* 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 phosphorus tribromide In chloroform at 0 - 60℃; for 2 h; Inert atmosphere
A 5 L round-bottom flask was substituted with nitrogen gas, and 107 g of Formula 1-c (0.43 mol) was added thereto, and dissolved by addition of 2.7 L of chloroform. At 0° C., 180.3 g of tribromophosphine (1.92 mol) was slowly dropwise added thereto, followed by stirring at 60° C. for 2 hours. The resultant product was cooled to room temperature, added to 2 L of water, added with a sodium hydroxide aqueous solution until pH reached 11, and extracted with methylene chloride. Then, an organic layer was separated. After removal of moisture, and removal of a solvent by vacuum distillation, the precipitated solid was washed with ethanol, and filtered so as to provide 100 g of Formula 1-d brown solid (yield 99percent).
98.7%
With phosphorus tribromide In chloroform at 0℃; for 5 h; Inert atmosphere; Reflux
Under a nitrogen atmosphere, asolution of 4-bromo-2,2’-bipyridineN-oxide (786 mg, 3.13 mmol) in drychloroform (10 mL) was cooled to0 °C and PBr3 (1.0 mL, 10 mmol) wasadded. After refluxing for 5 h, the solution was poured into ice water, basified with 6 Naqueous NaOH solution and extracted with CHCl3. The organic layer was dried overanhydrous Na2SO4 and concentrated to give white solid 8 (728 mg, 3.09 mmol, 98.7percent).1H NMR (CDCl3): = 8.69 (d, J = 5.0 Hz, 1H), 8.63 (d, J = 1.8 Hz, 1H), 8.49 (d, J =5.1 Hz, 1H), 8.39 (d, J = 8.0 Hz, 1H), 7.83 (dt, J1 = 8.0 Hz, J2 = 1.6 Hz, 1H), 7.48 (dd, J1= 5.1 Hz, J2 = 1.8 Hz, 1H), 7.34 (ddd, J1 = 7.5 Hz, J2 = 4.8 Hz, J3 = 1.6 Hz, 1H). IR(KBr): = 1565, 1545, 1452, 1386, 1280, 1066, 994, 833, 787, 687 cm-1. Mp:51.5-53 °C. ESI-MS: m/z = 256.9, 258.9 [8+Na]+ (calcd. for C10H7N2Br+Na = 256.9, 258.9).
20.9 g
With phosphorus tribromide In chloroform at 0℃; for 2 h; Reflux
The stirred suspension of C (27.0 g; 0.108 mol) in 500 ml ofchloroform was cooled to 0°C and 50 ml of phosphorus tribromide was added (0.526 mol)was added dropwise. The mixture obtained was refluxed for 2 h, poured onto ice andneutralized with 20percent NaOH. The organic phase was separated and the water layer wasextracted with dichloromethane (3 x 100 ml). The combined organic extracts were washedwith cold water (100 ml), dried with Na2SO4 and evaporated. The crude product wascrystallized from ethanol, to give 20.9 g of white powder crystals (mp 53-55 °C; yield 83percent).
Reference：
[1] Patent: US2012/247546, 2012, A1, . Location in patent: Page/Page column 29
[2] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[3] European Journal of Organic Chemistry, 2014, vol. 2014, # 28, p. 6295 - 6302
[4] Journal of the Chemical Society. Perkin Transactions 2, 1998, # 10, p. 2281 - 2288
[5] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1984, # 8, p. 1293 - 1302
[6] Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6653 - 6661
[7] Chemical Papers, 2012, vol. 66, # 8, p. 733 - 740
[8] Polyhedron, 2014, vol. 67, p. 381 - 387
[9] Inorganic Chemistry, 2015, vol. 54, # 6, p. 2742 - 2751
2
[ 14163-00-9 ]
[ 14162-95-9 ]
Yield
Reaction Conditions
Operation in experiment
75%
at 130℃; for 2 h; Microwave irradiation
Compound 3 (1.7 g, 8.1 mmol) was dissolved in 20.0 cm3glacial acetic acid. To this solution 3.0 cm3 acetylbromide (40.5 mmol) were added. The solution immediatelyturned yellow. The microwave vessel was sealedand heated to 130 C in a way that during a period of10 min 130 C had to be reached using a maximumpower of 1000 W. The reaction temperature then wasmaintained for 2 h after which the vessel was allowed tocool down to room temperature. After cooling, thesolution was poured onto ice and basified to pH 10–11with sodium hydroxide solution (6 N). The aqueous phasewas extracted three times with CH2Cl2 (40 cm3 each).The solvent was evaporated under reduced pressure. Theobtained light brown oil solidified at room temperatureovernight. The crude product was further purified bydistillation under reduced pressure to obtain a white solid.Yield: 75percent (1.6 g, 6.8 mmol); m.p.: 53–55 C; MS (EI):m/z (percent) = 234.3 (85) [M?], 235.9 (83) [M?], 155.1 (100)[M?–Br].
