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CAS No. : | 17135-74-9 | MDL No. : | MFCD00183574 |
Formula : | C10H6Br2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DLXBGTIGAIESIG-UHFFFAOYSA-N |
M.W : | 285.96 | Pubchem ID : | 625356 |
Synonyms : |
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 10 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 59.35 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.23 cm/s |
Log Po/w (iLOGP) : | 2.59 |
Log Po/w (XLOGP3) : | 3.97 |
Log Po/w (WLOGP) : | 4.36 |
Log Po/w (MLOGP) : | 4.72 |
Log Po/w (SILICOS-IT) : | 4.32 |
Consensus Log Po/w : | 3.99 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.73 |
Solubility : | 0.00532 mg/ml ; 0.0000186 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -3.67 |
Solubility : | 0.061 mg/ml ; 0.000213 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.77 |
Solubility : | 0.000483 mg/ml ; 0.00000169 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.44 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | Stage #1: With sulfuric acid; sodium nitrite In water at -5℃; for 4 h; Inert atmosphere Stage #2: With hydrogen bromide; copper(I) bromide In water at -5 - 80℃; for 3 h; Inert atmosphere |
Solid NaNO2 (3.5 g, 0.05 mol) was dissolvedin 20 mL H2O and cooled to 0 oC. The sodium nitrite solution was added drop wise into a solution of 1H-naphtho[1,8-de][1,2,3]triazine (6.8 g, 0.04 mol) in 6.9M H2SO4(100 mL) at -5 C over a period of 2 h with vigorous stirring with a mechanical stirrer.The mixture was stirred at -5 C for an additional 2 h. The solution of CuBr (14.6 g,0.1 mol) in aqueous HBr (47percent, 50 mL) was dropwised into the resulting mixture and stirred at -5C for 2 h. The reaction mixture was allowed to warm up to 85C and then stirred for 1 h. The reaction mixture was extracted with dichloromethane and the combined extracts were dried with Na2SO4 and evaporated in vacuum to produce crude product.Flash chromatography on silica gel with petroleum ether gave pure 1a(2.61 g, 23percent) as a pale yellow crystal. Melting point: 104-106 C. 1H NMR (300 MHz,CDCl3): 7.92 (d, J = 7.5 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.24 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | Solid NaNO2 (3.5 g, 0.05 mol) was dissolvedin 20 mL H2O and cooled to 0 oC. The sodium nitrite solution was added drop wise into a solution of 1H-naphtho[1,8-de][1,2,3]triazine (6.8 g, 0.04 mol) in 6.9M H2SO4(100 mL) at -5 C over a period of 2 h with vigorous stirring with a mechanical stirrer.The mixture was stirred at -5 C for an additional 2 h. The solution of CuBr (14.6 g,0.1 mol) in aqueous HBr (47%, 50 mL) was dropwised into the resulting mixture and stirred at -5C for 2 h. The reaction mixture was allowed to warm up to 85C and then stirred for 1 h. The reaction mixture was extracted with dichloromethane and the combined extracts were dried with Na2SO4 and evaporated in vacuum to produce crude product.Flash chromatography on silica gel with petroleum ether gave pure 1a(2.61 g, 23%) as a pale yellow crystal. Melting point: 104-106 C. 1H NMR (300 MHz,CDCl3): 7.92 (d, J = 7.5 Hz, 2H), 7.79 (d, J = 9.0 Hz, 2H), 7.24 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.7% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 10h;Inert atmosphere; Reflux; | In three 2L flask, 1,8-dibromo-naphthalene (81.2g, 0.28mol), 1- naphthyl boronic acid (53.6g, 0.31mol), potassium carbonate (78.4g, 0.57mol), toluene (540 g), to under deionized water (200 g of), absolute ethanol (180g), nitrogen, was added Pd (PPh3) 4 (1.1g), warmed to reflux, the reaction was kept 10H, cooled to 25 , liquid separation, the organic phase 200 g of deionized water once, 100g anhydrous sodium sulfate, suction filtered, the organic phase was collected, the organic phase flash silica gel column by 35cm thick, was passed through the column for solvent removal, the obtained crude product was recrystallized from a ethanol, to give a compound, light yellow The solid 65g, yield 68.7%, MS (m / s): 333.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With n-butyllithium; iodine; In tetrahydrofuran; hexane; at -70 - 25℃; for 1.25h; | l,8-dibromonaphthalene (5 g, 17.5 mmol, 1.0 eq) was dissolved in THF (40 mL). The mixture was cooled down to - 70 C and n-BuLi (2.5 M in hexane, 6.99 mL, 1.0 eq) was added dropwise. After 15 minutes, I2 (4.44 g, 17.5 mmol, 3.52 mL, 1.0 eq) dissolved in THF (40 mL) was added. The mixture was allowed to reach 25 C and stirred for 1 hour. The reaction was quenched with 30 mL of 1 M sodium thiosulfate solution in water. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (20 mL). The organic layer was washed with brine (20 mL), dried over Na2S04, filtered and concentrated under reduced pressure to give a residue. The residue was purified by column chromatography (Si02, Petroleum ether/Ethyl acetate=100/l to 10:1). l-bromo-8-iodo-naphthalene (3 g, 8.74 mmol, (0755) 50% yield, 97% purity) was obtained as a yellow solid. (0756) [0434] Tl NMR (400MHz, chloroform-d) d = 8.43 (dd, = 1.2, 7.6 Hz, 1H), 7.96 (dd, J= 1.2, 7.6 Hz, 1H), 7.89 - 7.77 (m, 2H), 7.28 (t, J= 8.0 Hz, 1FI), 7.08 (t, J = 7.6 Hz, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In toluene; at 110℃; for 18h;Inert atmosphere; | A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, (1.29 g, 4.5 mmol), 2-methyl-4-methoxyphenylboronic acid, 3, (2.24 g, 13.5 mmol), Pd(PPh3)4 (0.78 g, 0.68 mmol), and K3PO4, (4.30 g, 20.0 mmol) in 50 mL toluene was stirred at 110 C for 18 h. The resulting mixture was allowed to come to room temperature, quenched with water and extracted with CH2Cl2. The combined organic layers were dried over MgSO4 and concentrated in vacuo. Purification by flash chromatography on silica gel (CH2Cl2/hexanes 2:3) afforded 1.66 g (4.5 mmol, >99%) of off-white crystals containing syn- and anti-isomers of 4 in a ratio of approximately 1:3.1H NMR: δ=1.76 (s, 4.6H), 1.83 (s, 1.4H), 3.69 (s, 4.4H), 3.71 (s, 1.4H), 6.28-6.39 (m, 4H), 6.66 (d, J=8.2 Hz, 0.5H), 6.87 (d, J=8.2 Hz, 1.5H), 7.16 (d, J=6.8 Hz, 2H), 7.46 (dd, J=6.8, 8.0 Hz, 2H), 7.89 (d, J=8.0 Hz, 2H). 13C NMR: δ=20.9, 21.0, 55.1, 55.2, 109.9, 110.3, 114.3, 114.4, 124.8, 125.0, 128.5, 129.0, 130.2, 130.4, 131.0, 131.6, 132.3, 134.8, 134.9, 135.2, 135.4, 136.5, 136.9, 139.5, 157.6, 158.1. Anal. Calcd for C26H24O2: C, 84.75; H, 6.57. Found: C, 84.74; H, 6.61. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (1-2) Synthesis of Intermediate 2; 10 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 8.5 g of phenanthrene-9-yl boronic acid, 100 ml of tetrahydrofuran, 10.6 g of potassium carbonate and 50 ml of water were mixed in a 250 ml round-bottom flask with stirring. 2.2 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The organic layer was isolated from the reaction solution, washed twice with water, and dried over magnesium sulfate, which was distilled under a reduced pressure to remove the solvent therefrom. The residue thus obtained was subjected to purification by column chromatography using hexane, to obtain 10.5 g of the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (1-1) Synthesis of Intermediate 1; 6 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 4 g of 2-naphthalene boronic acid, 120 ml of tetrahydrofuran, 6.5 g of potassium carbonate and 50 ml of water were mixed in a 250 ml round-bottom flask with stirring. 1.3 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The organic layer was isolated from the reaction solution, washed twice with water, and dried over magnesium sulfate, which was distilled under a reduced pressure to remove the solvent therefrom. The residue thus obtained was subjected to purification by column chromatography using hexane, to obtain 5.5 g of the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (1-3) Synthesis of Intermediate 3; 58 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 50 g of 6-phenylnaphthalene-2-yl boronic acid, 500 ml of tetrahydrofuran, 42 g of potassium carbonate and 250 ml of water were mixed in a 2000 ml round-bottom flask with stirring. 11.7 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The organic layer was isolated from the reaction solution, washed twice with water, and dried over magnesium sulfate, which was distilled under a reduced pressure to remove the solvent therefrom. The residue thus obtained was subjected to purification by column chromatography using hexane, to obtain 50 g of the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; | 1,8-Dibromonaphthalene(10 g, 37 mmol), 2,2’-binaphthyl-6-yl boronic acid (11 g, 37 mmol),tetrahydrofuran (110 ml), potassium carbonate (21 g, 152 mmol) and water (76ml) were mixed in a round-bottom flask with stirring.Tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 mmol) was added to themixture, which was heated to 80C. The organic layer was isolated from thereaction solution, washed twice with water, and dried over magnesium sulfate,which was distilled under a reduced pressure to remove the solvent therefrom.The residue thus obtained was subjected to purification by columnchromatography using n-hexane, toobtain 15 g of the compound.Yield88% 1H-NMR (500 MHz, CDCl3) 8.54-8.52 (d, J=8.5 Hz, 1H),8.03-7.83 (m, 7H), 7.78-7.58 (m, 7H), 7.52-7.36 (m, 4H) ppm. EI-MS [M+H]+:m/z 459. |
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; | (1-4) Synthesis of Intermediate 4; 58 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 60 g of 2,2'-binaphthyl-6-yl boronic acid, 500 ml of tetrahydrofuran, 42 g of potassium carbonate and 250 ml of water were mixed in a 2000 ml round-bottom flask with stirring. 11.7 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The organic layer was isolated from the reaction solution, washed twice with water, and dried over magnesium sulfate, which was distilled under a reduced pressure to remove the solvent therefrom. The residue thus obtained was subjected to purification by column chromatography using hexane, to obtain 71 g of the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1,8-bis(3,3'-(3,5-dimethylphenyl)-9,9'-diacridyl)naphthalene, 15; A mixture of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 14, (143 mg, 0.50 mmol), tetrakis(tiphenylphosphine)palladium(0) (0.11 g, 0.10 mmol, 30 mol %), and CuO (80 mg, 1 mmol) in 5 mL DMF was stirred at 140 C. After 5 min, a solution of 3-(3,5-dimethylphenyl)-9-trimethylstannylacridine 13 (0.90 g, 2.0 mmol) in 2 mL of DMF was added in one portion. After 16 hours, the reaction mixture was quenched with 10% aqueous ammonium hydroxide, extracted with diethyl ether, dried over MgSO4 and concentrated in vacuo. Purification of the orange residue by flash chromatography (100:5:1 hexanes:ethyl acetate:triethylamine) afforded 15 (100 mg, 30%) as a yellow solid. The diastereoisomers were separated into 60% of the anti-isomer and 40% of the syn-isomer. anti-Isomer: 1H-NMR δ=2.45 (s, 12H), 6.62-6.68 (m, 2H), 6.83-6.86 (m, 4H), 7.00-7.03 (m, 2H), 7.07 (s, 2H), 7.31-7.39 (m, 8H), 7.67 (d, J=9.1 Hz, 2H), 7.73-7.78 (m, 2H), 7.91 (s, 2H). 8.31 (d, J=8.2 Hz, 21). 13C-NMR δ=22.3, 124.8, 125.4, 125.5, 125.6, 125.9, 126.2, 126.3, 126.6, 127.0, 129.3, 129.8, 130.1, 130.5, 131.2, 134.2, 134.6, 135.5, 139.0, 140.8, 141.9, 146.1, 147.5, 147.6. LC/APCI/MS: m/z=691(M+H). Anal. calcd. for anti-C52H38N2: C, 90.43; H, 5.55; N, 4.06. Found: C, 90.64; H, 5.30; N, 4.11. syn-Isomer. 1H-NMR 3=2.26 (s, 12H), 6.65-6.70 (m, 2H), 6.75-6.78 (m, 2H), 6.85-6.88 (m, 2H), 6.96-6.99 (m, 4H), 7.12 (s, 4H), 7.28-7.31 (m, 21), 7.36-7.42 (m, 2H), 7.69-7.75 (m, 4H), 7.91 (d, J=1.65 Hz, 2H), 8.27 (dd, J=1.1 Hz, 8.36 Hz, 2H). 