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CAS No. : | 935-14-8 | MDL No. : | MFCD00078375 |
Formula : | C10H6 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MVLGANVFCMOJHR-UHFFFAOYSA-N |
M.W : | 126.15 | Pubchem ID : | 120463 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 42.31 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.36 cm/s |
Log Po/w (iLOGP) : | 2.44 |
Log Po/w (XLOGP3) : | 2.41 |
Log Po/w (WLOGP) : | 1.81 |
Log Po/w (MLOGP) : | 4.3 |
Log Po/w (SILICOS-IT) : | 3.11 |
Consensus Log Po/w : | 2.81 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.58 |
Solubility : | 0.328 mg/ml ; 0.0026 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.05 |
Solubility : | 1.12 mg/ml ; 0.00887 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.52 |
Solubility : | 0.38 mg/ml ; 0.00301 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.54 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280 | UN#: | N/A |
Hazard Statements: | H317 | 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 |
---|---|---|
67% | With silver(I) nitrite; trichloroisocyanuric acid In acetonitrile at 20℃; for 8 h; Sealed tube | 4-ethynylphenylacetylene 63 mg (0.50 mmol), silver nitrite 154 mg (1 mmol), trichloroisocyanuric acid 232.4 mg (1 mmol)Add 10 mL of pressure-resistant sealed container in turn, and then add 5 mL of acetonitrile.The mixture was stirred at room temperature, and the reaction was checked by TLC. The reaction was completed in 8 hours.The reaction solution was diluted with 10 mL of dichloromethane, and filtered to give a clear liquid.Separation by column chromatography (with petroleum ether / ethyl acetate volume ratio of 100:1 as eluent)The eluate containing the desired product were collected and the solvent was evaporated to give a white solid 4-ethynyl-benzonitrile 42.5mg (67percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In diphenylether at 149.84℃; for 24h; Inert atmosphere; | |
65% | With 1,2,4-Trimethylbenzene at 180℃; for 48h; | General Procedure for the Diels-Alder Reaction: General procedure: 1,2,4-Trimethylbenzene (25 mL) was added to a mixture of phencyclone(1.0 g, 1.25 mmol) and 1,4-diethynylbenze (0.15 g,1.19 mmol) in a flask, and heated under reflux at 180 °C for 48 h. The reaction mixture was filtered by EtOH. The crude solid dissolved in toluene was filtered, and evaporated under reduced pressure. The crude product was then recrystallized from tetrahydrofuran/EtOH. |
With decahydronaphthalen-2-ol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With C28H26CuN8O10; sodium L-ascorbate In ethanol; water at 20℃; for 0.416667h; | 2.4 Typical Procedure forCuAAC General procedure: A 20-mL round-bottomed flask equipped with a magnetic stirrerwas charged with benzyl azide (0.133g, 1mmol), phenylacetylene (102g, 1mmol), and the copper(II) nitrate pyranopyridinecomplex 1 (1mol%). A solution of sodium ascorbate(0.5 equiv.) in 1:1 ethanol-water mixture (6mL) wasadded into it and stirred at room temperature for 10min. Aftercompletion of the reaction, as evident from TLC, ethanol wasremoved in a rotavapor under reduced pressure and the aqueoussolution was extracted with ethyl acetate (3 × 10mL).The organic part was dried over Na2SO4and the solventwas removed under reduced pressure to obtain the triazolederivative 3a in 94% yield (0.221g) as white solid with excellentpurity. |
In toluene at 110℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium carbonate In methanol; dichloromethane at 20℃; for 1h; | |
100% | With water; potassium hydroxide In methanol for 1h; | |
97% | With potassium carbonate In methanol at 20℃; |
95% | With potassium carbonate In methanol; dichloromethane at 20℃; for 12h; Inert atmosphere; | 2.2.3. Preparation of compound (3) General procedure: In a 100 mL three-neck flask, compound 2 (100 mg, 0.124 mmol)and K2CO3 (20 mg) were dissolved in solution of DCM (20 mL) andmethanol (20 mL). The mixture was stirred for 12 h at room temperature.The resulting mixture was extracted by dichloromethanefor 3 times, and then the organic phase was collected andconcentrated by a rotary evaporator. The crude material was purifiedby silica gel column chromatography using a mixture of petrolether and DCM (v:v 4:1) as the eluent to obtain the desiredproduct as a purple solid (60.8 mg, 74%). |
95% | With tetrabutyl ammonium fluoride In tetrahydrofuran at 25℃; for 0.25h; Inert atmosphere; | |
92% | With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 1h; | |
91% | With methanol; sodium hydroxide In dichloromethane at 20℃; for 12h; | |
91% | With methanol; potassium fluoride In tetrahydrofuran at 60℃; for 4h; | |
90% | With methanol; potassium hydroxide In dichloromethane at 20℃; for 3h; | |
90% | With potassium trimethylsilonate In dimethyl sulfoxide at 60℃; for 12h; Sealed tube; | 34 1,4-bis[(trimethylsilyl)ethynyl]benzene (1 mmol), inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) (0.1 (2 mmol), 2 mL of DMA or DMSO solvent were sequentially added to a 10 mL sealed tube, and the mixture was heated and stirred in a 60°C oil bath for 12 hours. The progress of the reaction was followed according to TLC. After the reaction was completed, an equivalent of mesitylene or tetradecane was added to the crude product. Alkane was used as an internal standard to determine the exact yield of the product by GC and GC-MS. According to GC and GC-MS, when DMSO is used as a reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) is used as a catalyst, and the yields of the products are as follows: : 63%, 69%, 75%, 79%, 90%, 86%. When DMA was used as the reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) was used as a catalyst. The yield of the product was: 55%, 58%, 63%, 69%, 79%, 73%. |
90% | With methanol; potassium carbonate In dichloromethane at 20℃; for 4h; | |
88% | With potassium hydroxide In methanol | |
86% | With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; for 1h; | |
83% | With potassium trimethylsilonate In dimethyl sulfoxide at 70℃; for 12h; Sealed tube; Schlenk technique; | |
81% | With tetrabutyl ammonium fluoride In tetrahydrofuran | |
81% | With potassium hydroxide In methanol; dichloromethane; water at 20℃; for 3h; | |
79% | With potassium hydroxide In tetrahydrofuran; methanol; water for 3h; | |
78% | With potassium hydroxide In methanol; dichloromethane for 2.5h; Ambient temperature; | |
77% | With potassium carbonate In methanol at 20℃; for 1h; | |
71% | With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 2h; Inert atmosphere; | |
70% | With potassium hydroxide In methanol; dichloromethane for 3h; | |
68.3% | With potassium carbonate In tetrahydrofuran; methanol for 3h; Darkness; | |
49.4% | With potassium hydroxide In tetrahydrofuran; methanol at 20℃; for 4h; Inert atmosphere; | |
With potassium carbonate In methanol | ||
With potassium hydroxide In methanol; dichloromethane at 20℃; for 2.5h; | ||
With tetrabutyl ammonium fluoride In tetrahydrofuran for 0.5h; | ||
With sodium carbonate In methanol | ||
With potassium carbonate In methanol for 16h; | ||
With potassium carbonate In methanol at 20℃; for 16h; | ||
With potassium carbonate In methanol at 20℃; | ||
With potassium hydroxide In tetrahydrofuran; methanol for 1h; | ||
With methanol; potassium hydroxide; water In dichloromethane at 20℃; for 18h; | 14 Synthesis Example 141,4-diethynylbenzene was prepared as follows. Firstly, a mixture of 1,4-diiodobenzene (4 g, 12.1 mmol), PdCl2(PPh3)2 (340 mg, 0.484 mmol) and CuI (92.4 mg, 0.484 mmol), was added with dist. THF (20 mL), dist. Et3N (60 mL) and trimethylsilylacetylene (3.77 mL, 26.7 mmol). The resultant mixture was stirred under a nitrogen atmosphere at 80° C. for 22 hours to obtain a reaction mixture. Then, the reaction mixture was diluted with CH2Cl2. After that, an organic layer was washed with sat. NaCl, and dried with MgSO4. The dried organic layer was filtered and concentrated to obtain a crude product. The obtained crude product was separated and purified by silica gel column chromatography (hexane/EtOAc=10/1) to obtain 1,4-diethynylbenzene.Subsequently, the obtained 1,4-bis(trimethylsilylethynyl)benzene (500 mg, 1.85 mmol) was added with dist. CH2Cl2 (15 mL), dist. MeOH (3 mL) and an aqueous solution of potassium hydroxide (KOH) (0.4 mL) of 50% by mass. The resultant mixture was stirred under a nitrogen atmosphere at room temperature for 18 hours to obtain a reaction mixture. Then, the reaction mixture was diluted with CH2Cl2. After that, an organic layer was washed with sat. NaCl, and dried with MgSO4. The dried organic layer was filtered and concentrated to obtain a crude product. Subsequently, the obtained crude product was separated and purified by silica gel column chromatography (hexane/EtOAc=20/1) to obtain 1,4-diethynylbenzene (147 mg, 63% yield (in two steps)).The obtained compound was subjected to a 1H NMR measurement. The obtained result is shown below.1H NMR (CDCl3) δ7.44 (s, 4H), 3.17 (s, 2H)From the NMR measurement result, it was confirmed that the obtained compound was 1,4-diethynylbenzene. | |
