.70 (brs, 1H), 7.48 (d, J = 6.4 Hz, 1H), 7.91 (d, J = 8.8 Hz, 1H), 7.96-7.99 (m, 2H), 8.03-8.07 (m, 2H), 8.10-8.13 (m, 2H), 8.35 (d, J = 7.6 Hz, 1H).
Stage #1: 2,4-dimethyl-1H-pyrrole; pyrene-1-aldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere;
Stage #2: With chloranil In dichloromethane at 0 - 20℃; for 0.333333h; Inert atmosphere;
Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 0 - 20℃; for 18h; Inert atmosphere;
26%
Stage #1: 2,4-dimethyl-1H-pyrrole; pyrene-1-aldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere;
Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 0.333333h; Inert atmosphere;
Stage #3: boron trifluoride diethyl etherate Further stages;
23%
Stage #1: 2,4-dimethyl-1H-pyrrole; pyrene-1-aldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 12h; Inert atmosphere;
Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 0.5h; Inert atmosphere;
Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 0.5h; Inert atmosphere;
22%
Stage #1: 2,4-dimethyl-1H-pyrrole; pyrene-1-aldehyde With trifluoroacetic acid In dichloromethane for 16h; Inert atmosphere;
Stage #2: With chloranil In dichloromethane for 0.5h; Inert atmosphere;
Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 3h; Inert atmosphere; Cooling with ice;
2.3.1.3. Pyrenyl-BODIPY (3)
Pyrenecarboxaldehyde (230 mg, 1mmol) and dimethylpyrrole (0.215 mL, 2 mmol) were put in a roundbottom flask then 30 mL of dry dichloromethane was added undernitrogen atmosphere, followed by one drop of trifluoroacetic acid.The solution became red, and the mixture was stirred for 16 h undernitrogen atmosphere. p-Chloranil (250 mg, 1 mmol) was added andthe solution was stirred for 30 min under nitrogen atmosphere. Triethylamine(3 mL, 22 mmol) and boron trifluoride diethyletherate(3 mL, 24 mmol) were added in the mixture that was previouslycooled in an ice bath. The mixture was stirred for 3 h at room temperature.Then the organic phase was washed with water and driedwith magnesium sulphate, and solvents were removed underreduced pressure. The resulting crude product was filtered on a plugof silica gel (dichloromethane). The filtrates were collected, the solventwas removed, and the resulting solid was subjected to silica gelcolumn chromatography (silica gel, eluent ethyl acetate:petroleumether, gradient from 6:94 to 12:88 vol). Yield = 22%.1H NMR (300 MHz, CDCl3, 300 K): d (ppm) = 0.87 (s, 6H); 2.6 (s,6H); 5.93 (s, 2H); 7.8-8.4 (m, 9H). 19F NMR (280 MHz, CDCl3, 300K): d (ppm) = 146 (q, 1JF-B = 32 Hz, 2F). 11B NMR (128 MHz, CDCl3,300 K): d (ppm) = 0.995 (t, 1JB-F = 32 Hz, 1B). ESI-MS: m/z = 471.17[M+Na]+, 447.18 [MH] (calcd for C29H23BF2N2: 448.19 (exactmass); 448.31 (FW)). UV-Vis (DCM): kmax (nm) = 327, 342, 504.
With acetic acid; In ethanol; at 80℃; under 760.051 Torr; for 3h;
S1. 1.0 mmol of 1-pyrene Formaldehyde is dissolved in 10 mL of absolute ethanol, 1.0 mmol of carbonic acid dihydrazide is added, and 0.5 mol% of glacial acetic acid is added to prepare a mixed solution.S2. The mixture was warmed to 80 C, under normal pressure and refluxed for 3h.S2. After cooling to room temperature, the solid precipitated and was filtered under reduced pressure. The residue was washed with absolute ethanol to give the desired acylhydrazone compound containing a pyrenyl group (a yellow solid in a yield of 79%).