13C-NMR δ=22.0, 124.8, 125.3, 125.4, 125.5, 125.8, 126.1, 126.3, 126.4, 126.9, 129.4, 129.7, 130.1, 130.4, 131.1, 134.2, 134.7, 135.5, 138.8, 140.7, 142.1, 146.1, 147.4, 147.5. Anal. calcd. for syn-C52H38N2: C, 90.43; H, 5.55; N, 4.06. Found: C, 90.70; H, 5.40; N, 4.36.; 1,8-Bis(3,3'-(3,5-dimethylphenyl)-9,9'-diacridyl)naphthalene, 32; A mixture of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (143 mg, 0.50 mmol), tetrakis(triphenylphosphine)-palladium(0) (0.11 g, 0.10 μmol, 30 mol %), and CuO (80 mg, 1 mmol) in 5 mL DMF was stirred at 140 C. After 5 min, a solution of 3-(3,5-dimethylphenyl)-9-trimethylstannylacridine 31 (0.90 g, 2.0 mmol) in 2 mL of DMF was added in one portion. After 16 hours, the reaction mixture was quenched with 10% aqueous ammonium hydroxide, extracted with diethyl ether, dried over MgSO4 and concentrated in vacuo. Purification of the orange residue by flash chromatography (100; 5:1 hexanes:ethyl acetate:triethylamine) afforded 32 (100 mg, 30%) as a yellow solid. The diastereoisomers were separated into 60% of the anti-isomer and 40% of the syn-isomer. anti-Isomer: 1H-NMR δ=2.45 (s, 12H), 6.62-6.68 (m, 2H), 6.83-6.86 (m, 4H), 7.00-7.03 (m, 2H), 7.07 (s, 2H), 7.31-7.39 (m, 8H), 7.67 (d, J=9.1 Hz, 2H), 7.73-7.78 (m, 2H), 7.91 (s, 2H). 8.31 (d, J=8.2 Hz, 2H). 13C-NMR δ=22.3, 124.8, 125.4, 125.5, 125.6, 125.9, 126.2, 126.3, 126.6, 127.0, 129.3, 129.8, 130.1, 130.5, 131.2, 134.2, 134.6, 135.5, 139.0, 140.8, 141.9, 146.1, 147.5, 147.6. LC/APC/MS: m/z=691(M+H). Anal. calcd. for anti-C52H38N2: C, 90.43; H, 5.55; N, 4.06. Found: C, 90.64; H, 5.30; N, 4.11. syn-Isomer: 1H-NMR δ=2.26 (s, 12H), 6.65-6.70 (m, 2H), 6.75-6.78 (m, 2H), 6.85-6.88 (m, 2H), 6.96-6.99 (m, 4H), 7.12 (s, 4H), 7.28-7.31 (m, 2H), 7.36-7.42 (m, 2H), 7.69-7.75 (m, 4H), 7.91 (d, J=1.65 Hz, 2H), 8.27 (dd, J=1.1 Hz, 8.36 Hz, 2H). 13C-NMR δ=22.0, 124.8, 125.3, 125.4, 125.5, 125.8, 126.1, 126.3, 126.4, 126.9, 129.4, 129.7, 130.1, 130.4, 131.1, 134.2, 134.7, 135.5, 138.8, 140.7, 142.1, 146.1, 147.4, 147.5. Anal. calcd. for syn-C52H38N2: C, 90.43; H, 5.55; N, 4.06. Found: C, 90.70; H, 5.40; N, 4.36. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1,8-Bis(4,4'-dimethyl-9,9'-diacridyl)naphthalene, 2; A mixture 1,8-dibromonaphthanene 1 (92 mg, 0.32 mmol), tetrakis(triphenylphosphine)palladium(0) (0.11 g, 0.10 mmol, 30 mol %), and CuO (51 mg, 0.64 mmol) in 10 mL DMF was stirred at 140 C. After 5 min, a solution of 4-methyl-9-trimethylstannanyl acridine 12 (0.46 g, 1.29 mmol) dissolved in 2 mL of DMF was added in one portion. After 16 hours, the reaction mixture was quenched with 10% aqueous ammonium hydroxide, extracted with diethyl ether, dried over MgSO4 and concentrated in vacuo. Purification of the orange residue by flash chromatography (100:5:1 hexanes:ethyl acetate:triethylamine) afforded 2 (41 mg, 25%) as a yellow solid. The diastereoisomers were separated on a Phenylglycine column (250 mm×4.6 mm) using hexanes/EtOH (98:2) as the mobile phase. The anti- and syn-conformation of the two isomer of 2 was determined by 1H-NMR spectroscopy using 1.2 mol equivalents of (+)-Eu(tfc)3 as a chiral shift reagent. anti-Isomer: 1H-NMR δ=2.72 (s, 6H), 6.50 (d, J=8.8 Hz, 1H), 6.52 (d, J=8.8 Hz, 1H), 6.58-6.78 (m, 6H), 7.18 (d, J=6.6 Hz, 2H), 7.22-7.27 (m, 2H), 7.35 (ddd, J=1.7 Hz, J=7.8 Hz, J=8.8 Hz, 2H), 7.68-7.73 (m, 4H), 8.25 (dd, J=1.3 Hz, J=8.8 Hz, 2H). 13C-NMR δ=18.87, 123.75, 124.67, 125.00, 125.70, 125.74, 128.18, 128.37, 129.72, 129.87, 130.58, 130.73, 134.37, 135.10, 135.90, 146.73, 146.81, 146.04, 146.32. LC/APCI/MS: m/z=511(M+H). syn-Isomer: 1H-NMR δ=2.67 (s, 6H), 6.45-6.52 (m, 2H), 6.58-6.70 (m, 4H), 6.80 (d, J=8.8 Hz 2H), 7.20-7.40 (m, 6H), 7.65-7.78 (m, 4H), 8.25 (dd, J=1.3 Hz, J=8.8 Hz, 2H). 13C-NMR 8=18.94, 123.42, 124.67, 125.00, 125.73, 125.76, 128.21, 128.41, 129.73, 129.85, 130.58, 130.73, 134.37, 135.10, 135.90, 146.72, 146.81, 146.04, 146.32. LC/APCI/MS: m/z=511(M+H). Anal. calcd. for syn and anti-C38H26N2: C, 89.38; H, 5.13; N, 5.49. Found: C, 89.80; H, 5.57; N, 4.99. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1,8-Bis(4,4'-diisopropyl-9,9'-diacridyl)naphthlalene, 3; A mixture 1,8-dibromonaphthanene 1 (10.25 g, 0.89 mmol), tetrakis(triphenylphosphine)palladium(0) (0.31 g, 0.27 mmol, 30 mol %), and CuO (0.14 g, 1.78 mmol) in 18 mL DMF was stirred at 140 C. After 5 min, a solution of 4-isopropyl-9-trimethylstannanyl acridine 12 (1.45 g, 3.8 mmol) dissolved in 2 mL DMF was added in one portion. After 16 hours, the reaction mixture was quenched with 10% aqueous ammonium hydroxide, extracted with diethyl ether, dried over MgSO4 and concentrated in vacuum. Purification of the orange residue by flash chromatography (100:5:1 hexanes:ethyl acetate:trimethylamine) afforded 3 (126 mg, 25%) as a yellow solid. The diastereoisomers were separated on a Phenylglycine column (250 mm×4.6 mm) using hexanes/EtOH (98.4:1.6) as the mobile phase. Isomer 1: 1H-NMR δ=1.22 (d, J=6.9 Hz, 6H), 1.52 (d, J=6.9 Hz, 6H), 4.23 (sept, J=6.9 Hz, 2H), 6.60-6.70 (m, 6H), 6.85 (d, J=8.4 Hz, 2H), 7.18-7.30 (m, 6H), 7.60-7.78 (m, 4H), 8.26 (dd, J=1.6 Hz, J=8.4 Hz, 2H). 13C-NMR 8=24.38, 27.25, 27.33, 123.58, 123.96, 124.68, 124.74, 124.74, 125.54, 125.58, 125.87, 128.21, 129.72, 129.90, 130.92, 134.93, 135.10, 144.95, 145.01, 145.61, 145.97, 146.79. LC/APCI/MS: m/z=567 (M+H). Isomer 2: 1H-NMR δ=1.22 (d, J=6.9 Hz, 6H), 1.52 (d, J=6.9 Hz, 6H), 4.23 (sept, J=6.9 Hz, 2H), 6.59-6.78 (m, 6H), 7.20-7.37 (m, 8H), 7.64-7.72 (m, 4H), 8.26 (dd, J=1.6 Hz, J=8.4 Hz, 2H). 13C-NMR 5=24.62, 26.98, 27.08, 123.54, 123.95, 124.60, 124.71, 125.16, 125.52, 125.74, 128.09, 129.69, 129.93, 130.79, 134.59, 134.70, 144.95, 145.01, 145.57, 145.77, 146.79. LC/APCI/MS: m/z=567 (M+H). Anal. calcd. for syn and anti-C42H34N2: C, 89.01; H, 6.05; N, 4.94. Found: C, 89.38; H, 6.25; N, 4.67. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71%Chromat. | With palladium diacetate; potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 8h; | General procedure: A solution of K2CO3 (6 mol/equiv) in 15 ml of water per 1 mmol of the limiting reactant was added to a solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (1 mol/equiv), arylboronic acid (4 mol/equiv), and Pd(OAc)2 (2 mol %) in the same volume of DMF. The resultant mixture was heated at 100 C for 8 h under stirring. The final solution was allowed to cool to room temperature, and extracted with ethyl acetate. The organic layer was washed with water and aqueous 0.1 M NaOH, dried over anhydrous sodium sulfate and evaporated, yielding the product as impure diarylnaphthalene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60%Chromat. | With palladium diacetate; potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 8h; | General procedure: A solution of K2CO3 (6 mol/equiv) in 15 ml of water per 1 mmol of the limiting reactant was added to a solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (1 mol/equiv), arylboronic acid (4 mol/equiv), and Pd(OAc)2 (2 mol %) in the same volume of DMF. The resultant mixture was heated at 100 C for 8 h under stirring. The final solution was allowed to cool to room temperature, and extracted with ethyl acetate. The organic layer was washed with water and aqueous 0.1 M NaOH, dried over anhydrous sodium sulfate and evaporated, yielding the product as impure diarylnaphthalene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57%Chromat. | With palladium diacetate; potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 8h; | General procedure: A solution of K2CO3 (6 mol/equiv) in 15 ml of water per 1 mmol of the limiting reactant was added to a solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (1 mol/equiv), arylboronic acid (4 mol/equiv), and Pd(OAc)2 (2 mol %) in the same volume of DMF. The resultant mixture was heated at 100 C for 8 h under stirring. The final solution was allowed to cool to room temperature, and extracted with ethyl acetate. The organic layer was washed with water and aqueous 0.1 M NaOH, dried over anhydrous sodium sulfate and evaporated, yielding the product as impure diarylnaphthalene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With palladium diacetate; In water; N,N-dimethyl-formamide; at 20℃; for 16h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), and palladium acetate (10 mol %) were placed in a flask under an atmosphere of nitrogen. DMF/H2O (4/1; 10 mL) was added, and the reaction mixture was stirred at room temperature for 16 h. The mixture was extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on sili |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With palladium diacetate; In water; N,N-dimethyl-formamide; at 20℃; for 16h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), and palladium acetate (10 mol %) were placed in a flask under an atmosphere of nitrogen. DMF/H2O (4/1; 10 mL) was added, and the reaction mixture was stirred at room temperature for 16 h. The mixture was extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on sili |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 14h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), Pd(PPh3)4 (10 mol %), and K2CO3 (2 equiv) were placed in flask under an atmosphere of nitrogen. DMF (15 mL) was added, and heated at 80 C for 14 h. After cooling to room temperature, 15 mL water was added, extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With palladium diacetate; 2,2'-bis(diphenylphosphino)biphenyl; copper(l) chloride; In N,N-dimethyl-formamide; at 80℃; for 14h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), palladium acetate (10 mol %), BIPHEP (11 mol), and CuCl (0.4 equiv) were placed in a flask under an atmosphere of nitrogen. DMF (15 mL) was added, and heated at 80 C for 14 h. After cooling to room temperature, 15 mL water was added, extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 14h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), Pd(PPh3)4 (10 mol %), and K2CO3 (2 equiv) were placed in flask under an atmosphere of nitrogen. DMF (15 mL) was added, and heated at 80 C for 14 h. After cooling to room temperature, 15 mL water was added, extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 14h;Inert atmosphere; | General procedure: The triolborate, dibromides (0.2 mmol), Pd(PPh3)4 (10 mol %), and K2CO3 (2 equiv) were placed in flask under an atmosphere of nitrogen. DMF (15 mL) was added, and heated at 80 C for 14 h. After cooling to room temperature, 15 mL water was added, extracted with dichloromethane, dried over MgSO4, and then purified by chromatography on silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 1h;Inert atmosphere; | General procedure: Under argon atmosphere a dry Schlenk tube was charged with sulfoximine 1a (0.10 g, 1.0 equiv, 0.5 mmol), aryl halide (0.19 g, 2.0 equiv, 1 mmol), CuI (46 mg, 0.5 equiv, 0.25 mmol), DMEDA (21 mg, 1 equiv, 0.5 mmol), Cs2CO3 (0.39 g, 2.5 equiv, 1.25 mmol), and degassed (or freshly distilled) toluene (2 mL). After heating to 110 C for 3 h, the mixture was cooled to room temperature and neutralized with aqueous HCl (10 mL at 1 M). The aqueous layer was extracted with dichloromethane (3×20 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by preparative chromatography (SiO2, pentane/diethyl ether, 9/1) to give 0.14 g (97%) of 3a as a yellow liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 1,8-diazabicyclo[5.4.0]undec-7-ene;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 150℃; for 4h; | Put in 50 mL of DMF were 2.28 g (5 mmol) of E12 and2.86 g (10 mmol) of E13. After 0.25 g (0.5 mmol) ofbis (triphenylphosphine) palladium ( II ) dichloride and 2.28 g(15 mmol) of 1, 