Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 42472-69-5 | MDL No. : | MFCD04974025 |
Formula : | C10H8O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WHFPFLKZXFBCSO-UHFFFAOYSA-N |
M.W : | 144.17 | Pubchem ID : | 5123626 |
Synonyms : |
|
Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
100% | With potassium carbonate In methanol at 20℃; for 0.25h; | 2.2 Synthesis of Compound 2 Dissolve 1.0 g of Compound 1 (5.04 mmol) and 690 mg of potassium carbonate (5.04 mmol) in 40 mL of methanol, and stir at room temperature for 15 minutes. The reaction solution is a mixture of dichloromethane and water (such as the volume of dichloromethane and water) (A mixed solution with a ratio of 1: 1) was extracted twice, and the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and spin-dried to obtain 666 mg of Compound 2 (yellow solid, yield 100%). |
100% | With methanol; potassium carbonate at 20℃; for 0.25h; | |
97% | With aluminum(III) oxide; potassium fluoride for 0.05h; microwave irradiation; |
97% | With potassium fluoride In methanol at 20℃; for 12h; | |
95% | With methanol; potassium hydroxide at 10 - 20℃; for 1h; | To a stirring solution of compound 1.9 (19 gs 88 rnrnoi) in MeOH (200 mL) was added a solution of KOH (2.46 g, 44 mrnoi) in MeOH (20 mL) at 10°C and the mixture was stirred at room temperature for 1 hr. AeOH was added until the pH was 7. and the reaction mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (200 mL), washed with 5% aqueous NaHCOa (100 mL), brine (1 Q0 mL), dried, and concentrated under reduced pressure to give compound 1.10 as a white solid (12 g, 95%). 1H N R (400 MHz, DMSO-efe) δ 7.95 (d, J = 8, 2H), 7.82 (d, J = 8, 2H), 4.49 (s, 1 H), 2.59 (s, 3 M), |
91% | With potassium carbonate In methanol at 25℃; for 3h; | |
91% | With potassium carbonate In methanol at 20℃; for 1h; | 8.2 Synthesis of 1-(4-ethynylphenyl)ethanone l-(4-((trimethylsilyl)ethynyl)phenyl)ethanone (0.86 g, 4.0 mmol), potassium carbonate (1.1 g, 8.0 mmol), and methanol (8 mL) were reacted at room temperature for 1 hour. After the solvent was distilled off under reduced pressure, water was added thereto, followed by extracting with ethyl acetate. The organic layer was washed with water and brine, and anhydrous sodium sulfate was added to dry the layer. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure and the residue was purified by flash chromatography to obtain 1-(4-ethynylphenyl)ethanone (0.53 g; yield, 91%). |
88% | With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 12h; Inert atmosphere; Schlenk technique; | |
85% | With potassium hydroxide In methanol for 1h; Ambient temperature; | |
85% | With sodium hydroxide In methanol; diethyl ether at 20℃; for 0.166667h; | |
68% | With potassium carbonate In methanol; lithium hydroxide monohydrate at 20℃; | |
32% | With potassium carbonate In methanol at 25℃; for 6h; | |
With sodium hydroxide; dibenzo-18-crown-6 In tetrahydrofuran; ethanol at 50℃; for 3h; | ||
With potassium carbonate In methanol at 20℃; for 2h; | ||
With methanol; potassium carbonate In dichloromethane at 20℃; for 2h; Inert atmosphere; | ||
0.69 g | With potassium carbonate In methanol at 20℃; for 3h; Inert atmosphere; | |
1.3 g | With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 0 - 20℃; for 0.5h; | |
With potassium carbonate In methanol at 20℃; for 3h; Inert atmosphere; | ||
6.2 g | With potassium fluoride In tetrahydrofuran; methanol at 25℃; for 0.5h; | |
1.06 g | With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere; | |
89 %Chromat. | With anhydrous potassium trimethylsilanolate In dimethyl sulfoxide at 70℃; for 6h; Sealed tube; Schlenk technique; | |
With copper (I) iodide; hydrofluorosilicic acid; N-ethyl-N,N-diisopropylamine In tetrahydrofuran; lithium hydroxide monohydrate at 60℃; for 2h; | ||
0.52 g | With methanol; sodium hydroxide In diethyl ether at 20℃; for 0.25h; | |
With potassium fluoride In methanol at 20℃; for 24h; Sealed tube; | ||
With methanol; potassium carbonate at 25℃; for 1.5h; Inert atmosphere; | ||
With potassium carbonate In methanol at 20℃; | ||
2.47 g | With methanol; potassium carbonate at 20℃; for 24h; | 1-Chloro-4-ethynylbenzene (1b) General procedure: According to the reported method, 1 the title compound 1b was prepared from 1-bromo-4-chlorobenzene by the Sonogashira coupling and subsequent desilylation as follows. Under an argon atmosphere, TMSA (2.58 g, 26.2 mmol) was added to a stirred mixture of 1-bromo-4-chlorobenzene (3.83 g, 20.0 mmol), PdCl2(PPh3)2 (350 mg, 0.499 mmol) and CuI (95.2 mg, 0.500 mmol) in Et3N (40 mL). The mixture was heated to 80 °C and stirred for 19 h. The resultant mixture was cooled to room temperature and passed through a short silica gel-activated carbon column. Evaporation of the filtrate under reduced pressure gave a light yellow solid (4.40 g). The crude product was dissolved in MeOH (40 mL) and treated with anhydrous K2CO3 (4.37 g, 31.6 mmol) at room temperature for 15h. The reaction mixture was quenched by dropwise addition of HCl (2 M in H2O, 10 mL) and extracted with CH2Cl2 (3 × 10 mL). The combined organic layer was washed with brine, dried overNa2SO4, and evaporated under reduced pressure. Purification of the residue by silica gel column chromatography (hexane) gave 1b as pale yellow solid (1.23 g, 9.22 mmol, 46%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With aluminum oxide; potassium hydroxide for 0.00694444h; microwave irradiation; | |
78% | With 18-crown-6 ether; potassium carbonate In toluene at 120℃; for 8h; | |
56% | With sodium hydroxide In toluene at 120℃; for 0.25h; | 44.2 1.45 g (7.17 mmol) of dimethylhydroxymethyl-4-acetylphenylacetylene and 301 mg (7.53 mmol) of NaOH (KISHIDA CHEMICAL CO., Ltd., 0.7 mm granular, 98 %) were placed in a 100 mL two-neck flask equipped with a reflux condenser and the air inside the flask was replaced with Ar. 36 mL of toluene was added thereto and the mixture was refluxed at 120°C for 15 minutes. Toluene was added to the reaction mixture and the mixture was washed with a saturated aqueous ammonium chloride solution and dried over magnesium sulfate, followed by distilling off of the solvent under reduced pressure by an evaporator. Then, 25 mL of hexane was added to the resulting crude reaction product and the mixture was cooled to give 4-acetylphenylethyne as a yellow solid. (0.74 g; yield: 56%). 1H-NMR (300 MHz, CDCl3) δ: 7.88-7.94 (m, 2H), 7.53-7.59 (m, 2H), 3.25 (s, 1H), 2.60 (s, 3H) [MS] EI (m/z): 144(M+-1), CI (m/z): 145 (MH+) |
51% | With sodium hydride In toluene at 110℃; | |
With 18-crown-6 ether; potassium carbonate In toluene for 8h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With N-chloro-succinimide; anhydrous sodium carbonate; silver(I) nitrate In propan-2-one at 50℃; for 8h; Schlenk technique; | |
30% | With N-chloro-succinimide; n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With palladium(II) oxide; triethylamine In water at 80℃; for 6h; | |
99% | With triethylamine In water at 80℃; for 6h; | |
96% | With copper(l) iodide; triethylamine; triphenylphosphine In water at 60℃; for 24h; Schlenk technique; Inert atmosphere; | 2.4 Catalysis General procedure: Sonogashira reactions. Typically, a mixture of aryl halide (0.2 mmol), Pd/MPC (2 mg, 0.004 mmol Pd), and CuI(0.02 mmol) and PPh3 (0.02 mmol) were added together into a Schlenk tube, and then terminal alkyne (0.4 mmol), NEt3 84 μL (0.6 mmol) and H2O 2 mL were added under N2 atmosphere. The mixture was heated in oil bath at 60 °C under stirring for 24 h. The reaction product was monitored by TLC and GC. Target product was isolated and purified by column chromatography, and the yields ofproduct were calculated on the basis of theoretical yield of aryl halide. The identification of product was conducted by NMR measurements on VNMRS 600 spectrometer. For recycling, the Sonogashira reaction was conducted with 4-nitrobromobenzene and phenylacetylene maintaining the same reaction conditions except using the recovered catalyst. The Pd/MPC was recovered by simple filtration, and then it was washed with ethanol and H2O thoroughly. The recovered catalyst was dried at 80 °C for the night and reuse in the next runs. |
93% | With copper(l) iodide; palladium; triphenylphosphine for 0.0416667h; microwave irradiation; | |
67% | With di(pyridin-2-yl)amine; diamminedichloropalladium(II); triethylamine In water at 25℃; for 6h; Inert atmosphere; | |
With copper(l) iodide; tri-1-napthylphosphine; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 14.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With caesium carbonate In toluene at 110℃; for 24h; | |
69% | With caesium carbonate In toluene at 110℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With polymethylhydrosiloxane; cesium fluoride; copper(l) chloride In 1-methyl-pyrrolidin-2-one at 20℃; for 6h; | |