With methanol; potassium carbonate In tetrahydrofuran | ||
With potassium carbonate In methanol at 20℃; | ||
With potassium hydroxide | ||
With tetrabutyl ammonium fluoride | ||
With tetrabutyl ammonium fluoride In tetrahydrofuran; water at 20℃; for 5h; Inert atmosphere; | ||
With potassium carbonate In methanol; water | 1 Materials and Methods 1,4-diethynylbenzene Methanol was added to a 100 mL round-bottomed flask. 1,4-bis((trimethylsilyl)ethynyl)benzene (0.63 mmol, 0.17 g) and K2CO3 (3.2 mmol, 0.44 g) were added. The mixture was allowed to stir at room temperature for 1 hr. under nitrogen. Methanol was removed under reduced pressure. Residual white solid was dissolved in water and washed twice with ether. The organic layer was collected and solvent removed under reduced pressure to yield a white solid (0.47 mmol, 0.059 g, 15%), which was used immediately without further purification. 1H NMR (400 MHz, CDCl3) δ: 7.42 (s, 2H), 3.15 (s, 1H). | |
With methanol; potassium carbonate In dichloromethane | ||
With potassium carbonate In methanol; water | 1 1,4-diethynylbenzene 1,4-diethynylbenzene Methanol was added to a 100 mL round-bottomed flask. 1,4-bis((trimethylsilyl)ethynyl)benzene (0.63 mmol, 0.17 g) and K2CO3 (3.2 mmol, 0.44 g) were added. The mixture was allowed to stir at room temperature for 1 hr. under nitrogen. Methanol was removed under reduced pressure. Residual white solid was dissolved in water and washed twice with ether. The organic layer was collected and solvent removed under reduced pressure to yield a white solid (0.47 mmol, 0.059 g, 15%), which was used immediately without further purification. 1H NMR (400 MHz, CDCl3) δ: 7.42 (s, 2H), 3.15 (s, 1H). | |
With potassium hydroxide In methanol | ||
With sodium hydroxide | ||
1.39 g | With potassium carbonate In methanol at 20℃; for 4h; | Diethynylbenzene (3) In a 250 mL three-necked round-bottomed flask was added 1,4-diiodobenzene (1; 5.0 g, 15.19 mmol), PdCl2(PPh3)2 (1.06 g, 1.51mmol), CuI (144 mg, 0.75 mmol), ethynyltrimethylsilane (2; 4.92 mL,34.94 mmol), anhyd THF (60 mL), and Et3N (10 mL, 72.91 mmol) underN2 atmosphere. Then the reaction mixture was stirred for 2 h atRT, and then filtered through a pad of Celite. The filter cake waswashed with EtOAc (100 mL) and the filtrate was washed with sat. aqNH4Cl (100 mL). The organic layer was dried (anhyd Na2SO4) and concentrated.The crude product was purified by column chromatographyusing PE as solvent to afford 1,4-bis[(trimethylsilyl)ethynyl]benzene;yield: 4.18 g (~100%); yellow solid.1H NMR (300 MHz, CDCl3): = 7.38 (s, 4 H), 0.24 (s, 18 H).12In a 250 mL round-bottomed flask, a mixture of 1,4-bis[(trimethylsilyl)ethynyl]benzene (4.18 g, 15.48 mmol), K2CO3 (8.54 g, 61.92mmol), and MeOH (80 mL) was stirred for 4 h at RT. The mixture wasconcentrated and redissolved in CH2Cl2 (150 mL). The organic phasewas washed with sat. aq NaHCO3 (100 mL), dried (anhyd Na2SO4) andconcentrated. The resulting residue was purified by column chromatographyusing PE as eluent to afford 3; yield: 1.39 g (71%); brown solid.1H NMR (300 MHz, CDCl3): = 7.43 (s, 4 H), 3.16 (s, 2 H).12 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Comparable results were obtained in the conversion of p-diacetylbenzene to p-diethynylbenzene following the procedure of this example. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With aluminum oxide; N-iodo-succinimide In acetonitrile at 80℃; for 1h; Molecular sieve; | |
98% | With N-iodo-succinimide; acetic acid In acetonitrile at 80℃; for 1.5h; Molecular sieve; | 2 Example 2: Synthesis of 1,4-(diiodoethynyl)benzene Combine 1,4-diethynylbenzene (2.0 mmol, 252.3 mg), acetonitrile (10 mL), 4A molecular sieve (200 mg), N-iodosuccinimide (2.2 mmol, 495.0 mg) and acetic acid (5.2 .0mmol, 312.2mg, 0.3ml) were added to a 25 mL reaction flask, and then heated to 80 for 1.5 h, after the reaction was completed, saturated sodium thiosulfate solution was added to quench the reaction, ethyl acetate extraction, saturated brine Washed, dried over anhydrous sodium sulfate, filtered, the filtrate was removed solvent under reduced pressure, using petroleum ether as eluent, silica gel column chromatography separation to obtain brownish yellow solid 1,4- (diiodoethynyl)benzene, yield 98%. |
98% | With N-iodo-succinimide; acetic acid In acetonitrile at 80℃; for 1.5h; Molecular sieve; | Iodination of Terminal Alkynes; General Procedure: General procedure: To amixture of terminal alkynes (2.0 mmol), acetic acid (2.6 mmol)and 4 Å MS (200 mg) in MeCN (10 mL) was added N-iodosuccinimide(2.2 mmol) and the resulting mixture was heated at 80 °Cfor 1.5 h. After completion of the reaction, the reaction wasquenched with saturated aqueous sodium thiosulfate and themixture was extracted with ethyl acetate (10 × 3 mL). The combinedorganic layers were dried over anhydrous sodium sulfate,filtered and concentrated under vacuum. The residue was purifiedby flash column chromatography on silica gel. |
95% | With N-iodo-succinimide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 0.666667h; Green chemistry; | |
92% | With dmap; iodine In dichloromethane for 12h; Heating; | |
90% | With N-iodo-succinimide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 0.0166667h; Inert atmosphere; | Preparation of 1,4-di(2-iodoethynyl)benzene reactant 1,4-diethynyl benzene (126mg, 1.0mmol) was dissolved in 2.0mL acetonitrile in a nitrogen atmosphere for 30 minutes, was added N- iodosuccinimide (NIS) 247.5mg (1.1mmol) and 1,8 - diazabicyclo [5.4.0]undec-7-ene (DBU) 0.159mL (1.1mmol). After stirring at room temperature for 1minute, the reaction system was poured into water and extracted with dichloromethane (3 × 10mL), dried over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure, it was purified by a silica gel column to give a white solid 1,4-di (2-iodoethynyl) benzene (340mg, 90%). |
90% | With N-chlorobenzenesulfonamide; potassium iodide In acetonitrile at 20℃; for 4h; | General Procedure for the Synthesis of 1-Iodoalkynes General procedure: A 25 mL round-bottom flask with a magneton was charged withterminal alkyne 1 (0.5 mmol), KI (99 mg, 1.2 equiv), and MeCN(3 mL) under air at room temperature, and then chloramine-B(160 mg, 1.5 equiv) was added. The mixture was stirred for 2 h.After that, the reaction mixture was filtered. The filtrate wasconcentrated under reduced pressure. Purification of theresidue by flash column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent afforded the desiredproduct 2. |
80% | Stage #1: 1,4-diethynylbenzene With silver nitrate for 0.5h; Darkness; Cooling with ice; Stage #2: With N-iodo-succinimide at 20℃; Cooling with ice; Darkness; | |
With n-butyllithium; iodine 1.) hexane, THF, 0 deg C, 2 h, 2.) THF, hexane, from -78 deg C to RT; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With n-butyllithium | |
73% | Stage #1: 1,4-diethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; Further stages.; | |
50% | With n-butyllithium In tetrahydrofuran Inert atmosphere; |
With n-butyllithium In tetrahydrofuran at -78℃; | ||
With n-butyllithium Inert atmosphere; | ||
With n-butyllithium In tetrahydrofuran at 50℃; | ||
Stage #1: 1,4-diethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; Inert atmosphere; | ||