8-diazabicyclo [5.4.0] undec-7-ene were put in the solution, it was heated to 150C and was stirred for four hours. After cooling, a precipitate was formed by adding 30 mL of methanol and was filtered out to yield a yellow solid. This solid was purified by columnchromatography (chloroform/heptane, 1:5) and wasrecrystallized twice from toluene/methanol to yield 3.27 g of a yellow crystal of E14 (yield: 72%). Next, 3.18 g (7 mmol) of E14 and 1.25 g (7 mmol) of E15 were put in 50 mL of chloroform, and the solution was heated to 60C and was stirred for eight hours. After cooling, the solution was washed twice with 50 mL of water. The organic layer was washed with saturated saline and was dried over magnesium sulfate. The solution was then filtered, and the filtrate was concentrated. This was purified by columnchromatography (chloroform/heptane, 1:2) and wasrecrystallized from toluene/ethanol to yield 3.17 g of E16 (yield: 85%) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 85℃; for 24h;Inert atmosphere; | In 50mL three-necked flask, 1,8-dibromo naphthalene 0.052g (0.181mmol), 4- (carbazole -9-N- yl) phenyl boronic acid pinacol ester 0.200g (0.542mmol), toluene 10m, ethanol 5mL , placed 2.0M-K2CO3 5mL, it was nitrogen bubbling for one hour. Then placed Pd (PPh3) 40.042g (0.036mmol), under a stream of nitrogen, and the mixture was stirred at 85 . After 24 hours, by thin layer chromatography (developing solvent hexane) 1,8-dibromo-naphthalene: After confirming the consumption of (Rf 0.38), and the reaction mixture was returned to room temperature. The organic layer was then extracted with toluene, washed with saturated brine, dried over anhydrous magnesium sulfate, after filtration, the solvent was evaporated under reduced pressure. Then, to recover the insoluble solids addition of hexane. Then, they separated and purified by silica gel column chromatography (developing solvent, toluene) to give a white solid 0.020 g (18% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (1.0 g, 3.5 mmol) in THF (18 mL) was cooled to -70 C. To this solution was added n-butyllithium (2.1 N in hexanes, 2.0 mL, 4.2 mmol) dropwise. After the mixture was stirred at -70 C for 30 minutes, N,N-dimethylformamide (0.6 mL) was added dropwise. The solution warmed to room temperature over one hour. The reaction was quenched with saturated aqueous NLLCl, the organics were separated, and the aqueous phase was extracted twice with DCM. The organics were dried over MgSCri and condensed. The material was purified by flash chromatography (RediSep Gold 24g column, 0-10% EtO Ac/hexane) to afford 8-bromo-l-naphthaldehyde (0.44 g, 53%). 1HNMR (400 MHz, CDCb): d 11.44 (s, 1H), 8.01 (d, J= 8.2 Hz, 1H), 7.91 (q, J= 7.6 Hz, 3H), 7.57 (t, J= 7.7 Hz, 1H), 7.40 (t, J= 7.7 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 90℃; for 6h; | A solution of 1,8dibromonaphthalene (500 mg, 1.7 mmol), 4-pyridineboronic acid (322 mg, 2.6 mmol), PdQ?Ph3)4 (151.5 mg, 0.13 mmol), and K3P04 (927,7 mg, 4.4 mmol) in 18 mL of toluene:EtOH:water (3:2:1 v/v) was stirred at 90 C for 6 hours. The resulting mixturewas allowed to cool to room temperature, quenched with water, and extracted with C1-12C12. Thecombined organic layers were dried over MgSO4 and concentrated in vacuo. Purification by flashchromatography on silica gel (CH2C12:EtOAc 2:1) afforded 360 mg (1.3 mmol, 75% yield) of a yellow solid.‘H NMR: 8 = 731-7.38 (m, 4H), 7.50 (dd, J = 7.3, Hz, 8.0 Hz, IH), 7.79 (d,J = 6.6 Hz, 1H), 7,90 (dd,j 8.3 Hz, 8.3 Hz, 21-i), 8.63 (d,J = 5.7 Hz, 2H). 13C NMR: 8 = 119.6,1253, 125.4, 1265, 1290, 129.9, 131.0, 134.0, 136.0, 137.5, 148.6, 151.4. Anal. Calcd. C15H10BrN:C, 63.40; H, 3.55; N, 4.93; Found: C, 63.39; H, 3.52; N, 4.82. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 36h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 48h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 48h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 14h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: Dibromoarene 1 (0.5 mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%, 5.6 mg ),Xantphos (5.5 mol%,16 mg), K2CO3 (1.5 mmol, 207 mg) were added into a Schlenkflask. The flask was evacuated and backfilled with nitrogen (3 cycles). Dry DMF (5mL) was added by syringe. The mixture was heated to 120 C and stirred until thereaction finished (TLC analysis). After cooling to room temperature, the mixture wasextracted three times with ethyl acetate. The organic layers were combined and driedover Na2SO4. After filtration, the solvents were evaporated. The crude product wasfurther purified by silica gel chromatography, using petroleum ether and ethyl acetateas eluents to provide the pure product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 4h; | A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (500 mg, 1.7 rmnol), 3-formyl-4- methoxyphcnylboronic acid (472.0 mg, 2.6 mrnol), Pd(PPh3)4 (151.5 mg, 0.13 rmnol), and K5P04 (927.7 mg, 4,4 mmol) in 18 mL of toluene:ethanol:water (3:2:1 v/v) was stirred at 80 C for 4 hours, The resulting mixture was allowed to cool to room temperature, quenched with water, andextracted with CH2C12. The combined organic layers were dried over MgSO4 and concentrated in vacuo. Purification by flash chromatography on silica gel (CH2C12:hexanes 4:1) afforded 417 mg (1.2 mmoi, 70% yield) of a yellow solid.‘H NMR 8 4.02 (s, 31-I), 7.12 (d,J = 8.5 I-Iz, 114), 7.39-7.50 (m, 31-1), 7.68 (d,J = 8.2 Hz, IH), 7.81 (dd, J 8.4 Hz, 8.2 Hz, 211), 7.90 (d, J = 8.0 Hz, lI-I), 7.98 (s, 111), 10.56 (s,IH). ‘3CNMR: 8 = 55.8, 110.7,119.8,124.0,125.3,126.1,129.0,129.1, 129.5, 129.8, 1314,133.8, 135.3, 136.1, 137.4, 138.6, 161.1, 190.0. Anal. Calcd. C,,H,3BrO,: C, 63.36; H 3.84; Found:C, 63.18; H, 4.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 4h; | A solution of 1,8-dibromonaphthalene (500 mg, 1.7 mmol), 4-isoquinohneboronic add (453.7 mg, 2.6 rnmol), Pd(PPh3)4 (151.5 mg, 0.13 mmol), and K3P04(927.7 mg, 4.4 mmol) in 18 mL of toluene:ethanol:water (3:2:1 v/v was stirred at 80 C for 4hours, The resulting mixture was allowed to cool to room temperature, quenched with water, and extracted with C1-1,C1,, The combined organic layers were dried over MgSO4 and concentrated in vacua. Purification by flash chromatography on silica gel (CH2C1,:EtOAc 2:1) afforded 470 mg (1.4 rumol, 80% yield) of a yellow solid.?H NMR: 6 = 7.26-7.36 (m, 2H), 7.51-7.61 (m, 4H), 7.71 (d,J 7.4Hz, 1H), 7.95(d, J = 8.0 Hz, IH), 8.01 (dd, f = 9.3 LIz, 9.3 Hz, 2H), 8.48 (s, IH), 9.33 (s, 1H). L3C NMR: 6 =1197, 125.2, 125.5, 126.4, 127,0, 127.5, 127.8, 129.2, 130.1, 130.3, 130.6, 132.1, 133.9, 134.0,134.2, 136.0, 136.6, 143.2, 151.7. Anal. Calcd. C191-I,9BrN: C, 68.28; H, 3.62; N, 4.19; Found: C,68.07; H, 3.62; N, 4.13. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 80℃; | 4-Chlorophenylboronic acid (6.6 g, 40 mmol), <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (15 g, 50 mmol), tetrakis(triphenylphosphine)palladium(0) and THF (300 mL) were stirred in a two-necked flask for 30 min. Into the above solution, was added potassium carbonate (29 g, 210 mmol) dropwise over a period of 20 min. The resulting solution was refluxed overnight at 80 C. The reaction mixture was extracted with dichloromethane and water. After the organic layer was evaporated with a rotary evaporator, the evaporated and resulting powdery product was purified by column chromatography using n-hexane to give a white crystalline solid. Yield 80% 1H NMR (500 MHz, DMSO) 8.090-8.052 (t, 2H), 7.843-7.826 (d, J = 8.5 Hz, 1H), 7.624-7.594 (t, 1H), 7.448-7.388 (m, 5H), 7.299-7.280 (m, 2H) ppm. EI-MS [M+H]+: 318. |
73% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Inert atmosphere; Reflux; | In a 2000-ml three-necked flask, 57.19 g of 1,8-Dibromo-naphthalene was placed.34.40 g of 4-Chlorophenylboronic acid,55.28 g of potassium carbonate and 6.93 g of Palladium-tetrakis (triphenylphosphine) were placed under a nitrogen atmosphere and 1000 ml of tetrahydrofuran (THF) and 500 ml of deionized water were added.After heating to reflux, the reaction was stirred for 12 hours. After the reaction was cooled, ethyl acetate was used for extraction.The organic layer was collected and concentrated for column separation (Hex:EA=10:1).After collection, it was concentrated to give a pale yellow oil, which gave 46 g of product in 73% yield. |
73% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Reflux; Inert atmosphere; | A 2000 ml three-necked flask was charged with 57.19 g of 1,8-Dibromo-naphthalene, 34.40 g of 4-Chlorophenylboronic acid, and 55.28 g of Potassium carbonate. 6.93 g of Palladium-tetrakis (triphenylphosphine), placed under a nitrogen system, 1000 ml of tetrahydrofuran (THF) and 500 ml of deionized water, heated to reflux, and stirred for 12 hours. After the temperature was lowered, the mixture was extracted with ethyl acetate. The organic layer was collected and concentrated, and then subjected to column separation (Hex: EA = 10:1), which was collected and concentrated to give a pale yellow oil to yield 46 g of product. |
72.4% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate; In ethanol; water; toluene; at 50 - 75℃; for 18h;Inert atmosphere; | Under the protection of nitrogen, add <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (58.37g, 204.13mmol), 4-chlorophenylboronic acid (30.4g, 194.41mmol), toluene (480mL), ethanol (240mL), water ( 120mL), potassium carbonate (59.11g, 427.70mmol), after the addition, stir and heat to 50-60, then quickly add tetrakis(triphenylphosphine)palladium (4.34g, 3.89mmol), tetrabutyl bromide Ammonium chloride TBAB (12.53g, 38.88mmol), after dripping, continue to heat up to 70-75C and reflux for 18h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase to neutrality, dry, filter, and concentrate. Recrystallize with ethyl acetate and n-heptane mixed solvent to LC>98%. Drying to obtain Intermediate A-1 (44.7 g, 72.4%) as a white solid. |
66% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; | <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (15 g, 52.5mmol), 4-chlorophenylboronic acid (6.5 g, 42 mmol), tetrahydrofuran (300 ml),potassium carbonate (29 g, 209 mmol) and water (75 ml) were mixed in around-bottom flask with stirring. Tetrakis(triphenylphosphine)palladium(0) (0.24 g, 0.2 mmol) wasadded to the mixture, which was heated to 80C. The organic layer was isolatedfrom the reaction solution, washed twice with water, and dried over magnesiumsulfate, which was distilled under a reduced pressure to remove the solventtherefrom. The residue thus obtained was subjected to purification by columnchromatography using n-hexane, toobtain 11g of the compound.Yield 66%1H-NMR (500 MHz, DMSO) 8.10-8.05 (t, 2H), 7.84-7.82 (d, J=8.5Hz, 1H), 7.62-7.59 (t, 1H), 7.44-7.36 (m, 6H) ppm. EI-MS [M+H]+: 318m/z. |
35 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 110℃; for 8h; | 1,8-dibromo-naphthalene (50g), 4-chlorophenylboronic acid (30. lg), toluene (500mL), potassium carbonate (132 · 9g)And water (250mL) was added 2L three neck round bottom flask and stirred. Tetrakis (triphenylphosphine) palladium in a mixture(0) (2. 22g), then heated at 110 C 8 hours. The reaction solution was cooled to room temperature, and extracted with ethyl acetate twoTimes. The organic layer was dried with magnesium sulfate, and then concentrated under reduced pressure, thereby removing the solvent. Separated by column using hexane and concentrated to yieldSubstance use and washed with methanol to obtain 35g of a white powder. |
