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CAS No. : | 1591-31-7 | MDL No. : | MFCD00019028 |
Formula : | C12H9I | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NXYICUMSYKIABQ-UHFFFAOYSA-N |
M.W : | 280.10 | Pubchem ID : | 15322 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P302+P352-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 5h;Inert atmosphere; | General procedure: Compounds (1b-1o) were prepared according to literature.17 To a mixture of Pd(PPh3)2Cl2 (70 mg, 2 mol%), CuI (38 mg, 4 mol%) and DMF (7 mL) taken in a flask, aryl iodide (5.0 mmol), propiolic acid (414 mg, 6.0 mmol) and diisopropylamine (1.30 g, 12.5 mmol) were added in that sequence under nitrogen atmosphere. After stirring the reaction mixture at room temperature for 5 h, the resulting mixture was diluted with ethyl acetate, filtered through Celite bed, the filtrate was washed with cold aqueous KOH solution (1 x 100 mL) and acidified with dilute sulfuric acid (10% solution) at 0 C. The solid obtained was extracted with dichloromethane and the extract was washed with water, brine solution and dried over anhydrous sodium sulfate. The organic layer was concentrated in vacuum at 40 C, dried to get the arylpropiolic acids. | |
With tetrakis(triphenylphosphine) palladium(0); 1,8-diazabicyclo[5.4.0]undec-7-ene; In dimethyl sulfoxide; at 20℃; for 12h; | In a reaction vessel, p-iodobiphenyl (10.0 mmol), DBU (3.66 g, 24 mmol, 2.4 equiv), Pd(PPh4)3 (288 mg, 0.26 mmol, 2.5 mol %) was dissolved in 12 ml of DMSO.Solution a was formed, then propynoic acid (840 mg, 12 mmol, 1.2 equiv) was dissolved in 12 ml of DMSO to form solution b, and finally solution b was slowly added dropwise to solution a.The reaction was allowed to stir at room temperature for 12 hours. After the reaction was completed, 25 ml of ethyl acetate was added to the reaction solution.Extract with saturated sodium bicarbonate solution, collect the aqueous layer, and adjust the pH to 2.0 with 1 mol/L hydrochloric acid.Finally, the organic layer was extracted with dichloromethane, the organic phase was separated, and the water was removed with anhydrous sodium sulfate.After drying, the solvent was distilled off under reduced pressure to obtain a crude product, and the crude product was separated by column chromatography to obtain a 3-(1,1'-biphenyl)propiolic acid compound. | |
With tetrakis(triphenylphosphine) palladium(0); 1,8-diazabicyclo[5.4.0]undec-7-ene; In dimethyl sulfoxide; at 35℃; for 10h;Inert atmosphere; | To a 100 mL of round-bottom flask were added Pd(PPh3)4 (577.8 mg, 5 mol%), aryl iodide (10.0 mmol, 1.0 equiv), DBU (3.040 g, 20 mmol, 2.0 equiv) and DMSO (15 mL). Then the solution of propiolic acid (771 mg, 11 mmol, 1.1 equiv) in DMSO (5 mL) was added dropwise. The round-bottom flask was put into a preheated oil bath (35 C). After stirring for 10 h, the reaction mixture was cooled to room temperature. The reaction mixture was diluted with EtOAc, and extracted with saturated aqueous NaHCO3 solution. The aqueous layer was separated, acidified to pH 2.0 by cold HCl (1N), and extracted with CH2Cl2. The combined organic layers were dried with Na2SO4, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified by flash chromatography on silica gel (PE/EA = 2:1 with HOAc (1%, v/v)) to give 1b-1q. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With copper(II) oxide; potassium hydroxide; In N,N-dimethyl-formamide; at 154℃; for 5h;Inert atmosphere; | To a solution of 3 (1.5 g, 7.5 mmol), 4-iodo-1, 1'-biphenyl (1.8 g, 8.3 mmol), KOH (0.87 g, 16.5 mmol) and CuO (0.26 g, 3.2 mmol) in 20 mL of DMF. After refluxing at 154 C under N2 protection for 5 h, the solution was poured into 300 mL of HCl (0.5 mol/L) with off white solid precipitation. The solid particles were filtered from water, the solid was then dissolved using EtOAc. The insoluble impurities were filtered from solution and the EtOAc was distillated under reduced pressure. Finally, the brown oil was purified by silica gel chromatography (PE/EA = 5:1, 0.3% HOAc) to generate compound 7b as a yellow powder solid. Yield: 41%, mp: 160-162 C. 1H NMR (400 MHz, DMSO-d6) delta 12.22 (s, 1H), 7.88 (d, J = 8.5 Hz, 2H), 7.82-7.70 (m, 2H), 7.57-7.46 (m, 4H), 7.42 (t, J = 7.4 Hz, 1H), 7.04 (d, J = 2.4 Hz, 1H), 7.01 (d, J = 8.8 Hz, 1H), 6.71 (dd, J = 8.8, 2.4 Hz, 1H), 3.79 (s, 3H), 3.68 (s, 2H), 2.26 (s, 3H). |