60 g | Stage #1: 1,4-diethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 6h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane for 24h; | 1 (Synthesis of Compound 5) After dissolving about 100 g of Compound 4 (1,4-diethynylbenzene) in tetrahydrofuran, the mixture was stirred for about 20 min at about -78 °C. About 500 ml of n-butyl lithium in 2.5M hexane was added thereto dropwise for about 2 h. After stirring the same for about 4 h, about 100 ml of chlorotrimethylsilane was added thereto and the mixture was stirred for about 24 h. Then, about 60 g of Compound 5 was obtained by extracting the reacted product with ethyl acetate and water, chemically drying the obtained organic layer, and refining the same with column chromatography. |
60 g | Stage #1: 1,4-diethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 6h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane for 24h; | 1 Synthesis of Compound 5 Synthesis of Compound 5 (0096) After dissolving about 100 g of Compound 4 (1,4-diethynylbenzene) in tetrahydrofuran, the mixture was stirred for about 20 min at about -78° C. About 500 ml of n-butyl lithium in 2.5M hexane was added thereto dropwise for about 2 h. After stirring the same for about 4 h, about 100 ml of chlorotrimethylsilane was added thereto and the mixture was stirred for about 24 h. Then, about 60 g of Compound 5 was obtained by extracting the reacted product with ethyl acetate and water, chemically drying the obtained organic layer, and refining the same with column chromatography. |
60 g | Stage #1: 1,4-diethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 6.33333h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane for 24h; | 1 (Synthesis of Compound 5) After about 100 g of compound 4 (1,4-diethynylbenzene) was dissolved in tetrahydrofuran,The mixture was stirred at about -78 deg.] C for about 20 minutes.About 500 ml of n-butyllithium dissolved in 2.5 M hexane was added dropwise over about 2 hours.After stirring for about 4 hours,About 100 ml of chlorotrimethylsilane was added,And the mixture was stirred for about 24 hours.then,The reaction product was extracted with ethyl acetate and water,The organic layer obtained by chemical drying,And the column chromatography was carried out using column chromatography to give about 60 g of compound 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 60℃; for 18h; Inert atmosphere; Schlenk technique; | |
67% | With copper(l) iodide; diisopropylamine In tetrahydrofuran at 47℃; for 3.75h; | |
51% | With bis-triphenylphosphine-palladium(II) chloride; copper (I) iodide; diethylamine for 36h; Ambient temperature; |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diethylamine at 20℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With N-Bromosuccinimide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 0.666667h; Green chemistry; | |
91% | With N-Bromosuccinimide; silver nitrate In acetone for 15h; | |
71% | With N-chlorobenzenesulfonamide; sodium bromide In water; acetonitrile at 70℃; for 24h; | General Procedure for the Synthesis of 1-Bromoalkynes General procedure: A 25 mL round-bottom flask with a magneton was charged withterminal alkyne 1 (0.5 mmol), NaBr (77 mg, 1.5 equiv), andMeCN/H2O (3:1, 4 mL,) under air at room temperature, and thenchloramine-B (320 mg, 3.0 equiv) was added. The mixture wasstirred at 70 °C for 24 h. After that, the reaction mixture wascooled to room temperature and then filtered. The filtrate wasconcentrated under reduced pressure. Purification of theresidue by flash column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent afforded the desiredproduct 3. |
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine In tetrahydrofuran at 50℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; | |
95% | With caesium carbonate; dimethyl sulfoxide at 115℃; for 12h; | |
84% | With Succinimide; potassium carbonate In dimethyl sulfoxide at 90℃; for 2h; Schlenk technique; Inert atmosphere; | General procedure for terminal alkynes preparation: General procedure: To an oven-dried Schlenk tube, 1,1-dibromoalkene (1 equiv), succinimide (2 equiv), K2CO3 (6 equiv) were added along with dry DMSO (3 mL). This mixture was stirred at 90°C for 2h. After that, the mixture was cooled to room temperature and extracted with ethyl acetate (30mL) and washed with water (10mL) followed by brine solution (10mL). The organic extract was dried over dry MgSO4 and concentrated. The pure product was obtained by silica gel column chromatography using ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0) | |
99% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 80℃; for 12h; Inert atmosphere; | |
99% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 80℃; for 12h; Inert atmosphere; |
99% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0) Inert atmosphere; | |
99% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 80℃; for 12h; Inert atmosphere; | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(l) iodide; triethylamine; triphenylphosphine In tetrahydrofuran at 20℃; for 10h; | |
65% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; triethylamine at 20 - 80℃; for 24.33h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(l) iodide; triethylamine; triphenylphosphine In tetrahydrofuran at 20℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(l) iodide; diisopropylamine In tetrahydrofuran at 25℃; |
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 |
---|---|---|
95% | With lithium hexamethyldisilazane In toluene at 100℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; | |
93% | In neat (no solvent) at 110℃; for 12h; Inert atmosphere; | |
91% | With bis(trimethylsilyl)amide yttrium(III) In toluene at 100℃; for 24h; Inert atmosphere; | 5 The preparation of 1,4-bis((E)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)benzene, the structural formula is as follows : Under the protection of nitrogen, add raw material 1,4-phenylacetylene (0.5mmol), and catalyst Y[N(SiMe3)2]3 (1mol%), HBpin (1.2mmol), toluene (2mL), react at 100 for 24h, the product Separation yield 91% |
88% | With triethylamine In cyclohexane (N2); addn. of a soln. of alkyne in cyclohexane to a soln. of rhodium complex, amine, phosphine and boron compd. in cyclohexane at room temp., stirring for 4 h at room temp.; evapn., column chromy. (silica gel, CH2Cl2/hexane 2:1); elem. anal.; | |
80% | With p-N,N-dimethylaminobenzoic acid In octane at 100℃; for 12h; Inert atmosphere; | |
78% | With lithium hexamethyldisilazane In toluene at 100℃; for 24h; Inert atmosphere; | 7 Preparation method: Under the protection of nitrogen, add raw material 1,4-phenylacetylene (0.5mmol), pinacol borane (1.2mmol), catalyst LHMDS (7mol%) and organic solvent toluene (0.5mL) into the reaction vessel and stir and mix After mixing uniformly, react at 100°C for 24h, filter and purify to obtain the product; the product separation yield is 78%. |
75% | With zinc trifluoromethanesulfonate; sodium triethylborohydride In tetrahydrofuran; toluene at 80℃; for 10h; Schlenk technique; Inert atmosphere; regioselective reaction; | |
75% | With tropylium tetrafluoroborate In neat (no solvent) at 70℃; for 12h; Inert atmosphere; | |
45% | With silver hexafluoroantimonate In toluene at 20℃; for 48h; Schlenk technique; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With triethylamine In tetrahydrofuran at 50℃; for 13h; | 17 Example 171,4-bis[4-(diallylethoxysilyl)phenyethynyl]benzene was prepared as follows. Firstly, a mixture of 1,4-diethynylbenzene (58.5 mg, 0.46 mmol) obtained in Synthesis example 14, 4-(diallylethoxysilyl)iodobenzene (277 mg, 0.77 mmol), PdCl2(PPh3)2 (10.9 mg, 0.0155 mmol) and CuI (2.94 mg, 0.0155 mmol) was added with dist. THF (5 mL) and dist. Et3N (1 mL). The resultant mixture was stirred under a nitrogen atmosphere at 50° C. for 13 hours to obtain a reaction mixture. Then, the reaction mixture was diluted with ether. After that, an organic layer was washed with dist. H2O and sat. NaCl, and was dried with MgSO4. The dried organic layer was filtered and concentrated to obtain a crude product. Then, the obtained crude product was separated and purified by silica gel column chromatography (hexane/EtOAc=10/1) to obtain 1,4-bis[4-(diallylethoxysilyl)phenylethynyl]benzene (215.3 mg, 95% yield).The obtained compound was subjected to 1H NMR and 13C NMR measurements. The obtained results are shown below.1H NMR (CDCl3) δ7.57 (d, J=8.1 Hz, 4H), 7.54 (d, J=8.1 Hz, 4H), 7.49 (s, 4H), 5.89-5.73 (m, 4H), 4.99-4.90 (m, 8H), 3.77 (q, J=7.0 Hz, 4H), 1.94 (d, J=8.1 Hz, 8H), 1.22 (t, J=7.0 Hz, 6H).13C NMR (CDCl3) δ135.8, 133.9, 132.8, 131.5, 130.7, 124.3, 123.0, 114.9, 91.3, 90.0, 59.3, 21.1, 18.4.From the NMR measurement results, it was confirmed that the obtained compound was 1,4-bis[4-(diallylethoxysilyl)phenylethynyl]benzene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With diisopropylamine at 20℃; | 4 As illustrated in Fig. 13, 2 eq. of PEG-PDIBr (obtained in a reaction of equimolar amounts of 1,7-PDEBr2, PEGOH and NaH in THF, purified by SiO2 column, yield 79%) was mixed with 1 eq. of diethynyl benzene in diisopropyl amine at room temperature overnight in the presence of Pd catalyst. The product was separated using column chromatography (SiO2, chloroform/MeOH as an eluent). Yield 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With diisopropylamine In chloroform at 20℃; for 6h; | An exemplary synthesis scheme for S-OPE-I-EO is shown in Fig. 8. |
