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CAS No. : | 2510-23-8 | MDL No. : | MFCD02177459 |
Formula : | C7H5N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | CLRPXACRDTXENY-UHFFFAOYSA-N |
M.W : | 103.12 | Pubchem ID : | 186003 |
Synonyms : |
|
Num. heavy atoms : | 8 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 32.17 |
TPSA : | 12.89 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.16 cm/s |
Log Po/w (iLOGP) : | 1.67 |
Log Po/w (XLOGP3) : | 1.08 |
Log Po/w (WLOGP) : | 1.14 |
Log Po/w (MLOGP) : | 1.05 |
Log Po/w (SILICOS-IT) : | 2.01 |
Consensus Log Po/w : | 1.39 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.71 |
Solubility : | 1.99 mg/ml ; 0.0193 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.94 |
Solubility : | 11.8 mg/ml ; 0.114 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.03 |
Solubility : | 0.956 mg/ml ; 0.00927 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.58 |
Signal Word: | Danger | Class: | 4.1 |
Precautionary Statements: | P210-P240-P241-P264-P280-P302+P352+P332+P313+P362+P364-P305+P351+P338+P337+P313 | UN#: | 1325 |
Hazard Statements: | H228-H315-H319 | Packing Group: | Ⅲ |
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 |
---|---|---|
78% | Stage #1: at 40℃; for 2 h; Schlenk technique Stage #2: With hydrogenchloride In waterSchlenk technique |
General procedure: The terminal alkyne (1.0 mmol) was added to a mixtureof HSi(OEt)2Me (5.0 mmol) and KOtBu (1.5 mmol) in a10 mL Schlenk tube with a magnetic stirrer. The Schlenktube was evacuated and back-filled with CO2 for 3 times.After a CO2 ballon was connected, the reactor was moved toa water bath of 40 °C. After being stirred for 2 h, the reactionmixture was diluted with water (30 mL), and was extractedwith CH2Cl2 (3×10 mL). The aqueous layer was acidifiedwith aqueous HCl (6 M) and then extracted with diethylether (5×20 mL). The combined organic extracts were driedover Na2SO4 and concentrated under vacuum to give the purepropiolic acid (such as compound 3-phenylpropiolic acid(3a): 98percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With copper(l) iodide In methanol; N,N-dimethyl-formamide at 100℃; for 12 h; Inert atmosphere | To a solution of 3-ethynylpyridine (0.20 g, 1.94 mmol, 1 eq) in DMF/MeOH 9:1 (4.0 mL), CuI (0.02 g, 0.097 mmol, 0.05 eq) and trimethylsilylazide (0.38 mL, 2.91 mmol, 1.5 eq) were added. The reaction was heated at 100 °C for 12 h under nitrogen. After cooling, the reaction was filtered off through a Celite pad and washed with EtOAc. Evaporation of the solvent gave a residue which was purified by column chromatography, using PE/EtOAc 3:7 and then EtOAc to give 2 as a white solid after crystallization with EtOAc (0.18 g, 64percent). Mp 187-192 °C. 1H NMR (300 MHz, CD3OD) δ 9.03 (s, 1-H), 8.51 (d, J = 3.7 Hz, 1-H), 8.29-8.27 (m, 2-H), 7.54-7.50 (m, 1-H); 13C NMR (75 MHz, CD3OD) δ 148.3, 146.1, 143.1, 133.9, 127.3, 124.3; MS (ESI) m/z 147 (M + H)+; IR (KBr) 3467, 3118, 1637, 1560, 1434, 1311, 1134 cm-1. Anal. Calcd for C7H6N4: C, 57.53; H, 4.14; N, 38.34. Found: C, 57.67; H, 4.25; N, 38.10. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium fluoride; at 20℃; for 16h; | General procedure: A mixture of a (hetero)aryl iodide 1 (2.00 mmol), Pd(PPh3)2Cl2(28.1 mg, 0.04 mmol, 2 mol%), and CuCl (7.92 mg, 0.08 mmol, 4mol%) was dissolved in DMSO (1.00 mL) in a 8 mL microwavevessel equipped with a stirring bar and a septum and was degassedwith N2 for 5 min. After the addition of TMSA (0.42 mL,3.00 mmol) and anhydrous Et3N (0.55 mL, 4.00 mmol), the solutionwas stirred at r.t. for 1 h. Then, KF (232 mg, 4.00 mmol) wasadded and the reaction mixture was vigorously stirred under air inthe open reaction vessel at r.t. for 16 h. After the addition of themethanethiol 2 (or 6, 8) (1.20 mmol, 0.6 equiv), KOH (224 mg,4 mmol), and DMSO (1.00 mL), the mixture was heated in the microwavecavity at 130C for 1 h. After cooling to r.t., the solventswere removed under reduced pressure. The residue was absorbed onCelite and purified by column chromatography on silica gel with n-hexane or n-hexane-THF (100:1) as eluent. The experimental detailsare shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With triethylamine In dichloromethane at 40℃; for 36h; Schlenk technique; | |
97% | With copper(l) iodide; 4-(1,2,5,6-di-O-isopropylidene-3-O-methyl-α-D-glucofuranos-3-yl)-1H-[1,2,3]-triazole; potassium carbonate In N,N-dimethyl-formamide at 20℃; for 10h; | |
92% | With copper(l) iodide; 1-(2-ethoxy-2-oxoethyl)-1-methyl-pyrrolidinium nonafluorobutanesulfonate; triethylamine at 20℃; for 3h; | Typical procedure for the Glaser coupling General procedure: Phenyl acetylene (2 mmol), CuI (5 mol%), TEA (1 mmol) and IL (1 g) were added in a 25 mL round bottom flask and stirred under aerobic conditions at RT for 2 h. Progress of reaction was monitored by thin layer chromatography (TLC) using aluminum backed silica gel 60 (F254) plates. The desired product was isolated from reaction mixture by extracting with diethyl ether (2×10 mL). The product obtained after evaporation of the solvent was purified by column chromatography (silica mesh size 60-120) and eluted with n-hexane to afford pure symmetrical 1,3-diyne. |
90% | With piperidine In dichloromethane at 25℃; for 5h; | |
88% | With copper(l) iodide; oxygen | |
88% | Stage #1: 3-Ethynylpyridine With copper(l) iodide; KF/Al2O3 for 0.166667h; zirconia vibration ball mill; neat (no solvent); Stage #2: at 20℃; for 0.5h; neat (no solvent); | |
88% | With copper(l) iodide; ethyl 2,2-dibromoacetoacetate; triethylamine In dichloromethane at 20℃; for 8h; | 4.4. General procedure for homo-coupling of alkynes General procedure: Ethyl α,α-dibromoacetoacetate 2a (46.1 mg, 0.16 mmol,30 mol %), alkynes 1a-v(0.55 mmol, 1.0 equiv), CuI (30.5 mg,0.16 mmol, 30 mol %), and triethylamine (0.15 mL, 1.1 mmol,2.0 equiv) were added under ambient temperature to 2 mL of CH2Cl2in air. After stirred at room temperature for the appropriate time (monitored by TLC), the reaction was quenched by addition of H2O (3 mL) and then extracted with ethyl acetate (33 mL). The combined organic layer was washed with brine, dried over Na2SO4,and concentrated. The crude product was purified by column chromatography on silica gel with mixture of petroleum ether and ethyl acetate as eluent to afford the corresponding products 3a-v |
83% | With oxygen; copper(l) chloride In dimethyl sulfoxide at 90℃; for 8h; | |
82% | With oxygen In benzonitrile at 99.84℃; for 2h; | |
82% | With oxygen In benzonitrile at 99.84℃; for 2h; | |
82% | With oxygen In benzonitrile at 100℃; for 2h; | |
80% | With copper(II) acetate monohydrate In dimethyl sulfoxide at 90℃; for 10h; | |
75% | With copper(l) iodide; air; potassium acetate In N,N-dimethyl-formamide at 40℃; for 25h; | |
73% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; 4-(4-bromophenyl)bromobenzene; triethylamine In dichloromethane for 14h; Reflux; | |
73% | With copper(II) nitrate In dimethyl sulfoxide at 100℃; for 4h; Schlenk technique; Sealed tube; | |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In neat (no solvent) for 16.7h; Milling; Green chemistry; | |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate for 6h; Milling; Green chemistry; | |
71% | With pyrrolidine; copper(II) ferrite In acetonitrile at 20℃; for 24h; | |
61% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In diethylamine for 5h; Reflux; | 1,4-di(3-pyridyl)buta-1,3-diyne (L) The ligand 1,4-di(3-pyridyl)buta-1,3-diyne (L) was synthesizedoptimizing the literature methods (6) by using smallquantity of bis(triphenylphosphine)palladium (II) dichloridecatalyst thus increasing the yield and slowing downthe reaction time. A mixture of 3-ethynylpyridine (0.996g,9.65mmol), copper iodide (0.056g, 0.30mmol), bis(triphenylphosphine)palladium(II) dichloride (0.133g 0.19mmol)and diethylamine (50mL) was stirred at reux temperaturefor 5h. The mixture was then cooled at room temperatureand ltered under reduced pressure, washed withbrine a saturated NH4Cl solution (20mL) and extractedwith ethyl acetate (3×15mL) dried with Na2SO4 and thesolvent evaporated under reduced pressure. The crystallizationof the yellow solid from dichloromethane-ethanolyielded L as colorless crystals (0.603g, 2,95mmol, 61%yield). M.p 148°C. Spectral data: 1H NMR (500MHz CDCl3298K) δ=8.77 (d, 2H,), δ=8.61 (dd), δ=7.82 (dt), δ=7.30(t). FT-IR (KBr, 4000-400cm-1) v=2128 (w), 1577 (m), 1473(m), 1412 (s), 1188 (m), 1022 (s), 802 (s), 698 (s), 627 (m),513 (w). Fluorescence (CHCl3; ex = 263 nm.; slit = 5x5):em=357nm and 369nm, M=1.14·10-6. |