(E)-1-(2-methoxyphenyl)-3-(pyren-1-yl)prop-2-en-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
With sodium hydroxide In ethanol; water at 20℃; for 6h;
2.3. Synthesis of (E)-1-(2-methoxyphenyl)-3-(pyren-1-yl)prop-2-en-1-one(PC-OCH3)
The corresponding pyrene chalcones were synthesized by Claisen-Schmidt condensation reaction from the respective aldehydes and ketone[33-38]. 2-Methoxyacetophenone (1 mol) and pyrenealdehyde(1 mol) were dissolved in absolute ethanol and stirred for about 10 minto get homogeneous solution. NaOH (1 mol) was dissolved in aminimum amount of H2O and added slowly to the solution for over20 min. The reaction mixture was slowly turned to yellow color precipitate,then stirred for 6 h at RT. The entire reaction was monitored byTLC technique. At the end of the reaction, the resultant mixture wasquenched with ice water, and set apart for 4 h to form a yellow coloredprecipitate which was filtered, dried for 12 h and subjected to columnchromatography to get the product. PC-OCH3, Yield: 89%: FT-IR (KBr,cm-1):3041 (vAr-C-H),2971 (vAli-C-H), 1599 (vC]O), 1589(v-C]C-). GC-MS calculated for [C26H18O2] 362.4397; found362.1308 M+.
With sodium hydroxide In ethanol at 60℃; for 16h;
4.2 General synthesis of chalcone
General procedure: In a 100 mL round bottom flask, acetophenone or acetonaphthone derivatives (1 equiv) and the 1-pyrenecarboxaldehyde (1 equiv) were solubilized in ethanol. Subsequently, sodium hydroxide (2.5 equiv) in water was added to the solution. The solution was stirred for 16 h at 60°C. After cooling down, the precipitate was filtered on a glass filter. The solid obtained was the recrystallized in a mixture of dichloromethane and ethanol two times to yield the pure ligands.
4 Synthesis step of compound 4
A solution of 1-pyrene formaldehyde in methanol(0.5 mmol 1-pyrene formaldehyde + 15 mL methanol)A solution of pentafluorophenylhydrazine in methanol was added dropwise(0.7 mmol pentafluorophenylhydrazine + 5 mL methanol)Plus 0.5 mL glacial acetic acid, heated at 70 ° C and reflux for 5 h,Cooled and filtered, purified by column chromatography (V (PE): v (DCM) = 8: 1)The final product compound 4 was obtained.
With sodium acetate; acetic acid; In methanol; at 70℃; for 5h;
A solution of 1-pyrene formaldehyde in methanol (0.5 mmol 1-pyrene formaldehyde + 15 mL methanol)Was added dropwise to a methanol solution of <strong>[40594-29-4]2,4-difluorophenylhydrazine hydrochloride</strong> and sodium acetate(0.7 mmol of <strong>[40594-29-4]2,4-difluorophenylhydrazine hydrochloride</strong> + 0.7 mmol of sodium acetate +5 mL of methanol)Plus 0.5 mL of glacial acetic acid, heated at 70 C and reflux for 5 h, cooled and filtered,Purification by column chromatography (V (PE): V (DCM) = 10: 1)The final product compound 2 was obtained.
dimethyl (2-methyl-3-(trifluoromethyl)phenylamino)(pyren-1-yl)methylphosphonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
97%
With chitosan; In neat (no solvent); at 75℃; for 0.0333333h;Microwave irradiation; Green chemistry;
General procedure: An equimolar mixture of <strong>[54396-44-0]2-methyl-3-(trifluoromethyl)aniline</strong> (0.351 g, 0.002 mol), corresponding aldehyde (0.002 mol), dimethyl phosphite (0.18 ml, 0.002 mol) and chitosan catalyst (10 molpercent) were taken in a reaction glass tube, degassed for 10 min and microwave irradiated at 180 W for 2 min at 60 °C. The progress of the reaction was monitored by TLC using petroleum ether and ethyl acetate (3:7) as solvent. After completion of the reaction, the mixture was diluted with ethyl acetate, washed with water (2 x 15 ml) followed by brine (1 x 10 ml), dried over Na2SO4 and evaporated to dryness. The crude mass was purified by column chromatography on silicagel (100-200 mesh) by using a 7:3 mixture of ethyl acetate in hexane to afford the pure alpha-aminophosphonates.