22% | With diisopropylamine In chloroform Inert atmosphere; | 11 5 (1.53 g, 5.01 mmol), CHC13 (21 mL), and diisopropylamine (2 mL) were mixed and degassed by purging argon gas for 30 min. 2 (383 mg, 3.0 mmol), Pd(PPh3)2C12(92 mg, 0.131 mmol) and Cul (46 mg, 0.24 mmol) were added to the mixture which was stirred overnight. The salt formed in the process was removed by filtration, and the solution was extracted with dichloromethane and washed with NH4C1 solution, H20, and saturated NaCl. The organic layer was dried over anhydrous MgS04 for 30 min, and filtered to remove the MgS04. The solvent was removed by vacuum rotary evaporation, and the residual solid was purified by column chromatography using a mixture of CH2C12 and CH30H to give 520 mg of a white solid. Yield: 22%. 1H NMR (CDC13, 500 MHz), δ 7.444 (m, 8H), 6.865 (d, 4H), 1H NMR (DMSO-d6, 500MHz), δ 4.054 (t, 4H), δ 2.461 (t, 4H), δ 2.264 (s, 12H), δ 1.970 (m, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In N,N-dimethyl-formamide at 50℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diethylamine In N,N-dimethyl-formamide at 60℃; for 16h; Inert atmosphere; | |
71% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique; | General procedure for the preparation of the alkynylanilines 2 General procedure: In a typical reaction, PdCl2(PPh3)2 (88 mg, 0.125 mmol), CuI (24 mg, 0.125 mmol) and THF (5 ml) were placed in an oven-dried, 2-neck RB flask. To this suspension, 2-iodoaniline (5.47 mg, 2.5 mmol) and triethylamine (702 μl, 5.0 mmol) were added. The reaction mixture was degassed by bubbling with argon for 15 min. Phenylacetylene (300 μl, 2.75 mmol) was then added, and the reaction mixture stirred at RT. After complete consumption of the 2-iodoanilines (~2 h, by TLC), the reaction mixture was filtered through celite, and the solvent rotary evaporated to obtain the crude product which was purified by silica gel (60-120 mesh) column chromatography using ethylacetate/ hexane (1:9, v/v) as eluent to give pure 2-phenylethynylaniline, 2a (400 mg, 83%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.8% | With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 120℃; for 0.5h; Inert atmosphere; microwave irradiation; | 8-1; 8.a Referring to Scheme 8-1, Pd(PPh3)2Cl2 (140 mg, 0.2 mmol) was added to a mixture of 1 (304 mg, 2.4 mmol), 2 (2.07 g, 4 mmol), Cul (20 mg, 0.1 mmol), PPh3 (208 mg, 0.8 mmol) and DIPA (2.24 mL, 16 mmol) in 8 mL DMF. The reaction mixture was flushed with nitrogen, heated with microwave at 120 °C for 30 min, amd then cooled to rt. The mixture was added to H20, extracted with EtOAc, washed with brine, dried over MgS04, filtered and concentrated in vacuo. The residue was purified by silica gel columnchromatography to provide 3 (1.37g, 62.8% yield) as an off-white solid. LC-MS (ESI): m/z calcd. for C48H52N608S2904.33, found 905.0 (M+H)+. |
62.8% | With copper(l) iodide; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 120℃; for 0.5h; Microwave irradiation; Inert atmosphere; | 8.a EXAMPLE 8 - Synthesis of compounds of Formula VIb[0366] Step a. Referring to Scheme 8-1, Pd(PPh3)2Cl2 (140 mg, 0.2 mmol) was added to a mixture of 1 (304 mg, 2.4 mmol), 2 (2.07 g, 4 mmol), CuI (20 mg, 0.1 mmol), PPh3 (208 mg, 0.8 mmol) and DIPA (2.24 mL, 16 mmol) in 8 mL DMF. The reaction mixture was flushed with nitrogen, heated with microwave at 120 °C for 30 min, amd then cooled to rt. The mixture was added to H2O, extracted with EtOAc, washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by silica gel column chromatography to provide 3 (1.37g, 62.8% yield) as an off-white solid. LC-MS (ESI): m/z calcd. for C48H52N6O8S2904.33, found 905.0 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With C16H20Cl2N2O2Pd; potassium hydroxide In water; acetonitrile at 20℃; for 1h; | 31. General procedure for Sonogashira coupling reaction General procedure: In a 10 mL round bottom flask, the palladium complex (0.010 mmol) was dissolved in acetonitrile (2 mL). Aryl halide (1.0 mmol), alkyne (1.2 mmol), KOH (2.00 mmol) and distilled water (2 mL) were added. The mixture was stirred at room temperature (or 60° C) for the required time. After reaction completion, the product was extracted with ethyl acetate (3x5 mL). The combined organic layers were dried with anhydrous sodium sulfate. The product was analyzed with GC and GC-MS. The product was purified using column chromatography with hexane-ethyl acetate as eluent. The characterization data were in entire agreement with the previously reported literature.32-39 |
97% | With 2,2′-(1,2-phenylene)bis(4,4-di-methyl-4,5-dihydrooxazole)-N,N′-dichloridopalladium(II); potassium hydroxide In water; acetonitrile at 20℃; for 1h; | |
69 %Spectr. | With 1,4-diaza-bicyclo[2.2.2]octane; palladium diacetate; silica gel for 0.333333h; Neat (no solvent); ball mill; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: 1,4-diethynylbenzene; methyl 3-tert-butyldimethylsilyloxy-2-diazobut-3-enoate With Rh2(S-PTAD)4 In dichloromethane at 0℃; for 2.5h; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride In dichloromethane at 23℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | 4.3. General procedure for Rh(II)-catalyzed decompositions of siloxyvinyldiazoacetate 5 in the presence of acetylenes General procedure: A mixture of alkyne 6 (0.5 mmol) and Rh2(S-PTAD)4 (0.01 mmol) was dissolved in 1 mL of dichloromethane and stirred at -45 °C under an atmosphere of argon. Siloxyvinyldiazoacetate 5 (1.0 mmol) in 10 mL dichloromethane was then added to the reaction mixture via syringe pump over 2 h. After the complete addition, the reaction mixture was stirred for additional 20 min followed by addition of TBAF (1.0 mmol) in one portion. The reaction mixture was further stirred at 23 °C followed by aqueous work-up. The organic layer was dried over MgSO4, filtered, and concentrated. The residue was purified on silica using 10:1 hexane/diethyl ether followed by 1:1 hexane/EtOAc as eluents to afford the desired cyclopropenyl ketones. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With palladium diacetate; triethylamine; triphenylphosphine In tetrahydrofuran at 110℃; for 20h; Autoclave; | 4.2. General procedure for the palladium-catalyzed acylation and homo-coupling reaction of terminal alkynes General procedure: A solution of terminal alkyne (1.0 mmol), aliphatic or aryl halide (1.5 mmol), Pd(AcO)2 (4 mg, 0.02 mmol), PPh3 (21 mg, 0.08 mmol), and Et3N (202 mg, 2.0 mmol) in THF (15 mL) was placed in a 45 mL autoclave. The autoclave was purged, pressurized (400 psi CO) and then heated at 110 °C, under magnetic stirring, for 6-36 h. After this time, the solution was cooled to room temperature and the solvent was removed under reduced pressure to give a crude material. The crude mixture was then purified by chromatography on silica gel (petroleum ether/Et2O 90:10) to afford, for each reaction shown in Table 1, the conjugated acetylenic ketone 1a-m and the corresponding diyne of the terminal alkyne 2a-f as pure compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium azide; [CuI(3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)3] In water; acetonitrile at 125℃; for 0.25h; Sealed tube; Microwave irradiation; | |
