| 96.6% |
With Mo2(O-t-Bu)6; Cs2CO3 In N,N-dimethyl-formamide at 50℃; for 10h; Schlenk technique; |
|
| 95% |
With Cs2CO3 In N,N-dimethyl-formamide at 24℃; for 20h; |
|
| 95% |
With [CuI(1,1′-bis(di-tert-butylphosphino)ferrocene)]; Cs2CO3 In N,N-dimethyl-formamide at 25℃; for 24h; Inert atmosphere; |
|
| 94% |
With hydrogenchloride; C54H44Cu2N2P4S2; Cs2CO3 In N,N-dimethyl-formamide at 25℃; for 12h; Inert atmosphere; |
|
| 94% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With Cs2CO3 In dimethyl sulfoxide at 60℃; for 24h; Schlenk technique;
Stage #2: With hydrogenchloride In lithium hydroxide monohydrate Schlenk technique; |
2.4. Catalytic tests
General procedure: The catalytic reaction was performed in a Schlenk reaction tube (10mL). Generally, a given amount of catalyst and dimethyl sulfoxide(DMSO) (3 mL) were loaded to the tube, and cesium carbonate (326 mg,1.0 mmol) was added under stirring. The atmosphere was exchange withCO2 and kept with a CO2 balloon, and meanwhile the tube was heatedwith an oil bath to 60 °C. Under rigorous stirring, a terminal alkyne (0.5mmol) was injected to initiate the reaction. After reacting for a giventime, the mixture was cool to room temperature and diluted with water(15 mL). After the catalyst was filtered off and washed with water, the filtrate was washed with dichloromethane (3 × 10 mL), acidified by 1 M HCl to pH≈1 and extracted with ethyl acetate (3 × 40 mL). The combinedorganic phase was washed by saturated NaCl solution and driedover anhydrous Na2SO4. The solvent was removed under vacuum toobtain the carboxylic acid product. For recycle tests, the used catalystobtained from the above procedures was further washed with acetone (3× 10 mL) to remove any unreacted alkyne and then heated at 60 °Cunder vacuum for 12 h. |
| 94% |
With Cs2CO3 In dimethyl sulfoxide at 50℃; for 20h; |
|
| 93% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With C24H30N3(1+)*Cl4Fe; Cs2CO3 In N,N-dimethyl-formamide at 50℃; for 16h;
Stage #2: With hydrogenchloride; lithium hydroxide monohydrate In N,N-dimethyl-formamide at 20℃; |
8 Embodiment 8: [{(RNC (CH3)) NCHCHN (CH2Ph)} CH] [FeCl4] (R is 2,6_-diisopropylphenyl) catalyzesCarboxy-4-chlorobenzene reaction of acetylene and carbon dioxide
Sequentially adding a catalyst in the reaction bottle (14.0 mg, 0.025 millimole, 5mol %), cesium carbonate (32.6 mg, 1.0 mmol), 4-chlorbenzene acetylene (68.3 mg, 0.5 mmol),N,N-dimethylformamide(3 ml), into the carbon dioxide, in the 50 °C, reaction under normal pressure 16 hours. Reaction cooling to room temperature, diluted with water, acidified with hydrochloric acid, diethyl ether extraction, washing with saturated sodium chloride for ether level, dry anhydrous sodium sulfate, obtained product is vacuum to remove the solvent, the yield is 93%. |
| 92% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With Cs2CO3 In N,N-dimethyl-formamide at 120℃; for 16h;
Stage #2: With hydrogenchloride; lithium hydroxide monohydrate In N,N-dimethyl-formamide |
|
| 92% |
With Cs2CO3 In dimethyl sulfoxide at 25℃; for 18h; |
|
| 92% |
With Cs2CO3 In dimethyl sulfoxide at 50℃; for 16h; Sealed tube; |
|
| 92% |
With 1-(6-acetylpyridin-2-yl)-3-propyl-1H-benzo[d]imidazol-3-ium iodide In dimethyl sulfoxide at 60℃; for 24h; |
|
| 91% |
With {(N,N'-cyclohexane-1,2-diylbis((4-(tert-butyl)benzoyl)amide))Nd[N(SiMe3)2](tetrahydrofuran)}2; Cs2CO3 In dimethyl sulfoxide at 40℃; for 24h; Schlenk technique; |
|
| 91% |
With C76H124N6Nd2O6Si4; Cs2CO3 In dimethyl sulfoxide at 40℃; for 24h; Inert atmosphere; |
29 4 mol% of {LNd [N (SiMe3) 2] · THF} 2 and 200 mol% of cesium carbonate catalyzed the carboxylation of 4-chlorophenylacetylene and carbon dioxide at 40 ° C under atmospheric pressure:
Under anhydrous anaerobic, argon protection, 0.0635 g (3.92 x 10-5 mol) of {LNd [N (SiMe3) 2] · THF} 2 was added to the reaction flask. Further, 0.6385 g (1.96 x 10-3 moles) of cesium carbonate was added, under the protection of carbon dioxide bags. 2 ml of dimethylsulfoxide was added. 0.116 ml (9.82 x 10-4 mol) of 4-chlorophenylacetylene was added. Then 3 ml of dimethylsulfoxide was added. The reaction was stirred in a constant temperature bath at 40 ° C. After 24 hours, the reaction was quenched by adding 10 mL of water, and then filtered. The clear solution is placed in a separatory funnel, a certain amount of hydrochloric acid solution was added to acidify, and extracted four times with ether. The extract was washed twice with saturated brine, liquid separation was carried out, solvent was spin-dried, and then the residual solvent was removed by pumping to obtain the product. The calculated yield was 91%. |
| 90% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 16h;
Stage #2: With hydrogenchloride In dichloromethane; lithium hydroxide monohydrate |
Table 5. Copper catalyzed carboxylation of terminal alkynes with CCv Reaction conditions: for LI, CuCl (2.0 mol %), TMEDA, 1.5 mol %; for L12, P(NHC)(NHC-Cu), 5 mol%; alkynes (2.0 mmol), base (2.4 mmol), C02 (1 atm), DMF (4 mL), r.t.. M monocarboxylic acid was obtained. General Procedure for Carboxylation of the Terminal Alkynes (lb as Example); CuCl (4.0 mg, 0.04 mmol, 2.0 mol %), TMEDA (3.5 mg, 0.03 mmol, 1.5 mol %), and K2C03 or Cs2C03 (2.4 mmol) were added to the DMF (4 mL) in the reaction tube (10 mL). C02 and 2 mmol of terminal alkynes (la, 204 mg) were introduced into the reaction mixture under stirring. The reaction mixture was stirred at room temperature (about 24 °C) for 16 hours. After completion of the reaction, the reaction mixture was transferred to the potassium carbonate solution (2 N, 5 mL) and the mixture was stirred for 30 mins. The mixture was extracted with dichloromethane (3 >< 5 mL) and the aqueous layer was acidified with concentrated HC1 to PH = 1 , then extracted with diethyl ether (3 χ 5 mL) again. The combined organic layers were dried with anhydrous Na2S04, filtered and the solution was concentrated in vacuum affording pure product. Element analysis calcd (%) for lb [C9H602 (146.0)]: C 73.97, H 4.14; found: C 73.82, H 4.07. Data for 1H and 13C NMR of acids were all conducted in d - DMSO or CDC13 and consistent with the data in reported literatures. |
| 90% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With Cs2CO3 In N,N-dimethyl-formamide at 20℃; for 12h; Irradiation;
Stage #2: With hydrogenchloride In lithium hydroxide monohydrate |
General procedure for photothermal carboxylation of terminal alkynes with CO2
General procedure: MIL-100(Fe) or Ag/MIL-100(Fe) (30 mg), Cs2CO3 (0.6 mmol) and CO2 balloon (1atm) were introduced into a reaction tube (10 mL). Terminal alkynes (0.5 mmol), andDMF (5 mL) were injected into the reaction tube. The reaction mixture was thenstirred and exposed to a 300 W Xe lamp with the light intensity of 200 mW/cm2(PLS-SXE 300C, Beijing Perfect Light Co., Ltd., China, 420 nm < λ< 780 nm Twocut-off filters: UVCUT420 and BRPASS) at room temperature for 12 h. A quartzwater cooling equipment with constant temperature of 10 °C was placed between thereaction tube and the lamp to further minimize heating effect caused by the lamp.After cooling to room temperature, the reaction mixture was diluted with water (10mL) and the catalyst was separated by centrifugation. The supernatant was washedwith CH2Cl2 (3 × 10 mL) and the aqueous layer was acidified with concentrated HClsolution to pH of 1, then extracted with ethyl acetate (3 × 10 mL). The combinedorganic phase was dried with Na2SO4 and filtered, followed by evaporation of thesolvent. The product was purified by flash chromatography and characterized byNMR spectroscopy. For recycling experiments, the residue solids after reaction werewashed with water and ethanol several times and dried under vacuum at 150 °C for 12h before each cycle. |
| 89% |
Stage #1: 4-n-chlorophenylacetylene With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Schlenk technique;