(pyrene-1-yl)-N-(3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl)methanimine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With acetic acid; In methanol; at 85℃; for 6h;
1.20 mmol of 1-pyrene monoaldehyde and1.00 mmol of 3,5-dipyridyl-4-amino-1,2,4-triazole was added to100 ml three-necked round bottom flask containing 20 ml of methanol.Under magnetic stirring,Slowly heated to 85 C,When all the ingredients are completely dissolved,Slowly add 3 drops of glacial acetic acid.The reaction was stopped after stirring for 6h at 85 C.The resulting reaction solution was cooled to room temperature,That is, yellow precipitate precipitation,filter,Washed three times with methanol,After drying that get L3,Yield 54%.
naphthalene-2-carboxylic acid pyren-1-ylmethylene-hydrazide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
In methanol at 50℃; for 2h;
2.5.1. Compound 1: Synthesis of 3-hydroxy-naphthalene-2-carboxylic Acid Pyren-1-ylmethylene-hydrazide (Compound 1)
General procedure: Compound 3-hydroxy-naphthalene-2-carboxylic acid hydrazide (1.5 mmol, 0.30 g) has been treated with 1-pyrene carboxaldehyde (1.5 mmol, 0.20 g) in methanol at 50 °C for 2 h. to form a yellow solid. The product thus obtained has been filtered and then dried under vacuum (yield: 0.35 g, 76%).
9-phenyl-10-(1-pyrenyl)-9H-pyreno[4,5-d]imidazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44%
With ammonium acetate; acetic acid; at 20 - 120℃; for 14h;Inert atmosphere;
1-pyrenal(0.58 g, 2.5 mmol), <strong>[6217-22-7]pyrene-4,5-dione</strong>(0.71 g, 3.0 mmol), aniline (1.16 g, 12.5 mmol), ammonium acetate (1.19 g, 10.2mmol), dissolved in 20ml of acetic acid solvent and transferred to a 100ml round bottom flask. After degassing once, nitrogen is used for protection. The gas was shielded, and the mixture was stirred and refluxed at a temperature of 120C for two hours. After the reaction was completed, the mixture was stirred at 20C for 12 hours. Buchner funnel Filter, rinse with a small amount of acetic acid (volume ratio 1:1), filter, and spin down the filtrate through a reduced pressure rotary evaporator. A dark brown solid was obtained, which was purified by column chromatography and washed with a solvent of petroleum ether:methylene chloride = 1:1 by volume. Remove agent. A pale yellow solid (0.56 g) was finally obtained, which was further sublimed and purified using a chemical vapor deposition system. The sublimation temperature was 350. C, 0.40 g of pale yellow target was obtained with a yield of 44%.
With tetrachlorosilane; Hexamethylphosphorous triamide; In 1,2-dichloro-ethane; at 60℃; for 24h;Inert atmosphere; Sealed tube; Glovebox;
General procedure: To a dry tube containing a dichloroethane (1 mL) solution of nitrone (0.40 mmol, 2.0 equiv.), SiCl4 (0.02 mmol, 10 mol%), P(NMe2)3 (0.24 mmol, 1.2 equiv.) and aldehyde (0.20 mmol) were added in a glove box. Then, the tube was sealed by polytetrafluoroethylene bottle stopper with rubber ring and thread. The mixture was then stirred and heated at 60 C. After reaction for 24 h, the mixture was cooled to room temperature. Removal of the solvent afforded the crude product, which was purified by thin layer chromatography on silica gel.
With titanium(IV) dioxide In neat (no solvent, solid phase) at 90℃; for 1.5h; Green chemistry;
2. Experimental
General procedure: To the mixture of aldehyde 1a (1 mmol) and 3,5-dimethyl-4-nitroisoxazole 2 (1 mmol) the TiO2 NPs (20 mol%) added and stirred for the 90 min at 90 °C. Reaction progresses was determinedby thin layer chromatography (TLC). After completion of the reaction was cooled to room temperature, the residuewas dissolved in dichloromethane and filtered. The organiclayer was concentrated under reduced pressure to give residue, recrystallized in methanol to give analytically pure product 3a as yellow solid.
ethyl 1-methyl-2-(pyren-1-yl)-1H-benzoimidazole-5-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
94%
With sodium dithionite; In dimethyl sulfoxide; for 0.08333330000000001h;Microwave irradiation;
General procedure: To the stirred solution of ethyl-4-(methyl/propyl/butyl amino)-3-nitrobenzoate (3a-c) (0.01 mol) and appropriate aldehyde (0.01 mol) in DMSO (30 mL), sodium dithionate (3 equiv.) was added and the reaction mixture was stirred under microwave irradiation 600 watts for appropriate time [Table 1]. After the completion of reaction, the reaction mixture was poured into water the solid separated was collected by filtration, dried and recrystallized from DMF: DMSO mixture.