95% | With sodium azide; [(tris(3,5-dimethyl-1-pyrazolyl)methane)2Cu](BF4)2 In methanol; water at 125℃; for 0.5h; Microwave irradiation; | 4.7 General procedure for three-component azide alkyne cycloaddition reaction General procedure: A mixture of benzyl bromide (0.3mmol, 1 equiv.), acetylene derivative (0.33mmol, 1.1 equiv.), NaN3 (0.33mmol, 1.1 equiv.) and 1.5mL of solvent was charged to a 10mL pyrex vial equipped with a magnetic stirring bar. The catalyst (0.5-5mol%) was then added, the vial tightly sealed, placed in the microwave reactor and irradiated (10W) at 125°C for the periods of time indicated in Tables 1 and 2. A precipitate was formed, the reaction mixture was cooled to ambient temperature and 5mL of water were added to force a complete precipitation of the triazole product. The product was filtered off, washed repeatedly with petroleum ether and dried in vacuum. 1,4-bis(1-benzyl-1H-1,2,3-triazol-4-yl)benzene (Table 2, entry 6) was prepared according to the general procedure described above except 0.6mmol of benzyl bromide, 0.33mmol of 1,4-diethynylbenzene and 0.62mmol of sodium azide were used. |
89% | With sodium azide In water at 40℃; for 3h; | General procedure for the formation of triazoles General procedure: Polymer supported metal catalyst (25mg, 21×10-3mmol) in water (5mL) was taken in a 50mL round bottom flask. Then phenylacetylene (1mmol), sodium azide (1.2mmol) and benzyl bromide (1mmol) were added and stirred at room temperature for 180 min. After the completion of the reaction, the catalyst was filtered off and washed with water followed by acetone and dried in oven. The filtrate was extracted with ethyl acetate (3×20ml) and the combined organic layers were dried with anhydrous Na2SO4 by vacuum. All the prepared compounds were confirmed by 1H and 13C NMR. |
84% | With sodium azide; copper(I) oxide In water at 100℃; for 1h; | 2.6 General procedure for the synthesis of bis-1,2,3-triazoles (Method-2) General procedure: The above-mentioned procedure was followed using 1,3-diethynylbenzene or 1,4-diethynylbenzene (0.5 mmol, 1equiv.), benzyl bromide (1.2 mmol, 1.2 equiv.) sodiumazide (1.2 mmol, 1.2 equiv.) and 5 mg Cu2ONPs. |
77% | With sodium azide; [Cu(κO1O2N-((Z)-2-(2-(1-amino-1,3-dioxobutan-2-ylidene)hydrazineyl)benzenesulfonato))(H2O)2]*2H2O In water; acetonitrile at 125℃; for 0.25h; Microwave irradiation; Sealed tube; | |
With sodium azide; copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 20℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.7% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; at 60℃; for 12h;Inert atmosphere; | General procedure: In a 50 mL two-neck round bottom flask, equipped with a magnetic stirrer and nitrogen inlet-outlet, iodine derivative (1 mmol), 1,4-diethynylbenzene (0.5 mmol), PdCl2(PPh3)2 (0.005 mmol), CuI (0.03 mmol), PPh3 (0.02 mmol) and triethylamine (10 mL) were introduced and stirred at 60 C for 12 h. Then the reaction mixture was cooled, triethylamine removed at vacuum and solid product washed with water and diluted HCl solution. The product was purified by flash chromatography on silicagel using CH2Cl2/hexane (1:5) as eluent.(0018)T6: 1,4-Bis(4-(diphenylamino)phenylethynylene)benzene was obtained as a yellow solid with 85.7% yield. M.p. = 129-130 C. FT-IR (KBr) nu, cm-1: 3435 (=C-H), 3034, 2923, 2852, 2207 (C-C triple bond), 1588, 1513, 1490, 1278, 833. 1H NMR (CDCl3, 400 MHz) delta, ppm: 7.46 (s, 8H), 7.39-7.35 (t, 4H), 7.29-7.25 (m, 12H), 7.12-7.10 (d, 8H). Anal. found: C, 90.02; H, 5.11; N, 4.67. C46H32N2 (618.776) requires C, 90.16; H, 5.26; N, 4.58. |
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 |
---|---|---|
96% | With Cu(at)PyIm-SBA-15 at 20℃; for 8h; chemoselective reaction; | synthesis of 1,4-disubstituted1,2,3-triazole General procedure: Aniline (0.5 g, 5.4 mmol) was placed into a 25 mL round bot-tomed flask which was then put in an ice water bath (0-5C).Subsequently, a mixture of conc. HCl-H2O (1.3 mL: 1.3 mL) wasadded to it and the mixture was stirred for 1 min. NaNO2(0.392 g,5.7 mmol), dissolved in 1 mL of water, was first cooled at 0-5Cand then added to the reaction mixture drop wise. After 2 min stir-ring, sodium azide (0.416 g, 6.4 mmol) was added and stirred for5 min. Then phenylacetylene (0.46 g, 4.6 mmol) and CuPyIm-SBA-15 (0.025 g, 0.1 mol%) were added to the reaction mixture followedby stirring at room temperature for 6 h (TLC). When the reactionwas over, the water layer was decanted off and the reaction mixturewas dissolved in ethanol. Then the catalyst was filtered througha sintered glass-bed (G-4), and washed with water (3 × 4 mL) fol-lowed by ethanol (3 × 3 mL) and acetone (2 × 4 mL). The productwas purified by a simple crystallization from ethanol to furnish thecorresponding triazole, 1,4-diphenyl-1H-[1,2,3]triazole, as a whitesolid (Yield = 98%), |
84% | With silver-graphene nanocomposite In water at 20℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 20℃; for 6h;Inert atmosphere; | General procedure: Pd(PPh3)2Cl2 (0.2 mmol) was added to a solution of bis(ethynyl)benzene, 3 (1 mmol) and 2-halonitroaryl, 6 (2.2 mmol) in freshly distilled triethylamine (20 mL) and DMF (10 mL), and the mixture was de-aerated with argon for 30 min. CuI (0.2 mmol) was added, and the mixture was de-aerated with argon for 10 min and stirred at room temperature for 6 h. The reaction mixture was partitioned between ethyl acetate and water. The organic layer was separated, washed with brine, dried (NaSO4), and concentrated, and the residue obtained was purified by column chromatography (cyclohexane in dichloromethane) to afford an intermediate, 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In tetrahydrofuran at 50℃; for 24h; Inert atmosphere; Sealed tube; | To a 50 mL test tube was added 1 (0.174 g, 0.48 mmol), p-diethynylbenzene (0.030 g, 0.24 mmol), Pd(PPh3)4(0.057 g, 0.05 mmol), and CuI (0.019 g, 0.10 mmol). To a separate test tube was added tetrahydrofuran (20mL), and triethylamine (5 mL). Each tube was sealed with a rubber septum and purged with a continuousstream of argon (5 min). The contents of the liquids tube were transferred to the solids tube via cannulaunder argon. The resulting mixture was stirred at 50C under argon for 24 h. The resulting suspension wasextracted between dichloromethane and 5% NH4OH (aq). The organic layer was separated and dried overMgSO4. After filtration to remove the drying agent, the solvent was removed via rotary evaporation to give aorange-tan powder. The crude product was purified via centrifugation under methanol-resulting in 2 as atan-orange powder. Isolated 0.132 g, 0.22 mmol, 93% yield. 1H NMR (DMSO-d6): δ = 5.75 (m, 4H), δ=7.36 (m,2H), δ=7.43 (d, J=8.3 Hz, 4H), δ=7.61 (s, 4H), δ=7.62 (d, J=8.3 Hz, 4H), δ=7.91 (m, 2H), δ=8.05 (m, 2H), δ=8.61(m, 2H), δ=8.74 (s, 2H). 13C NMR (DMSO): δ = 53.4, 90.0, 91.7, 120.2, 122.5, 123.1, 123.8, 124.4, 129.0, 132.4,132.6, 137.6, 138.0, 148.2, 150.4, 150.6. MS (MALDI-TOF): calculated for C38H26N8 595, found 596. [M+H].Mp=240C (decomp). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: carbon dioxide; 1,4-diethynylbenzene With C24H30N3(1+)*Cl4Fe; caesium carbonate In N,N-dimethyl-formamide at 70℃; for 18h; Stage #2: With hydrogenchloride; water In N,N-dimethyl-formamide at 20℃; | 13 Embodiment 13[{(RNC (CH3)) NCHCHN (CH2Ph)} CH] [FeCl4] (R is 2,6-diisopropylphenyl) catalyzed 1,4-ethynyl benzene and carbon dioxide carboxylation reaction Sequentially adding a catalyst in the reaction bottle (14.0 mg, 0.025 millimole, 5mol %), cesium carbonate (32.6 mg, 1.0 mmol), 1,4-di- acetylenylbenzene (63.1 mg, 0.5 mmol),N,N-dimethylformamide(3 ml), into the carbon dioxide, in the 70 °C, reaction under normal pressure 18 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 90%. |
85% | Stage #1: carbon dioxide; 1,4-diethynylbenzene With diethoxymethylane; potassium <i>tert</i>-butylate at 40℃; for 2h; Schlenk technique; Stage #2: With hydrogenchloride In water Schlenk technique; | 2.2 General procedure for silylation/carboxylationtandem reaction and characterization data General procedure: The terminal alkyne (1.0 mmol) was added to a mixtureof HSi(OEt)2Me (5.0 mmol) and KOtBu (1.5 mmol) in a10 mL Schlenk tube with a magnetic stirrer. The Schlenktube was evacuated and back-filled with CO2 for 3 times.After a CO2 ballon was connected, the reactor was moved toa water bath of 40 °C. After being stirred for 2 h, the reactionmixture was diluted with water (30 mL), and was extractedwith CH2Cl2 (3×10 mL). The aqueous layer was acidifiedwith aqueous HCl (6 M) and then extracted with diethylether (5×20 mL). The combined organic extracts were driedover Na2SO4 and concentrated under vacuum to give the purepropiolic acid (such as compound 3-phenylpropiolic acid(3a): 98%). |