Reference：
[1] Inorganic Chemistry, 2012, vol. 51, # 11, p. 5985 - 5987
[2] Monatshefte fur Chemie, 2017, vol. 148, # 6, p. 991 - 998
[3] Journal of Inorganic Biochemistry, 2014, vol. 134, p. 83 - 91
[4] Synthesis, 1998, # 3, p. 321 - 324
[5] Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6653 - 6661
[6] Journal of the Chemical Society. Perkin Transactions 2, 1998, # 10, p. 2281 - 2288
[7] Patent: US6605200, 2003, B1,
[8] Patent: US2012/247546, 2012, A1,
[9] Chemical Papers, 2012, vol. 66, # 8, p. 733 - 740
[10] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[11] Polyhedron, 2014, vol. 67, p. 381 - 387
[12] Inorganic Chemistry, 2015, vol. 54, # 6, p. 2742 - 2751
3
[ 33421-43-1 ]
[ 14162-95-9 ]
Reference：
[1] Chemical Communications, 2010, vol. 46, # 31, p. 5695 - 5697
[2] Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6653 - 6661
[3] Synthesis, 1998, # 3, p. 321 - 324
[4] Patent: US2012/247546, 2012, A1,
[5] Chemical Papers, 2012, vol. 66, # 8, p. 733 - 740
[6] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[7] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[8] Polyhedron, 2014, vol. 67, p. 381 - 387
[9] Journal of Inorganic Biochemistry, 2014, vol. 134, p. 83 - 91
[10] Inorganic Chemistry, 2015, vol. 54, # 6, p. 2742 - 2751
[11] Monatshefte fur Chemie, 2017, vol. 148, # 6, p. 991 - 998
4
[ 14163-00-9 ]
[ 14162-95-9 ]
[ 14163-03-2 ]
Yield
Reaction Conditions
Operation in experiment
80.3%
for 4 h; Inert atmosphere; Reflux
Under a nitrogen atmosphere, acetylbromide (2.0 mL, 27 mmol) wasadded to a solution of4-nitro-2,2’-bipyridine N-oxide (1.00g, 4.60 mmol) in glacial acetic acidand the mixture was refluxed for 4 h. After cooling to room temperature, the mixturewas poured into ice water and basified with 16 N aqueous NaOH solution and extractedwith CHCl3. The organic layer was dried over anhydrous Na2SO4 and concentrated toafford the mixture of 4-bromo-2,2’-bipyridine N-oxide and 8. The mixture was purified bysilica gel column choromatography with ethyl acetate/hexane/triethylamine (v/v/v,40/13/1) to obtain 4-bromo-2,2’-bipyridine N-oxide (927 mg, 3.69 mmol, 80.3percent) and 8(158 mg, 0.673 mmol, 14.6percent) as a white solid. 1H NMR (CDCl3): = 8.95 (d, J = 8.0 Hz, 1H), 8.74 (d, J = 4.9 Hz, 1H), 8.41 (d, J =8.0Hz, 1H), 8.15 (d, J = 6.9 Hz, 1H), 7.85 (dt, J1 = 7.8 Hz, J2 = 1.8 Hz, 1H), 7.40-7.35 (m,2H). IR (KBr): = 3065, 1584, 1567, 1463, 1437, 1396, 1254, 1235, 824, 737, 649 cm-1.Mp: 107-108 °C.ESI-MS: m/z = 272.9, 274.9 [M+Na]+ (calcd. for C10H7N2OBr+Na = 272.9, 274.9).
With phosphorus tribromide; In chloroform; at 0 - 60℃; for 2h;Inert atmosphere;
A 5 L round-bottom flask was substituted with nitrogen gas, and 107 g of Formula 1-c (0.43 mol) was added thereto, and dissolved by addition of 2.7 L of chloroform. At 0 C., 180.3 g of tribromophosphine (1.92 mol) was slowly dropwise added thereto, followed by stirring at 60 C. for 2 hours. The resultant product was cooled to room temperature, added to 2 L of water, added with a sodium hydroxide aqueous solution until pH reached 11, and extracted with methylene chloride. Then, an organic layer was separated. After removal of moisture, and removal of a solvent by vacuum distillation, the precipitated solid was washed with ethanol, and filtered so as to provide 100 g of Formula 1-d brown solid (yield 99%).
98.7%
With phosphorus tribromide; In chloroform; at 0℃; for 5h;Inert atmosphere; Reflux;
Under a nitrogen atmosphere, asolution of 4-bromo-2,2?-bipyridineN-oxide (786 mg, 3.13 mmol) in drychloroform (10 mL) was cooled to0 C and PBr3 (1.0 mL, 10 mmol) wasadded. After refluxing for 5 h, the solution was poured into ice water, basified with 6 Naqueous NaOH solution and extracted with CHCl3. The organic layer was dried overanhydrous Na2SO4 and concentrated to give white solid 8 (728 mg, 3.09 mmol, 98.7%).1H NMR (CDCl3): = 8.69 (d, J = 5.0 Hz, 1H), 8.63 (d, J = 1.8 Hz, 1H), 8.49 (d, J =5.1 Hz, 1H), 8.39 (d, J = 8.0 Hz, 1H), 7.83 (dt, J1 = 8.0 Hz, J2 = 1.6 Hz, 1H), 7.48 (dd, J1= 5.1 Hz, J2 = 1.8 Hz, 1H), 7.34 (ddd, J1 = 7.5 Hz, J2 = 4.8 Hz, J3 = 1.6 Hz, 1H). IR(KBr): = 1565, 1545, 1452, 1386, 1280, 1066, 994, 833, 787, 687 cm-1. Mp:51.5-53 C. ESI-MS: m/z = 256.9, 258.9 [8+Na]+ (calcd. for C10H7N2Br+Na = 256.9, 258.9).
20.9 g
With phosphorus tribromide; In chloroform; at 0℃; for 2h;Reflux;
The stirred suspension of C (27.0 g; 0.108 mol) in 500 ml ofchloroform was cooled to 0C and 50 ml of phosphorus tribromide was added (0.526 mol)was added dropwise. The mixture obtained was refluxed for 2 h, poured onto ice andneutralized with 20% NaOH. The organic phase was separated and the water layer wasextracted with dichloromethane (3 x 100 ml). The combined organic extracts were washedwith cold water (100 ml), dried with Na2SO4 and evaporated. The crude product wascrystallized from ethanol, to give 20.9 g of white powder crystals (mp 53-55 C; yield 83%).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,4-dioxane; water; for 24h;Reflux;