40 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 110℃; for 8h; | 2L 3 neck round bottom flask, <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (50 g),4-chlorophenylboronic acid (21 g), toluene (1000 mL),Into potassium carbonate (96 g) and water (250 mL) and stirred.put Tetrakis (triphenylphosphine) palladium(0) (0.81 g) in a mixture at 110 degree celcius was heated for 8 hours. The reaction mixture was cooled to room temperature and extracted twice with ethyl acetate.The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent.Column separation using a hexane-cost material produced by the concentratedWashed with methanol 40 g of a white powder obtained. |
64 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 110℃; for 12h; | Dibromonaphthalene (100 g), 4-chlorophenylboronic acid (43.8 g), toluene (2 L), potassium carbonate (241.7 g) and water (500 mL) were added to a 5 L three- And the mixture was stirred. Tetrakis (triphenylphosphine) palladium (0) (2.02 g) was added to the mixture, and the mixture was heated at 110 C for 12 hours. The reaction solution was cooled to room temperature and extracted twice with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material formed by concentration was purified by silica gel column chromatography (eluent: n-hexane) and washed with methanol to obtain 64 g of white powder I-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (5 g, 0.0175 moles) was taken in a round-bottomed flask and dissolved in toluene. Tetrakis triphenyl phosphine palladium (0.1 gm) was added to the above solution and stirred for 10 -15 min. To this solution the 2-indene boronic acid (6.71 g, 0.041 moles) dissolved in ethanol (15 ml) was added, followed by aqueous sodium carbonate (2M, 15ml). The reaction mixture was heated to 80C and stirred for 24hrs. It was cooled and extracted with dichloromethane (DCM; 5 x 50ml). The DCM portion was then extracted with water (2 x 50ml), dried over sodium sulfate and concentrated. The crude compound was purified by column chromatography by continuously eluting with hexane as the eluent. Yield = 30%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (5g, 0.0175 moles) was dissolved in diethylether (50ml) and cooled to -80C. Butyllithium (2.5M solution in hexane, 21 ml, 0.0525 moles in 50ml ether) was added dropwise using a dropping funnel. After the addition was completed, the reaction mixture was slowly brought to room temperature. The solution was stirred for 3 hours at room temperature. After this, the reaction mixture was again cooled to -80C and trimethyl borate (10ml, 0.07 moles in 100 ml ether) was added. The reaction mixture was left for stirring at room temperature overnight. The next day, the reaction was quenched by adding 50ml of water followed by addition of 100ml of 2N hydrochloric acid. The mixture was stirred for 45min and thereafter extracted with ether (3 x 50ml). The organic fraction was extracted with 5% sodium hydroxide solution (3 x 50ml). The alkaline fraction was acidified with concentrated hydrochloric acid until acidic. A white solid was precipitated. Yield = 2.6g (68%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; bis(dibenzylideneacetone)-palladium(0); In N,N-dimethyl-formamide; at 80℃; | <strong>[5570-18-3]2-aminophenylboronic acid</strong> and 10.0g of 1,8-bromonaphthalene to the reactor 22.97g, tetrakis (triphenylphosphine) palladium (0) tris (dibenzylideneacetone) di palladium was added to the (0) 8.44g dimethyl formamide was added to 200mL. To the reaction mixture was added dropwise an aqueous solution of potassium carbonate 2M- 170mL. After the temperature was raised and the reaction mixture was stirred with 80 . After the reaction was completed and then cooled to room temperature, it was added 400mL of ethyl acetate. After taking the organic layer was washed with 100mL of purified water was added. After adding anhydrous magnesium sulfate 10g on the organic layer it was stirred for 30 minutes. And it concentrated under reduced pressure after filtering the organic layer. The concentration residue to silica gel chromatography (hexane / dichloromethane = 3/1) to 2- (8-bromonaphthalen-1-yl) aniline to give the. (12.24g, yield 56.2%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.8% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 10h;Inert atmosphere; Reflux; | In three 500mL flask, 1,8-dibromo-naphthalene (28.6g, 0.1mol), 4- methoxy-naphthalene-1-boronic acid (20.2g, 0.1mol), potassium carbonate (27.6g, 0.2mol), toluene (180g), deionized water (80g), ethanol (180g), nitrogen, was added Pd (PPh3) 4 (1.1g), warmed to reflux, the reaction was kept 10H, cooled to 25 , liquid separation, the organic phase was washed with 200g of deionized once, 100g anhydrous sodium sulfate, suction filtered, the organic phase was collected, the organic phase flash silica gel column by 35cm thick, was passed through the column for solvent removal, the obtained crude product was recrystallized using ethanol as solvent, to give compound 6, 28.6 g of an off-white solid, yield 78.8%, MS (m / s): 362.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.8% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 16h;Inert atmosphere; Reflux; | In three 500mL flask, 1,8-dibromo-naphthalene (14.3g, 0.05mol), 4- (pentafluorophenyl) -1-naphthalene boronic acid (16.9g, 0.05mol), potassium carbonate (11.0g, 0.08mol), toluene (150g), deionized water (60g), dry ethanol (20g), the protection of nitrogen was added Pd (PPh3) 4 (0.8g), warmed to reflux, the reaction incubated 16h, cooling to 25 , liquid separation, the organic phase 200 g of deionized water once, 100g anhydrous sodium sulfate, suction filtered, the organic phase was collected, the organic phase flash silica gel column by 35cm thick, was passed through the column for solvent removal, the obtained crude product the solvent was recrystallized from isopropanol to give compound 27, 18.7g of white solid, yield 74.8%, MS (m / s): 498.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 120℃; for 3h; | In a flask, combine 170 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (594 mmol), 60 g of phenylboronic acid (492 mmol), 14.2 g of tetrakis(triphenylphosphine)palladium(0) (12.2 mmol) and 87 g of sodium carbonate (820 mmol) was dissolved in 1.6 L of toluene, 410 mL of ethanol and 410 mL of water, and the mixture was refluxed at 120C for 3 hours. After the reaction was completed, the organic layer was separated with ethyl acetate, and the remaining moisture was dried by using magnesium sulfate. The residue was separated by column chromatography to obtain 117 g of Compound 1-1 (yield: 84%). |
78% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 10h;Inert atmosphere; | In a 250ml three-necked flask, A'-1 (28.6g, 0.1mol), B'-1 (12.2g, 0.1mol) and potassium carbonate (16.6g,0.12) were added under nitrogen protection mol), toluene (100 mL), water (25 mL) and tetrakis (triphenylphosphine) palladium (5.8 g, 0.005mol) were added and stirred at 100 C for 10 hours. After the reaction it was cooled to room temperature. The reaction system was added with water and extracted with dichloromethane. The resulting extract was added to magnesium sulfate in order to dry, filtered and spin-dried. The obtained crude product was purified by chromatography (ethyl acetate / hexane volume ratio 1:10) to obtain C'-1 (22 g, 78% yield). |
73% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 19h;Inert atmosphere; Reflux; | Add a solution of N2 and S1 (57.193g, 1.0 equivalent (eq.)) into a 2500ml two-necked flask,Phenylboronic acid (29.263g, 1.2 equivalents), Pd(PPh3)4 (11.556g, 5mol%) and Na2CO3 (52.995g, 2.5 equivalents) in toluene/H2O (1000/100ml) were refluxed for 19 hours.After cooling to room temperature, H2O (300ml) was added and stirred for another 30 minutes.The reaction mixture was then extracted with ethyl acetate (3×200 ml).The organic layer was sequentially collected, dried over MgSO4, filtered, and concentrated to dryness.The crude product was purified by flash column chromatography (ethyl acetate/hexane, 1/30) to obtain S2 (41.343 g, 73%). |
72% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; water; at 80℃; for 5h;Inert atmosphere; | Under an atmosphere of argon (Ar), a 500 ml three-necked flask was charged with 8.80 g of 1,8-dibromonaphthlene, 4.69 g of phenylboronic acid, 4.89 g of Na2CO3,And 200 ml of a mixed solution of THF / water (20%) in which 1.07 g of Pd (PPh3) 4 was dissolvedAt 80 CAnd the mixture was heated and stirred for 5 hours.After air cooling,Dichloromethane was added to separate the organic layer and the solvent was evaporated.The obtained product was purified by silica gel column chromatography (hexane / toluene)To obtain 6.27 g (yield 72%) of Compound A as a pale yellow solid. |
72% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; water; at 80℃; for 5h;Inert atmosphere; | Under an atmosphere of argon (Ar), a 500 ml three-necked flask was charged with 8.80 g of 1,8-dibromonaphthlene, 4.69 g of phenylboronic acid, 4.89 g of Na2CO3,And 200 ml of a mixed solution of THF / water (20%) in which 1.07 g of Pd (PPh3) 4 was dissolved at 80 DEG C And the mixture was heated and stirred for 5 hours. After air cooling, dichloromethane was added to separate the organic layer, and the solvent was evaporated. The obtained product was purified by silica gel column chromatography (hexane / toluene) to give 6.27 g (yield 72%) of Compound A as a pale yellow solid. |
61% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 6h;Inert atmosphere; Reflux; | Under an Ar atmosphere, 8.65 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong>, 3.69 g of phenylboronic acid, 1.75 g of Pd(PPh3)4, and 3.55 g of K2CO3 were dissolved in a mixed solvent containing 90 mL of water and 300 mL of tetrahydrofuran (THF) and then refluxed and stirred for 6 hours in a 500-mL three-neck flask. An organic layer obtained therefrom was dried by using MgSO4, and the solvent was evaporated. The residue obtained therefrom was separated and purified by silica gel column chromatography, thereby completing the preparation of 5.23 g (61%) of Intermediate A. A molecular weight of the prepared Intermediate A was measured to be 283 by MS/FAB. |
48.4% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; for 6h;Reflux; Inert atmosphere; | Under a nitrogen atmosphere, <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (28.6 g, 0.1 mol), phenylboronic acid (12.2 g, 0.1 mol) and180 mL of toluene, 75 mL was added to a 500 mL three-necked flask, and then tetrakis (triphenylphosphine) palladium (0.116 g, 0.1 mmol)Tied to acidPotassium carbonate (20.7 g, 0.15 mol).The temperature of the system was heated to reflux for 6 hours, and the temperature was gradually cooled to 20 to 25 C. The solvent was removed and the crude product was crystallized from absolute ethanol to give 13.7 g of intermediate a in a yield of 48.4%. |
35 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 110℃; for 8h; | 2L 3 neck round bottom flask, 1,8-dibromo-naphthalene (50 g), phenylboronic acid (21 g), toluene (500 mL), was stirred into the potassium carbonate (48 g) and water (175 mL). Into the mixed solution of tetrakis (triphenylphosphine) palladium (0) (4.04 g) was heated in 8 hours at 110 . The reaction mixture was cooled to room temperature and extracted twice with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by the separation column was concentrated using a hexane and washed with methanol to give 35 g of white powder. |