55% | With oxygen; 1,8-diazabicyclo[5.4.0]undec-7-ene; copper dichloride In tetrahydrofuran at 20℃; for 24h; Air atmosphere; | |
49% | With copper(I) chloride; oxygen In pyridine at 40℃; for 3h; | |
With copper(l) chloride In dimethyl sulfoxide at 90℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With N-chlorobenzenesulfonamide; sodium bromide In water; acetonitrile at 70℃; for 9h; | General Procedure for the Synthesis of 1-Bromoalkynes General procedure: A 25 mL round-bottom flask with a magneton was charged withterminal alkyne 1 (0.5 mmol), NaBr (77 mg, 1.5 equiv), andMeCN/H2O (3:1, 4 mL,) under air at room temperature, and thenchloramine-B (320 mg, 3.0 equiv) was added. The mixture wasstirred at 70 °C for 24 h. After that, the reaction mixture wascooled to room temperature and then filtered. The filtrate wasconcentrated under reduced pressure. Purification of theresidue by flash column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent afforded the desiredproduct 3. |
64% | With chloramine-B; potassium iodide In water; acetonitrile at 70℃; for 9h; Schlenk technique; | 6 Example 6: Synthesis of 3-(bromoethynyl)pyridine (1f) 3-ethynylpyridine (52 mg, 0.5 mmol),Mixed solvent of acetonitrile and water(4mL, V acetonitrile / V water = 3:1), chloramine B (160mg, 0.75mmol) and potassium iodide(99 mg, 0.6 mmol) was added to a 25 mL Schlenk bottle in turn, and then reacted at 70 ° C.After reacting for 9 hours, after completion of the reaction, the mixture was filtered, and the organic solvent was removed under reduced pressure;Elution with petroleum ether/ethyl acetate, separation on silica gel column,The yield of 3-(bromoethynyl)pyridine was 64%. |
60% | With potassium hydroxide; 18-crown-6 ether; carbon tetrabromide In benzene for 7h; Ambient temperature; |
59% | With dibromamine-T; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; for 6h; | |
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; Inert atmosphere; | ||
Stage #1: 3-Ethynylpyridine With silver nitrate In acetone at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: With N-Bromosuccinimide In acetone at 20℃; Inert atmosphere; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With caesium carbonate In toluene at 110℃; for 12h; | |
51% | With caesium carbonate In toluene at 110℃; for 12h; | |
51% | With caesium carbonate In toluene at 110℃; for 8h; | 2.o 5-Pyridin-3-yl-pent-2-en-4-ynoic acid ethyl ester (Table 2, entry 15): The modified procedure was used to convert 3-Ethynyl-pyridine and (Z)-ethyl-3-iodoacrylate to the title product in 12 hours. Purification by flash chromatography (30% ethyl acetate in hexane as the eluent) gave the analytically pure product as a light yellow oil (200 mg, 51% yield). 1H NMR (400 MHz, CDCl3) δ 8.76 (s, 1H), 8.57-8.55 (dd, J=4.9, 1.5, 1H), 7.82-7.79 (td, J=7.8, 1.8, 1H), 7.29-7.26 (m, 1H), 6.38-6.35 (d, J=11.4, 1H), 6.21-6.18 (d, J=11.4, 1H), 4.29-4.23 (q, J=7.1, 2H), 1.34-1.31 (t, J=7.1, 3H). 13C NMR (100 MHz, CDCl3) δ 164.32, 152.25, 149.13, 138.58, 129.22, 122.86, 121.80, 119.68, 96.97, 89.03, 60.34, 14.08. Anal. Calcd. for C12H11NO2: C, 71.63; H, 5.51; N, 6.96; Found C, 71.77; H, 5.64; N, 6.73. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With sodium ethanolate; In ethanol; at 20℃; for 19h; | Under an argon atmosphere, Au(PPh3)Cl (297 mg, 0.60 mmol), 3-pyridylethyne (92.8 mg, 0.90 mmol) and ethanol (12 ml) were added to a 20 ml Schlenk tube, and then sodium ethoxide (250 µl, 0.63 mmol: 2.55 mol/l (liter) in ethanol solution) was added dropwise thereto and the mixture was stirred at room temperature for 19 hours. The precipitated white precipitate was filtered and successively washed with ethanol (12 mlxthree times), water (12 mlxthree times) and ethanol (6 mlxthree times), followed by drying under vacuum to give 0.23 g of the desired compound as a white powder (yield: 69%) . 1H-NMR (400 MHz, CDCl3) δ: 8.75-8.74 (m, 1H), 8.43-8.41 (m, 1H), 7.78-7.74 (m, 1H), 7.60-7.43 (m, 15H), 7.20-7.15 (m, 1H) (FAB-MS) (M/Z): 562 (M+H)+ Luminescence analysis: (CHCl3, 77K, Ex250nm) λ (nm): 422, 447 Elemental analysis: Found C: 53.20, H: 3.38, N: 2.50 Theoretical C: 53.49, H: 3.41, N: 2.50 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With copper(l) iodide; diisopropylamine In toluene at 100℃; for 12h; | |
81% | With diisopropylamine In toluene at 100℃; for 12h; | 5i; A Example 5i: Preparation of 2-Pyridin-3-ylethynyl-lH-indole A carousel reaction tube (24x150 mm) was charged with 2-(2,2-dibromovinyl)aniline (139 mg, 0.50 mmol), Pearlman's catalyst (Degussa E4) (10.6 mg, 0.010 mmol, 2 mol%), P(P-MeOPh)3 (14.1 mg, 0.040 mmol, 8 mol%), and CuI (3.8 mg, 0.020 mmol, 4 mol%), and was evacuated and purged with argon three times. To this mixture were added toluene (3 mL, degassed), zPr2NH (175 μL, 1.25 mmol) and 3-ethynylpyridine (80.0 mg, 0.77 mmol), and then heated to 100 0C with stirring for 12 h. The reaction mixture was then cooled to rt and H2O (10 mL) added. The mixture was extracted with EtOAc (2 x 15 mL), and combined extracts were washed with sat. NH4Cl and brine, then dried and solvent was removed in vacuo. The resulting crude material was purified by flash chromatography eluting with 40% EtOAc in hexane to afford the titled compound as a colorless solid (88.0 mg, 81%). m.p.: 209-2110C; IR (CHCl3) v 3403, 2157, 1652, 1558, 1539, 1506, 1457, 1249 cm"1; 1H-NMR (CDCl3) δ: 8.83 (IH, s), 8.60 (IH, s), 7.83 (IH, dt, J= 8.1, 1.8 Hz), 7.63 (IH, d, J= 8.1 Hz), 7.41-7.22 (4H, m), 7.19-7.10 (IH, m), 6.89 (IH, dd, J = 2.1, 0.9 Hz); 13C NMR (75 MHz, OMSO-d6) δ 152.0, 149.7, 139.0, 137.2, 127.7, 124.4, 123.9, 121.2, 120.6, 119.8, 118.1, 112.0, 109.0, 89.2, 86.5; HRMS (EI) m/z calcd.for: [M]+ 218.0844, m/z found: 218.0846. |
With copper(l) iodide; palladium on activated charcoal; diisopropylamine; triphenylphosphine In toluene at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With copper(l) iodide; diisopropylamine In toluene at 100℃; for 12h; | |
61% | With diisopropylamine In toluene at 100℃; for 12h; | 6h Example 6h: Preparation of 3-Benzofuran-2-ylethynyl-pyridine A carousel reaction tube (24x150 mm) was charged with 2-(2,2-dibromovinyl)phenol [prepared from salicylaldehyde according to the procedure by Bisseret (Thielges, S.; Meddah, E.; Bisseret, P.; Eustache, J. Tetrahedron Lett. 2004, 907)] (139 mg, 0.50 mmol), Pearlman's catalyst (Degussa E4) (5.3 mg, 0.0043 mmol, 1 mol%), P(p-OMePh)3 (7.1 mg, 0.020 mmol, 4 mol%), and CuI (2.0 mg, 0.010 mmol, 2 mol%), and was evacuated and purged with argon three times. To this mixture were added toluene (3 mL, degassed), /Pr2NH (180 μL, 1.28 mmol) and 3-ethynylpyridine (77.8 mg, 0.75 mmol), and then heated to 100 0C with stirring for 12 h. The reaction mixture was then cooled to rt and H2O (10 mL) added. The mixture was extracted with EtOAc (2 x 15 mL), and combined extracts were washed with sat. NH4Cl and brine, then dried and solvent was removed in vacuo. The resulting crude material was purified by flash chromatography eluting with 25%→ 30% EtOAc in hexane to afford the titled compound as a colorless solid (67.3 mg, 61%). m.p.: 75-76°C; IR (CHCl3) v 2357, 1558, 1506, 1472, 1447, 1407, 1257, 1169, 947 cm"1; 1H-NMR (CDCl3) δ: 8.83 (IH, s), 8.60 (IH, s), 7.86 (IH, dt, J = 7.9, 1.8 Hz), 7.60 (IH, d, J = 7.6 Hz), 7.49 (IH, d, J = 8.2 Hz), 7.40-7.23 (3H, m), 7.07 (IH, s); 13C NMR (75 MHz, DMSO-J6) δ 155.2, 152.4, 149.5, 138.6, 127.7, 126.2, 123.6, 123.3, 121.6, 112.7, 111.5, 91.8, 83.1; HRMS (EI) m/z calcd. for: [M]+ 219.0684, m/z found: 219.0683. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In toluene at 50℃; | |
