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CAS No. : | 1145-01-3 | MDL No. : | MFCD00039675 |
Formula : | C15H12N2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | JXHKUYQCEJILEI-UHFFFAOYSA-N |
M.W : | 220.27 | Pubchem ID : | 70840 |
Synonyms : |
|
Num. heavy atoms : | 17 |
Num. arom. heavy atoms : | 17 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 69.46 |
TPSA : | 28.68 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.13 cm/s |
Log Po/w (iLOGP) : | 2.1 |
Log Po/w (XLOGP3) : | 3.54 |
Log Po/w (WLOGP) : | 3.74 |
Log Po/w (MLOGP) : | 2.89 |
Log Po/w (SILICOS-IT) : | 4.12 |
Consensus Log Po/w : | 3.28 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.04 |
Solubility : | 0.0199 mg/ml ; 0.0000904 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -3.83 |
Solubility : | 0.0328 mg/ml ; 0.000149 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -6.28 |
Solubility : | 0.000117 mg/ml ; 0.00000053 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.01 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
79.3% | palladium; In water; 1,2-dichloro-ethane; | EXAMPLE 17 3,5-Diphenyl-2-pyrazoline (21.9 parts) is dissolved in ethylene dichloride (75 parts by volume). There is next added 5% palladium on carbon catalyst (4 parts containing 40% water) is added and the mixture is heated at reflux for 8 hours. There is obtained 3,5-diphenylpyrazole in a 79.3% yield whose melting point ranges from 196C. to 200C. |
79.3% | palladium; In water; 1,2-dichloro-ethane; | EXAMPLE 17 3,5-Diphenyl-2-pyrazoline (21.9 parts) is dissolved in ethylene dichloride (75 parts by volume). There is next added 5% palladium on carbon catalyst (4 parts containing 40% water) is added and the mixture is heated at reflux for 8 hours. There is obtained 3,5-diphenylpyrazole in a 79.3% yield whose melting point ranges from 196 to 200 C. |
With sulfuric acid; In neat (no solvent); at 20℃; for 3h;Green chemistry; | General procedure: A mixture of chalcones (2 mmol), hydrazine derivatives (2 mmol) and nano TiO2 (20%) was heated at 60 C. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was added TCM(2 mmol) and sulphuric acid (0.2 mL). The reaction mixture was stirred vigorously at room temperature for 3 h. The mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and the crude product was recrystallized from iso-propanol to afford the pure pyrazoles derivatives. 31 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrazine; In acetonitrile; at 50℃; for 3h; | General procedure: A test tube was charged with the acyl chloride (1.2 mmol), a terminal alkyne (1.0 mmol), SiO2-ZnBr2 (0.1 g, 0.12 mmol), and DIPEA(1.2 mmol), and the mixture was stirred at room temperature for 3 h under anhydrous conditions. On completion of the coupling reaction (monitored by TLC), hydrazine (3 mmol) in CH3CN (2 mL) was added, and the mixture was heated at 50 C with stirring for another 3 h. After completion of the reaction (monitored by TLC), the solvent was evaporated and the residue left was extracted with CH3CN. Concentrating the solution gave the crude product, which was subjected to column chromatography using CHCl3-CH3OH (98:2) as eluent to obtain an analytically pure product. | |
With hydrazine hydrate; In acetonitrile; at 20℃; for 16h;Inert atmosphere; | General procedure: To a 25mL round-bottomed flask, MCM-41-2N-Pd(OAc)2 (19mg, 0.005mmol), CuI (2mg, 0.01mmol), acid chloride (1.3mmol), terminal alkyne (1.0mmol) and Et3N (3mL) were added under argon. The mixture was stirred at 50C for 2h and cooled to room temperature. Then hydrazine (3.0mmol) and MeCN (2mL) were added and the reaction mixture was stirred at room temperature for an additional 16h. The reaction mixture was diluted with dichloromethane (20mL), and filtered. The MCM-41-2N-Pd(OAc)2 complex was washed with ethanol (2×5mL) and diethyl ether (2×5mL) and reused in the next run. The filtrate was washed with water (2×5mL), dried over MgSO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=4:1 to 2:1) to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With carbazic acid; at 90℃; for 5h;Green chemistry; | General procedure: A 10.0 mmol for alpha-keto acid compound or a 5.2 mmol for beta-diketones or alpha-keto acids was mixed with 0.40 g of hydrazinium carboxylate (1a, 5.2 mmol), respectively. (For solid di-carbonyl compound, the mixture was ground using a pestle and a mortar.) The mixture was stored in a closed vial, and then heated to 70 - 90 C until the reaction was complete. Complete conversion to related product was dependent upon the nature of di-carbonyl compounds. Typically, those di-carbonyl compounds take about <3 h to complete the reactions. CO2 and water were released during the reaction. All products obtained from the reactions of 1a with di-carbonyl compounds were basically characterized by 1H and 13C NMR spectroscopy. The products have over 97% of purity of reaction mixture based on 1H NMR spectroscopy and isolation yields are over 97% based on di-carbonyl compounds. The melting points, elemental analysis and UV-Vis spectra for all azines, pyrazoles and pyridazinones, were measured after purification using appropriate solvent. |