5 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; | 250ml 3 neck round bottom flask was charged with 1,8-dibromo-naphthalene (7g), phenylboronic acid (2.9 g), tetrahydrofuran (70 ml), potassium carbonate (6.7g) and water (24ml) and the mixture was stirred. Put the tetrakis (triphenylphosphine) palladium (0) (0.6g) in the mixture solution was heated to 80C . Separated by a salt layer was removed and the reaction solution and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. Through a column separation process using hexane The material produced by the concentrated to give the title compound 5g. |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 6h; | 1,8-Dibromonaphthalene (0.1mol, 1eq), phenylboronic acid (0.1mol, 1eq), potassium carbonate (0.2mol, 2eq), tetrakis (triphenylphosphine) palladium (0.001mol, 0.01eq) , Dioxane (300ml) and water (50mL) were added to the three-necked flask. The oil bath was heated to 90C for 6 hours, and TLC monitored the completion of the reaction. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The obtained crude product is purified by column chromatography to obtain intermediate M1-A. | |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 6h; | 1,8-Dibromonaphthalene (0.1mol, leq), phenylboronic acid (0.1mol, leq), potassium carbonate (0.2mol, 2eq), tetrakis(triphenylphosphine) palladium (0.001mol, 0.01eq),Dioxane (300ml) and water (50ml) were added to a three-necked flask.The oil bath was heated to 90C for 6 hours, and TLC monitored the completion of the reaction.The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure.The obtained crude product is purified by column chromatography to obtain intermediate M-A. | |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 6h; | 1,8-Dibromonaphthalene (0.1mol, 1eq), phenylboronic acid (0.1mol, 1eq), potassium carbonate (0.2mol, 2eq), tetrakis(triphenylphosphine) palladium (0.001mol, 0.01eq), Dioxane (300 mL) and water (50 mL) were added to a three-necked flask. The oil bath was heated to 90C for 6 hours, and TLC monitored the completion of the reaction. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The obtained crude product is purified by column chromatography to obtain intermediate M-A. | |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 90℃; for 6h; | 1,8-Dibromonaphthalene (0.1mol, 1eq), phenylboronic acid (0.1mol, 1eq), potassium carbonate (0.2mol, 2eq), tetrakis(triphenylphosphine) palladium (0.001mol, 0.01eq), two Oxane (300ml) and water (50ml) were added to a three-necked flask. The oil bath was heated to 90C for 6 hours, and TLC monitored the completion of the reaction. The reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The obtained crude product is purified by column chromatography to obtain intermediate M-A. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; | 100ml 3-neck round bottom flask was placed <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (7g), 2- formylphenylboronic acid (3.7g), tetrahydrofuran (37ml), potassium carbonate (5.05g) and water (18ml) was stirred with the tetrakis (triphenylphosphine) palladium (0) (0.28g) in a mixed liquid was heated to 80C . Separating the reaction solution layer was removed by the water and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. Through a separation column using hexane and the resulting substance by concentration to give the 3.0g of the title compound I-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | In tetrahydrofuran; at 25℃; for 3.5h;Inert atmosphere; | Step 1: Preparation of 1-bromo-8-methylnaphthalene To a solution of 1,8-dibromonaphthalene (21.2 g, 74.0 mmol, 1 eq) in THF (400 mL) at 0 C was added MeLi (1.6 M, 50.9 mL, 1.1 eq) dropwise, and the reaction mixture was stirred for 0.5 hour. CH3I (42.0 g, 296.1 mmol, 4 eq) was then added under N2, and the reaction mixture was stirred at 25 C for 3 hours. The reaction was quenched by addition of water (80 mL) at 0C, and the resulting mixture was extracted with EtOAc (2 x 300 mL). The combined organic extract was washed with brine (80 mL), dried over anhydrous sodium sulfate, filtered, and concentrated. The resulting residue was purified by prep-HPLC (55-95% CH3CN in water (0.225% formic acid)) to afford 1-bromo-8-methylnaphthalene (10.5 g, 45.1 mmol, 61% yield) as a yellow solid.1H- NMR (400 MHz, CDCl3) δ 7.85 (d, J = 7.6 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.76-7.70 (m, 1H), 7.40-7.35 (m, 2H), 7.23 (t, J = 8.0 Hz, 1H), 3.15 (s, 3H). |
58% | Under the protection of nitrogen, compound 1a (2.00g, 6.99mmol) was dissolved in tetrahydrofuran (15mL), the temperature was lowered to -78C, 2.5M n-butyllithium in n-hexane solution (3.08mL, 7.70mmol) was added to it, and the reaction For 0.5 hour, iodomethane (4.00 g, 2.81 mmol) was added dropwise at -78C. The reaction system was naturally warmed to room temperature. After the reaction was continued for 2.5 hours, it was diluted by adding water (20mL) and ethyl acetate (10mL), and the liquids were separated. The aqueous phase was extracted with ethyl acetate (10mL x 1). After the organic phases were combined, there was no water. It was dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from isopropanol (1 mL) to obtain 1b (903 mg), yield: 58%. | |
51% | Two separate reactions were run in parallel. For each reaction, to a solution of 1,8- dibromonaphthalene (75 g, 262 mmol, 1 equiv) in THF (1.5 L) at 0 C was added MeLi (1 M in 2- methyltetrahydrofuran, 420 mL, 1.6 equiv) dropwise, then the mixture was warmed to 13 C. After 0.5 h, MeI (253 g, 1.78 mol, 6.8 equiv) was added dropwise to the mixture. After 0.5 h, the two separate reaction mixtures were combined. H2O (2 L) was poured into the mixture and the aqueous phase was extracted with EtOAc (2 x 800 mL). The combined organic phase was washed with sat. aq. NaCl (800 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (100% petroleum ether) followed by reverse phase chromatography to afford 1-bromo-8-methyl-naphthalene (60 g, 51% yield) as a white solid. 1H NMR (400 MHz, Chloroform- d) δ 7.84 (dd, J = 1.2, 7.4 Hz, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.75 - 7.68 (m, 1H), 7.39 - 7.33 (m, 2H), 7.22 (t, J = 7.8 Hz, 1H), 3.14 (s, 3H). |
43% | To a solution of 1,8-dibromonaphthalene (1 g, 3.50 mmol, 1 eq) in THF (20 mL) was added MeLi (1.6 M in diethyl ether, 2.62 mL, 1.2 eq) at 0° C. dropwise. After stirring for 30 minutes at 0° C., iodomethane (3.38 g, 23.8 mmol, 1.48 mL, 6.81 eq) was added dropwise. The mixture was warmed up to 25° C. and stirred for another 3 hours. The reaction mixture was quenched with water (20 mL) and extracted with ethyl acetate (20 mL 3). The combined organic layers were washed with brine (20 mL), dried over Na 2SO 4, filtered and concentrated under reduced pressure to give a residue. The residue was purified by prep-HPLC (column: Phenomenex Gemini C18 250*50 mm*10 um; mobile phase: [water (0.05% ammonia hydroxide v/v)-ACN]; B %: 45%-70%, 28 MIN; 40% min). Title compound 1-bromo-8-methyl-naphthalene (340 mg, 1.49 mmol, 43% yield, 97% purity) was obtained as a yellow solid after lyophilisation. 1H NMR (400 MHz, chloroform-d) δ=7.75 (dd, J=0.8, 7.2 Hz, 1H), 7.69 (dd, J=0.8, 8.0 Hz, 1H), 7.66-7.59 (m, 1H), 7.30-7.22 (m, 2H), 7.13 (t, J=8.0 Hz, 1H), 3.05 (s, 3H). | |
43% | With methyllithium; In tetrahydrofuran; at 0 - 25℃; for 3.5h; | To a solution of 1,8-dibromonaphthalene (1 g, 3.50 mmol, 1 eq ) in THF (20 ml.) was added MeLi (1.6 M in diethyl ether, 2.62 mL, 1.2 eg) at 0C dropwise. After stirring for 30 minutes at 0C, iodomethane (3.38 g, 23.8 mmol, 1.48 mL, 6.81 eq) was added dropwise. The mixture was warmed up to 25C and stirred for another 3 hours. The reaction mixture was quenched with water (20 mL) and extracted with ethyl acetate (20 mL x 3). The combined organic layers were washed with brine (20 mL), dried over Na2S04, filtered and concentrated under reduced pressure to give a residue. The residue was purified by prep-HPLC (column: Phenomenex Gemini Cl 8 250*50mm* 10 um; mobile phase: [water (0.05% ammonium hydroxide v/v) - ACN]; B%: 45% - 70%, 28 MIN; 40% min). Ttitle compound l-bromo-8-methyl -naphthalene (340 mg, 1.49 mmol, 43% yield, 97% purity) was obtained as a yellow solid after lyophilisation.(0504) [0309] NMR (400MHz, chloroform-d) d = 7.75 (dd, J = 0.8, 7.2 Hz, 1H), 7.69 (dd, J = 0.8, 8.0 Hz, 1H), 7.66 - 7.59 (m, 1 H), 7.30 - 7.22 (m, 2H), 7.13 (t, j= 8.0 Hz, HI), 3.05 (s, 3H). |
2.15 g | In an ice-salt bath at -10C, the 1.8-dibromonaphthalene(4.70g) dissolved in anhydrous THF (50mL), under the protection of nitrogen,The ether solution of methyl lithium (1.6M, 11.2mL)Use a syringe to slowly add to the above solution,Keep at 0C and stir for 1 hour, then drop to -10C,Add methyl iodide (9.30g) in THF(10mL) The solution was slowly added to the reaction solution and slowly returned to room temperature.Continue to stir for 5 hours,The reaction was quenched with saturated aqueous sodium chloride solution,Then it was extracted with ethyl acetate, the organic phases were combined,Dry with anhydrous sodium sulfate, filter,The filtrate was concentrated under reduced pressure,The residue was separated by column chromatography to obtain a yellow solid (4.10g),The yellow solid was recrystallized from tert-butanol to obtain white flake crystals (2.15 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.9% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Inert atmosphere; Reflux; | In a 500 mL three-necked flask,<strong>[17135-74-9]1,8-dibromonaphthalene</strong> (24.9 g, 0.087 mol) was added,9,9-dimethyl-1-fluoreneboronic acid (23.8 g, 0.10 mol),Potassium carbonate (30 g, 0.22 mol),Toluene (150 g),Ethanol (50 g),Deionized water (65 g),Under nitrogen protection,Pd (PPh3) 4 (0.5 g) was added,Heating to reflux,Insulation reaction 12h,Cooled to 30 C,Liquid separation,The organic phase was dried over 40 g of anhydrous magnesium sulphate,Rapid 15cm thick silica gel column,Through the column liquid desolvent,The obtained crude product was recrystallized from ethyl acetate / absolute ethanol as a solvent,Compound 16 was obtained,29.8 g of a white solid,Yield 85.9% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.7% | With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In tetrahydrofuran; water; for 8h;Inert atmosphere; Reflux; | In a 1 L three-necked flask,<strong>[17135-74-9]1,8-dibromonaphthalene</strong> was added(28.6 g, 0.1 mol),Dibenzofuran-4-boronic acid(23.3 g, 0.11 mol),Potassium carbonate(34.5 g, 0.25 mol),Tetrahydrofuran(400 g),Deionized water (120 g),Under nitrogen protection,Pd (OAc) 2 (0.5 g) was added,Xantphos (2.3 g) was warmed to reflux,Insulation reaction 8h,Cooled to 40 C,Liquid separation,The organic phase was dried over 50 g of anhydrous magnesium sulphate,Fast over 12cm thick silica gel column,Through the column liquid desolvent,The resulting crude product was recrystallized from ethyl acetate / absolute ethanol as solvent to give compound 1,White solid 32g,The yield was 85.7% |