95% | In toluene at 20 - 50℃; for 16h; | 2 Commercially available 3-ethynyl-pyridine 3b (1.03 g, 10 mmol) and 4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (7.26 mL, 50 mmole) in toluene (40 mL) were combined with carbonylchlorohydridotris(triphenylphosphine) ruthenium (II), RuHCl(CO)(PPh3) (476 mg, 0.50 mmol) at ambient temperature and the reaction mixture was heated at 50° C. in an oil-bath for 16 h. The toluene was evaporated and the crude compound was diluted with ethyl acetate and washed with saturated sodium bicarbonate solution, saturated sodium chloride solution, and water. The organic extracts were dried over MgSO4, filtered, and evaporated in vacuo. The crude product was eluted with a gradient of 10:1 to 2:1 hexane/ethyl acetate by flash chromatography to yield 3-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-vinyl]-pyridine Compound 3c (2.2 g, 95% yield) as a yellow syrup. 1H NMR (300 MHz, CDCl3) δ 8.75 (d, 1H), 8.54 (dd, 1H), 7.83 (dt, 1H), 7.39 (d, 1H), 7.31 (dd, 1H), 6.27 (d, 1H), 1.34 (s, 12H); MS (ESI) m/z: 232.14 (M+H+). |
84% | With C28H40CuNO In acetonitrile at 20℃; for 4h; Schlenk technique; Inert atmosphere; | A General Protocol General procedure: To a flame dried Schlenk was added Et2CAACCuOPh (2.5 mol %) and a magnetic stir bar under an Ar atmosphere. 0.097 mL freshly distilled MeCN was added to fully dissolve catalyst and yield a 2.3 ± 0.1 M solution depending on the nature of the alkyne. Alkyne (0.56 mmol, 1 eq.) was added followed immediately by pinacolborane (0.57 mmol, 1.025 eq). The resulting solution is stirred at room temperature for 2 hours. After this time, the volatiles were evaporated under vacuum. 10 mL pentane was added to residue. This solution was passed through a pad of silica (5 cm diameter x 5 cm high) to remove insoluble components. Elution with 2 x 10 mL of pentane, followed by evaporation under vacuum yielding pure products 2a-m. |
50% | In toluene at 50℃; for 18h; Inert atmosphere; | 29.A Example 29. (1 R,2S)-2-(3-((E)-2-(pyridin-3-yl)vinyl)- 1 H-indazol-6-yl)spiro[cyclopropane- 1 ,3'-indolinl-2'-oneA. (E)-3-(2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)pyridineAn oven-dried round-bottom flask was cooled under N2 (g) and then charged with 3- ethynyl pyridine (104mg, 1 mmol), toluene (4 mL), and 4,4,5, 5-tetramethyl-l , 3,2- dioxaborolane (0.73 mL, 5 mmol). The mixture was purged with argon for 15 min. HRuCl(CO)(PPh3)3 (73 mg, 0.05 mmol) was then added and the reaction heated to 50 0C for 18 h. The reaction was quenched with NaHCO3 (sat.) (10 mL), extracted with EtOAc, and the organic layer washed with brine (10 mL) and then dried over MgSO4. The solvent was removed and the resulting residue purified by column chromatography (silica gel, Hexanes/EtOAc, 1 :1) to give the title compound as a white solid (115 mg, 50%). 1H NMR (400 MHz, CDCl3) δ 8.69 (s, I H) 8.52 (d, IH, J = 4.8 Hz), 7.81 (d, I H, J = 7.8 Hz), 7.38 (d, J = 18.6 Hz, I H), 7.28-7.26 (m, I H), 6.26 (d, I H, J = 18.5 Hz), 1.33 (s, 12H). |
21% | With sodium triethylborohydride; scandium tris(trifluoromethanesulfonate) In tetrahydrofuran; toluene at 100℃; for 24h; Microwave irradiation; Inert atmosphere; regioselective reaction; | |
52 %Spectr. | With zinc trifluoromethanesulfonate; sodium triethylborohydride In tetrahydrofuran; toluene at 80℃; for 24h; Schlenk technique; Inert atmosphere; regioselective reaction; | |
94 %Spectr. | With (hydroxido){N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene}copper(I) In neat (no solvent) at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C32H28BrFeIN3Pd; potassium acetate; silver(l) oxide In 1,2-dichloro-ethane at 80℃; for 24h; | |
85% | With C32H26FeIN2PPd; potassium acetate; silver(l) oxide In dichloromethane at 25℃; for 24h; | General Procedure for the Coupling of Terminal AlkynesWith Arylboronic Acids General procedure: A mixture of arylboronic acids (0.5 mmol), alkynes(0.6 mmol), the prescribed amount of catalysts, Ag2O(0.5 mmol), and KOAc (0.75 mmol) in 1,2-dichloroethane(DCE) (3 mL) under air was stirred at 80 or 25Cfor24 h. After being cooled, the mixture wasfiltered. The solvent was removed under reduced pressure. The resultingresidue was purified byflash chromatography on silica gelto afford the desired coupled products, which were characterized by comparing their m.p. and1HNMRspectra. |
71% | With potassium acetate; silver(l) oxide In dichloromethane at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With C32H28BrFeIN3Pd; potassium acetate; silver(l) oxide In 1,2-dichloro-ethane at 80℃; for 24h; | |
86% | With C32H26FeIN2PPd; potassium acetate; silver(l) oxide In dichloromethane at 25℃; for 24h; | General Procedure for the Coupling of Terminal AlkynesWith Arylboronic Acids General procedure: A mixture of arylboronic acids (0.5 mmol), alkynes(0.6 mmol), the prescribed amount of catalysts, Ag2O(0.5 mmol), and KOAc (0.75 mmol) in 1,2-dichloroethane(DCE) (3 mL) under air was stirred at 80 or 25Cfor24 h. After being cooled, the mixture wasfiltered. The solvent was removed under reduced pressure. The resultingresidue was purified byflash chromatography on silica gelto afford the desired coupled products, which were characterized by comparing their m.p. and1HNMRspectra. |
75% | With potassium acetate; silver(l) oxide In dichloromethane at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a solution of D-l 3-ethyne pyridine (8.0 g, 77.6 mmol) in THF (ISOmL) at -78 C, n-BuLi (1,6 M in hexanes, 54 mL, 85,3 mmol) was added dropwise (keeping the reaction temperature below -60 C), It was stirred at this temperature for another 2 hrs and warmed up to OC. It was cooled to -30 C again and a fresh chopped dry ice was added. It was stirred and allowed to warm up to 0 C and 20 mL 4.ON NaOH was added. Organic layer was separated, Aqueous layer was acidified to ph <1, Solid was filtered to yield the final product. Yield: 6.0 g |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 100℃; for 0.75h; | To a solution of S-iodo-lH-indazole--carbaldehyde (136 mg, 0.5 mmol),Pd(PPh3)2Cl2 (14 mg, 0.02 mmol) and CuI (7.6 mg, 0.04 mmol) in DMF (3 mL) was added Et3N (5 mL), followed by 3-ethynylρyridine (77 mg, 0.75 mmol). The resulting mixture was heated at 100 0C (oil temp.) for 45 min. After removal of Et3N, the residue was loaded directly onto a silical gel column. Flash chromatography (eluent: hex to ethyl acetate), followed by trituration with water and suction filtration gave the title compound (112 mg, 91%) as a light yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 14.16 (s, IH), 10.16 (s, IH), 8.90 (s, IH), 6.64 (d, J = 4.0 Hz, IH), 8.26 (s, IH), 8.12 (d, J = 8.0 Hz, IH), 8.07 (d, J = 8.4 Hz, IH), 7.74 (d, J = 8.4 Hz, IH), 7.52 (dd, J = 8.0 Hz, J = 5.2 Hz, IH); MS ESI 248.0 [M + H]+, calcd for [C15H9N3O + H]+ 248.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; for 1h;Reflux; | To a mixture of 3-ethynylpyridine (1.13 g, 11 mmol) and 2-fluoro^-chloro-6-iodoaniline (2.71 g, 10 mmol) in triethylamine (100 mL) is added PdCI2(PPh3)2 (175 mg, 0.25 mmol) and CuI (95 mg, 0.50 mmol) and the mixture is refluxed for 1 h. The solvent is removed in vacuo and the residue is purified by silica gel flash chromatography (dichloromethane- methanol, 1 :0 to 24:1 ) to give 4-chloro-2-fluoro-6-pyridin-3-ylethynyl-phenylamine. MS (ESI) m/z 247 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With copper(l) iodide; triethylamine;tetrakis(triphenylphosphine) palladium(0); In toluene; at 100℃; | 2,6-Difluoro-N-(2'-methyl-5'-(pyridin-3-ylethynyl)biphenyl-4-yl)benzamide[00148] To the solution of 2-bromo-4-iodo-l-methylbenzene (0.3 g, 1.0 mmol) in TEA (4 mL) and toluene (1 mL) was added 3-ethynylpyridine (0.115 g, 1.12 mmol), CuI (0.04 g, 0.2 mmol), and Pd(PPh3)4 (0.065 g, 0.06 mmol). The resulting solution was heated at 1000C overnight before it was diluted with water and extracted with EtOAc (3chi20mL). The combined organic phases were dried and concentrated, and the column chromatography (Hexanes/EtOAc=l/l) afforded 2 in 66% yield. The desired compound was obtained from 2 through Suzuki coupling.