98% | With carbazic acid; In neat (no solvent); at 90℃; for 5h; | 1,3-diphenylpropane-1,3-dione using 11.22 g was 5 hours at 90 C, the rest is the same as in Example 1. The obtained compound was 3,5-diphenyl-1H-pyrazole, the selectivity was> 99%, and the yield was 98%. |
88% | With hydrazine; In neat (no solvent); at 90℃; for 1h; | General procedure: A mixture of 1,3-diketone (1 mmol), hydrazine (1 mmol),and nano- SnCl4/SiO2 (0.06 g) was placed in a round bottom flask and heated at 90C for 1 hr. Progress of the reaction was followed by TLC using EtOAc/n-Hexane (ratio 2/1) as eluent. After completion of the reaction, the product was dissolved in chloroform and filtered to recover the catalyst.Then the solvent was evaporated, and the crude mixture was solidified from a mixture of ethanol and water. The pure product was obtained by recrystallization in ethanol. |
79% | With titanium(IV) oxide; hydrazine; In neat (no solvent); at 60℃;Green chemistry; | General procedure: A mixture of 1,3-diketone (2 mmol), hydrazine derivatives (2mmol) and nano TiO2 (20%) was heated at 60 C. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and the crude product was recrystallized from iso-propanol to afford the purepyrazoles derivatives in 75-92 % yields. |
58% | With hydrazine hydrate; In ethanol; at 20 - 78℃; for 0.5h; | 1,Dibenzoylmethane (1 eq) was added to a three-necked flask containing 50 ml of ethanol. After stirring and dissolving at room temperature, hydrazine hydrate (1 eq) was added.Then, the reaction was refluxed at 78 C for 0.5 hours. The reaction was detected by TCL, suction filtered, washed with 20 ml of ethanol, and the filter cake was recrystallized from a solvent system with a volume ratio of ethyl acetate: petroleum ether = 6: 1get3,5-diphenyl-1H-pyrazole(II-2-2),The yield is 58%, |
28% | With hydrazine hydrate; In methanol; at 85℃; for 2h; | General procedure B: Preparation of a pyrazole from the requisite diketone under heated conditions The requisite diketone was dissolved in MeOH (20.0 mL) and hydrazinyl reagent added. The mixture was heated to 85 C, stirred for 2 hrs, cooled to RT then poured in H2O. EtOAc was added (50.0 mL), the aqueous and organic layers separated and the aqueous layer extracted three times with EtOAc (50.0 mL) The combined organic layers were then washed with brine (100 mL), dried over MgSO4 and concentrated in vacuo. Following standard procedure B diketone 21 (0.40 g, 1.79 mmol) and hydrazine hydrate (0.51 mL, 8.95 mmol) gave pyrazole 5. The crude product was recrystallized from DCM/heptane 4:1 (total volume 10.0 mL) to yield pyrazole 5 (0.11 g, 28%) as a white crystalline solid; 1H NMR (400 MHz, CDCl3): delta=6.85 (1H, s),7.30-7.44 (6H, m), 7.73 (4H, d, J=7.51). |
With hydrazine; In ethanol; at 60℃; for 2.5h; | Step 1: 3,5-diphenyl-1H-pyrazole, 22 is prepared as follows: Hydrazine monohydrate (2.16 mL) is added to a solution of 1,3-diphenylpropane-1,3-dione (10.0 g) in ethanol (100 mL) and the mixture is heated to 60 C. for 2.5 h forming a white precipitate over this time. Ethanol is removed in vacuo and the residue is taken up in ethyl acetate. The resulting suspension is filtered to give 3,5-diphenyl-1H-pyrazole, 22 (3.44 g) as a white powder. The filtrate is washed with water (2*100 mL), dried over magnesium sulfate and concentrated to give further 3,5-diphenyl-1H-pyrazole, 22 (5.90 g) as a solid. The compound obtained in this step shows the following mass spectral data: LC/MS: C15H12N2 requires 220.1; observed M/Z 221.3 [M-H]-, 219.4 [M-H]-. RT 4.84 min. | |
With hydrazine hydrate; In ethanol; at 20℃; for 1h; | Reference Example 1 3,5-Diphenyl-1H-pyrazole To ethanol (22 mL, manufactured by Wako Pure Chemical Industries, Ltd.) solution of 1,3-diphenyl-1,3-propanedione (500 mg, manufactured by Tokyo Chemical Industry Co., Ltd.), hydrazine hydrate (228 mg, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for one hour at room temperature. To the reaction solution, water (20 mL) was added followed by extraction with ethyl acetate (3*20 mL), washing with brine (20 mL) and drying over MgSO4. The solvent was evaporated. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=8:1) to give the title compound (480 mg). LC-MS: HPLC retention time 4.63 minutes, m/z 221(M+H), Condition A-1. | |
With hydrazine hydrate; In methanol; for 2h;Reflux; | Take a 100ml round bottom flask, add magnetons, and add 1,3-diphenylpropane-1,3-dione inward. (4.49g, 20mmol, 1.0eq) And hydrazine hydrate (1.1g, 20mmol, 1.0eq), then add 50ml of methanol, Heated to reflux for 2 h, extracted with ethyl acetate and dried. Silica gel column chromatography to obtain 3,5-diphenyl 1-hydropyrazole |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With hydrazine hydrochloride; iodine In ethanol for 1h; Heating; | |
87% | With sulfur; hydrazine hydrate In ethanol at 150℃; for 2h; microwave irradiation; | |
80% | With hydrazine hydrate; acetic acid In ethanol for 4h; Heating; |
75% | Stage #1: 1,3-diphenyl-propen-3-one With sulfur In dimethyl sulfoxide at 20℃; Sealed tube; Stage #2: With hydrazine hydrate In dimethyl sulfoxide at 40℃; for 12h; Sealed tube; | |
68% | With hydrazine hydrate; sodium hydroxide In methanol for 8h; Reflux; | |
65% | With potassium carbonate; N,N-dimethyl-formamide; toluene-4-sulfonic acid hydrazide at 130℃; for 0.0833333h; microwave irradiation; | |