85% | With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 70℃; for 24h; | [Reaction formula 1-1]A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (35.0 mmol),Dibenzofuranyl-1-boronic acid (35.0 mmol),After tetrakis (triphenylphosphine) palladium (0) (1.5 mmol) was dissolved in 150 mL of THF to form a mixture,The mixture was stirred in a water bath at 70 C for 24 hours.After the reaction is completed,THF was removed from the mixture.After extracting the mixture with methylene chloride and water,The silica gel column process.After the solvent is distilled under reduced pressure,The mixture was recrystallized from methylene chloride and n-hexane,Thus, 10.4 g of solid compound A1-a (85%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 75℃; for 12h;Inert atmosphere; | In a four-necked flask, 1.72 g (6.0 mmol) of 1,8-dibromonaphthalene dissolved in 120 mL of toluene and 24 mL of ethanol, and 4- (4,4,5,5-tetramethyl-1,3,2- dioxaboron -2-yl) benzonitrile, followed by addition of an aqueous solution of potassium carbonate, and N 2 bubbling was carried out for about 1 hour. Subsequently, 0.349 g (0.302 mmol) of tetrakis (triphenylphosphine) palladium (0) as a catalyst was added under N 2 and stirred for about 12 hours while refluxing, thereafter extraction with toluene, extraction with a saturated brine The solution was washed, dried over anhydrous magnesium sulfate and purified by silica gel column chromatography (developing solvent hexane: ethyl acetate = 10: 1) to obtain 1.11 g (yield: 60.0%) of the objective compound |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With n-butyllithium; In diethyl ether; pentane; at -30 - 20℃; | Synthesis of digold(II) naphth-di-yl DEDT complex (1) A solution of 1,8-dilithionaphthalene (from the reaction of 21 mg, 0.072 mmol of dibromonaphthalene with 2.5 M, 0.06 mL, 0.15 mM nBuLi pentane solution) in ether (2 mL) was added to a precooled suspension of Au(DEDT)Cl2 (30 mg, 0.072 mmol) in ether (3 mL) at -30 C. The reaction mixture was maintained at -30 C for 45 min, slowly warmed to room temperature and stirred overnight. The reaction mixture was filtered and the resulting solid was washed with toluene (10 ml, 3 times) to remove perylene (∼2 mg) and dried in vacuo. The solid was extracted with CH2Cl2 (15 mL) and the mixture was filtered using diatomaceous earth to remove LiCl. The filtrate was vacuum dried to a solid. Recrystallization from CH2Cl2 at -30 C afforded complex 1 as bright reddish orange crystals. Yield: 20 mg (35%) 1H NMR (300 MHz, CD2Cl2): 7.22-7.26 (m, 2H), 7.30-7.31 (d, 2H), 7.61-7.63 (d, 2H), 3.81-3.87 (m, 8H), 1.37-1.41 (m, 12H). 13C NMR (75.5 MHz, CD2Cl2): 203.3, 136.4, 133.3, 129.2, 126.3, 125.3, 47.3, 46.3, 12.9, 12.8. Elemental analyses calculated for C20H26Au2N2S4 (%): C, 29.42; H, 3.21; N, 3.43. Found: C, 27.78; H, 3.14; N, 3.43; (dublicate) Found: C, 27.68; H, 3.12; N, 3.34. A second sample from a different batch was analyzed by another company: Found: C, 27.91; H, 4.10; N, 3.42. The 1H and 13C NMR spectra of complex 1 showed no significant impurities ( Supporting information). Perylene was confirmed by 1H NMR and UV-Vis spectroscopy |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 70℃; for 24h; | A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (26 mmol),Compound A2-b (26 mmol),After tetrakis (triphenylphosphine) palladium (0) (1.3 mmol) and K2CO3 15 g were dissolved in THF (120 mL) and distilled water to form a mixture,The mixture was stirred in a water bath at 70 C for 24 hours.After the reaction is completed,THF was removed from the mixture.After extracting the mixture with methylene chloride and water,The silica gel column process.After the solvent is distilled under reduced pressure,The mixture was recrystallized from methylene chloride and n-hexane,Thus, 11.8 g of a solid compound A2-c (70%) was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 110℃; for 24h;Inert atmosphere; | Add 0.011mol 1,8 dibromonaphthalene toAnd 0.01mol 2-methoxycarbonylbenzeneboronic acid dissolved in 100mL toluene:ethanol=3:1 mixed solvent,Add 10mL of 2M K2CO3 aqueous solution under the protection of nitrogenAnd 0.0002mol of Pd(PPh3)4,After reacting at 110C for 24 hours,Sampling point plate, after the reactants have reacted completely, cool and filter,Rotate the filtrate to remove the solvent, and pass the crude product through a silica gel column.Intermediate 1-2 was obtained; HPLC purity 96.97%, yield 88.5%; |
76.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 16h;Inert atmosphere; Reflux; | Preparation of compound 1:In a 2L three-necked flask, was added <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (71.2g, 0.25mol), 2- methoxycarbonylphenylboronic acid (36g, 0.2mol), potassium carbonate (41g, 0.3mol),Toluene (680g), deionized water (230g), under nitrogen, was added Pd (PPh3) 4 (3.20g), warmed to reflux, the reaction was kept for 16 h, cooled to 30 , liquid separation,The organic phase was removed from the solvent and the crude product was purified by silica gel column chromatography using petroleum ether as eluant:Ethyl acetate = 5: 1 (v / v) gave Compound 1 as an off-white solid 52.2 g, 76.5% yield, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | Compound b (337 mg, 0.84 mmol),<strong>[17135-74-9]1,8-dibromonaphthalene</strong> (300 mg, 1.05 mmol) and tetrakis(triphenylphosphine)palladium(48.5 mg, 0.042 mmol) was added to a 50 mL two-necked flask.Under a nitrogen atmosphere, anhydrous tetrahydrofuran (6 mL) was added.Stir at room temperature for 30 minutes.Then, a potassium carbonate solution (3 mL, 2 M) was slowly added dropwise to the reaction solution, and after the addition was completed,Stirring was carried out at 80 C for 12 hours under reflux. When the reaction is over,The fractions were extracted with dichloromethane and washed with water until the aqueous layer was free of fluorescence.The organic layer was dried with anhydrous magnesiumColumn chromatography (eluent is a mixture of dichloromethane and petroleum ether in a volume ratio of 1:4) to give compound c 151.5 mg.The yield was 38%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | A solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (12 g, 41.9 mmol, 1.0 eq ) in THF (550 mL) was added n-Buli (2.5 M, 16.8 mL, 1.0 eq) dropwise at -70 C for 40 minutes and then tributyl(chloro)stannane (13.7 g, 41.9 mmol, 11.3 mL, 1.0 eq) was added to the mixture. The mixture was stirred at - 50 C for 1 hour and warmed up to 20 C for 12 hours. The reaction mixture was diluted with water (500 mL) and extracted with ethyl acetate (3 c 500 mL). The combined organic layers were washed with brine (500 mL), dried over Na2SC>4, filtered and concentrated under reduced pressure to give a residue. The residue was purified by reversed phase flash chromatography [water (0.1% formic acid)/acetonitrile)] to give (8-bromonaphthalen-l-yl)tributylstannane (14 g, 67% yield) as yellow oil. 'H NMR (400MHz, chloroform-d) d = 7.89-7.78 (m, 4H), 7.49-7.42 (m, 1H), 7.29 (t, J= 7.6 Hz, 1H), 1.64-1.50 (m, 6H), 1.42-1.19 (m, 12H), 0.89 (t, J=7.2 Hz, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine; In toluene; for 7h;Reflux; Inert atmosphere; | The following regents and solvent were added into a 300 mL flask: Compound J1: 2.00 g (6.98 mmol) Compound J2: 1.38 g (6.98 mmol) Palladium acetate: 0.10 g (0.36 mmol) Tricyclohexylphosphine: 0.20 g (0.70 mmol) Sodium tert-butoxide: 2.01 g (21 mmol) Dehydrated toluene: 70 mL (0154) Next, the resulting reaction solution was heated to reflux for 7 hours with stirring in a nitrogen atmosphere. After the reaction, the solution was passed through a membrane filter to yield a filtrate. Then, the filtrate was washed with water, dehydrated with sodium sulfate, and concentrated under reduced pressure to yield a crude product. Subsequently, the crude product was purified by silica gel chromatography (eluent: toluene/heptane=1/4) to yield 1.50 g of Compound J3 (yield: 67%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; water; toluene; for 7h;Reflux; Inert atmosphere; | The following regents and solvents were added into a 300 mL recovery flask: Compound J1: 2.00 g (4.10 mmol) Compound J9: 1.83 g (10.3 mmol) Tetrakis(triphenylphosphine)palladium (0): 95 mg (0.08 mmol) Toluene: 40 mL Ethanol: 20 mL (0175) 2M cesium carbonate aqueous solution: 40 mL (0176) Next, the resulting reaction solution was heated to reflux for 7 hours with stirring in a nitrogen atmosphere. After the reaction, the reaction product was extracted with chloroform. The organic phase obtained by extraction was dehydrated with sodium sulfate and was subsequently concentrated under reduced pressure to yield a crude product. Subsequently, the crude product was purified by silica gel chromatography (eluent: chloroform/heptane=1/10) to yield 1.55 g of Compound J10 (yield: 75%). |
75.15% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate; In ethanol; water; toluene; at 50 - 75℃; for 17h;Inert atmosphere; | Under the protection of nitrogen, add <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (49.93g, 174.27mmol), 2-chlorophenylboronic acid (26.0g, 166.27mmol), toluene (480mL), ethanol (240mL), water ( 120mL), potassium carbonate (50.55g, 365.80mmol), after the addition, stir and heat to 50-60, then quickly add tetrakis(triphenylphosphine)palladium (3.71g, 3.33mmol), tetrabutyl bromide Ammonium TBAB (10.72g, 33.25mmol), after dropping, continue to heat up to 70-75C and reflux for 17h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water until neutral, dry, filter and concentrate . Recrystallize with ethyl acetate and n-heptane mixed solvent to LC>98%. After drying, intermediate C-1 (39.68 g, 75.15%) was obtained as a white solid. |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 100℃; for 18h; | To the flask, <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (100 g, 349.7 mmol), (2-chlorophenyl) boronic acid (82 g, 524.6 mmol), tetrakis (triphenylphosphine) palladium (O) (Pd (PPh3 ) 4) (20.2 g, 17.5 mmol), potassium carbonate (120.8 g, 874.5 mmol), 1500 mL of tetrahydrofuran and 400 mL of distilled water were dissolved and refluxed at 100 C. for 18 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, and the residual moisture was removed using magnesium sulfate, dried and separated by column chromatography to obtain compound 1-1 (78 g, yield: 70%). |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 100℃; for 18h; | In a flask, 100 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (349.7 mmol), 82 g of (2-chlorophenyl)boronic acid (524.6 mmol), 20.2 g of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (17.5 mmol), and 120.8 g of potassium carbonate (874.5 mmol) were dissolved in 1500 mL of tetrahydrofuran (THF) and 400 mL of distilled water, and the mixture was refluxed at 100 C. for 18 hours. After completion of the reaction, an organic layer was extracted with ethyl acetate, and the residual moisture was removed using magnesium sulfate. Thereafter, the resulting product was dried and separated by column chromatography to obtain 78 g of compound 1-1 (yield: 70%). |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 100℃; for 18h; | 100 g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (349.7 mmol), 82 g of (2-chlorophenyl)boronic acid (524.6 mmol), 20.2 g of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (17.5 mmol), and 120.8 g of potassium carbonate (874.5 mmol) were dissolved in 1500 mL of tetrahydrofuran and 400 mL of distilled water in a flask, and the mixture was refluxed at 100 C. for 18 hours. After completion of the reaction, an organic layer was extracted with ethyl acetate, the remaining moisture was removed using magnesium sulfate, and the residue was dried and separated with column chromatography to obtain 78 g of compound 1-1 (yield: 70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With tris-(dibenzylideneacetone)dipalladium(0); 1,8-diazabicyclo[5.4.0]undec-7-ene; tricyclohexylphosphine; In N,N-dimethyl-formamide; at 140℃; for 20h;Inert atmosphere; | <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (50 g, 175 mmol) and (4-methoxy-2-methylphenyl)boronic acid (29.0 g, 175 mmol) was added to a mixture of DMF (1000 ml) and DBU (78 ml, 525 mmol), and the mixture is degassed with bubbling nitrogen for 30 min. Tricyclohexylphosphane (17.31 g, 52.5 mmol) was added and degassing continued for 10 min. Pd2(dba)3 (20.01 g, 21.86 mmol) was added and the reaction mixture heated to an internal temperature of 140 C. which was maintained for 20 h. The reaction mixture was then allowed to cool to room temperature. The reaction mixture was decanted and the vessel washed with methylene chloride (DCM) (2*500 ml). The DMF was removed under reduced pressure to give a dark residue. The DCM washes were added to the residue and washed with brine (3*400 mL). The DCM layer was concentrated under reduced pressure onto silica (120 g). The crude product was purified by column chromatography (DCM in heptane, 2CV heptane, 10CV 0-20% DCM, 10CV 20-25% DCM) to yield the product as a yellow solid (33.7 g), yield of 54% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; In water; N,N-dimethyl-formamide; for 17h;Inert atmosphere; Reflux; | (Methylsulfanylphenyl] boronic acid and 28 g (87 mmol) cesium carbonate are mixed in 200 ml water and 200 ml N,N-Dimethylformamide. 