91% | With polymethylhydrosiloxane; cesium fluoride; copper(l) chloride In 1-methyl-pyrrolidin-2-one at 25℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) In 1,4-dioxane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate In toluene at 110℃; for 8h; | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With triethylamine In N,N-dimethyl-formamide at 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With triethylamine In N,N-dimethyl-formamide at 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With triethylamine In toluene at 80℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With triethylamine In N,N-dimethyl-formamide at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With sodium ethanolate; In ethanol; at 20℃; for 17h; | Under an argon atmosphere, Au(PPh3)Cl (297 mg, 0.60 mmol), 4-acetylphenylethyne (130 mg, 0.9 mmol) and ethanol (12 ml) were added to a 30 mL Schlenk tube, and then sodium ethoxide (247 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 17 hours. After completion of the reaction, the resulting white precipitate was filtered and successively washed with ethanol (12 mlx three times), water (12 ml× three times) and ethanol (6 mlx three times), followed by drying under vacuum to give 0.32 g of the desired compound as a white powder (yield: 89%). 1H-NMR (300 MHz, CDCl3) δ: 7.84-7.88 (m, 2H), 7.43-7.61 (m, 17H), 2.57 (s, 3H) FAB-MS (M/Z): 603 (M+H)+ Luminescence analysis: (CHCl3, 77K, Ex250nm) λ (nm): 465, 499 Elemental analysis: Found C: 55.86, H: 3.67 Theoretical C: 55.83, H: 3.68 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium acetate; silver nitrate; triphenylphosphine In N,N-dimethyl-formamide at 80℃; for 3h; | |
90% | With sodium carbonate; silver nitrate In acetonitrile at 50℃; for 2h; | 2 Example 2 1 mmol of p-acetylphenylacetylene,0.01 mmol silver nitrate and0.5mmol sodium carbonate added to the market1 ml of acetonitrile in a round bottom flask,50 ° C for 2 hours.After completion of the reaction, the solid was removed by filtration,Column separation products, the yield of 90%. |
83% | With copper(l) iodide; N,N,N,N,-tetramethylethylenediamine In dichloromethane at 25℃; |
82% | With copper(l) iodide; oxygen In acetonitrile at 20℃; for 15h; Irradiation; Green chemistry; | |
72% | With triethylamine In 1,4-dioxane Heating; | |
71% | With 4,4’‐bis(trimethylammoniummethyl)‐2,2’‐bipyridine; copper(l) iodide; diamminedichloropalladium(II); tetrabutylammomium bromide; triethylamine In water at 20℃; for 24h; | |
63% | With 4,4’‐bis(trimethylammoniummethyl)‐2,2’‐bipyridine; copper(ll) sulfate pentahydrate; iodine; potassium acetate In water at 120℃; for 24h; | |
50% | With oxygen In ethanol at 60℃; for 24h; | |
38% | With copper(I) oxide; tetrabutylammomium bromide; oxygen; sodium hydroxide In water at 80℃; for 24h; Green chemistry; | |
With copper diacetate In pyridine; methanol for 2h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18%; 65% | With water;methyl(triphenylphosphine)gold(I); sulfuric acid; In methanol; at 70℃; for 2h; | Example 46 To a solution in which 0.0024 g of methyl(triphenylphosphine)gold (0.005 mmol) was dissolved in 3 ml of methanol, 0.13 g of 1,4-diethynylbenzene (1 mmol) and an aqueous solution in which 0.05 g of concentrated sulfuric acid (0.5 mmol) was dissolved in 0.5 ml of water were added. After stirring at 70 C. for 2 hours, 4-ethynylacetophenone was obtained in 65% yield, and 1,4diacetylbenzene was obtained in 18% yield (catalyst turnover number: 202). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In toluene at 110℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(l) iodide; trifuran-2-yl-phosphane; diisopropylamine; palladium dichloride In toluene at 55℃; Inert atmosphere; chemoselective reaction; | General procedure for chemoselective Sonogashira cross-coupling reaction of benzyl 5-bromo-2-iodophenylcarbamate (3) and arylalkynes (4a-o). General procedure: To a degassed solution of benzyl 5-bromo-2-iodophenylcarbamate 3 (0.50 mmol) and an arylalkyne 4 (0.52 mmol) in dry toluene (10.0 mL) under N2 was added diisopropylamine (0.60 mmol), palladium(II) chloride (0.03 mol), tri-2-furylphosphine (0.60 mol) and copper(I) iodide (0.03 mol). This mixture was stirred at 55 C. After completion of the reaction (typically less than 1 h) as indicated by TLC analysis, toluene was removed in vacuo and the residue was dissolved in dichloromethane and adsorbed on silica gel. After flash chromatography (SiO2-gel, elution with EtOAc/hexane gradient) the solid residue was dissolved in chloroform and petroleum ether was added to precipitate. Finally, the solid was triturated and washed with a chloroform/petroleum ether mixture to afford the desired pure product 5a-o. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With palladium diacetate; copper dichloride; silver(l) oxide In toluene at 75℃; for 8h; | Representative procedure (Table 3, entry 1): To an oven-dried 10 mL round-bottom flask equipped with a stirrer bar was added 79 mg of 1a (0.4 mmol), followed by 4.8 mg of Pd(OAc)2 (0.021 mmol, 5 mol %), 6.0 mg of CuCl2 (0.045 mmol, 11 mol %), and 186 mg of Ag2O (0.8 mmol, 2.0 equiv). Toluene (2.5 mL) was added and the mixture was stirred at 75 °C while open to air. To this flask was added a solution containing 62 mg of 2a (0.6 mmol, 1.5 equiv) and another 4.8 mg of Pd(OAc)2 (0.021 mmol, 5 mol %) in 2.5 mL of toluene via syringe pump over 6 h. After complete addition, the reaction was continued for 2 h and judged complete by TLC. The mixture was then cooled to ambient temperature, filtered, and washed with EtOAc. The filtrate was washed once with brine and the aqueous layer was extracted twice with EtOAc. The combined organic extracts were dried over MgSO4, filtered, and evaporated. The residue was purified by column chromatography (petroleum ether/EtOAc = 4:1), to afford 81 mg of 3aa (69%) as a brown solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With bis-triphenylphosphine-palladium(II) chloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,4-di(diphenylphosphino)-butane In dimethyl sulfoxide at 0 - 60℃; for 5h; Sealed flask; | 21. Typical experimental procedure: General procedure: Method B; Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), 1,4-bis(diphenylphosphino)butane (42.6 mg, 0.1 mmol), Cu(acac)2 (52.4 mg, 0.2 mmol), aryl halides (2.0 mmol), and DBU (1.52 g, 10.0 mmol) were combined with DMSO (4.0 mL), in a small round-bottomed flask. Propiolic acid (1a) (140.0 mg, 2.0 mmol) was dropped at 0-5 °C, and the flask was sealed with a septum. The resulting mixture was stirred at 25 °C for 5 h. Then the reaction temperature was increased to 60 °C, and the mixture was stirred for 6 h. The reaction was poured into Ethyl acetate and washed with water saturated by NH4Cl. The organic layer dried over MgSO4, and filtered. The solvent was removed under vacuum, and the resulting crude product was purified by flash chromatography on silica gel to give 4a (230.9 mg, 79% yield). The spectroscopic data of 4a-j are as follows. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With formic acid; iron(II) tetrafluoroborate hexahydrate; tris(2-diphenylphosphinoethyl)phosphine In tetrahydrofuran at 40℃; for 5h; Inert atmosphere; | |
90% | With water; zinc(II) iodide; zinc In N,N-dimethyl-formamide at 90℃; Inert atmosphere; | 20 Example 20 In an anhydrous and oxygen-free glove box under an argon atmosphere, add ZnI2 (0.01mmol), Zn (0.3mmol) and 4-ethynylacetophenone (0.2mmol) to a 10mL reaction tube, and then add 2ml DMF (N,N-dimethylformamide), then add water (1.0mmol) and send it out of the glove box. The reaction was carried out in an oil bath at 90, and the progress of the reaction was monitored by TLC monitoring and I2 color development. After the reaction was completed, the organic phase was extracted and concentrated by adding water, and the column was passed through silica gel to obtain a styrene compound as a colorless liquid. The yield was 90% . |
89% | With water; zinc(II) iodide; zinc In 1,4-dioxane at 90℃; for 20h; Inert atmosphere; Schlenk technique; Green chemistry; |
80% | With copper(II)-citrate; hexamethylenetetramine; hypophosphorous acid In water; N,N-dimethyl-formamide at 130℃; for 6h; Inert atmosphere; Green chemistry; chemoselective reaction; | |
99 %Chromat. | With formic acid; gold nanoparticles on rutile titania; triethylamine In acetone at 60℃; for 0.5h; | |
With hydrogen In acetonitrile at 30℃; for 1.5h; | ||
51 %Chromat. | With hydrogen; diisobutylaluminium hydride In tetrahydrofuran at 30℃; for 10h; | |
With water; potassium hydroxide In 1,4-dioxane; ethanol at 20℃; Electrochemical reaction; | ||