[00149] 1H NMR (400 MHz, CDCb) delta 8.75 (d, / = 1.2 Hz, 1 H), 8.54-8.52 (m, 1 H), 7.81-7.78 (m, 1 H), 7.72-7.68 (m, 3 H), 7.45-7.43 (m, 3 H), 7.37-7.34 (m, 2 H), 7.29-7.27 (m, 2 H), 7.03 (t, / = 8.0 Hz, 2 H), 2.31 (s, 3 H); ESMS cacld (C27H18F2N2O): 424.1; found: 425.1 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With palladium diacetate; (RP,RP)-1,2-bis[(o-anisyl)(phenyl)phosphino]ethane In ethanol; acetonitrile at 80℃; for 24h; Inert atmosphere; | 23 Under N2 protection, 3-ethynylpyridine (0.20 mmol) and Pd(OAc) 2 (0.02 mmol, were added to a 15 ml pressure-resistant tube.4.48 mg), R, R-DIPAMP (0.2 mmol, 18.32 mg), 95% EtOH (10 mmol, 595L) and CH3CN (1.5 mL).After completion of the reaction, the mixture was cooled to room temperature, and ethyl acetate (10 mL) was evaporated. The crude product was separated and purified by column chromatography to give 3-vinylpyridine, 15.8 mg of colorless liquid, yield 75%. |
Stage #1: 3-Ethynylpyridine With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II); diisobutylaluminium hydride In tetrahydrofuran at 0 - 22℃; Inert atmosphere; Stage #2: With water; rochelle salt In tetrahydrofuran at 0℃; for 0.5h; | ||
98 %Chromat. | With hydrogen In ethanol at 20℃; for 3.2h; Schlenk technique; Sealed tube; chemoselective reaction; |
83 %Chromat. | With hydrogen In acetonitrile at 110℃; for 15h; chemoselective reaction; | |
99.5 %Chromat. | With hydrogen In methanol; dimethyl sulfoxide at 25℃; for 2.5h; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With tetrabutyl ammonium fluoride;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; at 20 - 80℃;Inert atmosphere; | C . Methyl 2-methoxy-5 -(pyridin-3 -ylethynyl)pyridine-3 -carboxylate; To a room temperature solution of methyl 5-bromo-2-methoxypyridine-3- carboxylate (0.40 g, 1.6 mmol) in JV-tetra-butyl ammonium fluoride (1.3 g, 4.9 mmol, 1M solution in THF) was added Pd(PPh3)2Cl2 (0.057 mg, 0.081 mmol) followed by 3- ethynylpyridine (0.184 g, 1.79 mmol) t. The reaction mixture was heated at 80 0C for 4 h. The reaction was then cooled to room temperature and the solvent was evaporated under reduced pressure. The residue was diluted with water (50 mL) and the precipitated solid was filtered, washed thoroughly with water (10 mL) and dried under vacuum to provide methyl 2-methoxy-5 -(pyridin-3 -ylethynyl)pyridine-3 -carboxylate as a yellow solid (0.11 g, 25%).LC-MS: [M+H] + 269.2.1H NMR (400 MHz, CDCl3) δ: ppm 8.80 (s, IH), 8.61 (d, IH), 8.5 (d, IH), 8.37 (m, IH), 7.81 (m, IH), 7.31 (m, IH), 4.11 (s, 3H), 3.8 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In acetonitrile; at 80℃;Inert atmosphere; | Method 1; 3-[4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl]ethynyl}pyridine; To a degassed solution of 2-(4-iodophenyl)-4,4,5,5-tetramethyl-l,3,2- dioxaborolane (3.2 g, 9.7 mmol) in 30 niL dry acetonitrile was added Pd(PPlIs)2Cb (140 mg, 0.19 mmol) followed by CuI (18.5 mg, 0.096 mmol) and the reaction mixture was degassed for another 10 min. To this reaction mixture was added triethylamine (2.9 g,29.1 mmol) followed by a solution of 3-ethynylpyridine (1.0 g, 9.7 mmol) in dry acetonitrile (20 mL) over a period of 15 min with stirring under nitrogen/argon atmosphere. The resulting reaction mixture was heated at 80 0C for 2 h. The reaction mass was cooled to room temperature, and diluted with water (50 mL). The precipitated solid was filtered, washed with water (100 mL), and then dried under vacuum to get the compound as yellow solid (2.5 g, 78% yield).LC-MS: [M+H]+ 306.0Mass: calculated for Ci9H20BNO2, 305.16 1H NMR (400 MHz, delta ppm, DMSO-d6): 8.8 (s, IH), 8.6 (s, IH), 7.82 (d, 3H), 7.55 (d,2H), 7.3 (m, 2H), 1.4 (s, 12H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In tetrahydrofuran; at 10 - 80℃;Inert atmosphere; | B. Methyl 4-(pyridin-3-ylethynyl)pyridine-2-carboxylate; A solution of <strong>[29681-42-3]methyl 4-bromopyridine-2-carboxylate</strong> (0.4 g, 1.9 mmol) and 3- ethynylpyridine (0.2 g, 2 mmol) in THF was purged with argon for 30 min. To this solution was added Pd(PPh3)2Cl2 (3.9 mg, 0.005 mmol) followed by CuI (35 mg, 0.19 mmol). The reaction mixture was cooled to 10 0C and triethylamine (0.8 mL, 5.6 mmol) was added. The resulting reaction mixture was heated at 80 0C for 5 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (50 mL) and washed with water (25 rnL). The aqueous layer was extracted with ethyl acetate (25 mL x 2) and the combined organic layers were washed with brine solution (30 mL), dried over anhydrous MgSO4 and evaporated under reduced pressure to provide the crude compound. The crude product was purified by column chromatography (Neutral alumina) using 50% ethyl acetate in pet-ether as mobile phase to yield methyl 4-(pyridin- 3-ylethynyl)pyridine-2-carboxylate as off-white solid (0.1 g, 23%). LC-MS: [M+H]+ 239.29 Mass calculated for Ci4Hi0N2O2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | With hydrogen; triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In acetonitrile; at 20 - 80℃; for 4.25h;Inert atmosphere; | C . Methyl 6-methoxy-5 -(pyridin-3 -ylethynyl)pyridine-3 -carboxylate; To an argon purged solution of methyl 5 -bromo-6-methoxypyridine-3 -carboxylate(0.45 g, 1.8 mmol) in 30 mL of dry acetonitrile was added Pd(PPh3)2C12 (0.06 mg, 0.09 mmol) followed by CuI (3.9 mg, 0.02 mmol). Triethylamine (0.77 mL, 5.5 mmol) was added to the reaction mixture and the solution was degassed for 15 min. The argon atmosphere was then replaced with 1 : 1 argon/hydrogen balloon atmosphere to which a solution of 3-ethynylpyridine (0.25 g, 2.4 mmol) in dry acetonitrile (20 mL) was added over a period of 15 min at room temperature. The reaction mixture was then heated at 80 0C for 4 h. The reaction was then cooled to room temperature and the solvent was evaporated under reduced pressure. The residue was diluted with water (50 mL) and the precipitated solid was filtered, washed thoroughly with water (10 mL) and dried under vacuum to provide methyl 6-methoxy-5 -(pyridin-3 -ylethynyl)pyridine-3 -carboxylate as a yellow solid (0.15 g, 31%). LC-MS: [M+H] + 269.2 1H NMR (400 MHz, CDC13): delta: ppm 8.80 (s, IH), 8.59 (m, IH), 8.35 (s, IH), 7.85 (m, 2H), 7.31 (m, IH), 4.11 (s, 3H) 3.93 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With triethylamine;bis-triphenylphosphine-palladium(II) chloride; In acetonitrile; at 60℃; for 2h;Inert atmosphere; | B. 3-((4-(5,5-dimethyl-l,3,2-dioxaborinan-2-yl)phenyl)ethynyl)pyridine; In an oven dried round bottom flask, a solution of <strong>[5572-94-1]2-(4-iodophenyl)-5,5-dimethyl-1,3,2-dioxaborinane</strong> (21 g, 66.47 mmol) and triethylamine (27.8 mL, 199.40 mmol) in acetonitrile (305 mL) was degassed with a stream of N2 for 5 minutes. After this time, 3- ethynylpyridine (7.20 g, 69.79 mmol), Pd(PPh3)2Cl2 (3.5 g, 4.99 mmol) and copper(I) iodide (0.633 g, 3.32 mmol) were added. The flask was then placed in a 60 0C oil bath and was stirred for 2 h, until TLC indicated formation of a new product. The reaction was allowed to cool to room temperature and was then concentrated in vacuo. The resulting brown solid was dissolved in DCM and then impregnated on silica gel. The crude material was purified by silica gel chromatography (5-50% Ethyl Acetate in Hexanes) to afford the desired product as a yellow solid (16.2 g, 83%). 