85% | With diethoxymethylane; potassium <i>tert</i>-butylate at 40℃; for 2h; Glovebox; Schlenk technique; Green chemistry; | 29 Example 29, carboxylation of 1,4-diethynylbenzene with CO2 to form 3,3'-(1,4-phenylene)dipropynoic acid In a glove box, 1,4-diacetylenylbenzene (1 mol) was added sequentially to a 10 ml Schlenk bottle.HSi(OEt)2Me (10 mol) and KOtBu (3 mol) were replaced with CO2; the Schlenk bottle was attached to a CO2 balloon and stirred at 40 ° C for 2 hours.After the reaction was completed, the reaction mixture was diluted with 30 mL of H 2, and extracted with CH 2Cl 2 (3×10 mL).The aqueous layer was acidified by adding HCl (6M) solution and finally extracted with diethyl ether (5×20 mL).The obtained organic layer was dried over anhydrous magnesium sulfate.It was then vacuum evaporated to give the pure product in an isolated yield of 85%. |
85% | With caesium carbonate In N,N-dimethyl-formamide at 80℃; for 12h; | |
82% | With {(N,N'-cyclohexane-1,2-diylbis((4-(tert-butyl)benzoyl)amide))Nd[N(SiMe3)2](tetrahydrofuran)}2; caesium carbonate In dimethyl sulfoxide at 40℃; for 24h; Schlenk technique; | |
81% | With caesium carbonate In dimethyl sulfoxide at 60℃; for 24h; | 20 Add 4 ml of dimethyl sulfoxide, 1 mmol of 1,4-diethynylbenzene, 2 mmol of cesium carbonate to the reaction tube,The reaction tube was pumped and ventilated 3 times, and filled with CO2. After the CO2 was filled, the gas pressure of the reaction tube was 1 atm. The reaction tube was stirred for 24 hours under the conditions of carbon dioxide atmosphere and 60°C. The stirring rate is 800 rpm, stop stirring, and cool to room temperature.Add water to the reaction liquid, extract 4 times with ethyl acetate, separate the layers, take the water layer, acidify the water layer with 2 moles of hydrochloric acid per liter to pH=1, then extract with ethyl acetate, take the organic layer, and wash the organic layer with saturated brine It was dried over magnesium sulfate, the filtrate was filtered, and concentrated under reduced pressure to obtain the target product with a yield of 81%. |
75% | With 18-crown-6 ether; cesium fluoride; trimethylsilylacetylene In dimethyl sulfoxide at 30℃; for 20h; Glovebox; Schlenk technique; | |
21% | With silver N,N-dimethylcarbamate; caesium carbonate In N,N-dimethyl-formamide at 50℃; for 24h; Inert atmosphere; Schlenk technique; | |
89 %Chromat. | With caesium carbonate In N,N-dimethyl-formamide at 70℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With lithium hexamethyldisilazane In tetrahydrofuran at -50 - 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 75℃; for 10h;Schlenk technique; | <strong>[29682-15-3]methyl 5-bromopicolinate</strong> (216 mg, 1 mmol) and 1,4-diethynylbenzene (60 mg, 0.48 mmol) were introduced in a Schlenk flask containing 8 mL of dry degassed THF. Pd(PPh3)4 (38 mg, 0.033 mmol) and NEt3 (0.2 mL, 1.435 mmol) were then added and the reaction mixture was stirred for 10 h. The precipitate was filtered and washed with water and methanol to afford 3a as a pale yellow solid (162 mg, 85%). Data for 3a: Anal. Calcd for C24H16N2O4·0.15H2O:C, 72.23; H, 4.12; N, 7.02. Found: C, 72.08; H, 3.95; N, 6.96. 1HNMR (CD2Cl2): delta= 8.85 (dd, 4J=1.8Hz, 5J=0.9Hz, 2H), 8.11 (dd, 3J=8.1Hz, 5J=0.6Hz, 2H), 7.98 (dd, 3J=8.1Hz, 4J=2.1Hz, 2H), 7.61 (s, 4H), 3.97 (s, 6H)ppm. 13C NMR (CDCl3): delta= 165.39, 152.28, 146.57, 139.50, 132.05, 124.73, 123.78, 123.06, 95.07, 87.86,53.33 ppm. ESI-TOF MS: m/z 397.12 [M + H]+. SelectedIR (KBr, cm-1): 1716.3, 1440.1, 1404.0, 1366.3, 1317.4, 1236.4, 1135.9,1116.3, 1016.2, 957.9, 866.6, 829.0, 819.7, 793.7, 698.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: tris-iso-propylsilyl acetylene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 1.5h; Darkness; Inert atmosphere; Stage #2: 5,12-naphthacenequinone In diethyl ether; hexane at 20℃; for 2h; Darkness; Inert atmosphere; Stage #3: 1,4-diethynylbenzene With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 18h; Darkness; Inert atmosphere; | One-Pot Synthesis of 12,12-[1,4-Phenylenebis(ethyne-2,1-diyl)]bis{5-[(triisopropylsilyl)ethynyl]-5,12-dihydrotetracene-5,12-diol} (13) The TIPS-ETLi solution (0.47 mmol) in Et2O (5 mL) was transferred slowly by using a cannula into a suspension of tetracenequinone (100mg, 0.39 mmol) in Et2O (5 mL) at r.t. under Ar. The mixture was stirred for 2 h at r.t., then the mixture was cooled to 0 C. A solution of(p-phenylenediethynylene)dilithium (12) in Et2O (5 mL), prepared from p-diethynylbenzene (24 mg, 0.19 mmol) and n-BuLi (250 L,0.40 mmol), was transferred slowly by using a cannula into the reaction mixture at r.t. The mixture was stirred for 18 h (reaction mixtureB), then the reaction was quenched with aq NH4Cl (30 mL). The organic materials were extracted with CH2Cl2 (3 ~ 30 mL). The combined organic solution was dried over MgSO4 and evaporated. The residue was purified by chromatography on silica gel (NH) (hexane.CH2Cl2, 1:1) to give the desired product 13. Yield: 153 mg (78%); colorless solid; mp 143.146 C; Rf = 0.86(CH2Cl2). The same reaction using a THF solution in the first additiongave 13 in 84% yield. 1H NMR (400 MHz, CDCl3): = 1.11.1.60 (m, 42 H), 3.16 (s, 2 H), 3.33(s, 2 H), 7.27 (s, 4 H), 7.47.7.51 (m, 4 H), 7.54 (dd, J = 3.4, 5.8 Hz, 4 H),7.90 (dd, J = 3.6, 6.0 Hz, 2 H), 7.94 (dd, J = 3.4, 6.2 Hz, 2 H), 8.12.8.14(m, 2 H), 8.22.8.24 (m, 2 H), 8.56 (s, 2 H), 8.72 (s, 2 H). 13C NMR (100 MHz, CDCl3): = 11.24, 18.64, 68.37, 69.86, 86.07,90.17, 93.56, 108.53, 122.21, 125.53, 125.94, 126.72, 126.81, 126.87,128.12, 128.96, 129.30, 131.39, 133.06, 133.22, 135.21, 136.68,137.50, 139.01 (two aromatic peaks were not observed). HRMS (FAB): m/z [M.2(OH)]+ calcd for C68H68O2Si2: 972.4758; found:972.4796. Anal. Calcd for C68H70O4Si2: C, 81.07; H, 7.00. Found: C, 80.68; H, 7.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | 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 |
---|---|---|
90% | With C16H20Cl2N2O2Pd; potassium hydroxide; In water; acetonitrile; at 20℃; for 3h; | General procedure: In a 10 mL round bottom flask, the palladium complex (0.010 mmol) was dissolved in acetonitrile (2 mL). Aryl halide (1.0 mmol), alkyne (1.2 mmol), KOH (2.00 mmol) and distilled water (2 mL) were added. The mixture was stirred at room temperature (or 60 C) for the required time. After reaction completion, the product was extracted with ethyl acetate (3x5 mL). The combined organic layers were dried with anhydrous sodium sulfate. The product was analyzed with GC and GC-MS. The product was purified using column chromatography with hexane-ethyl acetate as eluent. The characterization data were in entire agreement with the previously reported literature.32-39 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With boron trifluoride diethyl etherate; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform; toluene at 80℃; for 2h; Inert atmosphere; Schlenk technique; | |
75% | With boron trifluoride diethyl etherate; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform; toluene at 80℃; for 2h; | 8 Synthesis of 7-bromo-2- (4-ethynylphenyl) naphtho [2,1-b] furan To the reactor was added 0.24 mmol of 2,3-dichloro-5,6-dicyano-p-benzoquinone,0.20 mmol 6-bromo-2-naphthol,0.80 mmol 1,4-diethynylbenzene,1.6ml of mixed solvent toluene and 0.4ml of chloroform,Boron trifluoride diethyl ether solution 0.01 mmol.Heated to 80 ,Continue stirring 2h,Stop the reaction,Cool to room temperature,Washed with saturated sodium chloride solution,Extraction with dichloromethane,dry,The solvent was distilled off under reduced pressure,The crude product was separated by column chromatography to obtain the desired product,Yield 75%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate In tetrahydrofuran; water at 20℃; | General procedure for the synthesis of benzosuberone bearing 1,2,3-triazoles (5a-o): General procedure: To the mixture ofazido compounds3(1.00 mmol) and alkynes4(1.1 mmol) in THF/water (1:1), were added CuSO4.5H2O (20 mol %) and sodium ascorbate (20 mol %) at room temperature.The reaction mixture was stirred at RT for 5-6 h. After completion (TLC), the reaction mixture was extracted with ethyl acetate (2 x 10 mL) and water (5 mL). The organic layer was separated and dried over anhydrous Na2SO4, evaporated on rota evaporator.The residue was purified with flash column chromatography to furnish following triazoles: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 1,4-diethynylbenzene With trifluorormethanesulfonic acid; water In 2,2,2-trifluoroethanol at 60℃; for 48h; Inert atmosphere; Stage #2: With chloro([(S,2S)-(−)-2-amino-1,2-diphenylethyl](4-toluenesulfonyl)amido)(mesitylene)ruthenium (II); hydrogen; potassium hydroxide In 2,2,2-trifluoroethanol at 40℃; for 24h; Autoclave; | 4 Example 4: Asymmetric synthesis of (S,S)-1,4-bis(1-hydroxyethyl)benzene Add 0.5mmol of p-diethynylbenzene to the test tube, add CF3SO3H (40mol%, 18uL), H2O (4 equvi., 40uL), CF3CH2OH (1mL), and react at 60 for 48h, then add 0.005mmol of catalyst C. KOH (0.5 mmol, 28mg), put the reaction tube in the autoclave, replace it 3 times, then fill it with 4Mpa hydrogen, and react at 40°C for 24 hours. After the reaction, the water phase was washed with water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were concentrated to dryness. The separation yield was 93% (petroleum ether: ethyl acetate = 5:1). The product (S, S) was determined by HPLC. The enantiomeric excess of 1,4-bis(1-hydroxyethyl)benzene is 99%, and the diastereomeric excess is 90%. |
Multi-step reaction with 2 steps 1: trifluorormethanesulfonic acid; water / 2,2,2-trifluoroethanol / 48 h / 70 °C / Inert atmosphere 2: C30H32ClN2O2RuS; potassium hydroxide; hydrogen / 2,2,2-trifluoroethanol / 24 h / 40 °C / 30402 Torr / Autoclave |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium azide In water at 20℃; for 2h; Green chemistry; | General procedure for one-pot three-component 1,3-dipolar cycloaddition reaction catalyzed by Cu-Pol nanocomposite General procedure: Alkyne (1.0 mmol), sodium azide (1.2 mmol), benzyl chloride (1.0 mmol) and Cu-Pol nanocomposite (4.7 mg, 0.5 mol-%) were suspended in deionized water (3.0 mL). The resulting mixture was stirred at room temperature and the reaction was monitored by gas chromatography-mass spectrometry (GC-MS) until the starting reagents disappeared. After the completion of the reaction, the mixture was filtered, and the mother solution was extracted with ethyl acetate. The organic layer was dried with anhydrous sodium sulfate, and the solvent was evaporated to give the corresponding triazoles, which were purified by column chromatography (hexane/ethyl acetate, V : V= 8 : 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium azide; [Cu(κO1O2N-((Z)-2-(2-(1-amino-1,3-dioxobutan-2-ylidene)hydrazineyl)benzenesulfonato))(H2O)2]*2H2O In water; acetonitrile at 125℃; for 0.25h; Microwave irradiation; Sealed tube; | |
77% | With sodium azide; copper(I) oxide In water at 100℃; for 1h; | 2.6 General procedure for the synthesis of bis-1,2,3-triazoles (Method-2) General procedure: The above-mentioned procedure was followed using 1,3-diethynylbenzene or 1,4-diethynylbenzene (0.5 mmol, 1equiv.), benzyl bromide (1.2 mmol, 1.2 equiv.) sodiumazide (1.2 mmol, 1.2 equiv.) and 5 mg Cu2ONPs. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium azide; [Cu(κO1O2N-((Z)-2-(2-(1-amino-1,3-dioxobutan-2-ylidene)hydrazineyl)benzenesulfonato))(H2O)2]*2H2O In water; acetonitrile at 125℃; for 0.25h; Microwave irradiation; Sealed tube; | |
80% | With sodium azide; copper(I) oxide In water at 100℃; for 1h; | 2.6 General procedure for the synthesis of bis-1,2,3-triazoles (Method-2) General procedure: The above-mentioned procedure was followed using 1,3-diethynylbenzene or 1,4-diethynylbenzene (0.5 mmol, 1equiv.), benzyl bromide (1.2 mmol, 1.2 equiv.) sodiumazide (1.2 mmol, 1.2 equiv.) and 5 mg Cu2ONPs. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 20℃; for 24h; | General procedure for the preparation of compounds 4-7 General procedure: Appropriateazide(2.6 equiv.) anddialkyne(1equiv.) were dissolved in a 1:2 mixture of water andDMF. CuSO4.5H2O (0.04equiv) and sodiumascorbate(0.08equiv) were then added. The resultant mixture was stirred at room temperature for 24 h. The reaction solution was diluted with brine and extracted three times with chloroform. The organic layers were washed with water, dried over Na2SO4and evaporated under vacuum. The residue was purified by silica gel column chromatography using a mixture of dichloromethane/methanol as the mobile phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate In water; N,N-dimethyl-formamide at 20℃; for 24h; | General procedure for the preparation of compounds 4-7 General procedure: Appropriateazide(2.6 equiv.) anddialkyne(1equiv.) were dissolved in a 1:2 mixture of water andDMF. CuSO4.5H2O (0.04equiv) and sodiumascorbate(0.08equiv) were then added. The resultant mixture was stirred at room temperature for 24 h. The reaction solution was diluted with brine and extracted three times with chloroform. The organic layers were washed with water, dried over Na2SO4and evaporated under vacuum. The residue was purified by silica gel column chromatography using a mixture of dichloromethane/methanol as the mobile phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate; tris[(1-benzyl-1H-1,2,3-triazol-4yl)methyl]amine In N,N-dimethyl-formamide at 20℃; | 3.4. General Synthesis Procedures General procedure: Synthesis procedures for 7-chloro-N-(2-(4-(4-ethynylphenyl)-1H-1,2,3-triazol-1-yl)ethyl)quinolin-4-amine (compound JR1), a mixture of N-(2-azidoethyl)-7-chloroquinolin-4-amine (N3-CQ) (100 mg,0.4 mmol, 1 eq.), 1,4-diethynylbenzene (60.5 mg, 0.5 mmol, 1.2 eq.) and tris(benzyltriazolylmethyl)amine(TBTA, 2 mg, 0,004 mmol, 1 mol-%) was dissolved in DMF (0.7 mL). To this solution was added a watermixture (0.3 mL) of CuSO4.5H2O (1 mg, 0,004 mmol, 1 mol-%) and sodium ascorbate (8 mg, 0,04 mmol,0,1 eq.). The compounds were reacted overnight with stirring at room temperature. The compounds7-chloro-N-(2-(4-(4-ethynyl-3-fluorophenyl)-1H-1,2,3-triazol-1-yl)ethyl)quinolin-4-amine (JR2) and7-chloro-N-(2-(4-(4-ethynyl-2-fluorophenyl)-1H-1,2,3-triazol-1-yl)ethyl)quinolin-4-amine (JR3) wereprepared similarly by replacing the 1,4-diethynylbenzene with 1,4-diethynyl-2-fluorobenzene (72 mg,0.5 mmol, 1.2 eq.). Following the reaction, the solution containing JR1 was filtered and purified byHPLC (system 2). The crude reaction containing both JR2 and JR3 compounds was also filtered andthe filtrate freeze-dried. The remaining solid was redissolved in the minimal amount of DMF (0.2 mL)and completed with DCM/MeOH (0.4 mL, 9:1). The isomers were separated on a preparative TLCplate using DCM/MeOH (9:1) as eluent.7-Chloro-N-(2-(4-(4-ethynylphenyl)-1H-1,2,3-triazol-1-yl)ethyl)quinolin-4-amine (JR1): yield 123 mg(0.033 mmol, 83%). 1H NMR (500 MHz, DMF-[d7]): δ = 9.68 (t, J = 5.6 Hz, 1H), 8.82 (s, 1H), 8.70 (d,J = 6.9 Hz, 1H), 8.60 (d, J = 9.0 Hz, 1H), 8.23 (d, J = 2.0 Hz, 1H), 8.03 (s, 1H), 7.89 (d, J = 8.45 Hz, 2H),7.70 (dd, J = 7.76 Hz, 1H), 7.58 (dd, J = 8.35 Hz, 1H), 7.16 (d, J = 7Hz, 1H), 4.97 (t, J = 5.7 Hz, 2H), 4.31(dd, J = 5.3, 5.8 Hz, 2H), 4.20 (s, 1H) ppm; 13C NMR (125 MHz, CDCl3-[d1]): δ = 165.4, 157.1, 146.4,145.4, 141.1, 139.6, 135.8, 135.3, 128.4, 126.3, 124.5, 122.4, 121.6, 117.4, 113.0, 110.5, 100.1, 86.9, 77.8, 49.5,44.5 ppm; HR-ESI-MS (ESI+): [M + H]+ = 374.1176, calculated for C21H17N5Cl1 = 374.1167. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 20℃; | Synthesis of 2-(4-(4-ethynylphenyl)-1H-1,2,3-triazol-1-yl)-1-(2-(4-fluorophenyl)-3-((4-fluorophenyl)amino)-8,8-dimethyl-5,6-dihydroimidazo[1,2-a]pyrazin-7(8H)-yl)ethan-1-one (SN1): A mixture ofN3-SN1 (85 mg, 0.194 mmol, 1 eq.), 1,4-diethynylbenzene (29.40 mg, 0.233 mmol, 1.2 eq.) and Et3N(7.87 mg, 0.077 mmol, 40 mol-%) was dissolved in DMF (1 mL). CuI (3.70 mg, 0.019 mmol, 10 mol-%)was added to this solution. The compounds were reacted overnight with stirring at room temperature.After the reaction completion, brine (20 mL) and dichloromatane (20 mL) were added to the solution.The aqueous phase was extracted with 2 x 20 mL of CH2Cl2. The combined organic layers werewashed with brine (20 mL) and the organic layer separated and dried over Na2SO4. Then, the mixturewas filtered and finally CH2Cl2 was removed under reduced pressure. The crude product was purifiedby flash column chromatography to aord compound SN1 as a white solid. Yield: 93 mg (0.165 mmol,85%). 1H NMR (400 MHz, (CD3)2CO-[d6]): δ= 8.22 (s, 2H), 7.78 (m, 4H), 7.43 (d, J = 8.4Hz, 2H), 6.92(d, J = 8.6 2H), 6.82 (dd, J = 8.56 2H), 6.56 (dd, J = 4.48, 8.92 Hz 2H), 5.52 (s, 2H), 3.89 (t, J = 5.6 Hz, 2H),3.85 (t, J = 5.40 Hz, 2H), 3.55 (s, 1H), 1.77 (s, 6H); HR-ESI-MS (ESI+): [M + H]+ = 564.23, calculated forC32H28F2N7O = 564.23. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