With hydrogen In ethanol at 20℃; | 1.1.2.1 1.2.1 Provision of a precursor monomer In a 3-neck round bottom flask p-(ethynylphenyl)ethanone (10.0 g, 69.4 mmol) was suspended in EtOH (350 ml_) and Lindlar’s catalyst (300 mg, 3 w%) was added. Air was replaced by hh and the suspension was stirred at RT for 2-16 hours. To monitor the conversion (and thus preventing over-reduction of VPE into the alkane), samples were frequently taken from the reaction mixture and, after evaporation of EtOH under reduced pressure, the conversion was determined by1H-NMR (CDCI3). Afterthe conversion was >90%, the H2-filled balloon was removed and the reaction mixture was concentrated under reduced pressure. The crude product was re-dissolved in CH2CI2 and purified by filtration over Hyflo. The filtrate was concentrated under reduced pressure, giving crude pVPE (p-(vinylphenyl)ethanone) as a yellow liquid in a 99% yield (10.1 g, 69.0 mmol). Melting point 29 °C, melt enthalpy 90.6 J/g.1H-NMR (CDCI3, 600 MHz) d 7.92 (d, J = 8.3 Hz, 2H), 7.48 (d, J =8.2 Hz, 2H), 6.75 (dd, J = 17.6 Hz, 10.9 Hz, 1H), 5.87 (d, J = 17.6 Hz, 1 H), 5.39 (d, J = 10.9 Hz, 1 H), 2.59 (s, 3H). | |
With hydrogen In ethanol at 20℃; | 2.2.3 2.3 Synthesis of p-(VinylphenvDethenone (VPE) In a 3-neck round bottom flask p-(ethynylphenyl)ethenone (10.0 g, 69.4 mmol) was suspended in EtOH (350 mL) and Lindlar’s catalyst (300 mg, 3 w%) was added. Air was replaced by H2 and the suspension was stirred at RT for 2-16 hours. To monitor the conversion (and thus preventing over-reduction of VPE o into the alkane), samples were frequently taken from the reaction mixture and, after evaporation of EtOH under reduced pressure, the conversion was determined by 1H-NMR (CDCI3). After the conversion was >90%, the H2-filled balloon was removed and the reaction mixture was concentrated under reduced pressure. The crude product was re-dissolved in CH2CI2 and purified by filtration over Hyflo. The filtrate was concentrated under reduced pressure, giving crude VPE as a yellow liquid in a 99% yield (10.1 g, 69.0 mmol). Melting point 29 °C, melt enthalpy 90.6 J/g. 1H- NMR (CDCI3, 600 MHz) d 7.92 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H), 6.75 (dd, J = 17.6 Hz, 10.9 Hz, 1 H), 5.87 (d, J = 17.6 Hz, 1 H), 5.39 (d, J = 10.9 Hz, 1 H), 2.59 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With (E)-N-(pyren-1-ylmethylene)benzenamine; oxygen; palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 3h; | |
85% | With anthracen-9-ylmethylene-(4-methoxyphenyl)amine; palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 2.5h; | Typical procedure fortheoxidative coupling reaction General procedure: A mixture of arylboronic acid (1.0mmol), phenylacety-lene (1.2mmol), Pd(OAc) 2 (1.0mol%), L (1.0mol%) and 1,8-diazabicycloundec-7-ene (DBU) (2.0mmol) in DMF (5mL) was stirred at 100°C in air for 4h. The reaction mixture was then diluted with EtOAc (20mL) and washed with water (3 × 10mL). The organic layer was dried over anhydrous Na 2 SO 4 , filtered and the solvent was removed. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixture to afford the desired product. The products were characterized by 1 H and 13 C NMR analysis. |
58% | With iron(III) chloride hexahydrate; silver carbonate In dimethyl sulfoxide at 130℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With copper(ll) sulfate pentahydrate; diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In methanol; water at 20℃; for 10h; regioselective reaction; | 1-(4-(1-p-tolyl-1H-1,2,3-triazol-4-yl)phenyl)ethanone (Compound 13) General procedure: General Procedure for Cycloaddition of Alkyne-Azide: A solution of CuSO4*5H2O (10 mL, 2 mg, 1 mol % based on azide, with 2.00 g of CuSO4*5H2O in 10 mL H2O) was added to a mixture of azide (0.79 mmol) and alkyne(0.83 mmol), followed by a solution of dihydropyridine Hantzsch ester (10 mL, 2.2 mg, 1 mol % based on azide, with 2.20 g of dihydropyridine in 10 mL CH3OH) and finally methanol (1 mL) via syringes. The mixture was stirred for a period as indicated at roomtemperature. After being checked by thin-layer chromatography (TLC) (CHCl3/CH3OH), the reaction mixture was concentrated to dryness under reduced pressure. A small amount of water was used to wash the solid product followed by petroleumether (1H NMR spectrumshowed it is pure). If needed, the reaction mixture was loaded onto a short plug of silica gel using a fine solvent gradient (CHCl3/CH3OH) to affordthe analytically pure product. For some substrates, the scales were reduced. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(ll) sulfate pentahydrate; diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In methanol; water at 20℃; for 10h; regioselective reaction; | 1-(4-(1-butyl-1H-1,2,3-triazol-4-yl)phenyl)ethanone (Compound 17) General procedure: General Procedure for Cycloaddition of Alkyne-Azide: A solution of CuSO4*5H2O (10 mL, 2 mg, 1 mol % based on azide, with 2.00 g of CuSO4*5H2O in 10 mL H2O) was added to a mixture of azide (0.79 mmol) and alkyne(0.83 mmol), followed by a solution of dihydropyridine Hantzsch ester (10 mL, 2.2 mg, 1 mol % based on azide, with 2.20 g of dihydropyridine in 10 mL CH3OH) and finally methanol (1 mL) via syringes. The mixture was stirred for a period as indicated at roomtemperature. After being checked by thin-layer chromatography (TLC) (CHCl3/CH3OH), the reaction mixture was concentrated to dryness under reduced pressure. A small amount of water was used to wash the solid product followed by petroleumether (1H NMR spectrumshowed it is pure). If needed, the reaction mixture was loaded onto a short plug of silica gel using a fine solvent gradient (CHCl3/CH3OH) to affordthe analytically pure product. For some substrates, the scales were reduced. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 4-ethynylacetophenone With silver nitrate In acetone for 0.5h; Stage #2: With N-Bromosuccinimide In acetone at 20℃; for 14h; | To a stirring solution of compound 1.10 (12 g, 83.3 mmoi) in acetone (200 mL) was added AgjSSO* (1 .34 g, 7.9 mmoi) and the the reaction was stirred for 30 mm. MBS (17.7 g, 99.96 mmoi ) was then added and the reaction mixture was stirred at 2G*C for 14 hr. Solids were removed by filtration and the filtrate was concentrated under reduced pressure to give a crude, which was purified by flash chromatography (silica get/ ethyl acetate in petroleum ether 5%-10% v/v) to give compound 1.11 as a white solid (14 g, 76 %). N R (400 MHz, DM8O-0 δ 7.95 (d, J = B, 2H )., 7.62 J ~ 8, 2H), 2.58 (s, 3 H ). |
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | Stage #1: 4-Iodoacetophenone; trimethylsilylacetylene With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 20℃; for 16h; Inert atmosphere; Stage #2: With potassium carbonate In methanol at 20℃; for 2h; | 3. Synthesis of 1-(4-ethynylphenyl)ethan-1-one (3p) In a round bottom flask under Ar, Et3N (5.0 mmol, 1.0 eq) and TMS-acetylene (5.5 mmol, 1.1 eq) were added to a mixture of 4-iodoacetophenone (5.0 mmol 1.0 eq), Pd(PPh3)4 (0.15 mmol, 3 mol%), and CuI (0.45 mmol, 9 mol%) in dry toluene (0.4 M). The reaction was stirred overnight at room temperature. The solvent was then evaporated and the crude was dissolved in DCM and washed twice with water. The organic layer was then dried over MgSO4 and concentrated under reduced pressure. The crude was directly dissolved in MeOH (0.1 M) and K2CO3 (5.0 mmol, 1.0 eq) was added. After 2 hours the solvent was removed and the residue was directly purified through column chromatography (pentane/Et2O 95:5) to afford 3p as a white solid (2.2 mmol, 44%). 1H NMR (600 MHz, Chloroform-d) δ 7.91 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.4 Hz, 2H), 3.25 (s, 1H), 2.60 (s, 3H). 13C NMR (151 MHz, Chloroform-d) δ 197.4, 137.0, 132.5, 128.4, 127.1, 82.9, 80.5, 26.8. |
With potassium carbonate In methanol; acetonitrile at 40℃; | 2.2 General procedure for synthesis of diarylacetylenes General procedure: 4-Iodoanisole (1mmol), TMSA (1.1mmol) and K2CO3 (2mmol) were added to a freshly prepared solution of PdNPs (5mL) in a 25mL round bottomed flask fitted with stopper. Then, the reaction mixture was stirred at 40°C. The reaction progress was monitored by TLC, until complete consumption of aryl iodide. To the reaction mixture containing in situ formed 4-ethynylanisole the next batch of aryliodide (1mmol) was added and the reaction mixture was further allowed to stir until complete consumption of the arylacetylene. In this manner the targeted unsymmetrical diarylacetylene was formed. The detailed procedure is provided in the Supp. Info. Detailed procedure for synthesis of symmetrical diarylacetylenes is also mentioned in SI. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With 5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine; sulfuric acid; water In methanol at 80℃; for 84h; | General procedure: A mixture of alkyne 1a (0.5 mmol), F15CCo-PPh3 (0.3 mol%) in CH3OH (0.5 mL), H2SO4 (2 mol%) in CH3OH (0.5 mL) and H2O (4.4 eq.) was heated at 80 °C under air for 12 h in a closed J. Young tube. The progress of the reaction was checked using TLC and GC. After the tube was cooled to R.T., the volatiles were removed under reduced pressure and the pure product 2a as a colorless oil (58 mg, 95% yield) was obtained by flash chromatography of silica gel. acetophenone (2a) Colorless oil (58 mg, 95% yield). 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 7.7 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 2.60 (s, 3H). The spectral data were in agreement with literature values. |