A 1 L round-bottom flask was charged with 100 g of Formula 1-d (0.43 mol), 148.2 g of Formula 1-e (0.60 mol), 117 g of potassium carbonate (K2CO3) (0.85 mol), 24.6 g of Pd(PPh3)4, 200 mL of water, 500 mL of dioxane and 100 mL of tetrahydrofuran, followed by reflux for 24 hours. After the reaction was completed, the resultant product was subjected to phase separation. The aqueous phase was removed, and the organic layer was separated, and vacuum-evaporated. Then, the resultant product was purified with column chromatography using hexane and ethylacetate as developing solvents so as to provide a solid. Finally, through drying, 65.7 g of a solid (yield 55%) was obtained.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 85 - 100℃; for 22.33h;Inert atmosphere;
General procedure: Under a nitrogen atmosphere,Pd(PPh3)4 (37.2 mg, 0.032 mmol) and 2 M aqueous K2CO3solution were added to a solution of 12 (122 mg, 0.322mmol) and 8 (75.1 mg, 0.319 mmol) in dry toluene (40 mL)and ethanol (2 mL), and the solution was stirred at 85 C for20 min. The temperature was raised to 100 C and thereaction mixture was stirred for 22 h. After cooling to roomtemperature, the reaction mixture was washed with water(30 mL × 3) and the organic layer was dried over anhydrousNa2SO4. After concentration, ethanol (5 mL) was added tothe residue and the precipitate was filtered, washed with ethanol (5 mL × 2) and ether (5mL × 2) to give crude product. The crude product was purified by silica gel columnchromatography with chloroform / triethylamine (v/v, 40/1) to give L4 (111 mg, 0.274mmol, 85.9%) as a yellow solid. 1H NMR (CDCl3): = 8.81 (d, J = 5.1 Hz, 1H), 8.68 (d, J = 5.2 Hz, 1H), 8.60 (s, 1H),8.50 (d, J = 8.0 Hz, 1H), 8.28-8.23 (m, 4H), 7.87 (dt, J1 = 8.0 Hz, J2 = 1.4 Hz, 1H),7.78-7.71 (m, 3H), 7.55-7.47 (m, 5H), 7.34 (ddd, J1 = 7.5 Hz, J2 = 4.8 Hz, J3 = 1.2 Hz,1H). IR (KBr): = 1583, 1541, 1461, 1393, 813, 763 cm-1. Mp: 257-258 C.MALDI-TOF-MS: m/z = 406.8 [L4+H]+ (calcd. for C30H18N2+H = 407.1).
With Acetyl bromide; acetic acid; for 4h;Inert atmosphere; Reflux;
Under a nitrogen atmosphere, acetylbromide (2.0 mL, 27 mmol) wasadded to a solution of4-nitro-2,2?-bipyridine N-oxide (1.00g, 4.60 mmol) in glacial acetic acidand the mixture was refluxed for 4 h. After cooling to room temperature, the mixturewas poured into ice water and basified with 16 N aqueous NaOH solution and extractedwith CHCl3. The organic layer was dried over anhydrous Na2SO4 and concentrated toafford the mixture of 4-bromo-2,2?-bipyridine N-oxide and 8. The mixture was purified bysilica gel column choromatography with ethyl acetate/hexane/triethylamine (v/v/v,40/13/1) to obtain 4-bromo-2,2?-bipyridine N-oxide (927 mg, 3.69 mmol, 80.3%) and 8(158 mg, 0.673 mmol, 14.6%) as a white solid. 1H NMR (CDCl3): = 8.95 (d, J = 8.0 Hz, 1H), 8.74 (d, J = 4.9 Hz, 1H), 8.41 (d, J =8.0Hz, 1H), 8.15 (d, J = 6.9 Hz, 1H), 7.85 (dt, J1 = 7.8 Hz, J2 = 1.8 Hz, 1H), 7.40-7.35 (m,2H). IR (KBr): = 3065, 1584, 1567, 1463, 1437, 1396, 1254, 1235, 824, 737, 649 cm-1.Mp: 107-108 C.ESI-MS: m/z = 272.9, 274.9 [M+Na]+ (calcd. for C10H7N2OBr+Na = 272.9, 274.9).