1U NMR (300 MHz, DMSO-d6) δ: ppm 8.77 (s, IH); 8.61 (d, IH); 7.98 (d, IH); 7.76 (d, 2H); 7.58 (d, 2H); 7.48 (dd, IH), 3.78 (s, 4H); 0.97 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diethylamine; triphenylphosphine at 70℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 100℃; for 2h; | General procedure: In a dry Schlenk tube, the dihalopyridine, CuI (6 mol %), and PdCl2(PPh3)2 (3 mol %) were added in Et3N (2 mL per mmol of pyridine). After stirring for 10 min, the (hetero)arylacetylene (1.0 or 1.1 equiv) was added, and the solution was heated to 100 C in a silicone bath for 2 h. The reactions were monitored by TLC, following the disappearance of the starting materials. After completion, the mixture was allowed to cool to room temperature. Then ethyl acetate and water were added and the organic phase was separated, dried (MgSO4), and filtered. Removal of the solvent under reduced pressure gave either oils, which were submitted to column chromatography or pure products corresponding to the expected (hetero)arylethynylpyridines. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With copper(l) iodide; In methanol; N,N-dimethyl-formamide; at 100℃; for 12h;Inert atmosphere; | To a solution of 3-ethynylpyridine (0.20 g, 1.94 mmol, 1 eq) in DMF/MeOH 9:1 (4.0 mL), CuI (0.02 g, 0.097 mmol, 0.05 eq) and trimethylsilylazide (0.38 mL, 2.91 mmol, 1.5 eq) were added. The reaction was heated at 100 C for 12 h under nitrogen. After cooling, the reaction was filtered off through a Celite pad and washed with EtOAc. Evaporation of the solvent gave a residue which was purified by column chromatography, using PE/EtOAc 3:7 and then EtOAc to give 2 as a white solid after crystallization with EtOAc (0.18 g, 64%). Mp 187-192 C. 1H NMR (300 MHz, CD3OD) delta 9.03 (s, 1-H), 8.51 (d, J = 3.7 Hz, 1-H), 8.29-8.27 (m, 2-H), 7.54-7.50 (m, 1-H); 13C NMR (75 MHz, CD3OD) delta 148.3, 146.1, 143.1, 133.9, 127.3, 124.3; MS (ESI) m/z 147 (M + H)+; IR (KBr) 3467, 3118, 1637, 1560, 1434, 1311, 1134 cm-1. Anal. Calcd for C7H6N4: C, 57.53; H, 4.14; N, 38.34. Found: C, 57.67; H, 4.25; N, 38.10. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere; | General procedure: To a solution of 2-chloroquinoline (29.7 mg, 0.182 mmole) in THF (1.5 mL) was added PdCl2(PPh3)2 (2.6 mg, 0.0037 mmole), CuI (1.5 mg, 0.0063 mmol). The reaction mixture was stirred for 5 min and triethylamine (0.15 mL) and phenylacetylene (0.03 mL, 0.27 mmol) were added. After the resulting mixture was stirred at 80 C for 24 h, it was allowed to cool to room temperature and filtered through a pad of Celite by the aid of EtOAc. The filtrate was treated with water and extracted with EtOAc (3 x 10 mL). The organic layer was washed with water and brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude oil was purified by column chromatography on silica gel (EtOAc/hexane = 1:10) to give 2-(phenylethynyl)quinoline 5a (25 mg, 60%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 80℃; for 24h; Inert atmosphere; | 2-(Phenylethynyl)quinoline (5a) (Method A) General procedure: To a solution of 2-chloroquinoline (29.7 mg, 0.182 mmole) in THF (1.5 mL) was added PdCl2(PPh3)2 (2.6 mg, 0.0037 mmole), CuI (1.5 mg, 0.0063 mmol). The reaction mixture was stirred for 5 min and triethylamine (0.15 mL) and phenylacetylene (0.03 mL, 0.27 mmol) were added. After the resulting mixture was stirred at 80 °C for 24 h, it was allowed to cool to room temperature and filtered through a pad of Celite by the aid of EtOAc. The filtrate was treated with water and extracted with EtOAc (3 x 10 mL). The organic layer was washed with water and brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude oil was purified by column chromatography on silica gel (EtOAc/hexane = 1:10) to give 2-(phenylethynyl)quinoline 5a (25 mg, 60%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere; | General procedure: To a solution of 2-chloroquinoline (29.7 mg, 0.182 mmole) in THF (1.5 mL) was added PdCl2(PPh3)2 (2.6 mg, 0.0037 mmole), CuI (1.5 mg, 0.0063 mmol). The reaction mixture was stirred for 5 min and triethylamine (0.15 mL) and phenylacetylene (0.03 mL, 0.27 mmol) were added. After the resulting mixture was stirred at 80 C for 24 h, it was allowed to cool to room temperature and filtered through a pad of Celite by the aid of EtOAc. The filtrate was treated with water and extracted with EtOAc (3 x 10 mL). The organic layer was washed with water and brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude oil was purified by column chromatography on silica gel (EtOAc/hexane = 1:10) to give 2-(phenylethynyl)quinoline 5a (25 mg, 60%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With N-chlorobenzenesulfonamide; potassium iodide In acetonitrile at 20℃; for 2h; | General Procedure for the Synthesis of 1-Iodoalkynes General procedure: A 25 mL round-bottom flask with a magneton was charged withterminal alkyne 1 (0.5 mmol), KI (99 mg, 1.2 equiv), and MeCN(3 mL) under air at room temperature, and then chloramine-B(160 mg, 1.5 equiv) was added. The mixture was stirred for 2 h.After that, the reaction mixture was filtered. The filtrate wasconcentrated under reduced pressure. Purification of theresidue by flash column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent afforded the desiredproduct 2. |
93% | With aluminum oxide; N-iodo-succinimide In acetonitrile at 80℃; for 1h; Molecular sieve; | |
93% | With aluminum oxide; N-iodo-succinimide In acetonitrile at 80℃; for 1h; Molecular sieve; | 5 Synthesis of 3-(iodoethynyl)pyridine Combine 3-ethynylpyridine (2.0 mmol, 206.2 mg), acetonitrile (10 mL), aluminum oxide (2.6 mmol, 265.0 mg), 4A molecular sieve (200 mg), and N-iodosuccinimide (2.2 mmol, 495.0 mg) were added to a 25 mL reaction flask in turn, and then heated to 80°C for 1 hour. After the reaction, extraction, filtration, and reduced pressure to remove the organic solvent, using petroleum ether as the eluent, silica gel column chromatography, Obtained 425.9 mg of light yellow solid with a yield of 93% |
92% | With N-iodo-succinimide; acetic acid In acetonitrile at 80℃; for 1.5h; Molecular sieve; | Iodination of Terminal Alkynes; General Procedure: General procedure: To amixture of terminal alkynes (2.0 mmol), acetic acid (2.6 mmol)and 4 Å MS (200 mg) in MeCN (10 mL) was added N-iodosuccinimide(2.2 mmol) and the resulting mixture was heated at 80 °Cfor 1.5 h. After completion of the reaction, the reaction wasquenched with saturated aqueous sodium thiosulfate and themixture was extracted with ethyl acetate (10 × 3 mL). The combinedorganic layers were dried over anhydrous sodium sulfate,filtered and concentrated under vacuum. The residue was purifiedby flash column chromatography on silica gel. |
90% | With sodium 4-methylbenzenesulfinate; potassium iodide In ethanol at 20℃; for 12h; | 12 Add 0.6mmol KI, 0.75mmol sodium p-toluenesulfinate, 4mL ethanol and 0.5mmolAdd 3-ethynylpyridine to ordinary test tubes one by one, and open the test tube to the air.The reaction was stirred at room temperature for 12 hours. Follow the reaction to completion by TLC,The yellow oil was separated by column chromatography. The eluent was petroleum ether/ethyl acetate (volume ratio 10:1). The structure of the compound was tested by 1H NMR, 13C NMR and mass spectrometry.Yellow solid; isolated yield 90%; |
82% | With [bis(acetoxy)iodo]benzene; trimethylsulphonium iodide In acetonitrile at 20℃; for 0.5h; chemoselective reaction; | |