67% | With iron(III) sulfate hydrate; acetic acid at 95℃; for 24h; Schlenk technique; | Hydration of aromatic terminal alkynes catalyzed by Fe2(SO4)3·nH2O General procedure: Ferric sulfate hydrate (I, 8 mol%), glacial acetic acid (5 mL) and the alkyne (1 - 2 mmol) were introducedinto a 50 mL Schlenk tube, equipped with an air condenser, and the mixture kept under stirring at 95 °C or120 °C, until consumption of the substrate or no further conversion, as evidenced by TLC or GC. Uponcooling, the supernatant solution was poored into water and the residue washed twice with diethyl ether.After extraction with diethyl ether ( 2), the combined organic layers were washed with a saturated aqueoussolution of sodium bicarbonate and then water until neutrality. Alternatively, the crude from the reactions ofsubstrates featuring hydroxyl or carbonyl groups, as for 12, 15, 20 and 22, was obtained by removing aceticacid under vacuum, in order to reduce loss of material during biphasic extraction. The products were purified |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Wender's catalyst In 1,2-dichloro-ethane at 20℃; for 21h; | General alkyne dienophile method General procedure: To an oven-dried or flame-dried vial was added 1.1 equiv. TMSBO 2 as a neat liquid followed by 1,2-dichloroethane (DCE, 0.162 M with respect to VCP). To this solution was added 1 equiv. VCP 1 as a neat liquid, and then 2-5 mol% [(naph)Rh(COD)]SbF6 in one portion. The reaction was stirredfor 6 h or until consumption of 1 could be observed by TLC. The second alkyne was then added and the reaction monitored by TLC for consumption of the intermediate diene. The reaction was quenched with dilute acid and the resulting products purified via column chromatography. Results for these substrates are summarized in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56.5% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 50℃; for 12h; | 6.1.2 2-(2,4-Difluorophenyl)-1-(4-(4-ethyl-1H-1,2,3-triazol-1-yl)piperidin-1-yl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (8a) General procedure: To a solution of compound 7 (40mg, 0.11mmol) and but-1-yne (8mg, 1.3equiv) in tert-butyl alcohol (1mL) was added a mixture of CuSO4.5H2O (20mol %) and sodium ascorbate (40mol %) in H2O (0.5mL). The reaction mixture was stirred at 50°C overnight. Then, water (10mL) was added and was extracted with EtOAc (2×20mL). The combined organic layers were washed with water (10mL), dried over Na2SO4, and evaporated under reduced pressure. The crude product was purified by flash chromatography using EtOAc/ heptane as eluents (1:5) to give the target compound as a white solid: 20mg, yield 43.3%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 50℃; for 24h; Inert atmosphere; | 8.3 Synthesis of the desired substance In a nitrogen atmosphere, 3-allyl-4-bromopyridine (200 mg, 1 mmol), 1-(4-ethynylphenyl)ethanone (160 mg, 1.1 mmol), copper(I) iodide (10 mg, 0.05 mmol), tetrakis(triphenylphosphine)palladium(0) (60 mg, 0.05 mmol), triethylamine (4 mL),and N,N-dimethylformamide (4 mL) were reacted at 50°C for 24 hours. After the reaction mixture was allowed to cool to room temperature, water was added thereto, followed by extracting with ethyl acetate. The organic layer was washed with water and brine, and anhydrous sodium sulfate was added to dry the layer. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure and the residue was purified by flash chromatography to obtain the desiredsubstance (90 mg; yield, 34%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With trimethylsilylazide; lithium hydroxide monohydrate; anhydrous silver carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; | |
With trimethylsilylazide; lithium hydroxide monohydrate; anhydrous silver carbonate In dimethyl sulfoxide at 80℃; | III. General procedures for Synthesis of Viny Azides2. General procedure: To a solution of substrate (5 mmol), TMSN3 (0.98 ml, 7.5 mmol) and H2O (0.18 mL, 10 mmol) inDMSO (5 mL) at 80 oC was added Ag2CO3 (138 mg, 0.5 mmol). Then the mixture was stirred until (1-2 h)the complete consumption of substrate as indicated by TLC. The resulting mixture was concentrated andtaken up by dichloromethane (3 × 30 mL). The organic layer was washed with brine (3 × 40 mL), driedover MgSO4 and concentrated. The resulting crude materials were purified by flash columnchromatography (silica gel; hexane) to afford vinyl azides. | |
With trimethylsilylazide; lithium hydroxide monohydrate; anhydrous silver carbonate In dimethyl sulfoxide at 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(I) thiophene-2-carboxylate In toluene for 15h; Inert atmosphere; | ||
With copper(I) thiophene-2-carboxylate In water; toluene at 20℃; | ||
With copper(I) thiophene-2-carboxylate In toluene at 0 - 20℃; Inert atmosphere; |
With copper(I) thiophene-2-carboxylate In dichloromethane at 20℃; Inert atmosphere; Sealed tube; | 4.2. General procedures of the preparation of 2-(tetrahydrofuran-2-yl)-2H-1,2,3-triazole or 2-(tetrahydrothiophene-2-yl)-2H-1,2,3-triazole General procedure: Aryl ethynylene 1 (0.1 mmol, 1 equiv.) and copper(I) thiophene-2-carboxylate (0.01 mmol, 0.1 equiv.) was added in a 4 mL scintillationvial with a stir bar. After the charge of N2, dichloromethane(0.7 mL) and sulfonyl azide 2 (1.2 equiv.) were added into the sealedvial. The reaction mixture was stirred at room temperature overnightuntil judged by TLC. Dry tetrahydrofuran or tetrahydrothiophene3 (0.3 mL) was injected after the solvent was totally evaporated. The vial was tightly capped and stirred at 90 C overnight(or at 110 C for 6 h). After the completion of the reaction, themixture was cooled to room temperature and purified by columnchromatography using Petroleum ether/ethyl acetate mixture aseluent to afford the desired product 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In toluene at 60℃; for 2.5h; Inert atmosphere; | |
78% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In toluene at 65℃; Inert atmosphere; | 3.1. Preparation of 1-(R-Ethynyl)-9,10-antraquinones (1a-g) General procedure: A mixture of 1-iodo-9,10-anthraquinone (4.5 mmol) and corresponding 1-alkyne(4.5 mmol), CuI (0.027 mmol), PdCl2(PPh3)2 (0.013 mmol), and Et3N (12.7 mmol) in 50 mLof toluene was stirred under an argon atmosphere at 65 C (2-4 h) until iodide wasconsumed (TLC control). The reaction mixture was cooled and filtered through SiO2(25 30 mm) using toluene as the eluent. The solvents were evaporated, and subsequentrecrystallization gave pure compounds 1a-g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With Perfluorooctanesulfonic acid; C8AgF17O3S*H2O; In water; at 100℃; for 8h;Darkness; | General procedure: To the mixture of phenylacetylene (1 mmol), water (3.0 mL),silver perfluorooctanesulfonate (5 mol%) and perfluorooctane sulfonateacid (2 mol%) was added. The mixture was stirred at 100 Cfor 8 h. The solution was extracted with n-hexane (diethyl ether)(3 5 mL), the combined extract was dried with anhydrous MgSO4. The rest of the solution was used for the next cycle of reaction. Theextraction solvent was removed and the crude product was separatedby column chromatography to give the pure sample. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tert-butyl isocyanide; copper(II) nitrate trihydrate In benzonitrile at 60℃; Schlenk technique; Inert atmosphere; regioselective reaction; | |
71% | With copper(II) nitrate In benzonitrile at 60℃; | 3 3- (4-acetyl-benzoyl) -4,5-dihydro-isoxazole-5-carboxylic acid butyl ester using the following steps: at 1000Ml of the reaction vessel was charged with 21.7 g of 4-ethynylacetophenone,346.8 grams of n-butyl acrylate,145.0 grams of copper nitrate,25.0 grams2-hexanitrile addedObjects,750 ml of benzonitrile,Heated to 60 ° C.The reaction was followed by thin layer chromatography,To the reaction material disappeared; After the reaction,To the system to add water quenching reaction,The product was extracted with ethyl acetate,The organic phase was washed with saturated brine,After drying, the solvent was removed by rotary evaporator,The crude product;The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 5: 1)To give 33.65 g of butyl 3- (4-acetylbenzoyl) -4,5-dihydroisoxazolyl-5-carboxylate,The yield was 71%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; tri tert-butylphosphoniumtetrafluoroborate In 1,4-dioxane at 20 - 80℃; for 0.5h; Inert atmosphere; | 4.2.2. Typical procedure for the preparation of 2,5-disubstituted-7-alkynylindoles (6). General procedure: Synthesis of 5-methyl-2-phenyl-7-(phenyl-ethynyl)-1H-indole (6a). In a 50 mL Carousel Tube Reactor (RadelyDiscovery Technology) containing a magnetic stirring bar HP(t-Bu)3BF4 (5.8 mg, 0.02 mmol) and Pd2(dba)3 (9.2 mg, 0.01 mmol)were dissolved at room temperature with 1.0 mL of 1,4-dioxaneunder nitrogen. Then, 7-bromo-5-methyl-2-phenyl-1H-indole 5a(146.0 mg, 0.5 mmol), phenylacetylene (65.8 m l, 0.6 mmol), Cs2CO3(325.8 mg, 1 mmol), and 1.0 mL of solvent were added. The reaction mixture was stirred for 0.5 h at 80°C. After this time, the reaction mixture was cooled to room temperature, diluted with EtOAc, and washed with a saturated NaCl solution. The organic layer was separated, dried over Na2SO4, and concentrated under reduced pressure. The residue was puried by chromatography (silica gel, n-hexane/EtOAc 99/1) to afford 147.4 mg (96% yield) of 5-methyl-2-phenyl-7-(phenylethynyl)-1H-indole 6a as a brown solid. Mp:123 e 125C; IR (KBr): 3427, 3123, 2905, 2334, 2374, 1605, 1454,1071 (cm1);1H NMR (CDCl3): d 8.55 (br s, 1H), 7.73 e 7.67 (m, 4H),7.50 e 7.43 (m, 6H), 7.37 (t, J7.2 Hz, 1H), 7.30 (s, 1H), 6.81 (d,J2.0 Hz, 1H), 2.56 (s, 3H);13C NMR (CDCl3): d 138.3, 135.9, 132.2,131.7, 129.6, 129.2, 129.1, 128.5,128.4,127.9,127.1, 125.3,123.4,121.5,105.6, 100.1, 93.2, 85.8, 21.4; MS m/z (%): 307 (M, 100); 244 (80).Anal. Calcd for C23H17N, C, 89.87; H, 5.57; N, 4.56; found C, 89.95; H,5.58; N, 4.57. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With phosphonic Acid In hexane; water at 110℃; for 36h; Schlenk technique; Green chemistry; | Chalcone (3a); Typical Procedure General procedure: PhC≡CH (1a; 0.5 mmol), PhCHO (2a; 0.6 mmol), and 50% aq H3PO4 (0.5 mmol) were added to a 5 mL Schlenk tube, and the mixture was vigorously stirred at 110 °C for 24 h. The mixture was then cooled tor.t. and EtOAc (20 mL) was added. The solution was washed with water (2 × 6 mL) and the organic phase was dried (MgSO4), concentrated, and purified by column chromatography [silica gel, EtOAc-PE (1:20)] to give a pale-yellow solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With water; oxygen; lithium hydroxide In N,N-dimethyl-formamide at 60℃; for 3h; | β-Keto Phosphonate Derivatives 3a-w; General Procedure General procedure: alkyne 1 (0.25 mmol), H-phosphonate 2 (0.5 mmol), LiOH (0.05mmol), DMF (2 mL), and H2O (0.25 mL), and the mixture wasstirred at 60 °C for 3 h under O2 (balloon). When the reactionwas complete, it was quenched with aq NaHCO3 (20 mL) and themixture was extracted with EtOAc (3 × 10 mL). The combinedorganic layers were washed with sat. brine (×2) then dried(MgSO4), filtered, and concentrated in vacuum. The crudeproduct was purified by chromatography [silica gel, CH2Cl2-MeOH (30:1 to 50:1)]. |
74% | With silver orthophosphate; trimethylsilylazide; water; oxygen In dimethyl sulfoxide at 65℃; Schlenk technique; Inert atmosphere; | |
68% | With oxygen; rhodamine B In isopropyl alcohol at 20℃; for 12h; Irradiation; regioselective reaction; |
53% | With oxygen; copper(l) cyanide In dimethyl sulfoxide at 55℃; for 24h; | General procedure for construction of β-ketophosphine oxides General procedure: An oven-dried flask with the mixture of CuCN (0.025 mmol), alkynes 1 (0.5 mmol), H-phosphine oxides 2 (1.0 mmol) and DMSO (1.0 ml) was charged with O2. The reaction mixture was stirred at 55 °C for 24 hours. After completion of the reaction, water (10 ml) was added and extracted with EtOAc (5.0 ml×3). The combined organic layers were dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The resulting mixture purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired products 3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With N-Bromosuccinimide; perchloric acid In water; acetonitrile at 20℃; for 3h; Inert atmosphere; | General procedure for the preparationof α,α-dibromoketones 5 General procedure: Acetonitrile (2 cm3/mmol), water (1 cm3/mmol), and HClO4 (10 mol %) was added to a mixture of alkyne 4(1.0 mmol) and NBS (2.5 mmol). The resultant mixture was stirred for the time indicated in Table 1. Then, thereaction mixture was diluted with Et2O (8 cm3/mmol) andwashed with a saturated solution of Na2CO3 (3 cm3/mmol),Na2S2O3 (3 cm3/mmol), water (3 cm3/mmol), and brine (3 cm3/mmol). The organic layer was dried over MgSO4,concentrated under reduced pressure and column chromatographyon silica gel afforded the a,a-dibromoketones 5. |
77% | With N-Bromosuccinimide; eosin In water at 20℃; for 4h; Inert atmosphere; Irradiation; | |
75% | With toluene-4-sulfonic acid; lithium bromide In methanol; water at 20℃; for 4.5h; Inert atmosphere; Electrochemical reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 94% 2: 5 %Chromat. | With hydrogen In toluene at 110℃; for 4h; Schlenk technique; chemoselective reaction; | Semi-Hydrogenation of Alkynes 1a-l; General Procedure General procedure: The starting alkyne 1 (0.5 mmol) and dodecane as internal standard(0.22 mmol, 50 μL) were added to a suspension of the Cu-Pd-NPs/MCM-48 catalyst (10 mg) in toluene (5 mL). All reactions werecarried out in a Schlenk-type flask, fitted with a reflux condenser andsealed with a rubber septum. The reaction flask was purged and filledwith H2 (1 atm) through a balloon connected to the flask by a needle,and then heated at 110 °C. Then, the reaction mixture was centrifugedand the supernatant removed. The solvent was evaporated invacuo, and the crude product was purified by flash column chromatography(silica gel, hexane/EtOAc). The recovered solid catalyst waswashed with toluene (3 × 2 mL), dried in an oven, calcined at 150 °C(4 h), and reduced in H2 atmosphere at 200 °C before its reuse. The following known compounds included in Table 2 were characterizedby comparison of their chromatographic and spectroscopic data (FTIR,1H NMR, 13C NMR, and MS) with those described in the literature.Styrene (2a)18Yield: 46 mg (0.44 mmol, 89%); colorless liquid.IR (film): 3082, 3060, 3027, 1630, 1496, 1449, 992, 909, 777, 698 cm-1.1H NMR (300 MHz, CDCl3): δ = 7.35 (m, 2 H), 7.25 (m, 3 H), 6.7 (dd, J =10.8, 17.1 Hz, 1 H), 5.71 (d, J = 17.1 Hz, 1 H), 5.20 (d, J = 10.8 Hz, 1 H).13C NMR (75 MHz, CDCl3): δ = 137.5, 128.5, 127.7, 126.1, 136.9, 113.7.MS: m/z (%) = 104 (100, [M+]), 103 (40), 78 (35), 77 (17), 51 (17). |
With hydrogen; 1,3,5-trimethyl-benzene In acetonitrile at 30℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With air In N,N-dimethyl-formamide at 150℃; for 22h; | |
48% | Stage #1: Diphenylphosphine oxide With lithium tert-butoxide In tetrahydrofuran for 1h; Schlenk technique; Inert atmosphere; Stage #2: 4-ethynylacetophenone In tetrahydrofuran at 70℃; for 4h; Schlenk technique; Inert atmosphere; | 2 Experimental procedures for the base-catalyzed double addition of phosphine oxidesto alkyn General procedure: In a Schlenk flask wereplaced diphenylphosphine oxide (0.2 mmol), and tBuOLi of THF solution (5 mol%, 0.01 mmol) in THF (0.15mL) under nitrogen. The mixture was stirred at ambient temperature for 1 h. Etynylbenzene(0.1 mmol) was added to the solution under nitrogen and the mixture was heatedat 70 °C for 4 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 20℃; | To a solution of 1-(4-ethynylphenyl)ethanone (commercially available) (1 eq) <strong>[85331-33-5]3,5-dichloropicolinonitrile</strong> (1 eq), dichlorobis(triphenylphosphine)-palladium (II) (20 mol %), copper iodide (10 mol %) and DMF:Triethylamine (10:1) (0.13 M) was stirred at ambient temperature overnight. The reaction mixture was then diluted with ethyl acetate and sodium bicarbonate solution. The two phases were separated, and the aqueous phase was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated en vaccuo. The crude material was purified by flash chromatography on a COMBIFLASH system (ISCO) using 0-100% ethyl acetate in hexane and 5-((4-acetylphenyl)ethynyl)-3-chloropicolinonitrile was isolated as a yellow solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With copper(II) nitrate trihydrate In benzonitrile at 50℃; | 3 Example 3: 3-(4-acetylbenzoyl)isoxazolyl-5-carboxylic acid ethyl ester 3-(4-acetylbenzoyl)isoxazolyl-5-carboxylic acid ethyl ester using the following steps : (1) in 1000 ml according to the reaction vial 1 : 4.0: 8.0 to the molar ratio of 14.7 g propiolic acid ethyl ester, 86.7 g 4-ethynyl hypnone, 290.0 g copper nitrate, then adding 750 ml of benzonitrile, heating to 50 °C. Method for thin-layer chromatography for tracking of the reaction, to the reaction raw materials dematerialised ; (2) after the reaction, the reaction is quenched with water to the system, the extraction of the product with ethyl acetate, saturated salt water for washing, drying by rotary evaporimeter remove the solvent, get the crude product ; (3) of the crude product by column chromatography (petroleum ether: ethyl acetate = 30:1) purified, get 33.65 g 3-(4-acetylbenzoyl)isoxazolyl-5-carboxylic acid ethyl ester the yield is 77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Cu(at)C, generated by pyrolysis of Cu3(1,3,5-benzenetricarboxylate)2 In acetonitrile at 25℃; for 3h; Inert atmosphere; | 4. General procedure for the Cu(at)C-catalyzed N-sulfonyl amidine synthesis General procedure: A 15 mm flame-dried test tube, which was equipped with a magnetic stir bar and charged with Cu(at)C (5 mol %, 0.025 mmol), was evacuated and back filled with N2. After 0.5 mL of CH3CN was added, terminal