With tetrakis(triphenylphosphine) palladium(0); triethylamine; In 1,2-dimethoxyethane; at 120℃; for 3h;Microwave irradiation;
In a sealed tube under argon atmosphere 4-bromo-2,2?-bipyridine (4, 0.05 g, 0.23 mmol) and propargyl alcohol (0.019 g, 0.35 mmol, 0.02 mL, 1.5 eq) were added to 2.5 mL of anhydrous DME. To the reaction mixture 1.5 mL of triethylamine was added and the solution was degassed. Finally Pd(PPh3)4 (0.0129 g, 0.011 mmol, 0.05 eq) was added. The mixture was heated to 120 C for 3 h under microwave irradiations. After cooling down, solution was filtrated on the celite. Filtrate was evaporated and crude product was dissolved in a small amount of acetone. Then, under vigorous stirring diethyl ether and next hexane were added to allow triphenylphosphine derivative to precipitate. Mixture was filtrated on a Buechner funnel over a large plug of silica and washed with diethyl ether and hexane. The filtrate was evaporated under reduced pressure to afford the final product as a yellowish solid in 56% yield. IR (cm- 1): 664, 787, 853, 905, 973, 993, 1034, 1088, 1213, 1391, 1461, 1538, 1566, 1581, 1601, 2850, 2914, 3031, 3217. 1H NMR (400 MHz, CDCl3): delta/ppm = 2.19-2.12 (1H, t), 4.53 (2H, d, J = 6.2 Hz), 7.28 (1H, dd, J = 5.0, 1.4 Hz), 7.36 (1H, m) 7.87-7.79 (1H, m), 8.38 (1H, dd, J = 8.0, 1.0 Hz), 8.44 (1H, s), 8.63 (1H, d), 8.68(1H, dd, J = 3.5, 1.3 Hz); 13C NMR (101 MHz, CDCl3) delta/ppm = 156.25, 155.41, 149.15, 149.23, 137.02, 131.78, 125.35, 124.03, 123.30, 121.17, 92.01, 83.38, 51.44. HRMS [M + H]+ m/z calculated for C13H11N2O: 211.2319; found: 211.0868.
methyl 3-devinyl-3-ethynylpyropheophorbide-a[ No CAS ]
[ 14162-95-9 ]
methyl 3-[(2,2'-bipyridin-4-yl)ethynyl]-3-devinylpyropheophorbide-a[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
34%
With tris-(dibenzylideneacetone)dipalladium(0); diisopropylamine; In tetrahydrofuran; for 24h;Inert atmosphere; Darkness; Reflux;
General procedure: A THF (10mL) solution of H-Chl (20mg, 37mumol) was added dropwise to a refluxed THF solution (20mL) of 2-bromopyridine (77mg, 486mumol, 13equiv), Pd2(dba)3 (2.0mg, 2.2mumol), and diisopropylamine (1.0mL) for 1h in the dark under N2 (route B). After refluxing for 1h, the mixture was cooled down, poured into an aqueous saturated NaHCO3 solution, and extracted with CH2Cl2 several times. The combined organic phases were washed with H2O, dried over anhydrous Na2SO4, filtered, and concentrated in vacuo. The residue was purified by FCC (MeOH/CH2Cl2=2:98), followed by recrystallization from CH2Cl2 and hexane to give 2-py-Chl (16mg, 70%) as a black solid
With nickel(II) chloride hexahydrate; triphenylphosphine; zinc; In N,N-dimethyl-formamide; at 50℃; for 12h;Inert atmosphere;
PPh3 (4.51 g,17.2 mmol) and NiCl2*6H2O (1.03 g, 4.3 mmol) were dissolved in DMF (25 mL) under N2. Activated zinc powder (0.300 g,4.3 mmol) was added and the mixture was heated to 50C and stirred for 1 h until it turned dark red. After stirring for another hour, 4-bromo-2,2'-bipyridine (1.02 g, 4.3 mmol) was added and the mixture stirred at 50C for 12 h. After cooling to room temperature, the reaction mixture was poured into aqueous NH3 solution (150 mL, 32%) and then extracted with CH2Cl2 (3 * 50 mL). The organic phase was washed with water and dried over MgSO4.The solvent was removed under reduced pressure and the crude product purified by column chromatography (silica, MeOH/CH2Cl2,1:99) and then recrystallized from EtOH. Compound 1 was isolated as a white solid which was dried under vacuum (130 mg,0.419 mmol, 19%).
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