Multi-step reaction with 2 steps 1: 20 °C 2: copper diacetate; 1,4-diaza-bicyclo[2.2.2]octane; oxygen / dimethyl sulfoxide / 12 h / 100 °C / 760.05 Torr |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.5% | With sodium iodide; benzaldehyde; hydrazine hydrate; In water; | Example 6 60 parts (0.5 mol) of acetophenone and 53 parts (0.5 mol) of benzaldehyde were simultaneously added dropwise at 25 C. to 140 parts (1 mol) of initially introduced 70% strength by weight sulfuric acid. The mixture was stirred at 25 C. for 60 minutes and the reaction solution obtained was simultaneously added dropwise with 25 parts (0.5 mol) of hydrazine hydrate at 135 C. to 140 parts (1 mol) of initially introduced 70% strength by weight sulfuric acid and 0.5 parts (0.0033 mol)of sodium iodide in the course of 25 minutes. The mixture was stirred at 125 C. for 60 minutes. In order to keep the temperature at 135 C., 38 parts of water were distilled off. The mixture was diluted with 500 parts of water and neutralized with 247.8 parts (3.1 mol)of 50% strength by weight sodium hydroxide solution. After filtering off the solid it was washed until sulfate-free and dried. 109.7 parts of 3,5-diphenylpyrazole having a purity of 96.8% (HPLC) were obtained, which corresponds to a yield of 96.5% of theory. M.p.: 197 C. |
94.3% | With sodium iodide; benzaldehyde; hydrazine hydrate; In water; | Example 3 392 parts (2 mol) of 50% strength sulfuric acid and 1 part (0.0067 mol) of sodium iodide were initially introduced into the stirring flask. 60 parts (0.5 mol) of acetophenone, 53 parts (0.5 mol) of benzaldehyde and 25 parts(0.5 mol) of hydrazine hydrate were simultaneously added dropwise under reflux at 124 C. in the course of 30 minutes. The temperature fellto 112 C. By distilling off water, the temperature was brought to 130 C. and the mixture was stirred at 130 C. for 60 minutes. 120 ml of water were distilled off. The reaction mixture obtainedwas diluted with 250 ml of water and neutralized with 525 parts (3.28 mol) of 25% strength by weight sodium hydroxide solution and filtered. The filter residue was washed with water until sulfate-free and dried. 110.2 parts of 3,5-diphenylpyrazole having a purity of 94.1% (HPLC) were obtained, which corresponds to a yield of 94.3% of theory. M.p.: 194 C. |
94.8% | With sodium iodide; benzaldehyde; In water; | Example 7 490 parts (3 mol) of 60% strength by weight sulfuric acid and 1.5 parts (0.01 mol) of sodium iodide were initially introduced into the stirring flask. 46.9 parts (0.75 mol) of 80% strength by weight hydrazine hydrate, 90 parts (0.75 mol) of acetophenone and 79.5 parts (0.75 mol) of benzaldehyde were simultaneously added dropwise at 120 C. in the course of 2 hours. By distilling off 120 parts of water the temperature was kept at 120 C. for 2 hours. The reaction mixture obtained was diluted with the distilled-off water and neutralized with 936 parts (4.7 mol) of 20% strength by weight sodium hydroxide solution. The precipitate was filtered off at room temperature, and the filter residue was washed with water and dried. 162.7 parts of 3,5-diphenylpyrazole having a purity of 96.1% (HPLC) were obtained, which corresponds to a yield of 94.8% of theory. M.p.: 196 C. |
93.1% | With sodium iodide; benzaldehyde; hydrazine hydrate; In water; | Example 2 120 parts (1 mol) of acetophenone and 106 parts (1 mol) of benzaldehyde were simultaneously added dropwise at 70 C. to 490 parts (3 mol) of 60% strength by weight sulfuric acid. The mixture was stirred at 70 C. for 2 hours and the phases were then separated. The sulfuricacid phase was initially introduced with 2 parts (0.0133 mol) of sodium iodide and 62.5 parts (1 mol) of 80% strength by weight hydrazine hydrate were added dropwise. The reaction mixture was heated to reflux (116 C.) and the organic phase was added dropwise in the course of60 minutes. In order to keep the temperature at 116 C., water was distilled off. The mixture was stirred at 116 C. for 5 hours, 150 ml of water being distilled off in this process. The mixture was diluted with 500 ml of water, and the precipitate was filtered off at room 30 temperature and washed with water until neutral. After drying, 213.3 partsof 3,5-diphenylpyrazole having a purity of 96% (HPLC) were obtained, which corresponds to a yield of 93.1% of theory. M.p.: 196 C. |
93.7% | With sodium iodide; benzaldehyde; hydrazine hydrate; In water; | Example 4 25 parts (0.5 mol) of hydrazine hydrate and 60 parts (0.5 mol) of acetophenone were simultaneously added dropwise to 326.7 parts of initially introduced 60% strength by weight sulfuric acid. The mixture wasstirred at 120 C. for 2 hours and then cooled to 50 C. 53 parts (0.5 mol) of benzaldehyde were added dropwise to the reaction mixture and it was stirred at 120 C. for a further 2 hours. 5 parts (0.033 mol) of 10% strength by weight sodium iodide were added dropwise in the course of 10 minutes and the mixture was stirred under reflux for 4.5 hours. After cooling and diluting with 100 parts of water, the reaction product was filtered off and washed with water until neutral.111.2 parts of 3,5-diphenylpyrazole having a purity of 92.7% (HPLC) were obtained, which corresponds to a yield of 93.7% of theory. M.p.: 192 C. |