Stage #2: carbon dioxide In tetrahydrofuran at 0℃; for 0.5h; Schlenk technique; |
4.1.1.1 Procedure 4.1.1.1
General procedure: This procedure was adapted from Linstadt etal. [25] To a solution of alkyne (13.5mmol) in 40mL of dry THF at-78°C was added n-BuLi (13.5mmol). The resulting solution was stirred at-78°C for 30min. The reaction mixture was warmed to 0°C and the reaction was placed under a balloon of CO2 gas and vigorously stirred for 30min. Then concentrated HCl (10mL), water (10mL) and Et2O (30mL) were added. The aqueous layer was discarded, and the organic layer was extracted with NaOH (1M; 3×20mL). The aqueous extracts were acidified with concentrated HCl, extracted with Et2O (3×20mL), washed with water and brine, dried with anhydrous MgSO4 and concentrated in vacuo. The resulting oil was purified by column chromatography to afford the desired product. |
| 84% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With copper (I) iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene at 60℃; for 12h; Autoclave; Schlenk technique; Supercritical conditions; Green chemistry;
Stage #2: With hydrogenchloride In lithium hydroxide monohydrate Green chemistry; |
General procedure for CuI and DBU mediated carboxylation of terminal alkynes with CO2
General procedure: CuI (7.6 mg, 0.04 mmol), Alkyne (2.0 mmol), DBU (609 mg,4.0 mmol) were added to a 50 mL autoclave with a stir bar after the air was evacuated, respectively. The autoclave was pressurized to 8 MPa by CO2 at50 C. The reaction mixture was stirred for 12 h. After the reaction wasfinished, the system was cooled to room temperature and CO2 was carefullyreleased from the autoclave. The residue was diluted with water and thenacidified with aqueous HCl (2 N) at a low temperature. The mixture wasextracted with diethyl ether (4 30 mL). The combined organic layers werewashed with water and brine, respectively, dried over anhydrous Na2SO4, andfiltered. The solvent was removed under vacuum and the products (1b-9b)were obtained. |
| 83% |
With Cs2CO3 In N,N-dimethyl-formamide at 80℃; for 12h; |
|
| 82% |
With 18-crown-6 ether; caesium fluoride; trimethylsilylacetylene In dimethyl sulfoxide at 30℃; for 20h; Glovebox; Schlenk technique; |
|
| 80% |
With tetrabutylammonium bromide; potassium carbonate In dichloromethane at 60℃; for 18h; |
3 Example 3: Synthesis of 4-chlorophenylpropynoic acid
Potassium carbonate (552 mg, 4 mmol, 400 mol%) was accurately measured in a glove box,(Tetramethylammonium bromide) (644.6 mg, 2 mmol, 200 mol%), purified dichloromethane (5.0 mL)4-chlorophenylacetylene (136.5 mg, 1 mmol) was added successively to a 25 mL of reaction kettle,Glove box filled with CO2 (2MPa). The reaction vessel was closed and placed in an oil bath at 60 ° C for 18 h.After completion of the reaction, the reaction vessel was slowly cooled to room temperature, and then the remaining gas was slowly released.The remaining reaction solution in the autoclave was transferred to a single-necked flask, and 1 M hydrochloric acid was added to acidify to pH =The extract was extracted with ethyl acetate, the organic phase was collected, the solvent was removed in vacuo,Separation by silica gel column (eluent: petroleum ether / ethyl acetate = 6/1)To give 145 mg of 4-chlorophenylpropyne acid in a yield of 80%. |
| 78% |
Stage #1: 4-n-chlorophenylacetylene With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; for 0.000833333h; Flow reactor;
Stage #2: carbon dioxide In tetrahydrofuran at 20℃; for 0.000138889h; Flow reactor;
Stage #3: With lithium hydroxide monohydrate In tetrahydrofuran at 20℃; Flow reactor; |
|
| 73% |
With tetrabutylammonium bromide; copper (II) acetate; potassium carbonate In dichloromethane at 25℃; for 18h; Inert atmosphere; |
3 Example 3 Synthesis of 4-chlorophenylpropynic acid
