* 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
[ 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
3
[ 24463-15-8 ]
[ 16640-68-9 ]
[ 3029-19-4 ]
[ 74833-81-1 ]
Reference:
[1] European Journal of Organic Chemistry, 2006, # 19, p. 4367 - 4378
Reference:
[1] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 10, p. 1927 - 1932
7
[ 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
[26] Recueil des Travaux Chimiques des Pays-Bas, 1993, vol. 112, # 10, p. 535 - 548
[27] Nucleosides and Nucleotides, 1996, vol. 15, # 5, p. 1029 - 1039
[28] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 10, p. 1927 - 1932
[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
[35] ChemPlusChem, 2014, vol. 79, # 7, p. 1059 - 1064
[36] Applied Catalysis A: General, 2014, vol. 484, p. 84 - 96
[37] Supramolecular Chemistry, 2013, vol. 25, # 2, p. 69 - 78
[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 phosphorus tribromide; In tetrahydrofuran; at 20℃; for 0.5h;
Phosphorus tribromide (1.75 g) was dissolved in tetrahydrofuran (5 mL).Pyrenebenzyl alcohol (1.00 g) was added to the above solution in portions and the reaction was continued after the reaction was continued at room temperature for 30 minutes.The reaction mixture was suction filtered and washed with diethyl ether to give the target pyrene benzyl bromide (1.22 g, 96%).
With phosphorus tribromide; In tetrahydrofuran; at 20℃; for 1h;
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]+.
0.8 g
With phosphorus tribromide; In toluene; at 0℃; for 0.5h;Inert atmosphere;
Under the protection of Ar gas, put 1.0 g of pyrene methanol in a three-necked flask, and add 50 mL of freshly distilled toluene to the three-necked flask.The three-necked flask was cooled to 0 C, and then 0.5 mL of phosphorus tribromide was added dropwise to the system.After the addition was complete, stirring was continued at this temperature for 30 min.Then stirred at room temperature until the solution was clear.After the reaction was completed, 26 mL of a saturated sodium carbonate solution was added, and the layers separated, and the organic phase was washed twice with 26 mL of water and saturated brine, respectively. Followed by anhydrous magnesium sulfate, filtered, and then distilled off on a rotary evaporator most of the toluene, crystallization was cooled to give crystals after bromomethyl pyrene, filtered, and dried in vacuo to give bromomethyl pyrene 0.8g.The 0.8g bromomethyl pyrene was dissolved in 16mL of toluene,Add an equimolar amount of cetyl tertiary amine to the system,Stir at 50 C for 48 hours, during which a white precipitate appears.After the reaction was completed, the solid was filtered and the solid was washed with a small amount of toluene.Compound A was obtained by vacuum drying.Its structural formula is as follows
With triethylamine; In ISOPROPYLAMIDE; at 20℃; for 24.0h;
Synthetic Example 3Synthesis of 1-pyrenylmethyl 4'-nitrophenylcarbonate (First process); To the solution dissolved 5.0 g of <strong>[24463-15-8]1-pyrenemethanol</strong> (22 mmol; produced by Tokyo Chemical Industry Co., Ltd.) into 200 mL of dehydrated dimethylacetamide (dehydrated DMAc), 6.5 g of triethylamine (65 mmol) was added. After 4.3 g of 4-nitrophenyl chloroformate (22 mmol; produced by Wako Pure Chemical Industries, Ltd.) was added to this solution, the solution was reacted by stirring for 24 hours at room temperature. After completing the reaction, ice-water was poured into the reaction solution, and this mixed solution was extracted with dichloromethane, and further after organic layer after extraction was washed with water, the organic layer was condensed. Subsequently, toluene was poured into the condensed residue, and after the resultant crystal was filtered, the resultant crystal was dried to obtain 5.9 g of 1-pyrenylmethyl 4'-nitrophenylcarbonate (yield: 68%) as yellow crystal. Measurement results of 1H-NMR are shown as the follows:1H-NMR (400 MHz, CDCl3) delta (ppm): 6.02 (2H, s, OCH2), 7.25 (2H, d, J=9.3 Hz, ArH), 7.98-8.20 (9H, m, ArH), 8.27 (2H, d, J=9.3 Hz, ArH).
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.
With sodium hydride; In N,N-dimethyl-formamide; at 20℃; for 1h;Inert atmosphere;
General procedure: Appropriate diol (1 equiv), 1-bromomethyl pyrene (2.2 equiv), and 3 ml ([diol]=50 mM) anhydrous DMF were placed in a round-bottomed flask under N2. NaH (3.0 equiv) was added to the solution at room temperature. The reaction mixture was stirred for 1 h at this constant temperature. Following completion, the reaction was quenched with H2O. The solution was diluted with water, and extracted using DCM. The organic layer was filtered through Na2SO4 and evaporated to dryness. The resulting residue was purified over silica gel (1:5, EtOAc/Hexane) to yield the desired product.