With copper(II) perchlorate hexahydrate; triethylamine; potassium iodide In tetrahydrofuran at 20℃; for 0.333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23.3% | With gold(I) cyanide; tributylphosphine; In toluene; at 200℃; for 0.166667h;Microwave irradiation; Sealed tube; | General procedure: The microwave-assisted isoflavanone syntheses were conducted on a single-mode Discover System from CEM Corporation. To an oven-dried standard microwave reaction vial (capacity 10mL) equipped with a stirring bar was added AuCN (0.05mmol, 0.05equiv, 11.0mg), Bu3P (0.25mmol, 0.25equiv, 61.7muL), aldehyde (1mmol, 1equiv), alkyne (3mmol, 3equiv) and 1mL of freshly distilled toluene. The reaction vial was then sealed with a Teflon septum cap, and the sample was subjected to microwave irradiation at a power of 200W for 10min (hold time) at 200°C. After being cooled down, the vial was opened, and the crude mixture was loaded directly on silica gel and was purified by Medium Performance Liquid Chromatography eluding with an ethyl acetate/hexanes gradient to afford the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium carbonate; triphenylphosphine at 60℃; for 2.5h; | 2-Phenylbenzofuran (1a); Typical Procedure General procedure: A freshly prepared solution of PdNPs (12.5 mL) was taken up in a 25-mL round-bottomed flask. To this solution K2CO3 (0.276 g, 2 mmol)and Ph3P (0.052 g, 0.2 mmol) were added followed by 2-iodophenol(0.22 g, 1 mmol) and phenylacetylene (0.122 g, 1.2 mmol). Then, themixture was stirred at 60 °C under aerobic conditions. The reactionwas monitored by TLC until complete consumption of phenylacetylene.When the reaction was complete, the solvents were evaporatedand the residue was purified by column chromatography (hexane-EtOAc). Yields for all compounds are calculated after column chromatography.The catalyst could be recycled. The size of the PdNPs afterfour catalytic cycles was found in the range of 12-18 nm by TEM analysisindicating some agglomeration.The reactions of 2-iodophenol or methyl 4-hydroxy-3-iodobenzoatewith arylacetylenes were carried out as given in the typical procedure.However, reactions using alkylacetylenes did not require theuse of Ph3P. |
81% | With potassium phosphate In N,N-dimethyl-formamide at 160℃; Schlenk technique; Inert atmosphere; Glovebox; Green chemistry; | 2.3. Typical procedure for one-pot tandem reaction between o-iodophenolsand terminal alkynes General procedure: General produce: o-iodophenol (0.5 mmol), alkyne (1.0 mmol) andbase (1.0 mmol) were added into a 10 mL dry Schlenk tube under Ar,then anhydrous DMF (5 mL) was injected into the mixture using syringe.Then the solution stirred at preheated oil bath (160 °C). The reactionwas monitored by TLC and GC.The mixture was cooled down toroom temperature after full conversion, then diluted with dichloromethaneand washed with water three times. The organic layerwas separated and washed with brine followed by drying with anhydrousNa2SO4. The filtrate was concentrated in vacuo to afford thecrude product, which was purified by flash column chromatography onsilica gel (petroleum ether). |
58% | With bis(η3-allyl-μ-chloropalladium(II)); tetraphosphine N,N,N′,N′-tetra(diphenylphosphinomethyl)-pyridine-2,6-diamine; caesium carbonate In N,N-dimethyl-formamide at 130℃; for 4h; Schlenk technique; Inert atmosphere; |
81 %Spectr. | With potassium phosphate In N,N-dimethyl-formamide at 160℃; for 5h; Sealed tube; Inert atmosphere; | 9 Preparation of 2- (3-pyridyl) benzofuran: Weigh 10 mg of the above catalyst, 0.5 mmol of compound 1, and 1 mmol of K3PO4 solids into a 10 ml Shrek tube, seal the mouth of the tube with a rubber stopper, protect it with vacuum and argon, and use a micro sampler to pass 1 mmol of compound 2 and 5 ml DMF Solvent was injected into the reaction system. The reaction tube was placed in an oil bath at 160 ° C, and the reaction was completed after 5 hours. The catalyst was filtered off to obtain a uniform reaction solution, washed with water to remove DMF, and dried. Pyridyl) benzofuran with a NMR yield of 81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With silica coated copper nano-magnetite NHC-benzimi(at)Cu complex catalyst In ethanol at 80℃; for 0.566667h; | 2.5 General Method forSynthesisof1,4-Disubstituted 1,2,3-Triazoles General procedure: In a 50mL round bottom flask alkyl/aryl halide (1.0mmol),sodium azide (1.1mmol), alkyne (1.0mmol), nano-magnetiteNHC-benzimiCu (6) (40mg) was added to abovesolution and stirred in 5mL ethanol at 80°C. The reactionwas monitored by thin layer chromatography (TLC) usingaluminium backed silica gel 60 (F254) plates. The completionof the reaction, the catalyst was separated magneticallyusing bar magnet. Finally, the solid obtained was extractedwith ethyl acetate and dried over anhydrous Na2SO4the solventwas removed under reduced pressure then the productwas purified by silica gel column chromatography. |
70% | With sodium azide; copper(I) sulfate pentahydrate; sodium carbonate; sodium L-ascorbate; <i>L</i>-proline In water; dimethyl sulfoxide at 65℃; Sealed tube; regioselective reaction; | |
69% | With copper(l) iodide; sodium azide; diethylamine In glycerol at 20℃; for 2.5h; Schlenk technique; Inert atmosphere; Green chemistry; | General procedure: General procedure: A mixture of alkynes (0.24 mmol), sodium azide (0.24 mmol), halides (0.20 mmol) were added and stirred in glycerol (1.0 ml) in the presence of CuI (0.002 mmol) and diethylamine (0.01 mmol) at room temperature in a schlenk under nitrogen. The progress of the reaction was monitored by HPLC until the reaction was complete. The mixture was added water (10 ml) and extracted with ethyl acetate (3*20 mL). The onganic layer was dried over anhydrous Na2SO4. Then the residue was subjected to flash column chromatography on silica gel (petroleum ether/ethyl acetate) to afford the corresponding compounds 4. |
61% | With sodium azide; carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II); tetrabutylammomium bromide In water at 80℃; for 2h; Inert atmosphere; Schlenk technique; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46.6% | In a 50 mL three-neck round bottom flask equipped with magnetic stirrer, condenser and nitrogen inlet-outlet were introduced3-ethynylpyridine (0.165 g, 1.6 mmol), PdCl2*2PPh3 (0.056 g,0.08 mmol), CuI (0.03 g, 0.16 mmol), PPh3 (0.04 g, 0.16 mmol), triethylamine (15 mL) and tetrahydrofuran (5 mL). The mixture was stirred in nitrogen atmosphere at 50-60 °C for an hour after that 4,4',4''-trisiodotriphenylamine (1 g, 1.6 mmol) dissolved in a mixture of TEA (5 mL) and THF (5 mL) was added. Then the mixture was stirred at 80 °C when the solution color turned out in time from yellow to red and some solids are deposited on the flask's walls. After 24 h the mixture was precipitated in water, filtrated and dried. The pure orange compound 3 was obtained by silica gel chromatography using ethyl acetate/hexane (1:4 vol/vol) as eluent.Yield: 46.6percent. Mp 80 °C. ESI-MS 599.2 (M H). IR (KBr, cm-1): 3032, 2212, 1647, 1599, 1575, 1504, 1479, 1404, 1314, 1284, 1265, 1179, 1142, 1001, 818, 803, 700. 1H NMR (CDCl3, ppm): 8.75 (1H,pyridyl), 8.54 (1H, d, H, pyridyl), 7.81 (1H, d, pyridyl, J 8.0 Hz), 7.57(4H, d, J 8.8 Hz), 7.41 (2H, d, J 8.4 Hz), 7.28 (1H, t, pyridyl), 7.01(2H, d, J 8.4 Hz), 6.85 (4H, d, J 8.8 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide semihydrate In dimethyl sulfoxide at 70℃; for 4h; Overall yield = 56 %; Overall yield = 0.89 g; | General procedure for the reaction of ferrocenylalkanols 1a,bwith phenylacetylene and 3-ethynylpyridine in the KOH/DMSO system. General procedure: A mixture of alcohol 1a,b (5 mmol), arylacetylene (5 mmol),and KOH0.5H2O (0.163 g, 2.5 mmol) in DMSO (10 mL) was heated(70 C) and stirred for 4 h. The reaction mixture, after cooling(20e25 C), was diluted with H2O (20 mL), neutralized withaqueous NH4Cl, and extracted with Et2O (10 mL6). The organicextract was washed with H2O (10 mL3) and dried (Na2SO4). Columnchromatography (basic Al2O3, eluent hexane/diethyl etherwith gradient from 1:0 to 1:1) of the crude residue after removal ofthe solvent gave the pure adducts 2eeh and unreacted alcohols1a,b. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide semihydrate In dimethyl sulfoxide at 70℃; for 4h; Overall yield = 42 %; Overall yield = 0.70 g; | General procedure for the reaction of ferrocenylalkanols 1a,bwith phenylacetylene and 3-ethynylpyridine in the KOH/DMSO system. General procedure: A mixture of alcohol 1a,b (5 mmol), arylacetylene (5 mmol),and KOH0.5H2O (0.163 g, 2.5 mmol) in DMSO (10 mL) was heated(70 C) and stirred for 4 h. The reaction mixture, after cooling(20e25 C), was diluted with H2O (20 mL), neutralized withaqueous NH4Cl, and extracted with Et2O (10 mL6). The organicextract was washed with H2O (10 mL3) and dried (Na2SO4). Columnchromatography (basic Al2O3, eluent hexane/diethyl etherwith gradient from 1:0 to 1:1) of the crude residue after removal ofthe solvent gave the pure adducts 2eeh and unreacted alcohols1a,b. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With triethylamine; In ethanol; for 16h;Inert atmosphere; | General procedure: A representative synthesis for the Pt(alkynyl)2(COD) precursor complexes is described in the following modified procedure [17]. To a 100mL three-necked round-bottom flask equipped with a 25mL addition funnel and a magnetic stir bar was placed PtCl2(COD) (0.100g, 0.267mmol). Absolute ethanol (30mL) was added to the flask and the resulting suspension was stirred for 5min. Triethylamine (0.080g, 0.80mmol) was then added to the suspension followed by the dropwise addition of 4-ethynyltoluene (0.307g, 2.67mmol) over 5min with stirring. Additional absolute ethanol (5mL) was added and the solution was stirred over 16h and a white precipitate gradually formed. The resulting mixture was filtered using a sintered glass frit. The white solid obtained was washed with methanol (3×5mL) and dried in a vacuum desiccator for 6h. The solid was dissolved in a minimal amount of CH2Cl2 and filtered. The filtrate containing the product was evaporated and the resultant precipitate was washed with 5mL of diethyl ether and dried in vacuo. The product was obtained as a white solid (0.121g, 85% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26.7% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine at 40℃; for 216h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 70℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 75℃; for 46h;Schlenk technique; | methyl5-bromopicolinate (216 mg, 1 mmol) and 3-ethynylpyridine (103mg, 1 mmol) were introduced in a Schlenk flask containing 8 mL of dry degassed THF. Pd(PPh3)4 (38 mg, 0.033 mmol) and NEt3 (0.2 mL, 1.435 mmol) were then added and the reaction mixture was stirred for 46h. The reaction mixture was filtered and the filtrate was concentrated to dryness. Flash column chromatography (ethyl acetate:hexane, 1:2) yields 8a as a pure white solid (224 mg, 94%). Data for 8a: Anal. Calcd for C14H10N2O2·0.20H2O:C, 69.53; H, 4.33; N, 11.58. Found: C, 69.79; H, 4.26; N, 11.54. 1HNMR (CDCl3): delta = 8.86 (dd,4J=2.05 Hz, 5J=0.73 Hz, 1H), 8.80 (dd, 1H), 8.60 (dd,1H), 8.14 (dd, 3J=8.12 Hz,5J=0.74 Hz, 1H), 7.96 (dd,3J=8.12 Hz, 4J=2.08 Hz, 1H), 7.84 (m, 1H), 7.32 (m,1H), 4.02 (s, 3H) ppm. 13C NMR (CDCl3): delta = 165.40, 152.68, 152.26, 149.81, 146.77,139.69, 138.94, 124.79, 123.26, 119.44, 100.39, 92.27, 88.80, 53.31 ppm. ESI-TOFMS: m/z 239.08 [M + H]+. Selected IR (KBr, cm-1): 1719.3,1560.2, 1441.7, 1406.7, 1366.8, 1319.2, 1239.0, 1197.2, 1153.8, 1137.0, 1016.8,865.6, 794.9, 697.6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With 2C15H28N2*2Cu(1+)*2Br(1-); caesium carbonate In N,N-dimethyl-formamide at 40℃; for 12h; Schlenk technique; | General procedure: General procedure for the copper(I)-based IL-catalyzed carboxylationof terminal alkynes: In a 10 mL Schlenk flask, the terminalalkyne (0.5 mmol), [Cu(Im12)2][CuBr2] (0.019 g, 0.025 mmol),Cs2CO3 (0.1955 g, 0.6 mmol), nBuI (0.1104 g, 0.6 mmol) and DMF(2.5 mL) were added. The flask was sealed. Then gas exchangingprocess was operated by the freeze-pump-thaw method. The reactionmixture was stirred at room temperature (proceeded at 40 ∘Cfor substrate i-l) for 12 h under an atmosphere of CO2 (99.999%,balloon). Water was added to the resulting mixture, which wasextracted with acetic ether until no product was detected. Thecombined organic layer was washed with saturated aqueous NaCland then dried over anhydrous Na2SO4, then the solvent wasremoved under vacuum. The crude product was purified by columnchromatography on silica gel (200-300 mesh, eluting with6:1 to 3:1 petroleum ether/ethyl acetate) to afford the desiredproduct. The products were further identified by NMR and MS |
70% | With silver(I) tungstate; caesium carbonate In N,N-dimethyl-formamide at 25℃; for 24h; Green chemistry; | |
66% | With caesium carbonate at 80℃; for 2h; |
65% | With [Gd4Cu4I3(CO3)2(IN)9(isonicotinic acid)0.5(DMF)(H2O)]n*nDMF*nH2O; caesium carbonate at 80℃; for 4h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With copper diacetate; triethylamine; In 1,4-dioxane; at 110℃; for 72h; | A mixture of di-2-pyridinone(55 mg, 0.3 mmol), 3-pyridineacetylene (62 mg, 0.6 mmol), copper acetate (5.4 mg,0.03 mmol), and triethylamine (60 mg, 0.6 mmol) were dissolved in 1,4-dioxane (2 mL). The resulting mixture is obtainedThe reaction was heated to 110 C and the reaction was complete after 72 hours of reaction. The reaction was stopped, filtered and the crude product was passed through a silica gel columnChromatography (100-200 mesh, n-hexane: ethyl acetate = 1: 2) to give 68 mg of the desired product in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With palladium on activated charcoal; diethylamine In toluene at 110℃; for 20h; chemoselective reaction; | |
75% | With nickel(II) acetate tetrahydrate; triethylamine In 1,4-dioxane at 110℃; for 6h; | Experimental procedure for the synthesis of substituted aryl and α, β-alkynyl ketones: General procedure: A mixture of aryl iodide (2 mmol), aryl alkyne (2.4 mmol), Ni(OAc) 2 (10 mol %), Et3N (6 mmol) and 1,4-dioxane (15 mL) were charged into the reactor (steel bomb). The reactor was closed and pressurized to ~2bar CO and then stirred at 100 °C for 4 h. The reaction Progress was monitored by TLC. The reaction mixture was cooled to room temperature, before being filtered through a pad of Celite. The filtrate was concentrated and purified by silica gel with a mixture of hexane and ethyl acetate to give the pure product. For all examples, reactions were performed on 100 mg scale of corresponding aryl iodides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(ll) sulfate pentahydrate; sodium L-ascorbate; triethylamine; In tetrahydrofuran; water; at 80℃; for 0.5h;Microwave irradiation; | General procedure: Azide 6 (3.0mmol) and alkyne (3.0 mmol) was dissolved in a mixture ofTHF and water (1:1, v/v; 10 mL). CuSO4-5H2O (0.06 mmol),sodium ascorbate (0.3 mmol) and Et3N (0.3 mmol) wasadded under rigorous stirring. The mixture was heated to 80C under microwave irradiation for 30 min. The mixture wasdiluted with water and extracted with EtOAc (3x15 mL). Thecombined organic phases was dried with Na2SO4, concentratedand purified by column chromathography (Heptane/EtOAc/Acetic acid 10:9:1) to the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With copper(II) sulfate; sodium L-ascorbate In tetrahydrofuran; water at 20℃; | |
100% | With copper(II) sulfate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 20℃; | I-2.i.m Step m : To a solution of compound 3 (65 mg, 0.22 mmol) in DMF were successively added 3- ethynylpyridine (47 mg, 0.45 mmol), sodium ascorbate (0.13 mmol, 26 mg, in water (500 mI_)) and CuS04 (1 1 mg, 0.06 mmol, in water (500 mI_)). The heterogeneous mixture was stirred vigorously overnight at room temperature. EtOAc was then added, the phases were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried over MgS04, and concentrated under reduced pressure. The crude product was purified by flash chromatography using DCM/MeOH (96/4) as eluent to afford compounds 14 (88 mg, 100 %). (0264) HRMS: calculated for C21H23N6O2 [M+H]+: 391.1882; found: 391 .1882. |
100% | With copper(II) sulfate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 20℃; | I-2.i.m Step m To a solution of compound 13 (65 mg, 0.22 mmol) in DMF were successively added 3-ethynylpyridine (47 mg, 0.45 mmol), sodium ascorbate (0.13 mmol, 26 mg, in water (500 mI_)) and CuS04 (1 1 mg, 0.06 mmol, in water (500 mI_)). The heterogeneous mixture was stirred vigorously overnight at room temperature. EtOAc was then added, the phases were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried over MgS04, and concentrated under reduced pressure. The crude product was purified by flash chromatography using DCM/MeOH (96/4) as eluent to afford compounds 14 (88 mg, 100%). HRMS: calculated for C21H23N6O2 [M+H]+: 391.1882; found: 391 .1882. |