93.2% | With sodium iodide; benzaldehyde; In water; hydrazine hydrate; | Example 5 120 parts (1 mol) of acetophenone and 106 parts (0.5 mol) of benzaldehyde were simultaneously added dropwise at 25 C. to 980 parts (6 mol) of initially introduced 60% strength by weight sulfuric acid. The mixture was stirred at 25 C. for 30 minutes and the phases were then separated. The sulfuric acid phase was initially introduced with 2 parts (0.013 mol) of sodium iodide and the organic phase was simultaneously metered in in the course of 10 minutes with 62.5 parts (1 mol) of 80% strength by weight hydrazine hydrate. The mixture was stirred under refluxfor 4.5 hours, during the course of which the temperature fell from 123 C. to 119 C. After diluting with 500 parts of water, the mixture was cooled to room temperature and the solid was filtered off.The filter residue was washed with water until neutral and dried. 210.4 parts of 3,5-diphenylpyrazole having a purity of 97.5% (HPLC) were obtained, which corresponds to a yield of 93.2% of theory. M.p.: 198 C. |
With sodium iodide; benzaldehyde; hydrazine hydrate; In water; | Example 1 60 parts (0.5 mol) of acetophenone and 53 parts (0.5 mol) of benzaldehyde were simultaneously added dropwise at 40 C. to 326.7 parts (2.0 mol) of 60% strength by weight sulfuric acid in the course of 30 minutes. The mixture was stirred at 40 C. for 30 minutes and the phases were then separated. The sulfuric acid phase was initially introduced intoa four-necked flask with 0.5 parts (0.0033 mol) of sodium iodide and heatedto 130 C. The upper phase was then simultaneously added dropwise with 25 parts (0.5 mol) of hydrazine hydrate in the course of 30 minutes. The temperature fell from 130 C. to 120 C. during the addition. The temperature was again brought to 130 C. by distilling off water and kept at 130 C. for 2 hours by further distillation of water. The amount of water distilled off was 70 ml. The mixture was diluted at 100 C. with 250 ml of water and neutralizedat 70 C. with 497 parts (3.1 mol) of 25% strength sodium hydroxide solution. The precipitate was filtered off with suction at 25 C. and washed with water until sulfate-free. After drying, 105.5 parts of 3,5-diphenylpyrazole were obtained having a purity of 98.5% (HPLC), which corresponds to a yield of 94.4% of theory. M.p.: 199 C. | |
With sodium; | Example 8 490 parts (3 mol) of 60% strength by weight sulfuric acid were initially introduced into the stirring flask. 46.9 parts (0.75 mol) of 80% strength by weight hydrazine hydrate, 90 parts (0.75 mol) of acetophenone, 79.5 parts (0.75 mol) of benzladehyde and 1.5 parts (0.01 mol) of sodium iodidewere metered in in succession at room temperature. The reaction mixture wasbrought to 120 C. by distilling off water and kept at 120 C. for 2.5 hours. 110 parts of water were distilled off. The mixture was diluted with the distilled-off water and neutralized with 717 parts (4.5 mol) of 25% strength by weight sodium hydroxide solution. The precipitate was filtered off at room temperature, and the filter residue was washed with water and dried. 160.6 parts of 3,5-diphenylpyrazole having a purity of 94.4% (HPLC) were obtained, which corresponds to a yield of 91.9% of theory. M.p.: 194 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.5% | With sodium hydroxide; dimethyl sulfate; In water; 4-methyl-2-pentanone; | EXAMPLE 5 The preparation of 1 -methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e Five parts of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e are dissolved in 25 parts (by volume) of methyl isobutyl ketone. Solid anhydrous sodium hydroxide (1.1 parts) is added and the mixture is heated to 90C. Dimethyl sulfate (3.43 parts) is added and the mixture is next heated to 112C. to 115C. The reaction mixture is sampled after 1.5 hours, and no unreacted <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is found to be present. The reaction mixture is cooled to 50C., and 30 parts of water are added. The pH is next adjusted to between 11 and 12 by the addition of aqueous sodium hydroxide. The organic layer is washed twice with 30 parts water. For yield determination the methyl isobutyl ketone is removed in vacuo, producing 4.95 parts (93% crude yield) of an oil which crystallizes on cooling (melting point 52C. to 53C). Analysis of the product shows it to be 85.5% pure as 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e. |
85.5% | With sodium hydroxide; dimethyl sulfate; In water; 4-methyl-2-pentanone; | EXAMPLE 5 The preparation of 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e Five parts of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e are dissolved in 25 parts (by volume) of methyl isobutyl ketone. Solid anhydrous sodium hydroxide (1.1 parts) is added and the mixture is heated to 90 C. Dimethyl sulfate (3.43 parts) is added and the mixture is next heated to 112 to 115 C. The reaction mixture is sampled after 1.5 hours, and no unreacted <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is found to be present. The reaction mixture is cooled to 50 C., and 30 parts of water are added. The pH is next adjusted to between 11 and 12 by the addition of aqueous sodium hydroxide. The organic layer is washed twice with 30 parts water. For yield determination the methyl isobutyl ketone is removed in vacuo, producing 4.95 parts (93% crude yield) of an oil which crystallizes on cooling (melting point 52 to 53 C). Analysis of the product shows it to be 85.5% pure as 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e. |