alkyne (0.5 mmol), amine (0.6 mmol), sulfonyl azide (0.6 mmol), and CH3CN (0.5 mL) were added in sequence. Triethylamine (0.6 mmol) was added prior to the addition of amine, if necessary. The solution was stirred for 3 h at room temperature under N2 balloon. The reaction was diluted by adding EtOAc or DMF (if case of 4b, 4d, 4g, and 6d) and filtered through silica plugs. The silica were washed with EtOAc several times and the solvent was removed under vacuo. The crude residue was purified by column chromatography with EtOAc:hexane to give the N-sulfonyl amidine product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 82% 2: 6% | With [(Me3P)3Ru(-OH)3Ru(PMe3)3]+[OPh]-*(HOPh)0.2 at 100℃; for 2h; Inert atmosphere; Schlenk technique; | 4-Acetylphenylacetylene (2e) 2e (144.3 mg, 1.00 mmol) was treated by 1·(HOPh)0.2(4.3 mg, 0.0052 mmol) at 100C for 2 h to give(E)-1,4-bis(4-acetylphenyl)but-3-en-1-yne (E-3e) and (Z)-1,4-bis(4-acetylphenyl)but-3-en-1-yne (Z-3e) in 82% and 6% yields,respectively. These products were characterized by GC and NMR.E-3e:1H NMR (CDCl3): 2.61 (s, 6H, Me), 6.51 (d, J = 16 Hz, 1H,=CH), 7.11 (d, J = 16 Hz, 1H, =CH), 7.51 (d, J = 8 Hz, 2H, C6H4), 7.56(d, J = 8 Hz, 2H, C6H4), 7.93-7.96 (m, 4H, C6H4). Z-3e:1H NMR(CDCl3): 6.10 (d, J = 12 Hz, 1H, =CH), 6.80 (d, J = 12 Hz, 1H, =CH),the aromatic protons were obscured because of overlapping withE-3e. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 4-ethynylacetophenone With potassium hydroxide In methanol; water for 0.333333h; Inert atmosphere; Schlenk technique; Stage #2: ferrocenecarboxaldehyde In methanol; water at 20℃; Inert atmosphere; Schlenk technique; | 5.2.1. Synthesis of (h5-C5H5)-Fe-(h5-C5H4)-(E)-CH2]CH2-CO-C6H4-p-C≡C-H (2) Potassium hydroxide (2.0 g, 36 mmol) dissolved in methanol/H2O (30/10 mL) were mixed, portion wise, with 4-ethynylacetophenone, C, (300 mg; 2.1 mmol) and allowed toreact for 20 min. Later, ferrocenecarboxaldehyde (450 mg,2.1 mmol) was added, and allowed to react to room temperatureuntil the precipitation of red-purple color. The solid formed, containingto desired compound, was separated by fritted funnelfiltration. Yield 56% (395 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With iron(III) chloride hexahydrate In 2,2,2-trifluoroethanol at 90℃; for 3h; Inert atmosphere; | 8 Synthesis Example 8 Synthesis of (E) -1 - ((2-chloro-2- (4-ethanophenyl) ethenyl) sulfonyl) -4-methylbenzene 0.20 mmol was added to the reactorAcetylene acetylene acetylene, 0.30 mmolP-methylphenylsulfinic acidsodium,0.40 mmol of ferric chloride hexahydrate, 2.0 mL of trifluoroethanol solvent. Heated to 90 ° C under a nitrogen atmosphere,After stirring for 3 h, the reaction was stopped, cooled to room temperature, extracted with methylene chloride, dried, and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to give the desired product in 80% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With bis-triphenylphosphine-palladium(II) chloride; potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 20 - 50℃; for 12h; Inert atmosphere; | 26 Preparation Example 26 In 10mLThe reaction tube was added0.2 mmol of 8- (acetyl) aminoquinoline, 0.22 mmol of I2 and 1 mL of DMF under nitrogen atmosphere at 50 & lt; 0 & gt; C for 18 h. After completion of the reaction, the reaction was allowed to cool to room temperature and then added under a nitrogen atmosphere0.3 mmol of 4-acetylphenylacetylene, 2 mmol of potassium tert-butoxide, 0.002 mmol of bis (triphenylphosphine) phosphine dichloride, 1 mL of DMF,50 ° C for 12 hours. After the reaction, the reaction mixture was filtered, concentrated and separated by column chromatography5- (4-acetophenylethynyl) -8- (acetyl) aminoquinoline in 71% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | Stage #1: 4-toluenesulfonyl azide; 4-ethynylacetophenone With copper(l) iodide; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.5h; Schlenk technique; Sealed tube; Inert atmosphere; Stage #2: 3-phenyl-2H-azirine In dichloromethane at 0 - 20℃; for 12h; Schlenk technique; Sealed tube; Inert atmosphere; | 14 Example 14 In a 25 mL dry Schlenk reaction tube equipped with a magnetic stirrer, 0.010g (0.05 mmoL) of cuprousiodideand 0.094 g (0.65 mmoL) of para-acetylphenylacetylene were charged and sealed with a rubber stopper.The reaction tube pump vacuum, nitrogen,repeated 3 times.Separately, 1 mL of methylene chloride, 105 μL (0.6 mmol) of diisopropylethylamine, and 135 μL (0.6 mmol) of p-toluenesulfonyl azide in methylene chloride (70% strength) .The reaction tube was placed in an ice-water bathand stirred for half an hour. Then, 70 μL (0.5 mmoL) of 3-phenyl-2H-azirine was injected dropwise and the reaction was continued in an ice bath(ice bath slowly dissolving andwarmingto room temperature).After 12 hours of reaction in an ice-water bath and room temperature, the reaction mixture was directly passed through a silica gel column(volume ratio of ethyl acetate to petroleum ether being 1: 4) to give 0.098 g of a pale yellow solid product with a yield of 43% |
43% | Stage #1: 4-toluenesulfonyl azide; 4-ethynylacetophenone With copper(l) iodide; N-ethyl-N,N-diisopropylamine In dichloromethane for 0.5h; Inert atmosphere; Schlenk technique; Cooling with ice; Stage #2: 3-phenyl-2H-azirine In dichloromethane at 0 - 20℃; for 11.5h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | In tetrahydrofuran at 25℃; stereoselective reaction; | Typical procedure General procedure: To a flask equipped with a magnetic stirbar were added 1 (0.25 mmol, 1.1 equiv), alkyne 2 (0.23 mmol,1.0 equiv), and anhydrous THF (1 mL). The reaction was stirredat 25 °C for 15-18 hours (conversion was checked by 19F NMRwith PhOCF3 as internal standard). The crude residue was purifiedby chromatography to afford the desired products 3-5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With manganese powder; methanesulfonic acid; trifuran-2-yl-phosphane; palladium diacetate; Trimethylacetic acid In tetrahydrofuran at 40℃; for 24h; Inert atmosphere; Green chemistry; | 6 Example 6: Synthesis of 2,3-bis(4-acetylphenyl)-1,3-dibutylene In a 25 mL reactor, methane sulfonic acid (0.014 g, 0.15 mmol), pivalic acid (0.087 g, 0.85 mmol), manganese powder (0.027 g, 0.5 mmol),Tris(2-furyl)phosphine (0.009 g, 0.04 mmol), palladium acetate (0.005 g, 0.02 mmol), nitrogen substitution three times,Add 3 mL of dry tetrahydrofuran and add under stirring4-ethynylacetophenone (0.072 g, 0.5 mmol) was stirred at 40° C. for 24 h.Column chromatography (silica gel, 200-300 mesh; developing solvent, petroleum ether) gave 0.03 g of 2,3-bis(4-acetylphenyl)-1,3-dibutene in a 62% yield. white solid |
60% | With palladium (II) 2,4-pentanedionate; toluene-4-sulfonic acid; (tert-butyl)diphenylphosphane; zinc powder; Trimethylacetic acid In tetrahydrofuran at 35℃; for 2h; Schlenk technique; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With (2-di-tertbutylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl)AuNTf<SUB>2</SUB> In dichloromethane at 20℃; for 3h; regiospecific reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With 1,10-Phenanthroline; tetrakis(actonitrile)copper(I) hexafluorophosphate; potassium carbonate In toluene at 120℃; for 16h; Schlenk technique; Inert atmosphere; diastereoselective reaction; | |
54% | With 1,10-Phenanthroline; tetrakis(actonitrile)copper(I) hexafluorophosphate; potassium carbonate In toluene at 120℃; for 16h; Schlenk technique; Sealed tube; Inert atmosphere; | 22 Example 22 2-Bromopropiophenone (0.2 mmol) of the formula I-1, p-acetylphenylacetylene (0.1 mmol) of the formula II-4, Cu(MeCN)4PF6 (10 mol%) was added to the Schlenk tube-seal reactor. ),1,10-phen (20 mol%), K2CO3 (2equiv) and toluene (2 mL),The reaction was stirred at 120 ° C under argon.The reaction was completely detected by TLC (about 16 hours).Then will reverseThe solution was filtered through a short silica gel column and the filter cake was washed with ethyl acetate.Concentrated under reduced pressure to give a residue.The residue was separated by silica gel column chromatography to give the desired product of formula III-4.Yield 54% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With pyridine; bis(trichloromethyl) carbonate In 1,2-dichloro-ethane at 60℃; for 12h; Inert atmosphere; Sealed tube; | 6.1; 6.2; 8 Example 6 (1) 1.0 mmol of 4-ethynylacetophenone, 1.5 mmol of sodium trifluoromethanesulfinate, 1.0 mmol of phosgene, and 0.1 mmol of pyridine were added to 3 mL of DCE, sealed with nitrogen, sealed at 60 ° C. The tube reacted for 12 hours. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | Stage #1: N-Bromosuccinimide; 4-ethynylacetophenone With water at 80℃; for 1h; Stage #2: With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetone at 20℃; for 2h; | Representative procedure for the synthesis of α-imino ketones from alkynes General procedure: To a stirred solution of phenylacetylene 1a (102.12 mg, 1.0 mmol) and H2O (1.0 mL) in a vial (4.0 mL) were added N-Bromosuccinimide (356 mg, 2.0 mmol). Upon sealing by a septum cap and stirring at 80 °C for 1 h, the reaction mixture was then cooled to room temperature. Subsequently, acetone (1 mL) and DBU (3.0 mmol) were introduced into the reaction mixture, and the stirring was continued at room temperature for additional 2 h. After completion of reaction as monitored by TLC analysis, acetone was evaporated in vaccuo and crude product was poured into water and then extracted with CH2Cl2 (3×10 mL). The organic phase was washed with water (3×10 mL), dried over Na2SO4, filtered and concentrated in vaccuo.The crude product was purified by a short-pad silica gel column chromatography with petroleum ether as eluent to give compound 2a as a white solid (154.1 mg, 71% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: 4-ethynylacetophenone; ethyl 1-[(4-methylphenyl)sulfonyl]-2-aziridineacrylate With bis(norbornadiene)rhodium(l)tetrafluoroborate In 1,2-dichloro-ethane for 0.5h; Inert atmosphere; Stage #2: With 1,4-diaza-bicyclo[2.2.2]octane In 1,2-dichloro-ethane at 50℃; for 1h; Inert atmosphere; | General Procedure for Synthesis of Pyrroles 9 General procedure: To a solution of 5 (0.2 mmol, 1 equiv.) and [Rh(NBD)2]BF4 (5 mol%) in 1,2-DCE (1 mL) was added the corresponding acetylene (0.3 mmol, 1.5 equiv.) in 1,2-DCE (1 mL). The resulting mixture was stirred for 0.5 h. Upon the addition of DABCO (0.1 mmol, 0.5 equiv.), the mixture was heated to 50°C for 1 h. The reaction mixture was then quenched with the addition of trifluoroacetic acid (0.3 mmol,1.5 equiv). The solvent was removed under reduced pressure and the residue was purified by columnchromatography using CH2Cl2/hexane as the eluent to give the desired pyrrole 9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With triethylsilane; sodium t-butanolate In N,N-dimethyl-formamide at 110℃; for 12h; Schlenk technique; Sealed tube; Inert atmosphere; Green chemistry; stereoselective reaction; | 3 Example 3 A method of preparing a cis-trifluoromethylstyrene compound using the following process steps:in room temperature, Add NaOtBu 38 mg (0.4 mmol) to a 25 mL Schlenk tube equipped with a stir bar. Then seal the tube with a rubber stopper, Vacuum and refill with dry nitrogen three times . Next, 47 mg (0.4 mmol) of triethylsilane was weighed and dissolved in 2 mL of DMF solution. A mixture of the two was injected into the reaction tube through a syringe. The reaction tube was reacted in an oil bath at 110 ° C for 1 h. Subsequently, Weigh 35 mg (0.1 mmol) of copper trifluoromethyl compound 1 with a balance And 4-acetylphenylacetylene 14 mg (0.1 mmol), And dissolve the two in 1 mL of DMF. Then, the mixture is injected into the reaction tube with a syringe. Continue to react for 12 h. After the reaction is completed, it is cooled to room temperature. The reaction system was diluted with 15 mL of dichloromethane and filtered. The filtrate was washed three times with 60 mL of saturated brine. The organic layer was dried over anhydrous Na 2 SO 4 . Add a small amount of silica gel to spin column chromatography. The product 3c was obtained as a colorless oil (yield 51%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With potassium fluoride; sodium azide; silver carbonate In N,N-dimethyl-formamide at 50℃; for 6h; regioselective reaction; | 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 |
---|---|---|
47% | With diethylzinc In hexane; acetonitrile at 80℃; for 20h; Schlenk technique; Inert atmosphere; | General Procedures for the Et2Zn-mediated silylation of terminal alkynes: 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 |
---|---|---|
82% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine In tetrahydrofuran at 100℃; for 32h; Inert atmosphere; | 7 Synthesis of 1-(4-((5-(dimethylamino)-7-phenylnaphthalen-2-yl)ethynyl)phenyl)ethanone 0.20 mmol of 6-bromo-N,N-dimethyl-3-phenylnaphthalen-1-amine, 0.30 mmol of 4-(4-ethynylphenyl)ethanone, 0.01 mmol of Pd (PPh). )3Cl2, 0.01 mmol CuI, 0.40 mmol diisopropylamine, 1.0 mL THF was added to the reactor.Under a nitrogen atmosphere, heat to 100 ° C, stirring for 32 h, stop the reaction, cool to room temperature, wash with saturated ammonium chloride solution, then extract with dichloromethane, dry, distillate the solvent under reduced pressure, the crude product is separated by column chromatography The target product was obtained in a yield of 82%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine In tetrahydrofuran at 100℃; for 30h; Inert atmosphere; | 3 Synthesis of 1-(4-(4-(4-(dimethylamino)naphthalen-2-yl)phenyl)ethynyl)phenyl)ethanone 0.20 mmol of 3-(4-bromophenyl)-N,N-dimethylnaphthalen-1-amine, 0.26 mmol of 1-(4-ethynylphenyl)ethanone, 0.008 mmol of Pd (PPh)3Cl2, 0.01 mmol CuI, 0.40 mmol diisopropylamine, 1.0 mL THF was added to the reactor.Under a nitrogen atmosphere, heat to 100 ° C, stirring for 30 h, stop the reaction, cool to room temperature, wash with saturated ammonium chloride solution, then extract with dichloromethane, dry, distillate the solvent under reduced pressure, the crude product is separated by column chromatography The target product was obtained in a yield of 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃; Inert atmosphere; Schlenk technique; | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 40℃; Schlenk technique; Inert atmosphere; | 3. General Process for the Synthesis of 1a, 2a, 3a, 4a, 5a and 6a General procedure: A Schlenk flask was charged with Pd(PPh3)2Cl2 (2 mol %) and CuI (5 mol %) under N2 atmosphere.Dry triethyamine and 2-bromo-3,3,3-trifluoro-1-propene (1.2 equiv) were added subsequently followedby dropwise addition of phenylacetylene (1.0 equiv). The reaction mixture was stirred at 40 oC untilcompletion. The reaction was then quenched with saturated NH4Cl solution and extracted with pentane.Combined extracts were dried over Na2SO4 and solvent was removed under vacuum. The residue waspurified by column chromatography to afford the corresponding enyne 1a. All 1,3-enynes can beprepared in good yield by this procedure1-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tetrabutylammomium bromide In dimethyl sulfoxide for 1 - 3h; Electrolysis; | General procedure for the synthesis of 2/4/7/9/11.- General procedure: To a solution of 0.5 mmol of 2/4/7/9/11 in DMSO (3 ml) in a threeneck round bottom flask fitted with platinum electrodes (1 cm × 1cm) and passed a constant current of 15 mA was passed for 1-3 h from an amperostate. Reaction was monitored by thin layer chromatography. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate (30 ml), washed with brine(20 ml). The aqueous layer was extracted with ethyl acetate (30 ml).The combined ethyl acetate layer was washed with brine (20 ml).The organic layer was evaporated under reduced pressure. The crude products were purified by preparative TLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With tetrakis(triphenylphosphine) palladium(0); diisopropylamine; triphenylphosphine In toluene at 100℃; for 5h; | 3.3 Synthesis of compound 6 Dissolve 500 mg of compound 2 (3.47 mmol), 320 mg of tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4, 0.278 mmol) and 1210 mg of compound 5 (4.16 mmol) in a mixture of toluene and diisopropylamine (from 20 mL of toluene) Mixed with 20mL of diisopropylamine), heated to reflux at 100 for 5 hours, after the reaction solution is cooled with a mixture of dichloromethane and water (such as dichloromethane and water volume ratio of 1: 1 mix Liquid) extraction twice, the organic phase was washed with saturated brine, and then dried over anhydrous sodium sulfate, filtered, and spin-dried, and the crude product obtained was eluted with a normal phase silica gel column (eluent is a mixture of petroleum ether and dichloromethane Liquid, in which the volume ratio of the two is petroleum ether: dichloromethane = 1: 1), to obtain 440 mg of compound 6 (yellow solid, yield 36%). |