86% | With copper(II) sulfate; sodium L-ascorbate In tetrahydrofuran; water at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | General procedure: The terminal alkyne (1.0 mmol) was added to a mixtureof HSi(OEt)2Me (5.0 mmol) and KOtBu (1.5 mmol) in a10 mL Schlenk tube with a magnetic stirrer. The Schlenktube was evacuated and back-filled with CO2 for 3 times.After a CO2 ballon was connected, the reactor was moved toa water bath of 40 C. After being stirred for 2 h, the reactionmixture was diluted with water (30 mL), and was extractedwith CH2Cl2 (3×10 mL). The aqueous layer was acidifiedwith aqueous HCl (6 M) and then extracted with diethylether (5×20 mL). The combined organic extracts were driedover Na2SO4 and concentrated under vacuum to give the purepropiolic acid (such as compound 3-phenylpropiolic acid(3a): 98%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 70℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; triethylamine / 8 h / 70 °C / Inert atmosphere 2: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; triethylamine / 8 h / 90 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With C22H28N2; cobalt(II) acetate In tetrahydrofuran at 30℃; for 2h; Schlenk technique; Inert atmosphere; | |
75% | With sodium t-butanolate In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; regioselective reaction; | |
57% | With C21H28Cl2CoN3; sodium triethylborohydride In tetrahydrofuran at 20℃; for 0.0833333h; Inert atmosphere; Glovebox; Schlenk technique; | 10 Effect Example 10 Preparation of 3-(1-phenylsilyl)-vinyl)pyridine (TM-8a): In a nitrogen glove box, the complex 1-a (0.01 mmol),3-pyridylacetylene (0.5 mmol), phenylsilane(0.5 mmol) and 1 mL of dry tetrahydrofuran were added to a 10 mL Schleck tube.Then NaHBEt3 (0.03 mmol, 1 M in THF) was added.The reaction was carried out for 5 min at room temperature. Silica gel column chromatography,With dichloromethane/petroleum ether (1:1) as eluent,Colorless oil compound TM-8a(Yield 57%). |
54% | With sodium t-butanolate In tetrahydrofuran at 20℃; for 4h; Inert atmosphere; | 11 Preparation and characterization of 3-(1-(phenylsilyl))vinyl pyridine: Under an argon atmosphere, 20 mg of heterogeneous catalyst, 1.0 mmol 3-ethynylpyridine, 1.5 mmol phenylsilane and 1.5 mL of anhydrous tetrahydrofuran were added to a 25 mL branch tube with a magnetic stir bar, Then add 40mg sodium tert-butoxide, The reaction was stirred at room temperature for 4 hours, the solvent was removed in vacuo, The crude product was purified by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain a colorless liquid product with a yield of 54%. |
23% | With 4,4'-dimethyl-2,2'-bipyridines; cobalt(II) diacetate tetrahydrate In tetrahydrofuran at 50℃; for 3h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium azide; sodium L-ascorbate; In ethanol; at 80℃; for 0.333333h;Green chemistry; | General procedure: In a 50 mL round bottom flask alkyl/ aryl halide (1.0 mmol), sodium azide (1.2 mmol), alkyne (1.0 mmol), Cu-AcP-Am-Fe3O4(at)SiO2 (40 mg) and sodium ascorbate (29 mg, 0.15 mmol) were mixed and stirred in 5 mL ethanol. The reaction was allowed to proceed for 20 min at 80 C. Reactions were monitored by Thin Layer Chromatography (TLC) using aluminium backed silica gel 60 (F254) plates eluting with 20% ethyl acetate-petroleum ether (Rf = 0.46). After completion of the reaction, the catalyst was separated magnetically using bar magnet. Finally, the resulting solution was extracted with ethyl acetate and dried over anhydrous Na2SO4 the solvent was removed under reduced pressure then the product was purified by column chromatography over silica gel using EtOAc /Petroleum ether as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With copper(l) iodide; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran; hexane at 40℃; for 15h; Sealed tube; Glovebox; Inert atmosphere; | General procedure of the synthesis of 4 General procedure: In a glove box filled with nitrogen, to an oven-dried 5 mL pressure tube equipped with a stir bar were added CuI (0.015 mmol, 2.9 mg, 0.050 equiv), 4,4'-di-tert-butyl-2,2'-dipyridine (2.0 mg, 0.0075 mmol, 0.025 equiv), azide compounds (0.36 mmol, 1.2 equiv), terminal alkynes (0.30 mmol, 1.0 equiv), (CF3CF2CF2CO)2O (0.39 mmol, 159.9 mg, 1.3 equiv), Et3N (0.45 mmol, 45.5 mg, 1.5 equiv) and THF/n-C6H14 (1:2, 1.0 mL). The tube was sealed with Teflon screw cap and the solution was stirred at 50 °C for 15 h. The reaction mixture was cooled to room temperature and was filtered through a layer of Celite, eluted with dichloromethane. The solvent was removed by rotary evaporation and the resulting product was purified by column chromatography on silica gel with n-pentane/ dichloromethane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium fluoride; sodium azide; silver carbonate In N,N-dimethyl-formamide at 50℃; for 6h; | Typical synthetic procedure for compounds 3, 4 (with 3a asan example): General procedure: to a solution of phenylacetylene (1a)(0.055 mL, 0.5 mmol), 2,6-di-tert-butyl-4-methylphenol(BHT) (2a) (133 mg, 0.6 mmol), NaN3 (39 mg, 0.6 mmol)and KF (58 mg, 1.0 mmol) in DMF (1 mL) at 50 °C, Ag2CO3(41 mg, 0.15 mmol) was added. The reaction mixture wasthen stirred for 6 h when TLC conformed that substrate 1a was consumed. The resulting reaction mixture was cooled toroom temperature and extracted by dichloromethane(3×15 mL). The organic layer was washed with brine(3×40 mL), dried over MgSO4 and concentrated. Purificationof the crude product via flash column chromatography (silicagel; petroleum ether) and concentratinon in vacuo affordedthe desired product of 3a-N2/3a-N1 in 91% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With diethylzinc; In hexane; acetonitrile; at 80℃; for 20h;Schlenk technique; Inert atmosphere; | To a 25 mL Schlenk flask alkyne (2 mmol), chlorosilane (2 mmol), solvent (10 mL) and 1 M n-hexane solution of Et2Zn (1 mL) is added and the mixture is stirred at 80 C for 20 h unless otherwise stated. After cooling, the reaction mixture is evaporating solvent on a rotary evaporator and analyzed with 1H NMR using CH2Br2 as an internal standard. Silica gel column chromatography with hexane/ ethyl acetate as the eluent affords the purified alkynylsilane product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | 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 |
---|---|---|
37% | With copper(II) choride dihydrate; potassium carbonate In 1,4-dioxane at 60℃; for 36h; Schlenk technique; | Copper-Catalyzed Addition Reaction of Tryptanthrins andAlkynes - General Procedure General procedure: In air, a clean and dried Schlenk tube was charged with CuCl2·2H2O (0.02 mmol,10 mol%), K2CO3 (0.4 mmol, 2.0 equiv.),tryptanthrin 1a (0.2 mmol, 1.0 equiv.), alkyne 2 (1.0 mmol, 5.0 equiv.), and 1,4-dioxane or THF (2 mL). The resulting mixture was stirred at the 60 °C or 80 °C for 36 h until the reaction completed. The crude mixture was purified through flash column chromatography on a silica gel using DCM/EtOAc (100:1, v/v) as eluent to give the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: N,N-diisopropyl benzamide With bis(triphenylphosphine)carbonyliridium(I) chloride; H2SiEt2 In toluene at 20℃; for 0.166667h; Schlenk technique; Glovebox; Stage #2: 3-Ethynylpyridine With copper(l) iodide; (R)-BTFM-Garphos; triethylamine In toluene at 20℃; for 1h; Schlenk technique; Glovebox; enantioselective reaction; |
[ 352530-29-1 ]
4-Ethynylpyridine hydrochloride
Similarity: 0.79
[ 352530-29-1 ]
4-Ethynylpyridine hydrochloride
Similarity: 0.79
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P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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