(N1E,N8E)-N1,N8-bis(pyren-1-ylmethylene)naphthalene-1,8-diamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
77.7%
With acetic acid In methanol at 60 - 65℃; for 12h;
2.3.1. Synthesis of (N1E,N8E)-N1,N8-bis(pyren-1-ylmethylene)naphthalene-1,8-diamine (BPND)
Scheme 1 shows the step involved in the synthesis of Schiff base ligand. 50 mg (0.22 mM) of 1-Pyrenecarboxaldehyde was dissolved in 25 mL of dry methanol. To this 100 μL of acetic acid was added which acts as a catalyst during the reaction. To this clear solution, 17 mg(0.11 mM) of 1,8-Diaminonaphthalene was added which resulted in theimmediate colour change from yellow to orange-brown solution. Thereaction mixture was then refluxed at 60-65 °C for 12 h. The precipitateformed was filtered and washed several times with methanol to obtain final pure product. Yield: 197 mg (77.7%). m.p.: 243 °C. 1H NMR (DMSO-d6, 500 MHz): δ 8.96 (d, 2H, J=10 Hz), 8.3 (m, 14H), 7.2 (t, 3H, J=10 Hz), 7.07 (d,2H, J=5 Hz), 7.01 (s, 2H), 6.5 (d, 2H, J=5 Hz), 6.3 (S, 2H). 13C NMR (DMSO-d6, 125 MHz): δ 143.07, 133.97, 133.33, 130.55, 130.16,129.59, 128.35, 127.76, 127.14, 126.76, 126.50, 126.18, 125.70,124.66, 124.12, 123.64, 123.26, 114.84, 112.00 and 103.75. FT-IR KBr Pellet, cm-1) 3043-3044 (Sharp, Aromatic C-H), 1660-1680 (Sharp, C=N), 1589-1609 (Sharp, C=C), 1078-1082 (Sharp, C-N),874-815 (Sharp, aromatic SP2 C-H bend). ESI-MS calculated forC44H26N2 [M+H]+: 583.21 and found is 583.21.
(1H-benzoimidazol-2-yl)pyren-1-ylmethylene-amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92.2%
With acetic acid In ethanol at 20℃; for 3h;
2.2. General synthesis procedure for receptors 1-3
General procedure: A good percentage yield of receptors 1-3 has synthesized through the condensation of Pyrene-1-carbaldehyde (1.1 mmol) with Thiazol-2-ylamine (1.1 mmol) (receptor 1), 1H-Benzoimidazol-2-ylamine (1.1 mmol) (receptor 2) and 2-Thiophene carboxylic acid hydrazide (1.1 mmol) (receptor 3) in ethanol as a solvent and a drop of acetic acid as catalyst by refluxing at RT for 3 h as represented in Scheme 1.
N’-(pyren-4-ylmethylene)thiophene-2-carbohydrazide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
With acetic acid In ethanol at 20℃; for 3h;
2.2. General synthesis procedure for receptors 1-3
General procedure: A good percentage yield of receptors 1-3 has synthesized through the condensation of Pyrene-1-carbaldehyde (1.1 mmol) with Thiazol-2-ylamine (1.1 mmol) (receptor 1), 1H-Benzoimidazol-2-ylamine (1.1 mmol) (receptor 2) and 2-Thiophene carboxylic acid hydrazide (1.1 mmol) (receptor 3) in ethanol as a solvent and a drop of acetic acid as catalyst by refluxing at RT for 3 h as represented in Scheme 1.
82%
In ethanol for 8h; Reflux;
2.2 General method for the syntheses of thiophene-2-carboxylic acid hydrazide derivatives
General procedure: The thiophene-2-carboxylic acid hydrazide precursors (HL1-3) were prepared by refluxing a mixture of equimolar amounts of thiophene-2-carboxylic acid hydrazide (1mmol) and 1-naphthaldehyde (HL1), 9-anthracenecarboxaldehyde (HL2) or 1-pyrenecarboxaldehyde (HL3) in 15mL of ethanol for 8h. The solutions were then concentrated and the precipitates obtained were washed with distilled water and dried in vacuum.