With benzenesulfonic acid; In methanol; | Example 10 As in Example 2, a melt of 10 g (0.0455 mol) of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e and 0.72 g (0.00455 mol) of benzenesulfonic acid was introduced and reacted over the course of 4.5 hours with 245 g (7.66 mol) of gaseous methanol (vaporized at 160 C.). 9.6 g (88.5%) of 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e were obtained, boiling point 190 C./3 mbar, with a content of 98.2% (GC). |
With methanesulfonic acid; In methanol; | Example 11 As in Example 2, a melt of 10 g (0.0455 mol) of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e and 0.44 g (0.0045 mol) of methanesulfonic acid was introduced and reacted over the course of 4 hours with 175 g (5.46 mol) of gaseous methanol (vaporized at 160 C.). 10 g (92%) of 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e were obtained, boiling point 190 C./3 mbar, with a content of 98% (GC). | |
With sodium hydroxide; dimethyl sulfate; In 5,5-dimethyl-1,3-cyclohexadiene; water; | EXAMPLE 6 The preparation of 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e Twenty parts of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is dissolved in 100 parts xylene containing 7.26 parts of solid anhydrous sodium hydroxide. The reaction mixture is heated to 120 C., and 13.8 parts of dimethyl sulfate are added. The reflux temperature drops to 95 C., and after 15 minutes at 95 C., a reaction mixture sample indicates no unreacted <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is remaining (tlc.) After 30 minutes, the reaction mixture is cooled to 80 C. and 50 parts of water are added. Fifty percent aqueous sodium hydroxide is added to bring pH of aqueous phase to between 10 and 11. The organic layer is washed twice with 50 parts of water. For yield determination the xylene is removed in vacuo, producing 19.7 parts of an oil which crystallizes on seeding. Analysis of the product shows it to be 98.5% pure. | |
With sodium hydroxide; dimethyl sulfate; In 5,5-dimethyl-1,3-cyclohexadiene; water; | EXAMPLE 6 The preparation of 1-methyl-<strong>[1145-01-3]3,5-diphenylpyrazol</strong>e Twenty parts of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is dissolved in 100 parts xylene containing 7.26 parts of solid anhydrous sodium hydroxide. The reaction mixture is heated to 120C., and 13.8 parts of dimethyl sulfate are added. The reflux temperature drops to 95C., and after 15 minutes at 95C., a reaction mixture sample indicates no unreacted <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e is remaining (tlc.) After 30 minutes, the reaction mixture is cooled to 80C. and 50 parts of water are added. Fifty percent aqueous sodium hydroxide is added to bring pH of aqueous phase to between 10 and 11. The organic layer is washed twice with 50 parts of water. For yield determination the xylene is removed in vacuo, producing 19.7 parts of an oil which crystallizes on seeding. Analysis of the product shows it to be 98.5% pure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 1h; | A mixture of 3,5-diphenylpyrazole (7.32 g, 33 mmol), [4-(chloromethyl)phenyl]methanol (5.00 g, 32 mmol), potassium carbonate (6.90 g, 50 mmol) and N,N-dimethylformamide (50 mL) was stirred at 120C for 1 hr. The reaction mixture was poured into 1 N hydrochloric acid and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound (7.10 g, yield 63%) as colorless crystals. 1H NMR (CDCl3) delta: 1.59-1.68(1H, m), 4.66(2H, d, J=5. 8Hz), 5.39(2H, s), 6.67(1H, s), 7.10(2H, d, J=8.1Hz), 7.24-7.47(10H, m), 7.84-7.90(2H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | To a solution of 3,5-diphenyl-1H-pyrazole (0.36 g, 1.65 mmol) in N,N-dimethylformamide (8.6 mL) was added sodium hydride (60% in oil, 66 mg, 1.65 mmol) under stirring at room temperature, and the mixture was stirred at the same temperature for 30 min. To the reaction mixture was added sodium iodide (22 mg, 0.15 mmol) and a solution of methyl 4-(bromomethyl)-3-isopropoxybenzoate (0.43 g, 1.50 mmol) in N,N-dimethylformamide (4.3 mL), and the mixture was stirred at room temperature for 3 hr. The reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1-hexane/ethyl acetate=4/1) to give the title compound (0.59 g, yield 92%) as a colorless oil. MS (ESI+): 427 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With iodine; potassium carbonate; toluene-4-sulfonic acid hydrazide; In ethanol; at 75℃; for 2h;Green chemistry; | General procedure: To a stirred mixture of alpha,beta-unsaturated aldehydes/ketones 1 (0.5 mmol) and TsNHNH2 (0.6 mmol) in EtOH (2.0 ml) was added molecular iodine (2.5 mg, 2 mol%) in an oven-dried flask, and then the reaction was heated to 75 C for 10 min followed by the addition of K2CO3 immediately. The reaction proceeded under an air atmosphere for 1.5-2.0 h until complete consumption of starting material as monitored by TLC. The reaction mixture was concentrated under vacuum and the crude product was purified by column chromatography using petroleum ether/ethyl acetate as eluent to provide the product 2. |