36% | With tetrakis(triphenylphosphine) palladium(0); diisopropylamine In toluene at 100℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: 4-ethynylacetophenone With acetic acid; lithium chloride; lithium iodide In dichloromethane at 0℃; for 0.166667h; Stage #2: With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 13h; | 8 Take 4-acetylphenylacetylene (28mg, 0.2mmol), lithium iodide (32mg, 0.24mmol), lithium chloride (10mg, 0.24mmol) into a 10mL reaction flask, then add 1mL of acetic acid and 0.5mL of dichloromethane , Cool to 0°C and stir for 10 minutes, add m-chloroperoxybenzoic acid (50mg, 0.24 mmol), stir for 1 hour, slowly increase the temperature to room temperature, and continue the reaction for 12 hours. After the reaction is over, add ethyl acetate 10 mL of the ester was added with 5 mL of water for extraction, the organic phase was dried with anhydrous sodium sulfate, and 50 mg of the target compound was obtained by column chromatography. The yield of the target compound was determined to be 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: sodium 4-methylbenzenesulfinate With 2-Picolinic acid; copper(l) iodide; trimethylsilylazide In methanol for 0.0833333h; Green chemistry; Stage #2: 4-ethynylacetophenone With oxygen In methanol at 25 - 28℃; Irradiation; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With palladium(II) trifluoroacetate; 5-chloro-2-hydroxybenzoic acid; boric acid; bis[2-(diphenylphosphino)phenyl] ether In acetonitrile at 110℃; for 14h; Autoclave; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With trifuran-2-yl-phosphane; 5-chloro-2-hydroxybenzoic acid; boric acid; bis(dibenzylideneacetone)-palladium(0) In acetonitrile at 120℃; for 14h; Autoclave; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With {(π-CH2CHCH2)PdCl}2; chloro[1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]copper(I); bis[2-(diphenylphosphino)phenyl] ether; sodium t-butanolate In toluene; <i>tert</i>-butyl alcohol at 20 - 80℃; for 12h; Inert atmosphere; Autoclave; | 2.2.2 General procedure II General procedure: A vial (4 mL) was charged with (η3-C3H5-PdCl)2 (0.7 mol%),DPEPhos (2.8 mol%), IMesCuCl (5.0 mol%), B2pin2(76.2 mg, 1.5 equiv.), NaOtBu (28.8 mg, 1.5 equiv.), and astirring bar. The vial was closed by PTFE/white rubberseptum (Wheaton 13 mm Septa) and phenolic cap andconnected with atmosphere with a needle. The vial wasevacuated under vacuum and recharged with argon for threetimes. Then, toluene (1.0 mL) was injected under argon byusing a syringe. After that aryl iodides 1 (0.25 mmol, 1.25equiv.), and internal alkynes 2 (0.2 mmol, 1.0 equiv.) wereadded, and the vial (or several vials) was placed in an alloyplate, which was transferred into a 300 mL autoclave of the4560 series from Parr Instruments. After flushing the autoclavethree times with CO, a pressure of 10 bar of CO wasadjusted at ambient temperature. Then, the reaction wasperformed for 12 h at 80 °C. When the reaction was completed,the autoclave was cooled down with ice water toroom temperature and the pressure was released carefully.The solution was then filtered through celite and concentratedin vacuo. After that NaBH4 (0.6 mmol, 3 equiv.)and CH3OH (1.0 mL) were added into the residue, the reactionwas stirred at room temperature for 1.0 h, and then the crude reaction mixture was diluted with Et2O (10 mL)and H2O (5 mL). The organic phase was separated, and theaqueous layer was extracted twice with Et2O. The combinedorganic layers were washed with brine, dried over MgSO4,filtered and concentrated on a rotary evaporator. Finally, theresidue was purified by silica gel chromatography (hexane/ethyl acetate) to afford the corresponding products 3ax-3bb (Reaction 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With ferric(III) bromide; palladium diacetate; triethylamine hydrobromide; tert-butyldiphenylphosphine In tetrahydrofuran at 80℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With N-ethyl-N,N-diisopropylamine In ethyl acetate at 20℃; for 20h; Inert atmosphere; Irradiation; | 3.2. General Procedure for ATRA/ATRC Reaction General procedure: A Pyrex test tube from Corning (Tokyo, Japan) (12.5 cm 1.6 cm) containing amixture of alkyne 1 or alkene 4 (1.0 equiv, 0.1 mmol), -halogencarbonyl 2 (3.0 equiv,0.3 mmol) and N,N-diisopropylethylamine (1.0 equiv, 0.1 mmol) in ethyl acetate (0.75 mL)was degassed via FPT cycling three times and backfilled with Ar. The tube was placed ca.0.5 cm from 3W420 nm LED. The resulting solution was stirred at ambient temperaturefor 20 h. The residue was concentrated in vacuo. The resulting mixture was purified byflash column chromatography on silica gel to yield product 3, 5 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With (carbonyl)(chloro)(hydrido)tris(triphenylphosphine)ruthenium(II) In toluene at 20℃; for 96h; regioselective reaction; | 4.3.16. Synthesis of 1-[(E)-2-(4-acetylphenyl)ethenyl]- 1,1,2,2-tetramethyl-2-phenyldisilane ( E-2i ) A mixture of 1 (95 mg, 0.49 mmol), 4-ethynylacetophenone (111 mg, 0.77 mmol), RuHCl(CO)(PPh 3 ) 3 (24 mg, 0.025 mmol) and tridecane (56 mg, 0.30 mmol) in toluene (2 mL) was stirred at room temperature for 4 days. After evaporation of the solvent, the residue was separated by column chromatography over silica gel (eluent: hexane-ethyl acetate (20:1)) to give 2i (106 mg, 64%, E / Z = 96/4) as a colorless oil. E -2i . 1 H NMR (600 MHz, CDCl 3 ): δ0.23 (s, 6H), 0.39 (s, 6H), 2.60 (s, 3H), 6.63 (d, 1H, J = 18.6 Hz), 6.80 (d, 1H, J = 18.6 Hz), 7.33-7.35 (m, 3H), 7.44-7.47 (m, 4H), 7.92 (d, 2H, J = 8.4 Hz). 13 C NMR (151 MHz, CDCl 3 ): δ-4.1, -3.7, 26.8, 126.5, 127.9, 128.7, 128.9, 132.5, 134.0, 136.3, 139.1, 142.8, 142.9, 197.8. 29 Si NMR (119 MHz, CDCl 3 ): δ-23.3, -20.9. IR (NaCl): 3070, 2950, 1680, 1600, 1430, 1410, 1360, 1270, 830, 800, 730, 700 cm -1 . MS (EI, 70 eV): m/z 338 (M + , 11), 323 (10), 260 (52), 245 (12), 239 (12), 207 (13), 187 (10), 177 (10), 145 (12), 137 (21), 135 (100), 75 (18), 73 (13), 59 (16). HRMS (FD): found 338.1531, calcd for C 20 H 26 OSi 2 338.1522. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | Stage #1: 1,1,2,2-tetramethyl-2-phenyldisilane; 4-ethynylacetophenone With [RuCl2pentamethylcyclopentadiene]n In toluene at 20℃; for 41h; Stage #2: With N,N,N,N,-tetramethylethylenediamine; copper(l) chloride In acetone at 20℃; for 1h; regioselective reaction; | 4.3.23. Synthesis of 1-[1-(4-acetylphenyl)ethenyl]-1,1,2,2- tetramethyl-2-phenyldisilane ( α-2i ) A mixture of 1 (95 mg, 0.49 mmol), 4-ethynylacetophenone (107 mg, 0.742 mmol), [Cp RuCl 2 ] n (9.4 mg, 0.031 mmol) and tridecane (59 mg, 0.32 mmol) in toluene (2 mL) was stirred at room temperature for 41 h. After evaporation of the solvent, the residue was separated by column chromatography over silica gel (eluent: hexane-ethyl acetate (20:1)). The crude product was dis- solved in acetone (2 mL), and TMEDA (10 mg, 0.086 mmol) and copper(I) chloride (8 mg, 0.08 mmol) were added. The mixture was stirred at room temperature for 1 h in air. After evaporation of the solvent, the residue was separated by column chromatography over silica gel (eluent: hexane-ethyl acetate (20:1)) to give 2i (87 mg, 53%, α/ E = 98/2) as a colorless oil. α-2i . 1 H NMR (600 MHz, CDCl 3 ): δ0.23 (s, 6H), 0.30 (s, 6H), 2.58 (s, 3H), 5.59 (d, 1H, J = 2.7 Hz), 5.87 (d, 1H, J = 2.7 Hz), 7.10 (d, 2H, J = 8.4 Hz), 7.28-7.32 (m, 3H), 7.36-7.38 (m, 2H), 7.81 (d, 2H, J = 8.4 Hz). 13 C NMR (151 MHz, CDCl 3 ): δ-3.6, -3.0, 26.7, 127.1, 127.9, 128.4, 128.7, 129.0, 133.9, 135.2, 138.8, 150.3, 151.9, 197.9. 29 Si NMR (119 MHz, CDCl 3 ): δ-21.1, -20.3. IR (NaCl): 3070, 2950, 2890, 1680, 1600, 1430, 1400, 1360, 1270, 1110, 850, 830, 790, 770, 730, 700 cm -1 . MS (EI, 70 eV): m/z 338 (M + , 9), 239 (15), 177 (47), 135 (100), 130 (11). HRMS (FD): found 338.1522, calcd for C 20 H 26 OSi 2 338.1522. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | In dimethyl sulfoxide at 25℃; for 12h; Inert atmosphere; | General synthetic procedure A: General procedure: To a test tube was added 1-(4-ethynylphenyl)ethan-1-one 1(0.2 mmol, 1.0 equiv.), trifluoromethyl thianthrenium triflate 2(0.4 mmol, 2.0 equiv.) and sodium sulfinate 3 (0.4 mmol, 2.0 equiv.).Then the tube was purged with argon for 3 times. DMSO (2.0 mL)was added by a syringe and the tube was stirred at 25 C for 12 h.After the scheduled time, the mixture was quenched with waterand extracted with EtOAc (20 mL * 3). The combined organic phaseswere washed with brine and dried over anhydrous Na2SO4. The solvent was then evaporated under reduced pressure and the residuewas purified directly by flash column chromatography toafford the corresponding product 4 as white solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium peroxodisulfate; Orthoboric acid; copper(II) bis(trifluoromethanesulfonate) In 1,2-dichloro-ethane at 80℃; for 12h; | 2.2 Example 2: (2) Weigh 4-ethynylacetophenone (0.4 mmol), quinoxalin-2(1H)-one (0.2 mmol), copper trifluoromethanesulfonate (0.03 mmol), K2S2O8 (0.6 mmol) and Boric acid (0.4 mmol) was transferred to a 10 ml there-necked flask, 2 ml of 1,2-dichloroethane was added, and magnetic stirring was carried out at 80 degrees Celsius for 12 hours. After rotary evaporation, the crude product 2-(4-ethynylphenyl)furo[2,3-b]quinoxaline (B) was obtained. Finally, the pure target product was obtained by column chromatography. The eluent was petroleum ether:ethyl acetate=3:1, and the separation yield was 87%. Brown solid; |
Tags: 42472-69-5 synthesis path| 42472-69-5 SDS| 42472-69-5 COA| 42472-69-5 purity| 42472-69-5 application| 42472-69-5 NMR| 42472-69-5 COA| 42472-69-5 structure
[ 147492-77-1 ]
1-(3-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 147492-77-1 ]
1-(3-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 147492-77-1 ]
1-(3-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
[ 1942-31-0 ]
1-(4-(Phenylethynyl)phenyl)ethanone
Similarity: 0.93
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
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 |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :