* 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 tetrakis(triphenylphosphine) palladium(0); hexamethyldistannane In benzene for 72 h; Heating
To the 250 ml 2-neck flask was added 2,5-Dibromopyridine (8 g, 33.8 mmol), hexamethylditin (5.53 g, 0.0169 mmol) and Pd (PPh3) 4 (0.80 g)And the mixture was heated with stirring for 72 hours.After completion of the reaction, the temperature was lowered to room temperature,After the excess ether was added, the resulting solid product was filtered and subjected to column chromatography using chloroform and methanol to obtain 4.21 g (yield: 80percent) of Compound A
80%
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin) In m-xylene at 130℃; for 72 h; Darkness
With m-xylene as the solvent, 2,5-dibromopyridine (5.0 mmol) was addedReacts with n-butyltin (5.5 mmol),Using tetrakis(triphenylphosphine)palladium as a catalyst, the reaction was carried out at 130°C in the dark for three days. After the reaction, ethylenediaminetetraacetic acid disodium salt was added to remove the remaining tin reagent. The organic phase was collected by extracting the mixture with dichloromethane and concentrating. The crude product was isolated by column chromatography to give the pure product. Yield: 80percent.
42%
Stage #1: With bis(tri-n-butyltin) In xylene at 60℃; for 0.25 h; Stage #2: at 120℃; for 8 h;
A reaction vessel was charged with 6.0 g of 2,5-dibromopyridine, 7.0 ml of bistributyltin, and 120 ml of xylene, followed by heating and stirring at 60°C for 15 minutes. Further, 700 mg of tetrakis(triphenylphosphine)palladium was added thereto, followed by stirring at 120°C for 8 hours. After cooling to room temperature, the insoluble materials were removed by filtration, and the filtrate was washed with 150 ml of an aqueous ethylenediamine tetraacetate solution. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: cyclohexane/toluene) to obtain 1.7 g (yield 42percent) of 5,5'-dibromo-[2,2']bipyridine as a yellow powder.
Reference:
[1] Journal of the Chemical Society. Perkin Transactions 1, 2002, # 10, p. 1226 - 1231
[2] Patent: KR2017/79357, 2017, A, . Location in patent: Paragraph 0231-0234
[3] Patent: CN104086596, 2017, B, . Location in patent: Paragraph 0035; 0036
[4] Synthesis, 2005, # 3, p. 458 - 464
[5] Chemistry - A European Journal, 2006, vol. 12, # 16, p. 4351 - 4361
[6] Patent: EP2241568, 2010, A1, . Location in patent: Page/Page column 43
[7] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
[8] Journal of Organic Chemistry, 2002, vol. 67, # 2, p. 443 - 449
[9] European Journal of Inorganic Chemistry, 2009, # 32, p. 4850 - 4859
[10] Patent: WO2018/127540, 2018, A1,
2
[ 366-18-7 ]
[ 15862-18-7 ]
Yield
Reaction Conditions
Operation in experiment
86%
at 150℃; for 15 h;
2,2′-bipyridine (1, 4.99 g, 0.032 mol) and bromine (10.24 g,0.064 mol) were first added in a hydrothermal reaction container andheated to 150 °C and annealed for 15 h. Then, the mixture was cooledand the hard solidwas powdered and following treatedwith Na2SO3 solutionto remove the unreacted bromine. Finally itwas basifiedwith sodiumhydroxide and filtered. The white solid product 5,5′-dibromo-2,2′-bipyridine was obtained by the chromatography on silica(CH2Cl2). 5,5′-dibromo-2,2′-bipyrimidine, 8.64 g (86percent). m.p. 221.6–222.1 °C. 1H-NMR (400 MHz, CDCl3, δ): 7.95 (d, 2H), 8.28 (s, 2H),8.71(d, 2H); 13C-NMR (100 MHz, CDCl3, δ): 121.47 (C5), 122.25 (C3),139.64 (C4); 150.28 (C6),153.64 (C2); IR (KBr): 3049 (C\\H,stretching), 1562, 1453, 1356 (Ar, stretching), 636 (C\\Br, stretching).Anal. calcd for C10H6N2Br2: C 38.22, H 1.91, N 8.92, Br 50.95; found: C38.26, H 1.94, N 8.90, Br 50.97.
86%
at 150℃; for 15 h;
2,2'-bipyridyl (4.99 g, 0.032 mol) and liquid bromine (10.24 g, 0.064 mol)Put into a reaction kettle at a pressure of 2.0 atm at 150 ° C for 15 hours, then cool to room temperature after the reaction, pulverize the solid, add to the Na2SO3 solution and stir to remove unreacted bromine, filter, and alkalizate the acid with a 5percent NaOH solution. , filtration, to obtain a crude product, column separation with ethyl acetate / petroleum ether,8.64 g of white 5,5'-dibromo-2,2'-bipyridine was obtained in a yield of 91percent.
Reference:
[1] Reactive and Functional Polymers, 2016, vol. 106, p. 93 - 98
[2] Patent: CN105130885, 2018, B, . Location in patent: Paragraph 0024; 0026; 0027; 0030; 0033; 0036
[3] New Journal of Chemistry, 2018, vol. 42, # 17, p. 14067 - 14070
[4] Chemistry - A European Journal, 2015, vol. 21, # 51, p. 18576 - 18579
[5] Patent: WO2009/118742, 2009, A1,
3
[ 223463-13-6 ]
[ 15862-18-7 ]
Yield
Reaction Conditions
Operation in experiment
4.4 g
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin) In toluene at 120℃; for 72 h; Inert atmosphere
3-Bromo-6-iodopyridine (Tokyo Chemical Industry Co., Ltd., 11.3 g),Dissolved in dehydrated toluene (Wako Pure Chemical Industries, Ltd., 320 ml), hexabutyl distannane (Bu 3 SnSnBu 3, Tokyo Chemical Industry Co., Ltd., 10 ml), tetrakistriphenylphosphine palladium (0) (Tokyo Chemical Industry Co., , The mixture was degassed by nitrogen bubbling for 1 hour, and reacted with stirring at 120 ° C. for 3 days. After the reaction, the temperature was returned to room temperature, washed with water, the organic layer was dried over sodium sulfate, filtered and concentrated, and the residue was purified by silica gel column chromatography to obtain 4.4 g of 5,5'-dibromo-2,2'-bipyridine Obtained
4.4 g
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin) In toluene at 120℃; for 72 h; Inert atmosphere
3-Bromo-6-iodopyridine (Tokyo Chemical Industry Co., Ltd., 11.3 g),Hexabutyl distannane(Bu3SnSnBu3, Tokyo Chemical Industry Co., Ltd., 10 ml),Tetrakistriphenylphosphine palladium (0)(Tokyo Chemical Industry Co., Ltd., 1.2 g) was dissolved in dehydrated toluene(Wako Pure Chemical Industries, Ltd., 320 ml)Degassed by nitrogen bubbling for 1 hour, and reacted with stirring at 120 ° C. for 3 days.After the reaction, the temperature was returned to room temperature, then washed with water, the organic layer was dried with sodium sulfate, filtered and concentrated,The residue was purified by silica gel column chromatography,4.4 g of 5,5'-dibromo-2,2'-bipyridine was obtained.Synthesis was confirmed by 1 H-NMR measurement (FIG. 6).