89% | With iron(III)phthalocyanine chloride; potassium carbonate; hydrazine hydrate; In ethanol; at 20℃; for 3h;Green chemistry;Catalytic behavior; | General procedure: alpha,beta-Unsaturated ketones (0.5 mmol), hydrazine hydrate (1.5 mmol, 3 equiv.), iron(III) phthalocyanine chloride (5 mol%), K2CO3 (0.5 mmol, 1 equiv.), and ethanol (3.0 mL) were added successively to a dry round-bottomed flask. The mixture was stirred at room temperature for 3 h under air. When the reaction was complete, as indicated by thin-layer chromatography, the reaction mixture was washed with saturated NaCl aqueous solution (2 × 10 mL) and extracted with ethyl acetate (2 × 10 mL); the organic layers were combined. After drying with anhydrous Na2SO4 and evaporation under reduced pressure, the crude product was purified by column chromatography on silica gel using petroleum ether:ethyl acetate (4:1) as the eluent to afford 3,5-disubstituted 1H-pyrazoles. 3,5-Diphenyl-1H-pyrazole (2a). White solid, yield: 89%; 1H NMR (400 MHz, CDCl3) delta: 7.71 (d, J = 7.2 Hz, 4H), 7.39-7.30 (m, 6H), 6.82 (s, 1H); 13C NMR (100 MHz, CDCl3) delta: 148.7, 131.2, 128.8, 128.1, 125.6, 100.0; HRMS (ESI) m/z calcd. for C15H12N2 [M + H]+: 221.1073, found: 221.1073. |
65% | With hydrazine hydrate; In ethanol; for 16h;Reflux; | To a solution of chalcone 3 (200 mg, 0.960 mmol) in EtOH (5 mL) was added hydrazine hydrate (57.7 mg, 1.153 mmol) and the mixture was refluxed for 16 h. After evaporation of the solvent in vacuo the compound was purified by silica-gel column chromatography using chloroform as an eluent, then was characterized by IR, NMR and ESI+-MS, and identified as 3,5-diphenyl-1H-pyrazole 4 (65% yield). 3,5-Diphenyl-1H-pyrazole, 430: m.p. 200 C. IR (KBr): 3408, 1637 cm-1; 1H NMR (CDCl3): delta 4.94 (bs, 1H, NH), 6.88 (s, 1H, CH), 7.36-7.44 (m, 6H, CHar), 7.75 (d, 4H, JHH = 7.8 Hz, CHar); 13C NMR (CDCl3): delta 100.4 (CH), 125.9, 128.3, 128.4, 128.5, 128.6, 128.7, 128.8, 128.9, 130.1, 133.1 (CHar), 130.4 (Car), 148.4 (C=N) and (C=CH); DEPT-135 NMR delta(CDCl3): 100.4 (CH), 125.9, 128.3, 128.4, 128.5, 128.6, 128.7, 128.8, 128.9, 130.1, 133.1 (CHar); ESI+-MS: m/z 221.10656 [M+H]+. Tandem MS m/z 194.1, 167.1, 119.1, 106.1. Anal. Calcd for C15H12N2: C, 81.79; H, 5.49; N, 12.72. Found: C, 81.87; H,5.55; N, 12.87%. |
35% | With tetrabutylammomium bromide; toluene-4-sulfonic acid hydrazide; sodium hydroxide; In water; at 80℃; for 20h;Air atmosphere; | General procedure: A Schlenk tube with a magnetic stir bar charged with alpha,beta-unsaturated carbonyl compounds (0.5 mmol, 1 equiv), tosyl hydrazide (0.6 mmol, 1.2 equiv), NaOH (1.5 equiv), (n-Bu)4NBr (1.5 equiv). The reaction vessel was placed in an 80 C oil bath, and then stirring at this temperature for 10 h. The reaction mixture was then allowed to cool to ambient temperature, and diluted with 20 mL of ethyl acetate, and washed with brine (15 mL), water (15 mL), and then the organic layer was dried over Na2SO4. After concentrated in vacuo, the crude product was purified by column chromatography. The identity and purity of the known product was confirmed by 1H NMR, 13C NMR, and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With N-iodo-succinimide; trifluorormethanesulfonic acid; hydrazine hydrate; In toluene; at 111℃; for 5h;Sealed tube; | The preparation process is as follows: adding a propargyl alcohol derivative, a halogen source and an acid in a sealed tube, and carrying out the reaction under the condition of heating under reflux at 111 C; and adding hydrazine after monitoring that the propargyl alcohol derivative has completely disappeared by TLC,After 5 hours of reaction, saturated brine was added to quench the reaction. The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated to obtain a pyrazole derivative. The purity of the product was improved by column chromatography. Among them, propargyl alcohol, halogen source, hydrazine, solvent and acid were added as 1,3-diphenylprop-2-yn-1-ol (2 mmol), NIS (2 mmol), hydrazine hydrate (2.8 mmol), Toluene (10 mL) and trifluoromethanesulfonic acid (0.3 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sodium hydride; In dimethyl sulfoxide; at 20℃; for 16h; | General procedure: Synthesis of the previously reported pyrazolyl ligands 1-4 firstinvolved the preparation of 3,5-ditertbutylpyrazole and <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e. In a typical procedure, 3,5-disubstituted pyrazole(1 mmol) was reacted with methyl-4-(chloromethyl)benzoate(1 mmol) or benzyl bromide (1 mmol) in DMSO in the presence ofNaH (4 mmol) at room temperature for 16 h. Water was thenadded to the reaction mixture and the product extracted usingEtOAc. The crude product was then purified via column chromatographyusing a 1:3 v:v diethyl ether:hexane mixture [18]. |