In ethanol for 8h; Reflux;
2. Experimental section
The synthetic route of PSD was shown in Scheme S1. The compound2-thiophene-1-pyraniazide (PSD) was synthesized by 1.42g of 2-Thiophenecarboxylicacid hydrazide (0.01mol) reacting with 1-Pyrenecarboxaldehyde(2.53g, 0.01mol) in ethanol (150 mL) under refiluxcondition for 8 h. The crude product was isolated and purified byrecrystallization from THF for further 1H NMR, 13C NMR (Fig. S1), MS(Fig. S2), FT-IR measurements and elemental analysis experiments. Themelt point of PSD is 273 C.1H NMR (300 MHz, DMSO-d6), (ppm, from TMS): 12.10-12.01 (d,1H), 9.50-9.28 (d, 1H), 8.84-8.73 (m, 1H), 8.60-8.52(m, 1H), 8.40-8.36(m, 4H), 8.30-8.22 (d, 2H), 8.20-8.10 (m, 1H), 8.08-7.84 (d, 2H), 7.31-7.28 (m, 1H).13C NMR (75 MHz, DMSO-d6), (ppm, from TMS): 146.28, 142.18,135.00, 131.91, 130.86, 130.13, 128.73, 128.43, 127.40, 126.84,126.64, 126.13, 125.81, 125.33, 124.11, 123.77, 122.42, 121.71.FT-IR (silicon pellet, cm 1): 3358, 3167, 3034, 2920, 2848, 1637,1597, 1412, 1384, 1326, 1107, 842, 704, 606.Elemental analysis: calculated for C22H14N2OS: C, 74.55; H, 3.98; N,7.90; S, 9.05. Found: C, 74.97; H, 4.053; N, 7.89; S, 9.21.MS: calcd for C22H14N2OS: 354.08, found: 355.09.
tri-tert-butyl 11-(pyren-1-ylmethyl)-1,4,8,11-tetraazacyclotetradecane-1,4,8-tricarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃; for 26h;Molecular sieve; Inert atmosphere;
[00132] To a solution of 1 -pyrenecarboxaldehyde (35 mg, 0.15 mmol) in 1 ml_ DCE, Boc3Cyclam (50 mg, 0.10 mmol) was added and stirred together with 4A molecular sieves for 2 h under nitrogen atmosphere. To this solution sodium triacetoxyborohydride (42 mg, 0.2 mmol) was added and the reaction mixture was allowed to stir at ambient temperature over 24 h under nitrogen atmosphere. Subsequently, the reaction mixture was diluted with sodium bicarbonate and extracted with DCM. The extract was purified by flash chromatography with 30% ethyl acetate/hexanes to give the product (63 mg, 88%); 1H NMR (400 MHz, CDC) delta 8.47 (d, J = 9.3 Hz, 1H), 8.21 - 7.93 (m, 8H), 4.22 (s, 2H), 3.34 (s, 10H), 3.13 (s, 2H), 2.78 (s, 2H), 2.50 (s, 2H), 1.88 (s, 2H), 1.76 - 1.66 (m, 2H), 1.51 - 1.17 (m, 27H); 13C NMR (100 MHz, CDCb) delta 155.55, 132.64, 131.33, 130.87, 130.77, 129.71, 128.41, 127.47, 127.10, 125.83, 125.00, 124.83, 124.50, 124.06, 79.67, 79.44, 58.59, 54.24, 53.43, 47.81, 47.07, 29.72, 28.50, 28.46, 28.31 ; LRMS (ESI+) m/z calc'd for CHssN-OeNa [M + Na]+ 737.42, found 737.65.
Stage #1: pyrene-1-aldehyde; N-(3-acetyl-4-hydroxyphenyl)butanamide With sodium hydroxide In ethanol; water at 0 - 40℃; for 5h;
Stage #2: With dihydrogen peroxide In ethanol; water at 20℃; for 12h; Cooling with ice;
(E)-3-((pyren-1-ylmethylene)amino)-2-thioxothiazolidin-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
In ethanol; at 20℃;
General procedure: General procedure for synthesis of N-substituted-rhodanine derivatives RhAs: To a solution of aldehydes (3a-3h, 1.0 equiv.) in ethanol (10 mL) was added slowly to the solution of <strong>[1438-16-0]3-amino-2-thioxothiazolidin-4-one</strong> (2, 1.0 equiv.) in EtOH. The reaction mixture was stirred at room temperature without a catalyst for between 4 h and 12 h, and was monitored by TLC. After, the mixture product was recrystallized from EtOH. After recrystallization, N-substituted-rhodanine derivatives (RhAs) were obtained as follows.
A mixture of 1-adamantanamine hydrochloride (200 mg, 1.1 mmol)and sodium hydroxide (1.6 g, 0.04 mol) were heated at 40 C in methanol (25 ml) with magnetic stirring for 1 h. The solution was recovered by filtration and the solution was transferred to flask, the 1-pyrenecarboxaldehyde (230 mg, 1 mmol) in 20ml methanol was then added. The solution was refluxed for 12 h and cooled to room temperature. The cooled solution was added NaBH4 (500 mg, 13.2 mmol) and then refluxed about 6 h and cooled to room temperature. The mixture was concentrated by rotary evaporator and the solid was dissolved in 60 ml CH2Cl2 and washed with 100ml water three times. The organic layer was then concentrated by rotary evaporator and dissolved in 10 ml acetone solution accompany addition of small amount of HCl (1 M, 0.5 ml). The precipitation was collected under vacuum to obtain a yellow solid258 mg (yield 64.2%). m.p. >250 C .1H NMR (500 MHz, D2O), delta 7.67-8.33 (9HPyrene-H), 4.10 (2H, CH2), 2.20 (3H, CH), 1.90 (6H, CH2), 1.64-1.76 (6H, CH2) ppm.13C NMR (125 MHz, CD3OD-d4): delta 132.46, 131.30, 130.63, 129.69, 128.87, 128.74,128.35, 127.01, 126.38, 125.88, 125.67, 124.84, 124.75, 124.53, 124.20, 121.62,58.25, 40.40, 38.07, 35.26, 29.39 ppm. MALDI-TOF: m/z calcd for C27H28N+: 366.52;found: 366.91; elemental analysis calcd (%) for C27H28NCl: C 80.67, H 7.02, N 3.48;found: C 79.56, H 7.64, N, 3.31.
In toluene at 70℃; for 4h; Inert atmosphere; Dean-Stark;
In a double neck round bottom flask fixed with Dean-Stark assemblyunder nitrogen atmosphere, polycyclic aromatic hydrocarbon(2.40 mmol) and 3-(diethoxy (methyl)silyl) propan-1-amine(2.40 mmol) were mixed in toluene (20 ml). The reaction mixturewas refluxed for 4h at 70 °C to yield (Z)-N- (anthracen-10-ylmethylene)-3-(diethoxy(methyl)silyl) propan-1-amine (2a). The obtained compound 2a (1.94 mmol) was then treated with diethanolamine(1.94 mmol) along with addition of catalytic amount ofpotassium hydroxide (0.2 mmol) and the solution was againrefluxed for 5h at 100 °C. After refluxing, the reaction mixture wascooled to room temperature followed by solvent evaporation whichgave semi-solid residue as desired product (3a). The obtainedorganosilocane was isolated by adding hexane (5 ml) and stirringthe solution for 1 h. The solid pure compound was obtained afterfiltration and drying under vacuum. To confirm its structure, silane(2a) was also isolated by first evaporating the solvent and thenadding hexane (5 ml) to the obtained oil.