1.68 g
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin) In toluene for 72 h; Inert atmosphere; Reflux
5-Bromo-2-iodopyridine (6.60 g, 23.2 mmol) and Pd(PPh3)4 (0.72 g, 0.6 mmol) were dissolved in anhydrous PhMe (120 mL) under N2. Hexa-n-butylditin (7.25 g, 12.5 mmol)was added and the solution heated at reflux for 3 days. The mixture was filtered through celite and the solvent removed. The residue was chromatographed on silica using a DCM to EtOAc gradient. The resulting residue was crystallised from EtOAc/hexanes to give the 5,5’- dibromo-2,2’-bipyridine (1.22 g, 33 percent) as a pale yellow powder. The crystallisation liquors were evaporated under reduced pressure and the residue dissolved in DCM, hexanes wereadded and the volume of solvent reduced. The resulting precipitate was collected by filtration and air dried to give a second crop of the product (0.46 g, 13 percent) as a cream powder.
Reference:
[1] Journal of the American Chemical Society, 2012, vol. 134, # 22, p. 9488 - 9497
[2] ACS Catalysis, 2017, vol. 7, # 12, p. 8413 - 8419
[3] Inorganic Chemistry, 2015, vol. 54, # 21, p. 10429 - 10439
[4] Chemical Communications, 2015, vol. 51, # 79, p. 14785 - 14788
[5] European Journal of Inorganic Chemistry, 2015, vol. 2015, # 29, p. 4878 - 4884
[6] Patent: JP2016/199508, 2016, A, . Location in patent: Paragraph 0052-0055
[7] Journal of the American Chemical Society, 2017, vol. 139, # 38, p. 13308 - 13311
[8] Patent: JP2016/199507, 2016, A, . Location in patent: Paragraph 0078; 0079-0081
[9] Patent: WO2018/127540, 2018, A1, . Location in patent: Page/Page column 21
4
[ 626-55-1 ]
[ 15862-18-7 ]
Reference:
[1] Tetrahedron, 2013, vol. 69, # 48, p. 10284 - 10291
[2] Patent: CN107935919, 2018, A, . Location in patent: Paragraph 0049; 0051
5
[ 626-55-1 ]
[ 16663-58-4 ]
[ 15862-18-7 ]
Yield
Reaction Conditions
Operation in experiment
60%
Stage #1: With lithium diisopropyl amide In diethyl ether at -78℃; Inert atmosphere Stage #2: at -78℃; Inert atmosphere
5,5'-Dibromo-2,2'-bipyridine (9b) LDA (16.5 mmol) was added to a suspension of 2b (15.0 mmol) in diethyl ether at -78 °C. Compound 1b (2.60 g, 1.58 mL, 16.5 mmol) was added to it. Purification by column chromatography (60-120 mesh silica gel and 3percent EtOAc/hexane) gave 9b (2.8 g, 60percent) as a white solid; mp 190-192 °C; [Found: C, 38.32, H, 1.81, N, 8.43. C10H6N2Br2 requires C, 38.25, H, 1.92, N, 8.92percent]; Rf (3percent EtOAc/hexane) 0.92; 1H NMR (400 MHz CDCl3) δ 8.70-8.71 (d, J=2.08 Hz, 2H), 8.28-8.30 (d, J=8.20 Hz, 2H), 7.92-7.95 (dd, J=2.35, 8.50 Hz, 2H); 13C NMR (100 MHz CDCl3) δ 153.5, 150.2, 139.6, 122.2, 121.4; MS m/z 314 (M+, 92), 233 (100), 206 (20), 154 (43), 127 (24), 103 (12), 76 (37), 63 (7), 50 (36percent).
With n-butyllithium In toluene at 0℃; for 0.0833333 h;
EXAMPLE 1 2-(3-hydroxy-pentane-3-yl)-5-bromo-pyridine(Batch Process) A toluene solution (24 mL) containing 2,5-dibromopyridine (21.11 mmoles) ad 3-pentanone (21.11 mmoles) were placed in a 125 mL jacketed flask under N2 at 20 C. in an ice bath. n-BuLi in hexanes (17.2 mL, 1.3 M, 22.36 moles; 1.06 equiv) was added via a syringe pump delivering at 0.25 mL/min. The mixture was stirred for 5 min and then quenched with 30 mL of MeOH. The reaction mixture was diluted with EtOAc (10 ?L in 1 mL EtOAc) and analyzed by GC/MS. The major product was 2-(3-hydroxy-pentane-3-yl)-5-bromo-pyridine (55.33percent) indicating selective lithiation at the 2 position. The major product was isolated and purified by column chromatography to afford 33percent isolated yield.
With tetrakis(triphenylphosphine) palladium(0); hexamethyldistannane; In benzene; for 72h;Heating;
To the 250 ml 2-neck flask was added 2,5-Dibromopyridine (8 g, 33.8 mmol), hexamethylditin (5.53 g, 0.0169 mmol) and Pd (PPh3) 4 (0.80 g)And the mixture was heated with stirring for 72 hours.After completion of the reaction, the temperature was lowered to room temperature,After the excess ether was added, the resulting solid product was filtered and subjected to column chromatography using chloroform and methanol to obtain 4.21 g (yield: 80%) of Compound A
80%
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin); In m-xylene; at 130℃; for 72h;Darkness;
With m-xylene as the solvent, 2,5-dibromopyridine (5.0 mmol) was addedReacts with n-butyltin (5.5 mmol),Using tetrakis(triphenylphosphine)palladium as a catalyst, the reaction was carried out at 130C in the dark for three days. After the reaction, ethylenediaminetetraacetic acid disodium salt was added to remove the remaining tin reagent. The organic phase was collected by extracting the mixture with dichloromethane and concentrating. The crude product was isolated by column chromatography to give the pure product. Yield: 80%.