276 mg | With sodium hydroxide; In acetonitrile; at 20℃; for 2h; | General procedure: A mixture of chalcone (1d) (208 mg, 1.0 mmol) and TsNHNH2 (205 mg, 1.1 mmol) in EtOH (2 mL) were stirred at room temperature for 48 h and then EtOH (2 mL), NaOH (44.0 mg, 1.1 mmol) were added and the mixture was heated at reflux for 15 h, then the solvent was removed under reduced pressure, then CH3CN (4 mL), NaOH (60 mg, 1.5 mmol) and benzyl bromide (255 mg, 1.5 mmol) were subsequently added and the mixture was stirred at room temperature for 2 h. The product was extracted with Et2O and the organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. Purification by chromatography on silica gel afforded the desired product 4n as white crystalline solid (276 mg, 89% yield). Mp 114-117 C; deltaH (400 MHz, CDCl3) 5.38 (2H, s), 6.66 (1H, s), 7.09 (2H, d, J 7.2 Hz), 7.21-7.30 (4H, m), 7.32-7.42 (7H, m), 7.87 (2H, d, J 7.2 Hz); deltaC (100 MHz, CDCl3) 53.2, 103.7, 125.6, 126.7, 127.4, 127.6, 128.55, 128.56, 128.6, 128.8, 130.6, 133.4, 137.7, 145.4, 150.9; HRMS (ESI): MH+, found 311.1536. C22H19N2 requires 311.1543, numax (liquid film) 3060, 2955, 2924, 2853, 1452, 1361, 1307 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium methylate In 1,2-dichloro-ethane; acetonitrile Inert atmosphere; | [Fe(Ph2Tp)(HLF)(Ph2pz)] (1F) 3,5-Diphenylpyrazole (236 mg, 1.04 mmol), K(Ph2Tp) (714 mg, 1.01 mmol), and 2,6-dimethylhydroquinone (H2LF, 164 mg, 1.19 mmol) were dissolved in a 3 : 1 mixture of DCE-MeCN. To this solution was added FeCl2 (129 mg, 1.02 mmol) in MeCN and NaOMe (0.23 mL of 4.37M MeOH solution, 1.00 mmol). The reaction was stirred overnight. The solvent was evaporated under vacuum to give a pale orange solid. The crude solid was taken up into DCE andfiltered, providing a bright yellow solution. Yellow crystals were obtained by layering this DCE solution with pentane. Anal.Calcd for C68H55BFeN8O2 (MW = 1082.88 g mol-1): C, 75.42;H, 5.12; N 10.35. Found: C, 75.22; H, 5.00; N 10.21. UV-vis[λmax, nm (ε, M-1 cm-1) in CH2Cl2]: 374 (2530). FTIR (cm-1,solid): 3355 (OH), 3060, 3038, 2912, 2631 (BH), 1598, 1543, 1477, 1465, 1430, 1410, 1339, 1306, 1212, 1165, 1062, 1004,967, 913, 851, 810, 754, 688. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(l) iodide; potassium carbonate; L-proline; In dimethyl sulfoxide; at 80℃;Inert atmosphere; | 2d. Under argon atmosphere, CuI (0.38 g, 2 mmol), proline(0.46 g, 4 mmol) and K2CO3(2.76 g, 20 mmol) were added toa dimethyl sulfoxide (15 mL) solution of 6-bromopyridine-2-carboxylate (4.60 g, 20 mmol) and 3,5-diphenylprazole (4.44 g,20 mmol). The formed mixture was stirred at 80C overnight.Water was added after cooling down to room temperature, and theresulting mixture was extracted with ethyl acetate (3× 20 mL). Theorganic layers were combined and the solvent was removed to givethe crude product, which was purified by column chromatography(3.76 g, 83% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Potassium hydroxide (0.800 g, 14 103 mol) was treated with 9.0 mL of DMSO and the resulting mixture was magnetically stirred at room temperature (ca. 298 K) for 30 min. After this period 3,5-diphenylpyrazole (0.788 g, 3.58 103 mol) was added and the stirring was maintained for 30 min at 298 K. Then, 1-chloro-2-methoxyethane (4.0 mL, 45 103 mol) was gradually added and the reaction mixture was left overnight under stirring at 298 K. After this period, 50 mL of iced cold water was added to eliminatethe unreacted KOH; the organic phase was then extracted with diethylether and washed repeatedly with water, dried over Na2SO4 and filtered. Then, the filtrate was concentrated to dryness on arotary evaporator. The solid formed was collected and later on dried in vacuum for 3 days. [Yield: 0.880 g, (88%)]. Characterization data:Anal (%). Calc. for C18H18N2O (MW 278.35): C, 77.67; H, 6.52; N,10.06%; found: C, 77.8; H, 6.6 and N, 10.1. MS (ESI): m/z 279.15[M] H}. IR selected data: 3059-3015 [n(CeH)] and 2987-2952[n(CeH)], 1481(m), 1462(s), 1441(m), 1363(m), 1300(m), 1115(s),1012(m), 762(s), 691(s) cm1. UV-vis data (c 5.74 x 10-5 M in CH2Cl2): l (epsilon) 223 (1.5 104) and 253 (3.1 104). Rf (inCHCl3) 0.24. 1H NMR data: d 3.32 (s, 3H, OMe); 3.91 [t,3JH,H 7.2, 2H, (-CH2-d)]; 4.34 [t, 3JH,H 7.2, 2H, (-CH2-c)]; 6.65(s, 1H, H4); 7.35 (t, 3JH,H 7.7, 1H, H4b); 7.47e7.60 (m, 5H, H3a, H4a,H5a, H3b and H5b); 7.70 (d, 2H, 3JH,H 7.6, H2b and H6b), 7.92 (d, 2H,3JH,H 7.5, H2a and H6a). 13C{1H} NMR data: 49.1 (Cd); 58.9 (OMe);71.4 (Cc); 103.4 (C4); 125.3 (C2b and C6b); 125.7 (C2a and C6a); 126.0(C4b); 126.8 (C4a); 128.7 (C3a and C5a); 129.2 (C3b and C5b); 130.7(C1b); 133.6 (C1a); 145.9 (C5) and 150.9 (C3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74%; 20% | With Selectfluor; In acetonitrile; at 80℃; for 0.666667h;Inert atmosphere; | To a flame dried flask was added <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e (0.21 g, 0.95 mmol), Selectfluor (0.76 g, 2.1 mmol), and dried, ground molecular sieves (3 A) (0.5 g) followed by dry acetonitrile (distilled from CaH2 and stored over molecular sieves) (3 mL) and the mixture was heated at 80 C (oil bath temp) under N2 for 40 min. The dark yellow solution was then diluted with EtOAc and filtered. The filtrate was evaporated onto silica gel and subjected to flash chromatography on silica gel using 10:1 hexanes/EtOAc as eluent to give first difluoropyrazole 2 (0.19 g, 74% yield) and then the hydrated difluoropyrazole 3 (0.054 g, 20% yield) as yellow solids. The products were recrystallized from hexanes (2) or cyclohexane (3) to give analytical samples as pale yellow crystals. Data for 4,4-difluoro-3,5-diphenyl-4H-pyrazole (2): mp 91.2-91.8 C. IR (ATR): 3071, 3054, 1594, 1582, 1556, 1497, 1447, 1379, 1353, 1339, 1220, 1101, 1021, 872, 777, 720, 698, 681 cm-1. 