At -78 C, n-butyllithium (4.8mL, 2.5mol / L, 2.4 equivalent) was added dropwise to a tetrahydrofuran solution (15 mL) of 1,4-diethynylbenzene (630.8 mg, 1.0 equivalent) for 1 h, Add isopropyl alcohol pinacol borate (2.4 mL, 2.4 equivalents) dropwise to the mixed solution, The reaction was continued for 2h, quenched by the addition of a 1,4-dioxane solution of hydrogen chloride (3.8mL, 4M indioxane, 3.0 equivalents), and the reaction was warmed to room temperature. After the solvent was rotary evaporated, the solution was prepared into an acetone solution (0.3M), A potassium peroxymonosulfonate solution (0.5M, 9.2214g, 3.0 equivalents) was added, transferred to 50 C and stirred for 12h, and separated and purified to obtain 689.4 mg of 1,4-benzenediacetic acid with a purity of 71%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With bis-triphenylphosphine-palladium(II) chloride; triethylamine at 50℃; for 28h; | 2.2. Synthesis of bis[1-(thiophenyl)propynone] dyes General procedure: General procedure: in a typical run, diethynylarene (1.0 mmol),thiophene acid chloride (2.5 mmol), PdCl2(PPh3)2 (2 mol%) and Et3N(20 mL) were mixed together in a 50 mL two-necked round bottom flask.The resulting mixture was left under stirring for 28 h at 50 C, then it wascooled to room temperature, hydrolyzed with saturated ammoniumchloride solution (20 mL) and extracted with CH2Cl2 (3x30 mL). Thecombined organic phases were washed with brine, dried over anhydrousNa2SO4 and the solvent was removed under vacuum. All the crudeproducts were purified through column chromatography on silica geland characterized with 1H NMR, 13C NMR, LC-MS and elemental analysistechniques. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With bis-triphenylphosphine-palladium(II) chloride; triethylamine at 50℃; for 28h; | 2.2. Synthesis of bis[1-(thiophenyl)propynone] dyes General procedure: General procedure: in a typical run, diethynylarene (1.0 mmol),thiophene acid chloride (2.5 mmol), PdCl2(PPh3)2 (2 mol%) and Et3N(20 mL) were mixed together in a 50 mL two-necked round bottom flask.The resulting mixture was left under stirring for 28 h at 50 C, then it wascooled to room temperature, hydrolyzed with saturated ammoniumchloride solution (20 mL) and extracted with CH2Cl2 (3x30 mL). Thecombined organic phases were washed with brine, dried over anhydrousNa2SO4 and the solvent was removed under vacuum. All the crudeproducts were purified through column chromatography on silica geland characterized with 1H NMR, 13C NMR, LC-MS and elemental analysistechniques. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With sodium azide; copper(I) oxide In water at 100℃; for 0.5h; | 2.4 General procedure for the one-pot synthesisof mono-1,2,3-triazoles bearing one free acetylene General procedure: In a 50 mL round-bottomed flask benzyl halide (1 mmol,1 equiv), NaN3 (1.2 mmol, 1.2 equiv.), diethynylbenzene(1 mmol, 1 equiv.) and 5 mg Cu2ONPs were taken alongwith 10 mL water. The mixture was magnetically stirredunder reflux condition (100 °C) for 30 min. Progress of thereaction was monitored by TLC and after completion ofreaction products were purified via columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium azide; copper(I) oxide In water at 100℃; for 0.5h; | 2.4 General procedure for the one-pot synthesisof mono-1,2,3-triazoles bearing one free acetylene General procedure: In a 50 mL round-bottomed flask benzyl halide (1 mmol,1 equiv), NaN3 (1.2 mmol, 1.2 equiv.), diethynylbenzene(1 mmol, 1 equiv.) and 5 mg Cu2ONPs were taken alongwith 10 mL water. The mixture was magnetically stirredunder reflux condition (100 °C) for 30 min. Progress of thereaction was monitored by TLC and after completion ofreaction products were purified via columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sodium azide; copper(I) oxide In water at 100℃; for 0.5h; | 2.4 General procedure for the one-pot synthesisof mono-1,2,3-triazoles bearing one free acetylene General procedure: In a 50 mL round-bottomed flask benzyl halide (1 mmol,1 equiv), NaN3 (1.2 mmol, 1.2 equiv.), diethynylbenzene(1 mmol, 1 equiv.) and 5 mg Cu2ONPs were taken alongwith 10 mL water. The mixture was magnetically stirredunder reflux condition (100 °C) for 30 min. Progress of thereaction was monitored by TLC and after completion ofreaction products were purified via columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium azide; copper(I) oxide In water at 100℃; for 0.5h; | 2.4 General procedure for the one-pot synthesisof mono-1,2,3-triazoles bearing one free acetylene General procedure: In a 50 mL round-bottomed flask benzyl halide (1 mmol,1 equiv), NaN3 (1.2 mmol, 1.2 equiv.), diethynylbenzene(1 mmol, 1 equiv.) and 5 mg Cu2ONPs were taken alongwith 10 mL water. The mixture was magnetically stirredunder reflux condition (100 °C) for 30 min. Progress of thereaction was monitored by TLC and after completion ofreaction products were purified via columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium azide; copper(I) oxide In water at 100℃; for 0.5h; | 2.4 General procedure for the one-pot synthesisof mono-1,2,3-triazoles bearing one free acetylene General procedure: In a 50 mL round-bottomed flask benzyl halide (1 mmol,1 equiv), NaN3 (1.2 mmol, 1.2 equiv.), diethynylbenzene(1 mmol, 1 equiv.) and 5 mg Cu2ONPs were taken alongwith 10 mL water. The mixture was magnetically stirredunder reflux condition (100 °C) for 30 min. Progress of thereaction was monitored by TLC and after completion ofreaction products were purified via columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-iodo-1H-pyrazole-1-carboxylic acid tert-butyl ester With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 1,4-diethynylbenzene In tetrahydrofuran at 20℃; for 15h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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48% | With copper(I) bromide In acetonitrile at 20℃; | 4.2.12. Synthesis of 19a-c by [3 + 2] click reaction of 17 General procedure: Alkyne (2 equiv.) and CuBr (1 equiv.) were added to a stirredsolution of 17 (1 equiv.) in CH3CN at room temperature. When thereactionwas finished as indicated by TLC, the reaction mixture was filtrated and evaporated. Flash chromatography of the residue oversilica gel, using PE/EtOAc, gave the corresponding triazole products(48 %e99 %). 4.2.12.1. (S)-4-((3aS,4S,7R,7aS)-4-acetoxy-7-(4-(4-ethynylphenyl)-1H-1,2,3-triazol-1-yl)-6-methyl-3-methylene-2-oxo-2,3,3a,4,7,7ahexahydrobenzofuran-5-yl)pentyl acetate (19a). Yield: 48 %. 1H NMR(500 MHz, CDCl3) δ 8.38 (s, 1H, ArC]CH), 7.89 (d, J 8.4 Hz, 2H, Ar),7.59 (d, J 8.3 Hz, 2H, Ar), 6.53 (d, J 2.4 Hz, 1H, H-13a), 6.18 (dd,J 2.8, 1.5 Hz, 1H, H-13b), 6.14 (d, J 2.2 Hz, 1H, H-9), 5.30 (d,J 1.7 Hz, 1H, H-6), 5.22e5.11 (m, 1H, H-8), 3.16 (s, 1H), 4.04e3.90(m, 2H, H-1), 2.71 (ddd, J 9.1, 6.8, 4.8 Hz, 1H, H-4), 2.16 (s, 3H, AcO-1), 2.06 (s, 3H, AcO-6), 1.46 (d, J 1.5 Hz, 3H, H-14), 1.31e1.24 (m,3H, H-3a, H-2), 1.10e1.04 (m, 1H, H-3b), 0.94 (d, J 6.8 Hz, 3H, H-15); 13C NMR (125 MHz, CDCl3) δ 171.2 (CH3CO-1), 170.8 (CH3CO-6),168.3 (C-12), 147.7 (ArC]CH), 134.7 (C-11), 134.1 (C-5), 132.7 (Ar),130.6 (C-13), 127.2 (C-10), 125.7 (Ar), 122.0 (Ar), 121.7 (Ar), 83.4 (Ar-CCH), 78.1 (Ar-CCH), 76.4 (C-8), 68.6 (C-6), 64.0 (C-1), 61.9 (C-9),45.8 (C-7), 34.2 (C-4), 31.1 (C-3), 26.6 (C-2), 21.0 (CH3CO-1), 20.8(CH3CO-6), 18.3 (C-14), 14.3 (C-15); HR-ESI-MS: calcd forC29H31N3O6Na [MNa]: 540.2111; found: 540.2107. HPLCtR 4.244 min (>99 % purity). |
Tags: 935-14-8 synthesis path| 935-14-8 SDS| 935-14-8 COA| 935-14-8 purity| 935-14-8 application| 935-14-8 NMR| 935-14-8 COA| 935-14-8 structure
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