42%
A reaction vessel was charged with 6.0 g of 2,5-dibromopyridine, 7.0 ml of bistributyltin, and 120 ml of xylene, followed by heating and stirring at 60C for 15 minutes. Further, 700 mg of tetrakis(triphenylphosphine)palladium was added thereto, followed by stirring at 120C for 8 hours. After cooling to room temperature, the insoluble materials were removed by filtration, and the filtrate was washed with 150 ml of an aqueous ethylenediamine tetraacetate solution. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: cyclohexane/toluene) to obtain 1.7 g (yield 42%) of 5,5'-dibromo-[2,2']bipyridine as a yellow powder.
With diisopropylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In tetrahydrofuran; at 20℃; for 24h;Inert atmosphere;
Under dry nitrogen atmosphere, successively trimethylsilyl -acetylene (619 mg, 6.30 mmol), [Pd(PPh3)2Cl2] (112 mg, 159 mumol), CuI (54.5 mg, 286 mumol) and DIPA (4 ml) were added to a stirred suspension of 3 (500 mg, 1.59 mmol) in 30 ml THF. While the mixture was stirred for 24 hours at room temperature, its color turned black. It was stirred together with activated carbon for 20 minutes and filtered over celite. Then the solvent was removed under reduced pressure, the residue was resuspended in hexane, sonicated for 15 minutes and filtered over celite again yielding an orange solution. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography on silica (eluent: CH2Cl2) to yield 430 mg (1.23 mmol, 78%) of pure 4 as an off-white solid. 1H NMR (CDCl3, 250 MHz): delta = 8.71 (s, 2H, bpy-H), 8.33 (d, 2H, JHH = 8.3 Hz, bpy-H), 7.85 (d, 2H, JHH = 7.8 Hz, bpy-H), 0.27 (s, 18H, Si(CH3)3).
With diisopropylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In tetrahydrofuran; at 20℃; for 29h;
Synthesis Example 165,5'-diethynyl-2,2'-bipyridyl was prepared as follows. Firstly, a mixture of 5,5'-dibromo-2,2'-bipyridyl (300 mg, 0.96 mmol), PdCl2(PPh3)2 (60 mg, 0.085 mmol) and CuI (30 mg, 0.16 mmol) was added with dist. THF (18 mL), dist. i-Pr2NH (2.4 mL) and trimethylsilylacetylene (467 muL, 3.3 mmol). The resultant mixture was then stirred under a nitrogen atmosphere at room temperature for 29 hours to obtain a reaction mixture. Subsequently, a salt contained in the reaction mixture was removed through a celite filtration process. The organic layer thus obtained was concentrated to obtain a crude product (I) Then, the obtained crude product (I) was separated and purified by silica gel column chromatography (CH2Cl2=100) to obtain 5,5'-bis(trimethylsilylethynyl)-2,2'-bipyridyl.Subsequently, the obtained 5,5'-bis(trimethylsilylethynyl)-2,2'-bipyridyl (120 mg, 0.34 mmol) and potassium fluoride (KF: 42 mg, 0.72 mmol) were added with dist. methanol (MeOH: 12 mL). The resultant mixture was then stirred under a nitrogen atmosphere at room temperature for 11 hours to obtain a reaction mixture. After that, an organic layer in the reaction mixture was then concentrated to obtain a crude product (II). Subsequently, the obtained crude product (II) was separated and purified by silica gel column chromatography (CH2Cl2=100) to obtain 5,5'-diethynyl-2,2'-bipyridyl (59.5 mg, 85% yield (in two steps)).The obtained compound was subjected to a 1H NMR measurement. The obtained result is shown below.1H NMR (CDCl3) delta8.77 (dd, J=0.5 Hz, 1.9 Hz, 2H), 8.40 (dd, J=0.5 Hz, 8.1 Hz, 2H), 7.90 (dd, J=1.9 Hz, 8.1 Hz, 2H), 3.31 (s, 2H).From the NMR measurement result, it was confirmed that the obtained compound was 5,5'-diethynyl-2,2'-bipyridyl.
In tetrahydrofuran; hexane;
Synthesis of 5,5'-Bis((trimethylsilyl)ethynyl)-2,2'-bipyridine (4) Under dry nitrogen atmosphere, successively trimethylsilyl-acetylene (619 mg, 6.30 mmol), [Pd(PPh3)2Cl2] (112 mg, 159 mol), CuI (54.5 mg, 286 mol) and DIPA (4 ml) were added to a stirred suspension of 3 (500 mg, 1.59 mmol) in 30 ml THF. While the mixture was stirred for 24 hours at room temperature, its color turned black. It was stirred together with activated carbon for 20 minutes and filtered over celite. Then the solvent was removed under reduced pressure, the residue was resuspended in hexane, sonicated for 15 minutes and filtered over celite again yielding an orange solution. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography on silica (eluent: CH2Cl2) to yield 430 mg (1.23 mmol, 78%) of pure 4 as an off-white solid. 1H NMR (CDCl3, 250 MHz): delta=8.71 (s, 2H, bpy-H), 8.33 (d, 2H, JHH=8.3 Hz, bpy-H), 7.85 (d, 2H, JHH=7.8 Hz, bpy-H), 0.27 (s, 18H, Si(CH3)3).
A solution of HBr in acetic acid (5 ml, 33 wt%) was added dropwise to a solution of 1 (0.992 g, 6.35 mmol) in MeOH (2 ml). The instantly forming precipitate was filtered and dried to yield 1.80 g (5.66 mmol, 89%) of 2 as a crude salt. Subsequently, a mixture of 2 (0.975 g, 3.07 mmol) and bromine (981 mg, 6.14 mmol) was heated in a pressure flask to 160 0C for 48 hours with stirring. The reaction was stopped and the hard solid was powdered using mortar and pestle. In order to remove unreacted bromine, a concentrated aqueous solution of Na2S2O3 (60 ml) was added to the brown powder and the mixture was stirred for 10 minutes. Subsequently, it was treated with 1 N NaOH (10 ml) and the product was extracted with CH2Cl2 (6 x 40 ml). The combined organic phases were concentrated under reduced pressure. This lead to partial precipitation of 3 together with unreacted 1. The precipitate was filtered and the two compounds were separated by flash column chromatography on silica gel, using CH2Cl2 as an eluent. The mother liquor contained 3, mono-brominated bipyridine, and other products of <n="83"/>bromination. 3 was separated from the side products by silica flash column chromatoj the mother liquor using CH2Cl2 as an eluent. A total amount of 420 mg (1.34 mmol, 44%) of pure 3 as a white solid was obtained. 1H NMR (CDCl3, 250 MHz): delta = 8.70 (dd, 2H, JHH = 0.6 Hz, 2.4 Hz), 8.28 (dd, 2H, JHH = 0.6 Hz, 8.5 Hz), 7.93 (dd, 2H, JHH = 2.3 Hz, 8.5 Hz).
With diisopropylamine;tetrakis(triphenylphosphine) palladium(0); In benzene; at 80℃; for 30h;
Example 235,5'-bis[4-(diallylhydroxysilyl)phenylethynyl]-2,2'-bipyridyl was prepared as follows. A mixture of 4-(diallylhydroxysilyl)ethynylbenzene (157 mg, 0.69 mmol), Pd(PPh3)4 (66 mg, 0.057 mmol) and 5,5'-dibromo-2,2'-bipyridyl (90 mg, 0.29 mmol) was added with dist. benzene (12 mL) and dist. i-Pr2NH (4 mL). The resultant mixture was then stirred under a nitrogen atmosphere at 80 C. for 30 hours to obtain a reaction mixture. Subsequently, the reaction mixture was diluted with CH2Cl2. After that, an organic layer was washed with dist. H2O and sat. NaCl, and then the organic layer was dried with MgSO4. The dried organic layer was filtered and concentrated to obtain a crude product. After that, the obtained crude product was separated and purified by silica gel column chromatography (from CH2Cl2=100 to CH2Cl2/Acetone=30/1) to obtain 5,5'-bis[4-(diallylhydroxysilyl)phenylethynyl]-2,2'-bipyridyl (103.5 mg, 59% yield).The obtained compound was subjected to a 1H NMR measurement. The obtained result is shown below.1H NMR (CDCl3) delta1.93 (ddd, J=8.1 Hz, 1.1 Hz, 0.8 Hz, 8H), 2.17 (s, 2H), 4.95 (ddt, J=10.3 Hz, 1.6 Hz, 0.8 Hz, 4H) 4.98 (ddt, J=16.2 Hz, 1.6 Hz, 1.1 Hz, 4H), 5.81 (ddt, J=16.2 Hz, 10.3 Hz, 8.1 Hz, 4H), 7.55 (d, J=8.4 Hz, 4H), 7.60 (d, J=8.4 Hz, 4H), 7.90 (dd, J=8.4 Hz, 1.9 Hz, 2H), 8.39 (dd, J=8.4 Hz, 0.5 Hz, 2H), 8.77 (dd, J=1.9 Hz, 0.5 Hz, 2H).From the NMR measurement result, it was confirmed that the obtained compound was 5,5'-bis[4-(diallylhydroxysilyl)phenylethynyl]-2,2'-bipyridyl.
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 8h;Reflux;
To 2.8 g of the resulting 5-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl) phenyl]-5H-pyrido[4,3-b]indole were added 1.2 g of 5,5'-dibromo[2,2']bipyridine that had been synthesized in advance, 440 mg of tetrakis(triphenylphosphine)palladium, 9.4 ml of a 2 M aqueous potassium carbonate solution, 32 ml of toluene, and 8 ml of ethanol, followed by heating with reflux while stirring for 8 hours. After cooling to room temperature, the precipitate was separated by filtration. The precipitate was dissolved in a mixed solvent of chloroform/methanol, the insoluble materials were removed by filtration and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: chloroform) to obtain 1.7 g (yield 71%) of 5,5'-bis[3-(5H-pyrido[4,3-b]indol-5-yl]phenyl]-[2,2']bipyridine(Compound 99) as a yellowish white powder. The structure of the resulting yellowish white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 1. The following 28 hydrogen signals were detected on 1H-NMR (CDC13). delta (ppm)=9.42(2H), 9.01 (2 H), 8.57(4 H), 8.25(2 H), 8.11(2 H), 7.78-7.86(6 H), 7.63(2 H), 7.52(4 H), 7.42(2 H), 7.38(2 H).
With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; water; toluene; for 2h;Inert atmosphere;
9.4 g (29.95 mmol) of 5,5'-dibromo2,2'-bipyridine synthesized by a known method (see J. Org. Chem., 67, p.443 (2002)), 20 g (29.95 mmol) of 3,5-dichlorophenylboric acid, 376 ml of toluene, 188 ml of ethanol, 66 ml of 2M sodium carbonate aqueous solution, and 2.1 g (2.995 mmol) of Pd(PPh3)2Cl2 were prepared and reacted in a nitrogen atmosphere for 2 hours. The precipitated crystal was filtered and washed with water and methanol. The filtrate was separated and a toluene layer was fractioned. The toluene layer was washed with water twice. After washing, a crude material obtained by collecting toluene was mixed with the filtered precipitate crystal. This crude material was subjected to a silica gel process, and the resulting crude material was recrystalized from dimethylacetamide and purified. Structure identification was performed by way of mass spectrometry (MS) and 1H-NMR, and it was confirmed that it was a target. Its yield was 10.1 g (75.6percent yields).
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin); In toluene; at 120℃; for 72h;Inert atmosphere;
3-Bromo-6-iodopyridine (Tokyo Chemical Industry Co., Ltd., 11.3 g),Dissolved in dehydrated toluene (Wako Pure Chemical Industries, Ltd., 320 ml), hexabutyl distannane (Bu 3 SnSnBu 3, Tokyo Chemical Industry Co., Ltd., 10 ml), tetrakistriphenylphosphine palladium (0) (Tokyo Chemical Industry Co., , The mixture was degassed by nitrogen bubbling for 1 hour, and reacted with stirring at 120 C. for 3 days. After the reaction, the temperature was returned to room temperature, washed with water, the organic layer was dried over sodium sulfate, filtered and concentrated, and the residue was purified by silica gel column chromatography to obtain 4.4 g of 5,5'-dibromo-2,2'-bipyridine Obtained
4.4 g
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin); In toluene; at 120℃; for 72h;Inert atmosphere;
3-Bromo-6-iodopyridine (Tokyo Chemical Industry Co., Ltd., 11.3 g),Hexabutyl distannane(Bu3SnSnBu3, Tokyo Chemical Industry Co., Ltd., 10 ml),Tetrakistriphenylphosphine palladium (0)(Tokyo Chemical Industry Co., Ltd., 1.2 g) was dissolved in dehydrated toluene(Wako Pure Chemical Industries, Ltd., 320 ml)Degassed by nitrogen bubbling for 1 hour, and reacted with stirring at 120 C. for 3 days.After the reaction, the temperature was returned to room temperature, then washed with water, the organic layer was dried with sodium sulfate, filtered and concentrated,The residue was purified by silica gel column chromatography,4.4 g of 5,5'-dibromo-2,2'-bipyridine was obtained.Synthesis was confirmed by 1 H-NMR measurement (FIG. 6).
1.68 g
With tetrakis(triphenylphosphine) palladium(0); bis(tri-n-butyltin); In toluene; for 72h;Inert atmosphere; Reflux;
5-Bromo-2-iodopyridine (6.60 g, 23.2 mmol) and Pd(PPh3)4 (0.72 g, 0.6 mmol) were dissolved in anhydrous PhMe (120 mL) under N2. Hexa-n-butylditin (7.25 g, 12.5 mmol)was added and the solution heated at reflux for 3 days. The mixture was filtered through celite and the solvent removed. The residue was chromatographed on silica using a DCM to EtOAc gradient. The resulting residue was crystallised from EtOAc/hexanes to give the 5,5?- dibromo-2,2?-bipyridine (1.22 g, 33 %) as a pale yellow powder. The crystallisation liquors were evaporated under reduced pressure and the residue dissolved in DCM, hexanes wereadded and the volume of solvent reduced. The resulting precipitate was collected by filtration and air dried to give a second crop of the product (0.46 g, 13 %) as a cream powder.
With tetrabutylammomium bromide; sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; toluene; for 48h;Inert atmosphere; Reflux;
Example 16: Production of Compound (3b-1) To a 50-mL Schlenk flask containing a stirring bar were added Compound (4a) obtained in Synthesis Example 5 (103 mg, 99.1 mumol), 5,5'-dibromo-2,2'-bipyridine (315 mg, 1.00 mmol), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) (PdCl2(dppf)) (7.4 mg, 10 mumol), sodium carbonate (Na2CO3) (53.9 mg, 509 mumol), and tetra-n-butylammonium bromide (n-Bu4NBr) (32.7 mg, 101 mumol), and the flask was evacuated and backfilled with argon gas three times. Thereafter, dry toluene (5 mL) and degassed water (5 mL) were added thereto, and the mixture was stirred under reflux for 48 hours. Thereafter, the mixture was extracted with CH2Cl2, dried over Na2SO4, and filtered under reduced pressure. The crude product was purified by column chromatography (CHCl3/MeOH = 20:1) to yield a white solid (73.4 mg). This white solid was identified by nuclear magnetic resonance (1H-NMR) analysis and mass spectrometry as a compound (hereinafter sometimes referred to as "Compound (3b-1)") represented by the following General Formula (3b-1): [Show Image] [Show Image] The yield of this compound was 59%. 1H NMR (400 MHz, CDCl3 2.05-2.50 (brm, 16H), 3.45 (d, J = 3 Hz, 12H), 4.50 (d, J = 5 Hz, 8H), 7.51-7.66 (brm, 20H), 7.94 (dd, J = 9 Hz, 2H), 7.99 (dd, J = 8 Hz, 2H), 8.34 (d, J = 8 Hz, 2H), 8.43 (d, J = 9 Hz, 2H), 8.73 (s, 2H), 8.88 (s, 2H); MS(FAB) m/z calcd for C70H69Br2N4O8[M+H]+: 1251.3482, found 1254.
[Cu2(5,5′-dibromo-2,2′-bipyridine)2(μ-Ph2P(CH2)5PPh2)2](ClO4)2·2CH2Cl2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76.6%
at 20℃; for 5h;Inert atmosphere; Schlenk technique;
General procedure: [Cu(CH3CN)4][ClO4] (65.2mg, 0.200mmol) was added to a degassed DCM solution (about 10mL) of BrbpyBr (62.4mg, 0.200mmol) and dppm (78.4mg, 98%, 0.200mmol). The color of the solution gradually changed to pale yellow. The solution was then stirred for 5h at room temperature. After filtration, layering n-hexane onto the DCM solution gave the product as pale yellow crystals.
[Cu2(5,5′-dibromo-2,2′-bipyridine)2(μ-Ph2P(CH2)6PPh2)2](ClO4)2·2CH2Cl2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70.5%
at 20℃; for 5h;Inert atmosphere; Schlenk technique;
General procedure: [Cu(CH3CN)4][ClO4] (65.2mg, 0.200mmol) was added to a degassed DCM solution (about 10mL) of BrbpyBr (62.4mg, 0.200mmol) and dppm (78.4mg, 98%, 0.200mmol). The color of the solution gradually changed to pale yellow. The solution was then stirred for 5h at room temperature. After filtration, layering n-hexane onto the DCM solution gave the product as pale yellow crystals.
With Ni(NO3)2-Ce(NO3)3-La(NO3)3-Mn(NO3)2-impregnated solid catalyst; In ethanol; at 300℃; under 13351.3 Torr;
General procedure: The raw material of the reaction system is a pyridine derivative, at 115-130 , 20-30kpa reaction liquid discharged light component separated by distillation and a mixture of the crude 2,2'-bipyridine derivative, pyridine derivative apply.The crude 2,2'-bipyridyl atmospheric boiling point less than 300 deg.] C, and 2,2'-bipyridine derivative crude was purified by distillation, rectification column plate number of 28.1, a pressure of 2.4kPa, tower bottom temperature of 190 , column top temperature of 148 , a reflux ratio of 0.3: 1.An atmospheric boiling point above 300 deg.] C of the crude 2,2'-bipyridyl derivative using a solvent and recrystallized from methanol, and petroleum ether Purification: The crude product that is dissolved in an equal weight of a solvent, heated to 40 , to be dissolved was cooled to 5 crystallized solid was filtered, dried to give 2,2'-bipyridine derivative finished, the crystallization mother liquor applied.
With copper(l) iodide; sodium iodide; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 110℃; for 18h;Inert atmosphere; Schlenk technique;
Aromatic Finkelstein Reaction; General ProcedureThe reaction was carried out under argon using standard Schlenktechniques due to the moisture and oxygen sensitivity of the copper(I) iodide. A two-neck pear-shaped flask equipped with a refluxcondenser was charged with the (het)aryl bromide starting material,NaI (2 equiv per bromine to exchange), and CuI (5 mol% per bromineto exchange). N,N?-Dimethylethylenediamine (L1) or N,N?-dimethyl-1,2-cyclohexanediamine (L2) (10 mol% per bromine toexchange) and anhydrous 1,4-dioxane (0.5 mL per 1 mmol NaI)were added. The resulting suspension was heated to 110 C for 18h. After cooling to r.t., the mixture was poured into aq 25% NH3 solution.The blue solution was diluted to a doubled volume with H2Oand was extracted three times with CH2Cl2. In the case of the 2,2?-bipyridines, the combined organic phases were additionally washedwith aq EDTA solution. Otherwise, the combined organic phaseswere solely washed with brine and dried with MgSO4. The solventwas removed under reduced pressure to give the desired product inpure form. If needed, the crude product can be purified by columnchromatography or recrystallization.
5,5'-bis(methoxycarbonylethenyl)-2,2'-bipyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
66%
With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine; In N,N-dimethyl-formamide; at 120℃; for 48h;Inert atmosphere;
(0248) 5,5?-dibromo-2,2?-bipyridine (646 mg, 2.0 mmol) was dissolved in a mixture of 10 mL of DMF and 10 mL of triethylamine and degassed with nitrogen. Palladium acetate (19 mg), tris(o-tolyl)phosphine (84 mg), and methyl acrylate (2.5 mL, 27.6 mmol) were then added to the solution. The solution was sealed in a pressure vessel under nitrogen and heated at 120 C. for 2 days. After cooling to r.t., the solution was concentrated to afford a yellow solid as the crude product, which was purified through Soxhlet extraction with chloroform to afford the pure 5,5?-bis(methoxycarbonylethenyl)-2,2?-bipyridine as a light yellow solid (428 mg, 66%). 1H NMR (500 MHz, CDCl3) delta 8.83 (s, 2H), 8.51 (d, 2H, 3JHH=8.2 Hz), 8.01 (dd, 2H, 3JHH=8.2 Hz, 4JHH=2.0 Hz), 7.77 (d, 2H, 3JHH=16.0 Hz), 6.61 (d, 2H, 3JHH=16.0 Hz), 3.87 (s, 6H).
[Cu(5,5'-dibromo-2,2'-bipyridine)(9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene)]ClO4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86.1%
In dichloromethane; at 20℃; for 5h;Inert atmosphere; Schlenk technique;
General procedure: [Cu(CH3CN)4]ClO4 (32.6 mg, 0.100 mmol) was added to a dichloromethane (DCM) solution (about 10 mL) of BrphenBr (33.6 mg, 0.100 mmol) and BINAP (63.5 mg, 98%, 0.100 mmol) under a stream of dry argon using Schlenk techniques at room temperature. After stirring for 5 h at room temperature, n-hexane was carefully dropped over the DCM solution, and orange-yellow crystals were obtained a few days later in 52.5% yield (67.9 mg).
2,2?-bipyridine (1, 4.99 g, 0.032 mol) and bromine (10.24 g,0.064 mol) were first added in a hydrothermal reaction container andheated to 150 C and annealed for 15 h. Then, the mixture was cooledand the hard solidwas powdered and following treatedwith Na2SO3 solutionto remove the unreacted bromine. Finally itwas basifiedwith sodiumhydroxide and filtered. The white solid product 5,5?-dibromo-2,2?-bipyridine was obtained by the chromatography on silica(CH2Cl2). 5,5?-dibromo-2,2?-bipyrimidine, 8.64 g (86%). m.p. 221.6-222.1 C. 1H-NMR (400 MHz, CDCl3, delta): 7.95 (d, 2H), 8.28 (s, 2H),8.71(d, 2H); 13C-NMR (100 MHz, CDCl3, delta): 121.47 (C5), 122.25 (C3),139.64 (C4); 150.28 (C6),153.64 (C2); IR (KBr): 3049 (CH,stretching), 1562, 1453, 1356 (Ar, stretching), 636 (CBr, stretching).Anal. calcd for C10H6N2Br2: C 38.22, H 1.91, N 8.92, Br 50.95; found: C38.26, H 1.94, N 8.90, Br 50.97.
86%
With bromine; at 150℃; under 1140.08 Torr; for 15h;
2,2'-bipyridyl (4.99 g, 0.032 mol) and liquid bromine (10.24 g, 0.064 mol)Put into a reaction kettle at a pressure of 2.0 atm at 150 C for 15 hours, then cool to room temperature after the reaction, pulverize the solid, add to the Na2SO3 solution and stir to remove unreacted bromine, filter, and alkalizate the acid with a 5% NaOH solution. , filtration, to obtain a crude product, column separation with ethyl acetate / petroleum ether,8.64 g of white 5,5'-dibromo-2,2'-bipyridine was obtained in a yield of 91%.
5,5′-bis [(4-amino) phenoxy]-2,2′bipyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 195℃; for 12h;
5,5'-dibromo-2,2'-bipyridine (6.28 g, 0.02 mol),4-aminophenol (5.23g, 0.048mol) was added to the threeIn a flask, 100 ml of water-removed N-methylpyrrolidone was added, and anhydrous potassium carbonate K2CO3 (2.73 g, 0.02 mol) was added, and the reaction was reacted at 195 C for 12 hours, and cooled to room temperature.Pour into 5% NaOH solution and stir for 1 hour. Filter out the solid and wash it several times with distilled water.Recrystallized with water and ethanol,Obtaining white 6.40 g of 2,6-bis[(4-amino)phenoxy]-2,2'-bipyridine,Yield 92%,
87%
With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 175℃; for 12h;
5,5?-dibromo-2,2?-bipyridin (2, 6.28 g, 0.02 mol) and 4-aminophenol (3, 5.23 g, 0.048mol) were dissolved in 100mL NMP. AnhydrousK2CO3 (2.73 g, 0.02 mol) was added to the solution, and themixture was heated at 175 C for 12 h. After cooling to room temperature,the mixture was poured into 5 wt% sodium hydroxide solution,and stirred for 1 h. The solution was filtered, and the filter cake waswashed repeatedly with distilled water. The white crystals of 5,5?-bis[(4-amino)phenoxy]-2,2?-bipyrimidine (BPBPA, 4) was recrystallizedfrom H2O/ethanol. 6.44 g (87%), m.p. 204.0-204.6 C. 1H-NMR(400 MHz, DMSO-d6, delta): 5.06 (s, 4H), 6.61 (d, 4H), 6.85 (d, 4H), 7.29(d, 2H), 8.21 (s, 2H), 8.29 (d, 2H). 13C-NMR (100 MHz, DMSO-d6, delta):114.89 (C3?), 120.82 (C2?), 123.92 (C3, C4), 138.43 (C6), 144.75 (C4?),146.04 (C1?), 148.84 (C2), 155.36 (C5); FTIR (KBr): 3396, 3302 (NH,stretching), 1633, 1558, 1503, 1455 (Ar, stretching). Anal. calcd forC22H18N4O2: C 71.35, H 4.86, N 15.14, O 8.65; found: C 71.31, H 4.89, N15.11, O 8.70.
With tetrakis(triphenylphosphine) palladium(0); In N,N,N,N,N,N-hexamethylphosphoric triamide; at 160℃; for 96h;
5.5'-dibromo-2,2'-bipyridine (4.4 g), hexamethyldisilane (Tokyo Chemical Industry Co., Ltd., 10 ml), tetrakistriphenylphosphine palladium (0) (Tokyo Chemical Industry Co., ) Was dissolved in hexamethylphosphoric acid triamide (HMPA, Tokyo Chemical Industry Co., Ltd., 14 ml), and reacted with stirring at 160 C. for 4 days. After the reaction, the temperature was returned to room temperature and then washed with water, the organic layer was dried over sodium sulfate, filtered and concentrated,The residue was purified by silica gel column chromatography,3.15 g of 5,5'-bis (trimethylsilyl) -2,2'-bipyridine was obtained.
3.15 g
With N,N,N,N,N,N-hexamethylphosphoric triamide; tetrakis(triphenylphosphine) palladium(0); at 160℃; for 96h;
5,5'-dibromo-2,2'-bipyridine (4.4 g),Hexamethyldisilane (Tokyo Chemical Industry Co., Ltd., 10 ml),Tetrakistriphenylphosphine palladium (0)(Tokyo Chemical Industry Co., Ltd., 0.5 g)Was dissolved in hexamethylphosphoric acid triamide (HMPA, Tokyo Chemical Industry Co., Ltd., 14 ml), And reacted with stirring at 160 C. for 4 days. After the reaction, after returning to room temperature,The organic layer was washed with water, dried over sodium sulfate, filtered and concentrated,The residue was purified by silica gel column chromatography to obtain 3.15 g of 5,5'-bis (trimethylsilyl) -2,2'-bipyridine.The synthesis was confirmed by 1 H-NMR measurement (FIG. 7).
After adding 3 mL of THF to sodium hydride (1.52 g, 38.0 mmol) in a 250 mL 2-neck flask,Malononitrile (2.1 g, 32.2 mmol) was added at 0 and stirred at room temperature for 1 hour.Compound A (5 g, 15.9 mmol), PdCl 2 (0.6 g) and PPh 3 (0.84 g) were added to the reaction mixture, and the mixture was heated and stirred for 12 hours.After completion of the reaction, a small amount of water was added to the mixed reaction solution, and the mixture was extracted with water and ethyl acetate. The ethyl acetate solvent was distilled off under reduced pressure, and recrystallized from dichloromethane and hexane to obtain 2.4 g (yield: 53%
4-(cyanomethyl)-2,3,5,6-tetrahydrofluorobenzonitrile[ No CAS ]
C28H8F8N6[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44%
3 ml of THF was added to sodium hydride (1.52 g, 38.0 mmol) in a 250 ml 2-neck flask, followed by addition of Compound B-1 (6.8 g, 31.8 mmol) at 0 C and stirring at room temperature for 1 hour. Compound A (5 g, 15.9 mmol), PdCl2 (0.6 g) and PPh3 (0.84 g) were added to the reaction mixture, and the mixture was heated and stirred for 12 hours. After completion of the reaction, a small amount of water was added to the mixed reaction solution, and the mixture was extracted with water and ethyl acetate. The ethyl acetate solvent was distilled off under reduced pressure,Recrystallization was performed using dichloromethane and hexane to obtain 4.1 g (yield: 44%) of Compound H.
3 ml of THF was added to sodium hydride (1.4 g, 35.0 mmol) in a 250 ml 2-neck flask, and the compound C-1 (9.3 g, 31.8 mmol) was added at 0 C and stirred at room temperature for 1 hour. Compound A (5 g, 15.9 mmol), PdCl2 (0.6 g) and PPh3 (0.84 g) were added to the reaction mixture, and the mixture was heated and stirred for 12 hours. After completion of the reaction, a small amount of water was added to the mixed reaction solution, and the mixture was extracted with water and ethyl acetate. The ethyl acetate solvent was distilled off under reduced pressure,Recrystallization was performed using dichloromethane and hexane to obtain 6.4 g (yield: 54%) of Compound I
To a 250 ml 2-neck flask was added 3 ml of THF to sodium hydride (1.4 g, 34.9 mmol) followed by the addition of compound D (9.5 g, 31.8 mmol) at 0 C and stirring at room temperature for 1 hour. Compound A (5 g, 15.9 mmol), PdCl2 (0.6 g) and PPh3 (0.84 g) were added to the reaction mixture, and the mixture was heated and stirred for 12 hours. After completion of the reaction, a small amount of water was added to the mixed reaction solution, and the mixture was extracted with water and ethyl acetate. The ethyl acetate solvent was distilled off under reduced pressure,Recrystallization was performed using dichloromethane and hexane to obtain 4.9 g (yield: 41%) of Compound J
3 ml of THF was added to sodium hydride (2.35 g, 38.0 mmol) in a 250 ml 2-neck flask, and the compound E-1 (4.3 g, 32.2 mmol) was added at 0 C and stirred at room temperature for 1 hour. Compound A (2.3 g, 7.3 mmol), PdCl 2 (0.26 g) and PPh 3 (0.38 g) were added to the reaction mixture, and the mixture was heated and stirred for 12 hours. After completion of the reaction, a small amount of water was added to the mixed reaction solution, which was then extracted with water and ethyl acetate, and the ethyl acetate solvent was distilled off under reduced pressureAnd recrystallized using dichloromethane and hexane to obtain 1.7 g (yield: 44%) of compound K
3 ml of THF was added to sodium hydride (2.35 g, 38.0 mmol) in a 250 ml 2-neck flask, and the compound E-1 (4.3 g, 32.2 mmol) was added at 0 C and stirred at room temperature for 1 hour. The reaction temperature was again lowered to 0 , and Compound A (2.3 g, 7.3 mmol), PdCl2 (0.26 g) and PPh3 (0.38 g) were added, followed by heating and stirring for 12 hours. After completion of the reaction, A small amount of water was added to the solution, extracted with water and ethyl acetate, the ethyl acetate solvent was distilled off under reduced pressure, Recrystallization was performed using dichloromethane and hexane to obtain 1.7 g of compound L (yield: 44%)
With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In toluene at 110℃; for 48h; Schlenk technique; Inert atmosphere;
benzene-1,3-dicarboxylic-5-boronic triacid[ No CAS ]
[ 15862-18-7 ]
[ 20255-70-3 ]
C66H42N4O16[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
N, N, N', N' - four-biphenyl multi-carboxylic acid aryl diamine compound (24) preparation: under the protection of nitrogen, to 10 ml of the reaction tube Schlek (water-free oxygen-free operation often for a glass instrument) adding 1.0mmol 5, 5 '- two bromines are joint pyridine, 2.5mmol double (4 - bromophenyl) amine, 0.10mmol palladium acetate, 0.10mmol tert-butylphenol (2', 4 ', 6' - triisopropyl - 3, 6 - dimethoxy biphenyl -2 - yl) phosphine, 6.0mmol tert butoxide potassium, and 5 ml toluene, replace the nitrogen reaction tube 3 times, then in the oil bath for magnetic stirring under heating to 100 C, reaction refluxing 48 hours. To room temperature; and then to the reaction solution, 8.0mmol 3, 5 - two carboxyl boric acid, 0.06mmol palladium acetate, 0.10mmol 2 '- dicyclohexyl phosphino - 2, 6 - II - I - propyl -4 - sulphur acid radical - 1, 1' - biphenyl sodium, 16.0mmol cesium carbonate, and 200mmol water; then under magnetic stirring for oil bath is heated to 100 C, reaction refluxing 48 hours. To room temperature; filtering the obtained solid employ 20 ml in water, aqueous solution of concentrated hydrochloric acid for adjusting the PH to 1, room temperature stirring 6h after, filtering, washing with ethanol, drying to obtain products 24, yield 70%.
N, N, N', N' - four-biphenyl multi-carboxylic acid aryl diamine compound (22) preparation: under the protection of nitrogen, to 10 ml of the reaction tube Schlek (water-free oxygen-free operation often for a glass instrument) adding 1.0mmol 5, 5 '- two bromines are joint pyridine, 3.0mmol double (4 - iodo phenyl) amine, 0.06mmol palladium chloride, 0.06mmol dicyclohexyl (3, 6 - dimethoxy -2', 4 ', 6' - three isopropyl (1, 1' - biphenyl) -2 - yl) phosphine, 6.0mmol tert butoxide potassium, and 5 ml dioxane, replace the nitrogen reaction tube 3 times, then in the oil bath for magnetic stirring under heating to 110 C, reaction reflux 24 hours. To room temperature; and then to the reaction solution, boric acid 5.0mmol 4 - carboxyl, 0.07mmol palladium acetate, 0.07mmol 2 '- dicyclohexyl phosphino - 2, 6 - II - I - propyl -4 - sulphur acid radical - 1, 1' - biphenyl sodium, 14.0mmol sodium carbonate, and 120mmol water; then under magnetic stirring for oil bath is heated to 100 C, reaction reflux 24 hours. To room temperature; filtering the obtained solid employ 20 ml in water, aqueous solution of concentrated hydrochloric acid for adjusting the PH to 1, room temperature stirring 6h after, filtering, washing with ethanol, drying to obtain products 22, yield 78%.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine In tetrahydrofuran at 60℃; for 8h; Inert atmosphere; regioselective reaction;
Weigh the C^N ring metal ligands dichloro bridge (1 mmol), 5,5?-dibromo-2,2?-dipyridyl (2.3 mmol), and addIn a three-necked flask, a vacuum is applied to the double-row tube - nitrogen-vapour-vacuum is circulated three times, and nitrogen is used to protect the entire reaction.system. A 2:1 mixture of dichloromethane and methanol was injected into the system, the temperature was raised to 50C, and the mixture was stirred and refluxed.After reacting for 5 hours, 0.72 mmol of potassium hexafluorophosphate solid was added and stirring was continued at room temperature for 1 hour. After the reaction is overThe product is purified by condensation and finally recrystallized with dichloromethane and n-hexane to give a solid product as a ruthenium complex intermediate. Yield: 80%
With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 100℃; for 24h;
4,4'-Dibromobipyridine (3.14 g, 10 mmol), phenoxazine (4.40 g, 24 mmol), bis(dibenzylideneacetone) palladium (Pd(dba)2, 0.46 g, 0.8 mmol), sodium tert-butoxide (NaOt-Bt, 2.88 g, 30 mmol), and tri(tert-butyl)phosphonium tetrafluoroborate (tBu3P.HBF4, 0.116 g, 0.4 mmol) were added to 50 mL of dehydrated toluene, and heated for 24 hours while maintaining the inner temperature to 100C. After the reaction liquid was allowed to cool, 200 mL of water was added thereto, and the mixture was separated. The organic layer was concentrated, and the concentrate was purified by SiO2 column chromatography with a mixed solvent of chloroform and hexane (1/1) as a developing solvent. According to the procedures, the compound 1 was obtained at a yield amount of 3.10 g and a yield of 60%. The purified product of the compound 1 was further subjected to sublimation purification under condition of 320C. and 1 Pa or less. (0131) 1H NMR (600 MHz, CDCl3) delta 8.9-8.5 (2H), 7.8-7.5 (2H), 7.4-6.8 (18H); MS (70 eV, EI) m/z=518 (M+)