Copper acetate (10 mg, 0.05 mmol), potassium carbonate (552 mg, 4 mmol), n-tetrabutylammonium bromide (644.6 mg,(272.2 mg, 2 mmol) 4-chlorophenylacetylene (136.5 mg, 1 mmol) were added sequentially to a 25 mL reaction kettle and the mixture was purged with nitrogen three times. Purified methylene chloride (5.0 mL), charged with CO2 (0.1MPa). Closed reactor, placed in a 25 ° C oil bath reaction 18h, after the reaction, open the valve on the reactor slowly release the remaining gas, and then the reaction vessel was transferred to a single port flask to concentrate, and with 5mL deionized water Diluted and then extracted with n-hexane. The aqueous layer was acidified to pH = 1 at low temperature by addition of 1 M hydrochloric acid and extracted with ether. The organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and the solvent removed in vacuo. 4-chlorophenylpropynoic acid was obtained in a yield of 73%. |
| 72% |
With [Cu4(μ3-OH)2(atrz)2(SIP)2]•4H2O}n; Cs2CO3 In N,N-dimethyl-formamide at 100℃; for 16h; Autoclave; |
|
| 72% |
With Cs2CO3 In dimethyl sulfoxide at 60℃; Schlenk technique; Green chemistry; |
|
| 71% |
With 1,3-bis(4-methylbenzyl)imidazol-2-ylidene silver(I) chloride; Cs2CO3 In N,N-dimethyl-formamide at 20℃; for 16h; Schlenk technique; |
|
| 71% |
With Cs2CO3 In N,N-dimethyl-formamide at 60℃; for 14h; |
|
| 64% |
With [3,5-(CF3)2Pz]Cu}3 In N,N-dimethyl-formamide at 20℃; for 12h; |
|
| 63% |
Stage #1: 4-n-chlorophenylacetylene; carbon dioxide With [Cu(1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene)2(NO3)2]n; Cs2CO3 In N,N-dimethyl-formamide at 100℃; for 16h; Autoclave;
Stage #2: With hydrogenchloride In lithium hydroxide monohydrate |
2.5. General procedure for carboxylation of the terminal alkynes
General procedure: In a typical experiment, a 50-mL stainless steel autoclave, equipped with a magnetic stirring bar, was charged with catalyst (40.6 mg, 1 mol%), Cs2CO3 (1.96 g, 6 mmol), 1-ethynylbenzene (0.41 g, 4.0 mmol) and DMF (20 mL). Once added, CO2 (0.3 MPa) was introduced into the reaction mixture under stirring at 100 °C for 16 h. After the reaction, the mixture was cooled to room temperature and monitored by high performanceliquid chromatography (HPLC, Shimadzu LC-10AD) with a UV detector at 241 nm, a Hypersil ODS2 column (250 mm 4.6 mm, 5μm), and a mixture of methanol and H2O (3/1, v/v) as eluent with a flow rate of 0.8 mL min1. The conversions and yields were determined by HPLC analysis using 1-ethynylbenzene and phenylpropiolic acid as standards, respectively. The catalyst was recovered in the solid residue after centrifugation and separation from the organic layer (DMF solution). For the other terminal alkynes, after the reaction, the solid residue was separated via centrifugation, and the filtrate was diluted with water (30 mL). The mixture was washed with CH2Cl2 (20 mL 3) and the aqueous layer was acidified with concentrated HCl (6 mol L1) to pH 1, then extracted with CH2Cl2 (20 mL 3). The combined organic layers were dried over anhydrous Na2SO4, filtered and then evaporated. The residue was purified by column chromatography on silica gel with petroleum ether/ethyl acetate/formic acid (200/100/1, v/v/v) as the eluent to afford the propiolic acids. |
|
Stage #1: 4-n-chlorophenylacetylene With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Schlenk technique;
Stage #2: carbon dioxide In tetrahydrofuran at -78 - 0℃; for 0.5h; Inert atmosphere; Schlenk technique; |
|
|
Stage #1: 4-n-chlorophenylacetylene With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Schlenk technique;
Stage #2: carbon dioxide In tetrahydrofuran at 0℃; Inert atmosphere; Schlenk technique; |
|
|
With 18C8H9S(1-)*Ag24Au(18+); Cs2CO3 In N,N-dimethyl-formamide at 50℃; Autoclave; |
|
|
With potassium carbonate In dimethyl sulfoxide at 50℃; for 24h; |
|
|
Stage #1: 4-n-chlorophenylacetylene With n-butyllithium In hexane; toluene at -30℃; for 0.25h; Inert atmosphere;
Stage #2: carbon dioxide In hexane; toluene at -30 - 25℃; Inert atmosphere; |
|
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