2-(pyren-1-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
93%
In dimethyl sulfoxide at 90℃; for 18h;
2.3. General procedure for the synthesis of naphthoquinone-imidazolehybrids (3a, 3b)
General procedure: A solution of 1H-indole-3-carbaldehyde, or pyrene-1-carbaldehyde(1.05 mmol) in DMSO (10 mL) was added dropwise at room temperatureto a stirred solution of 2,3-diaminonaphthalene-1,4-dione(1 mmol) in DMSO (10 mL). The mixture was then stirred and heatedat 90 °C for 18 h (Scheme 1). After the reactionwas completed, the mixturewas allowed to cool and poured into H2O (50 mL) and then extractedwith EtOAc (3 × 50 mL). The combined organic extracts wereevaporated under reduced pressure. The crude mixture was washedwith water several times and followed by methanol, acetone, anddiethyl ether, respectively. Thus, the pure desired compoundswere successfullyobtained without any further purification process
1.2 The synthesis method of compound PH-RISS-1, the specific steps are as follows:
(2) In a 10mL round bottom flask, The intermediate compound 1a (0.09g, 0.3mmol) and 1-pyrenecarbaldehyde (0.069g, 0.3mmol) obtained through step (1) were dissolved in 3mL of absolute ethanol, Then add anhydrous sodium acetate (0.024g, 0.03mmol) to the round bottom flask, The reaction mixture was refluxed for 16h at 85°C, A red solid precipitated after cooling to room temperature, Filter to get the red compound, Reuse the dichloromethane/methanol system with a volume ratio of 15:1 to separate and purify the product through the column. To obtain the compound PH-RISS-1, The yield was 90.1%;
3-amino-2,4-dicyano-1-(pyren-1-yl)-9H-fluorene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30%
With pyrrolidine In acetonitrile at 20℃; for 0.75h;
2.3.6. Method F - conventional one-pot procedure
General procedure: Compound 1 (1.00 mmol), appropriate aldehyde (1.50 mmol) andmalononitrile (1.50 mmol) were dissolved in acetonitrile. Pyrrolidine(1.20 mmol) as a catalyst was slowly added. The solution was stirred for45 min at room temperature. The precipitated solid was filtered andwashed with ethanol.
(E)-2-(2-(pyren-1-ylmethylene)-2,3-dihydro-1H-inden-1-ylidene)malononitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With piperidine In cyclohexane Reflux;
2.3.2. Method B - conventional procedure
General procedure: Compound 1 (1.00 mmol) and appropriate aldehyde (1.00 mmol)were dissolved in cyclohexane (10 mL). A few drops of piperidine wereadded under stirring. After adding piperidine, and the reaction mixturebecomes reddish. After refluxing for 3-4 h, The reaction mixture wasthen cooled to room temperature, and the precipitated solid was filteredand recrystallized from ethanol.
With potassium <i>tert</i>-butylate In ethanol at 90℃; for 24h; Inert atmosphere;
2 Example 2 Preparation of 2-[4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl]-3-(1-pyrenyl)acrylonitrile (Py-2Ph-Cz)
Under the protection of nitrogen, the prepared (4-(carbazol-9-yl)-1,1'-biphenyl-4'-yl)acetonitrile in Example 1 and 1-pyrenecarboxaldehyde and potassium tert-butoxide were addedIn a double-necked flask (molar ratio is 1: (1~3):3), then add 10~20mL of absolute ethanol, stir vigorously, and keep the temperature at 90°C, reflux for 24h, cool to room temperature, wash with ethanol and filter to obtain the initial product, which is further mixed in dichloromethane and n-hexaneRecrystallize from solvent to obtain2-[4'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl]-3-(1-pyrenyl)acrylonitrile (Py-2Ph Cz ), its molecular structure is shown in formula (2) in 2a, its synthetic route is shown in formula (2), and its yield is about 74%
2-(pyren-1-yl)naphtho[1,2-d]oxazole-5-sulfonic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With sodium hydroxide In ethanol at 20℃; for 168h;
2.2. Synthesis of the fluorophores 1-2
General procedure: 2-Aryl-substituted naphtho[1,2-d]oxazoles 1-2 were synthesizedaccording to the modified literature procedure (Scheme 1) [27]. 4-Amino-3-hydroxynaphthalene-1-sulfonic acid (0.84 mmol) and NaOH (0.84mmol) were dissolved in ethanol (50 mL) at 20 C. The correspondingaldehyde derivative (1.01 mmol) was added to the reaction mixture inportions with vigorous stirring for 2 h. The resulting mixture was stirredfor 2 h and kept at room temperature for 7 days. Then ethanol wasevaporated under reduced pressure. The crude product was purifiedusing column chromatography (silica gel, ethanol/36% solution of HCl(3:1 v/v) as the eluent) to give the target naphtho[1,2-d]oxazole derivatives1-2, which were characterized by 1H NMR and 13C NMRspectroscopy and mass spectrometry (Figs. S3-S6, ESI).
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