0.71 g (1 .7 mmol) SPhos and 1 ,68g (1 ,7 mmol) Pd2(dba)3 are added and the mixture is refluxed for 17 h. After cooling down to room temperature the organic phase is separated and washed with water (3x200 ml) and with 200 ml brine. Afterward it is dried over magnesium sulfate and reduced under reduced pressure to give a gray residue, which is further purified by crystallization out of heptane. Yield: 5.9g, (15.9 mmol; 91 %) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 110℃;Inert atmosphere; | Step 1: In a nitrogen atmosphere, weigh 0.02 mol of raw material I-1 and 0.02 mol of intermediate I-1 and dissolve them in 60 ml of a toluene: ethanol mixed solvent of 2: 1.To the reaction solution were added 0.0002 mol Pd (PPh3) 4 and 0.04 mol potassium carbonate aqueous solution,The reaction system was prepared at 110 C for 10 to 24 hours.After cooling to room temperature, the reaction solution was filtered, and the filtrate was subjected to rotary evaporation under reduced pressure.After passing through a neutral silica gel column, intermediate II-1 was obtained. The HPLC purity was 95.91%.The yield was 95.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | With tris-(dibenzylideneacetone)dipalladium(0); zinc fluoride; tri-tert-butyl phosphine; In N,N-dimethyl-formamide; toluene; at 110℃; for 36h;Inert atmosphere; | To tris(dibenzylideneacetone)dipalladium(0) (160 mg, 0.17 mmol) in N,N-dimethylformamide (20 mL) was added a solution of tri-tert-butylphosphine (0.35 mL, 0.35 mmol, 1M in toluene) and degassed by vacuum/nitrogen purge *3. To this red/brown solution was added ((1-(tert-butoxy)vinyl)oxy)(tert-butyl)dimethyl silane (2.42 g, 10.5 mmol), <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (1.0 g, 3.5 mmol) and zinc fluoride (181 mg, 1.75 mmol). The mixture was heated at 110 C. for 18 hours. Starting material was still present (ca. 39%) so additional tris(dibenzylideneacetone)dipalladium(0) (90 mg, 0.10 mmol), ((1-(tert-butoxy)vinyl)oxy)(tert-butyl)dimethylsilane (2.42 g, 10.5 mmol) and zinc fluoride (181 mg, 1.75 mmol) was added. The mixture was heated at 110 C. for a further 18 hours then the reaction mixture was cooled and poured onto aqueous ammonium chloride (150 mL) and product extracted with tert-butylmethyl ether (2*60 mL). Notably the emulsion required addition of Dicalite filter aid followed by filtration to remove inorganic impurities. The combined organic layer was washed with water (60 mL) and aqueous ammonium chloride (60 mL) and dried (magnesium sulfate). Solvent was removed under reduced pressure to afford a crude red/brown oil (3.5 g). The crude material was absorbed onto silica and purified by flash column chromatography eluting with 0-5% tert-butylmethyl ether-heptane to afford di-tert-butyl 2,2'-(naphthalene-1,8-diyl)diacetate as a yellow solid (303 mg, 24% yield). 1H NMR (400 MHz, CDCl3): δ 7.77 (d, 2H), 7.31-7.38 (m, 4H), 4.08 (s, 4H), 1.43 (s, 18H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 8h;Inert atmosphere; Reflux; | 1000 ml three-necked flask, mechanically stirred, oil bath, under nitrogen protection, three-necked flask equipped with condensation tube was charged with 1,8 dibromonaphthalene (50g, 0.189mol), M-1 (50g, 0.208mol), potassium carbonate (79g, 0.57mol), 300ml toluene, 100ml ethanol and 100ml water, stir the reaction system until all the components are dissolved, then add Pd (PPh3) 4 (2.2g, 1.9mmol), heat and reflux for 8 hours.TLC showed the reaction was complete.After cooling, the water solution was added, and the organic layer was decolorized and concentrated to dryness to obtain 81 g of a black oil with a yield of 100%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene;Reflux; | General procedure: In a round bottom flask, 19.4 g (158 mmol) of phenyl boronic acid, 34 g (132 mmol) of 9-bromoanthracene, 36.6 g (264 mmol) of potassium carbonate, 3 g (2 mmol) of Pd(PPh3)4, 70 ml of water, 180 ml of toluene and 180 ml of tetrahydrofuran 180 ml was added and reacted at reflux.After the reaction, the layer was separated and the aqueous layer was removed and the organic layer was concentrated under reduced pressure to obtain 27.2 g of 9-phenyl anthracene (yield 81%) using column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 100℃; for 18h; | To the flask, <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (50 g, 174.8 mmol), (2-methoxyphenyl) boronic acid (24 g, 157.3 mmol), tetrakis (triphenylphosphine) palladium (O) (10 g , 8.7 mmol), potassium carbonate (60 g, 437.0 mmol), 880 mL of tetrahydrofuran and 200 mL of distilled water were dissolved and refluxed at 100 C. for 18 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, and the residual moisture was removed using magnesium sulfate, dried and separated by column chromatography to obtain compound 2-1 (55 g, yield: 100%). |
88.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 110℃; for 24h;Inert atmosphere; | Add 0.011mol 1,8 dibromonaphthalene toAnd 0.01mol 2-methoxyphenylboronic acid dissolved in 100mL toluene:ethanol=3:1 mixed solvent,Under the protection of nitrogen, add 10mL of 2M K2CO3 aqueous solution and 0.0002mol of Pd(PPh3)4,After reacting at 110C for 24 hours,Sampling point plate, after the reactants have reacted completely, cool and filter,Rotate the filtrate to remove the solvent, and pass the crude product through a silica gel column.Intermediate 1-3 was obtained; HPLC purity 96.97%, yield 88.5%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 10h;Inert atmosphere; | In a 250 ml three-necked flask, add A'-1 (28.6 g, 0.1 mol), B'-1 (16.7 g, 0.1 mol), potassium carbonate (16.6 g, 0.12 mol), toluene (100 ml) under nitrogen protection ), Water (25 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.005 mol), stirred at 100 C for 10 hours, and cooled to room temperature after the reaction. The reaction system was added with water and extracted with dichloromethane. The resulting extract was added to magnesium sulfate in order to dry, filter and spin-dry; the crude product was purified by chromatography (ethyl acetate / hexane volume ratio, 1:10), C'-1 (22.9 g, 70% yield). |
43% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 10h;Inert atmosphere; | In a 50 ml three-neck flask, under the protection of nitrogen, add raw material 1 (2.86 g, 0.01 mol), raw material 2 (1.67 g, 0.01 mol), potassium carbonate (1.66 g, 0.01 mol),Toluene (25ml), water (5ml), tetrakis(triphenylphosphine)palladium (5.8g, 0.5mmol), stir at 100C for 10 hours,After the reaction, it was cooled to room temperature. Then water was added to the reaction system, extracted with dichloromethane, the obtained extract was dried with magnesium sulfate, filtered and spin-dried; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to obtain an intermediate 1-3 (1.41 g, yield 43%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In tetrahydrofuran; at -78 - 20℃; for 12h; | To a mixture of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (10 g, 34.9 mmol, 1.0 eq) and Pd(dppf)Cl2 (1.79 g, 2.45 mmol, 0.07 eq) in THF (75 mL) was added ZnEt2 (1 M, 17.5 mL, 0.5 eq) at -78 C, and the mixture was stirred at 20 C for 12 hours. The reaction mixture was concentrated under reduced pressure to dryness. The residue was diluted with water (50 mL) and extracted with ethyl acetate (3 c 50 mL). The combined organic layers were washed with brine (2 x 30 mL), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to dryness. The crude product was triturated with petroleum ether (50 mL) at 25 C for 20 minutes, then filtered and washed with petroleum ether (20 mL). The filtrate was concentrated under reduced pressure to dryness. The crude product was purified by reversed phase chromatography (0.1% formic acid condition) to give l-bromo-8-ethyl- naphthalene (3.3 g, 38% yield). Yellow oil; NMR (400 MHz, CDCb-d) d = 7.70 (dd, J = 2.0, 7.6 Hz, 1H), 7.65 (dd, J = 1.2, 8.0 Hz, 1H), 7.58 (dd, J = 2.4, 7.2 Hz, 1H), 7.30-7.23 (m, 2H), 7.12-7.04 (m, 1H), 3.44 (q, J= 7.2 Hz, 2H), 1.23 (t, J = 7.6 Hz, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 110℃; for 24h;Inert atmosphere; | Add 0.011mol 1,8 dibromonaphthalene toAnd 0.01mol 2-formylphenylboronic acid dissolved in 100mL toluene:ethanol=3:1 mixed solvent,Under the protection of nitrogen, add 10mL of 2M K2CO3 aqueous solution and 0.0002mol of Pd(PPh3)4,After reacting at 110C for 24 hours,Sampling point plate, after the reactants have reacted completely, cool and filter, the filtrate is rotary evaporated to remove the solvent, and the crude product is passed through a silica gel column.Intermediate 1-1 is obtained; HPLC purity 98.97%, yield 84.5%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; triphenylphosphine; at 80℃; for 3h;Inert atmosphere; | A mixture of ethynyl(triisopropyl)silane (25.51 g, 140 mmol, 31.4 mL, 1.0 e^),l,8-dibromonaphthalene (40 g, 140 mmol, 1.0 eq), Cul (2.66 g, 14.0 mmol, 0.1 eq), PPh3 (3.67 g, 14.0 mmol, 0.1 eq ) and dichlorobis(triphenylphosphine)palladium(II) (4.91 g, 6.99 mmol, 0.05 eq) in TEA (650 mL) was degassed and purged with N23 times, and then the mixture was stirred at 80 C for 3 hours under N2 atmosphere. The reaction mixture was diluted with ethyl acetate (800 mL) and washed with water (3 x 500 mL). The organic layer was washed with brine (200 mL), dried over Na2S04, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (S1O2, Petroleum ether/Ethyl acetate=l/0 to 10/1) to afford bromonaphthalen-1- yl)ethynyl)triisopropyl silane (51 g, 94% yield) as a yellow solid. 'H NMR (400MHz, chloroform- d) d = 7.87 - 7.85 (m, 1H), 7.80 - 7.74 (m, 3H), 7.39 - 7.37 (m, 1H), 7.26 - 7.24 (m, 1H), 1.18 - 1.15 (m, 21H). |
74% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; triphenylphosphine; at 80℃; for 3h;Inert atmosphere; | [0464] A mixture of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (7 g, 24.5 mmol, 1.0 equiv), ethynyl(triisopropyl)silane (4.91 g, 26.9 mmol, 6.04 mL, 1.1 equiv), Cul (466 mg, 2.45 mmol, 0.1 equiv), PPI13 (642 mg, 2.45 mmol, 0.1 equiv) and Pd(PPh3)2Ch (859 mg, 1.22 mmol, 0.05 equiv) in TEA (100 mL) was stirred at 80 C for 3 h under N2. The mixture was cooled to room temperature and was diluted with water (50 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layer was washed with brine (50 mL), dried over anh NaiSCL, filtered and concentrated under vacuum. The residue was purified by column chromatography (S1O2, petroleum ether) to afford ((8-bromonaphthalen-l -yl)ethynyl)triisopropylsiIane (7 g, 18.1 mmol, 74% yield) as a yellow solid. NMR (400 MHz, chloroform-d): d = 7.87 (dd, J= 1.2, 7.2 Hz, 1H), 7.82 - 7.73 (m, 3H), 7.41 - 7.34 (m, 1H), 7.24 (t, J= 7.6 Hz, 1H), 1.19 - 1.16 (m, 21H). |
74% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; triphenylphosphine; at 80℃; for 3h;Inert atmosphere; | A mixture of 1,8- dibromonaphthalene (7.0 g, 25 mmol), ethynyl(triisopropyl)silane (4.9 g, 27 mmol), Cui (0.47 g, 2.5 mmol), PPhs (0.64 g, 2.5 mmol) and Pd(PPh3)2Ch (0.86 g, 1.2 mmol) in TEA (100 mL) was stirred at 80 C for 3 hours under N2. The mixture was diluted with water (50 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiCb, petroleum ether) to give 2-(8-bromo-l -naphthyl) ethynyl-triisopropyl- silane (7.0 g, 74% yield). ’H NMR (400 MHz, chloroform-d) 8 = 7.87 (dd, J= 1.2, 7.2 Hz, 1H), 7.82 - 7.73 (m, 3H), 7.41 - 7.34 (m, 1H), 7.25 (t, J = 7.6 Hz, 1H), 1.19 - 1.16 (m, 21H). |
74% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; triphenylphosphine; at 80℃; for 3h;Inert atmosphere; | A mixture of 1,8- dibromonaphthalene (7.0 g, 25 mmol), ethynyl(triisopropyl)silane (4.9 g, 27 mmol), Cui (0.47 g, 2.5 mmol), PPhs (0.64 g, 2.5 mmol) and Pd(PPh3)2Ch (0.86 g, 1.2 mmol) in TEA (100 mL) was stirred at 80 C for 3 hours under N2. The mixture was diluted with water (50 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiCb, petroleum ether) to give 2-(8-bromo-l -naphthyl) ethynyl-triisopropyl- silane (7.0 g, 74% yield). ’H NMR (400 MHz, chloroform-d) 8 = 7.87 (dd, J= 1.2, 7.2 Hz, 1H), 7.82 - 7.73 (m, 3H), 7.41 - 7.34 (m, 1H), 7.25 (t, J = 7.6 Hz, 1H), 1.19 - 1.16 (m, 21H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃; for 10h;Inert atmosphere; | In a 100 ml three-necked flask, under the protection of nitrogen, add raw material 1 (2.86 g, 0.01 mol), raw material 15 (2.17 g, 0.01 mol), potassium carbonate (1.66 g, 0.012 mol), toluene (30 ml), water ( 5ml), tetrakis(triphenylphosphine)palladium (5.8g, 0.5mmol), stirred at 100C for 10 hours, cooled to room temperature after the reaction, added water to the reaction system, and extracted with dichloromethane to obtain the extract The crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to obtain Intermediate 1-123 (1.77 g, yield 47%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; at 70℃; for 12h; | General procedure: To a solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (572 mg, 2.0 mmol), PPh3 (13 mg, 0.05 mmol), and PdCl2(PPh3)2 (70 mg, 0.1 mmol) in Et3N (15.0 mL), phenylacetylene (0.23 mL, 1.05 equiv) was added, and the mixture was stirred for 10 min at room temperature. After that time, CuI (10 mg, 0.05 mmol) was added in one portion to the reaction mixture, and the resulting brown suspension was then stirred at 70 C for 12 h. The reaction mixture was then diluted with diethyl ether and the resulting dark solution was filtered through a pad of silica gel. The filtrate was concentrated under vacuum and purified via flash column chromatography on silica gel (n-hexane) to afford 1aa. Light yellow oil; yield: 50% (0.307 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; at 70℃; for 12h; | General procedure: To a solution of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (572 mg, 2.0 mmol), PPh3 (13 mg, 0.05 mmol), and PdCl2(PPh3)2 (70 mg, 0.1 mmol) in Et3N (15.0 mL), phenylacetylene (0.23 mL, 1.05 equiv) was added, and the mixture was stirred for 10 min at room temperature. After that time, CuI (10 mg, 0.05 mmol) was added in one portion to the reaction mixture, and the resulting brown suspension was then stirred at 70 C for 12 h. The reaction mixture was then diluted with diethyl ether and the resulting dark solution was filtered through a pad of silica gel. The filtrate was concentrated under vacuum and purified via flash column chromatography on silica gel (n-hexane) to afford 1aa. Light yellow oil; yield: 50% (0.307 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With palladium diacetate; caesium carbonate; XPhos; In toluene; at 105 - 110℃; for 18h;Inert atmosphere; | Into a 100 mL round bottom flask that was dried and replaced with nitrogen, added <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (2.0g; 7.0mmol), intermediate 1-1 (7.1g; 21.0mmol), palladium acetate (0.3g; 1.4mmol) ), 2-Dicyclohexylphosphorus-2,4,6-triisopropylbiphenyl (0.7g; 1.4mmol), cesium carbonate (6.8g; 21.0mmol), toluene (30mL),Under stirring, the temperature was raised to 105-110C and kept for 18h; then the reaction mixture was cooled to room temperature, deionized water (90mL) was added, and the mixture was stirred for 30 minutes.Separate the organic phase, add anhydrous magnesium sulfate and dry, then remove the solvent under reduced pressure;The obtained crude product was purified by silica gel column chromatography using a volume ratio of 1:3 dichloromethane/n-heptane as a mobile phase to obtain a white solid compound A1 (1.9 g; yield 38%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate; In ethanol; water; toluene; at 75 - 80℃; for 12h;Inert atmosphere; | Into a 250 mL round bottom flask that was dried and replaced with nitrogen, intermediate 2 (10.0 g; 34.6 mmol), <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (10.9 g; 38.0 mmol) were added,Tetratriphenylphosphine palladium (0.8g; 0.7mmol), tetrabutylammonium bromide (2.2g; 6.9mmol), potassium carbonate (7.2g; 51.9mmol), toluene (100mL), ethanol (20mL),Deionized water (20mL), heated to 75-80 with stirring, and kept for 12h;Then the reaction mixture was cooled to room temperature, deionized water (200 mL) was added, and the mixture was stirred for 10 minutes.Separate the organic phase, add anhydrous magnesium sulfate and dry, then remove the solvent under reduced pressure;The crude product obtained was purified by silica gel column chromatography using dichloromethane/n-heptane in a volume ratio of 1:5 as the mobile phase to obtain a white solid intermediate a (11.7g; 75%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With bis-triphenylphosphine-palladium(II) chloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; In N,N-dimethyl acetamide; at 170℃; for 24h;Inert atmosphere; | The following reagents and solvent were charged into a 50 ml recovery flask. Compound E8: 1.80 g (2.35 mmol) Compound E9: 673 mg (2.35 mmol) PdCl2(PPh3)2: 329 mg (0.47 mmol) DBU: 1.41 g (9.40 mmol) DMAc: 30 ml (0121) Subsequently, the reaction solution was heated to 170 C. in a nitrogen stream and stirred at this temperature (170 C.) for 24 hours. After the completion of the reaction, the resulting product was extracted with toluene and water, then concentrated, purified by silica gel column chromatography (heptane:toluene=4:1), and then washed by dispersion with heptane/ethanol. Thus, 448 mg of a yellow compound E10 (yield: 25%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 80℃; for 12h;Inert atmosphere; | (17.6g, 61.4mmol), tetrakis(triphenylphosphine)palladium (5mol%), K2CO3 (17.0g, 122.8mmol), 1,4-dioxane (200mL) and water (50mL). The reaction system was heated to 80C and reacted for 12 hours under nitrogen protection.After the reaction was completed, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water.The organic layer was dried with anhydrous magnesium sulfate, concentrated, and the crude product obtained by recrystallization was passed through a silica gel column to obtain the middle 25-1-2 (35.9 g, yield 75%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 80℃; for 12h;Inert atmosphere; | Add Intermediate 25-1-3 (23.5g, 61.4mmol), <strong>[17135-74-9]1,8-dibromonaphthalene</strong> (17.6g, 61.4mmol), tetrakis(triphenylphosphine)palladium (5mol%), K2CO3 in a 500mL reaction flask (17.0 g, 122.8 mmol), 1,4-dioxane (200 mL) and water (50 mL). The reaction system was heated to 80C and reacted for 12 hours under nitrogen protection. After the reaction was completed, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried with anhydrous magnesium sulfate, concentrated, and the crude product obtained by recrystallization was passed through a silica gel column to obtain the middle 25-1-2 (21.3g, yield 75%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In dimethyl sulfoxide; at 100℃; for 6h;Inert atmosphere; | Reagents and a solvent described below were charged into a 200-mL recovery flask. Compound H4: 0.90 g (1.4 mmol) Compound H5: 0.37 g (1.3 mmol) Pd(PPh3)2Cl2: 0.01 g DMSO: 90 mL Sodium carbonate: 0.88 g The reaction solution was heated to 100 C. under a stream of nitrogen and stirred at this temperature (100 C.) for 6 hours. After completion of the reaction, water was added to the mixture to prepare a dispersion, which was filtered. The resultant filtered product was purified by column chromatography (toluene), and dispersed and washed with heptane to give 0.50 g (yield: 50%) of compound H6 as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate; In water; toluene; for 8h;Inert atmosphere; Reflux; | S1, Under the protection of nitrogen, add 700ml of toluene, 300ml of water and 100.0g of <strong>[17135-74-9]1,8-dibromonaphthalene</strong> into a 2000ml three-necked flask equipped with mechanical stirring, thermometer and condenser.2-Methoxy-5-chlorobenzeneboronic acid 65.18g,72.50g of anhydrous potassium carbonate, 22.50g of tetrabutylammonium bromide, turn on the heating, increase the temperature to 45±5, add 1.21g of tetratriphenylphosphine palladium to the system, continue heating to reflux, keep refluxing for reaction 8h, after the reaction is complete, cool to 45C±5C, separate the liquids, extract the aqueous phase with toluene, combine the organic phases and wash with water until neutral, dry with anhydrous magnesium sulfate, filter, and concentrate the filtrate under reduced pressure to obtain the oily formula (I) The compound is about 121.57g, without further purification, directly put into the next step, the yield is calculated as 100% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In dimethyl sulfoxide; at 90℃; for 5h;Inert atmosphere; | The following reagents and solvent were charged into a 200 ml recovery flask. Compound H7: 2.00 g (3.64 mmol) Compound H8: 4.17 g (14.6 mmol) PdCl2(PPh3)2: 128 mg (0.18 mmol) Sodium carbonate: 1.54 g (14.6 mmol) DMSO: 100 ml Subsequently, the reaction solution was heated to 90 C. in a nitrogen stream, and stirring was performed at this temperature (90 C.) for 5 hours. After the completion of the reaction, 100 ml of methanol was added thereto and stirring was performed at room temperature for 30 minutes. After that, filtration was performed. The resulting product was purified by silica gel column chromatography (heptane:chlorobenzene=3:1) and then washed by dispersion with methanol to obtain 1.24 g of a white compound H9 (yield: 48%). |
48% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In dimethyl sulfoxide; at 90℃; for 5h;Inert atmosphere; | The following reagents and solvent were charged into a 200 ml recovery flask. Compound E7: 2.00 g (3.64 mmol) Compound E8: 4.17 g (14.6 mmol) Pd(PPh3)2Cl2: 128 mg (0.18 mmol) Sodium carbonate: 1.54 g (14.6 mmol) DMSO: 100 ml (0189) Subsequently, the reaction solution was heated to 90 C. in a nitrogen stream, and stirring was performed at this temperature (90 C.) for 5 hours. After the completion of the reaction, 100 ml of methanol was added thereto and stirring was performed at room temperature for 30 minutes. After that, filtration was performed. The resulting product was purified by silica gel column chromatography (heptane:chlorobenzene=3:1) and then washed by dispersion with methanol to obtain 1.24 g of a white compound E9 (yield: 48%). |
Tags: 17135-74-9 synthesis path| 17135-74-9 SDS| 17135-74-9 COA| 17135-74-9 purity| 17135-74-9 application| 17135-74-9 NMR| 17135-74-9 COA| 17135-74-9 structure
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