49%
With sodium hydride; In N,N-dimethyl-formamide; at 20℃; for 1h;Inert atmosphere;
General procedure: In the initial mixed solution prepared in the round flask in Example 1, 3-chloro-2-(chloromethyl)prop-1-ene(50 [mu] L, 0.47 mmol)By following the same procedure as in Example 1 except for using 1-pyrene methanol (240 mg, 1.03 mmol)Experiments were conducted to obtain a solid state of the compound containing pyrene dimer, 120 mg in 49% yieldOctane-1,8-diol (99 mg, 0.68 mmol) (1 eq.)And 1-(bromomethyl)pyrene (440 mg, 1.49 mmol) (2.2 eq.),3 mL ([diol] = 50 mM) in anhydrous dimethylformamide in (DMF)To room temperature in the presence and condition of N2 and NaH (3 eq.), It was added to the round bottom flask. The mixed solution in the flask was stirred at room temperature for 1 hour.After that,Then quenched and diluted with distilled water was added to the solution.next, The organics were extracted by the addition of methyl-dichloro (DCM) to the mixed solution,The resulting organic layer was again distilled under reduced pressure to reotgo so that solution filtered through a filter containing sodium sulfate (Na2SO4).The resultant was purified by silica gel column chromatography (EtOAc: Hexane = 1: 5 (volume ratio)) of the solid state compound containing pyrene dimer increasing the purity of the resultant using,To give the 120 mg at a yield of 31%.
With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 0 - 20℃;Inert atmosphere;
The pyrene based-CTA (py-CTA) was prepared as follows: CDP (1.00 g, 2.48 mmol) and <strong>[24463-15-8]1-pyrenemethanol</strong> (0.69 g, 2.97 mmol) was dissolved in dry DCM (40 mL) and the solution was purged with dry N2. Then, a solution of DCC (0.61 g, 2.97 mmol) and DMAP (30.0 mg, 0.25 mmol) in 10 mL of dry DCM was added dropwise to the reaction mixture in ice-water bath under stirring and was allowed to react at room temperature for 18 h. After removing insoluble N,N?-dicyclohexylurea (DCU) by suction filtration, the organic layer was further washed with 1 N HCl, saturated NaHCO3 and brine solution, and dried over anhydrous Na2SO4. The organic solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography using hexanes/ethyl acetate as mobile phase (4:1, v/v), to get a yellowish solid compound (yield=85%). 1H NMR (Fig.1 A, CDCl3, delta, ppm): 8.0-8.33 (ArH, 9H, m), 5.88 (ArCH2O, 1H, s), 3.20-3.29 (SCH2CH2, 2H, t), 2.34-2.73 (OOCCH2CH2, 4H, m), 1.83 (CH2C(CH3)S, 3H, s), 1.57-1.67 (SCH2CH2, 2H, m), 1.25-1.37 (SCH2CH2(CH2)9CH3, 18H, m), 0.84-0.90 (CH2CH3, 3H, t). The 13C NMR spectrum (Fig.S1) can be found in the Supporting Information.
pyren-1-ylmethyl 3-(2-hydroxyphenyl)propanoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
Stage #1: 1-pyrenemethanol With n-butyllithium In tetrahydrofuran; hexane at -10℃; for 0.0333333h;
Stage #2: C6H4(CH2CH2C(O)O) In tetrahydrofuran; hexane at 20℃; for 16h;
pyren-1-ylmethyl 2-(thiophen-3-yl)acetate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 0 - 20℃; for 12.5h;Inert atmosphere;
General procedure: General SynthesisThe appropriate thiophene alcohol (0.82 mmol), the selected carboxylic acid (1.23 mmol), DCC(2.46 mmol) and DMAP (2.05 mmol) were dissolved in CH2Cl2 (15 mL) at 0 C for 30 min. The resultingmixture was stirred at room temperature for 12 h under inert atmosphere. The suspension was filteredin order to remove DCU formed during the reaction, and the filtrates were concentrated under reducedpressure at 45 C. The crude product was purified by column chromatography in silica gel, usingn-hexane/CH2Cl2 (2:5) and then pure CH2Cl2 as eluent to give the desired product TPM1 (Figure 1).All monomers were characterized by 1H- and 13C-NMR spectroscopy and the spectra are included inthe Supplementary Materials.
Stage #1: 11-bromoundecanoic acid With thionyl chloride In toluene for 5h; Reflux; Enzymatic reaction;
Stage #2: 1-pyrenemethanol With triethylamine In tetrahydrofuran at 20℃; for 4h;
General procedure: SOCl2 (7 mL) wasadded into a solution of 11-bromoundecanoic acid (2.69 g, 10.0 mmol) in drytoluene (10 mL), and then the mixture was refluxed for 5 h. The solvent wasremoved under reduced pressure, and re-dissolved by dry tetrahydrofuran (THF, 5mL). It was added dropwise into a solution of 9-anthracenylmethanol (2.00 g,9.6 mmol) and triethylamine (TEA, 1.5 mL) in dry THF (20 mL), and then themixture was stirred at room temperature for 4 h. Afterthat, the solvent was removed under reduced pressure, and re-dissolved bydichloromethane. The organic layer was washed by water, brine, dried withsodium sulfate, filtered, and followed by the removal of the solvent undervacuum. Finally, the crude wasdissolved in pyridine (10 mL), and the mixturewas stirred at 50 oC for 6 h. The solvent was removed under reducedpressure, and re-dissolved by methanol. The methanol solution precipitated inether, and the precipitates were filtered and dried to afford a yellow solid, 9-AP-10. The synthesis of 1-BP-10, 2-NP-10, 2-AP-10, and 1-PP-10were carried out by the same methodof 9-AP-10.The difference wasthat 1-phenylmethanol,2-naphthalenylmethanol, 2-anthracenylmethanol, and 1-pyrenylmethanol were used insteadof 9-anthracenylmethanol, respectively.