1H NMR (300 MHz, DMSO-d6): 8.05 (d, J = 7.5 Hz, 4H), 7.74-7.64 (m, 6H). 13C NMR (75 MHz, DMSO-d6): 161.8 (t, J = 22.7 Hz), 133.8 (s), 129.9 (s), 127.8 (s), 125.7 (t, J = 265.9 Hz), 124.7 (s). 19F NMR (282 MHz, DMSO-d6): -116.4 (s). Anal. calcd for C15H10F2N2: C, 70.30; H, 3.93; N, 10.93; found: C, 70.41; H, 4.02; N, 10.82. Data for 4,4-difluoro-3,5-diphenyl-4,5-dihydro-1H-pyrazol-5-ol (3): mp 105.6-106.3 C. IR (ATR): 3354, 3238 (broad), 1593, 1571, 1491, 1332, 1449, 1238, 1136, 1068, 1050, 1016, 964, 889, 778, 688, 656, 635 cm-1. 1H NMR (300 MHz, DMSO-d6): 8.77 (s, 1H), 7.69 (d, J = 7.2 Hz, 2H), 7.59-7.56 (m, 2H), 7.48-7.40 (m, 6H), 7.31 (s, 1H). 13C NMR (75 MHz, acetone-d6): 143.9 (dd, J = 22.5 Hz, 24.0 Hz), 136.8 (d, J = 2.3 Hz), 134.2 (s), 130.1 (s), 129.8 (s), 129.6 (s), 128.9 (s), 128.2 (d, J = 1.6 Hz), 126.2 (d, J = 1.6 Hz), 125.3 (dd, J = 251.7 Hz, 261.9 Hz), 92.9 (dd, J = 20.8 Hz, 32.4 Hz). 19F NMR (282 MHz, DMSO-d6): -103.4 (d, J = 259 Hz), -122.7 (d, J = 259 Hz). Anal. calcd for C15H12F2N2O: C, 65.68; H, 4.41; N, 10.21; found: C, 65.58; H, 4.39; N, 10.23. |
29%; 67% | With water; Selectfluor; In acetonitrile; at 80℃; for 2.33333h; | A mixture of <strong>[1145-01-3]3,5-diphenylpyrazol</strong>e (1) (0.0927 g, 0.42 mmol) and Selectfluor (0.34 g, 0.97 mmol) in non-dried, stock-grade acetonitrile (1.5 mL) was heated at 80 C (oil bath temp) in an open atmosphere for 2 h and 20 min (140 min) and then cooled. Water was added to the dark yellow solution followed by extraction with EtOAc. The organic layers were combined and dried over Na2SO4 and filtered. The filtrate was evaporated onto silica gel and subjected to flash chromatography on silica gel using 10:1 hexanes/EtOAc as eluent to give first difluoropyrazole 2 (0.031 g, 29%) and then hydrated difluoropyrazole 3 (0.077 g, 67%) as yellow solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With palladium dichloride; hydrazine; In water; N,N-dimethyl-formamide; at 70℃; for 6h; | General procedure: To a mixture of PdCl2 (5.0 mol%, 0.008 g), Cr(CO)6 (1.0 mmol, 0.22 g), aryl iodide (1.0mmol), and terminal alkyne (1.4 mmol) in DMF (3.0 mL), was added to a solution of aqueous hydrazine (1.5 mmol, 0.11 mL) and the resulting mixture was heated at 70 C. After completion of the reaction the mixture was cooled to room temperature and quenched with water. The reaction was extracted with EtOAc (3×10 mL), and the organic phase was dried over Na2SO4. The crude pyrazole product was purified by column chromatography (n-hexane/EtOAc gradient: 0 to 30% EtOAc). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62.5% | under nitrogen conditions, to a stirred solution there 1.1g (50mmol) 3,5- diphenyl-pyrazole 50ml of dimethylformamide (DMF) was added 0.12g (50mmol) of sodium hydride, stirred for several minutes , and then slowly added 1.07g (50mmol) 2- chloro-1,10-phenanthroline, the reaction was refluxed for 72h, cooled, cold water, the white precipitate was filtered off, and then recrystallized with ethanol to give white crystals of 2- (3, 5-phenylpyrazole) 1,10-phenanthroline, a yield of 62.5percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In tetrahydrofuran; at 25℃; for 48h;Inert atmosphere; | A solution of ethyl 3,5-diphenyl-1-hydropyrazole (0.25 mmol ), methyl alpha-diazoacetoacetate ( 0.30 mmol) was added in a 25 mL Schrocker tube at room temperature, [Cp * RhCl2] 2 (0·0125 mmol), AgSbF6 (0.04 mmol) and tetrahydrofuran (2.00 mL) were added and argon was bubbled through argon for 2 minutes. Tighten the lid. Stir at 25 C for 48 hours. he reaction was stopped and concentrated under reduced pressure to give a crude product. The column was finally rinsed with a mixture of petroleum ether and ethyl acetate and subjected to rapid column chromatography (silica gel column) to give the corresponding nitrogen-containing fused heterocyclic compound (74 mg of white solid, 94% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In tetrahydrofuran; at 40℃; for 48h;Inert atmosphere; | A solution of ethyl 3,5-diphenyl-1-hydro-pyrazole (0.25 mmol ), alpha-tert-butyl diazoacetoacetate ( 0.30 mmol) was added in a 25 mL Schrocker tube at room temperature, [Cp * RhCl2] 2 (0·0125 mmol), AgSbF6 (0.04 mmol) and tetrahydrofuran (2.00 mL) were added and argon was bubbled through argon for 2 minutes. Tighten the lid. Stir at 40 C for 48 hours. The reaction was stopped and concentrated under reduced pressure to give a crude product. The column was finally rinsed with a mixture of petroleum ether and ethyl acetate and subjected to rapid column chromatography (silica gel column) to give the corresponding nitrogen-containing fused heterocyclic compound (82 mg of white solid, 92% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In tetrahydrofuran; at 60℃; for 24h;Inert atmosphere; | A solution of ethyl 3,5-diphenyl-1-hydropyrazole (0.20 mmol ), tert-butyl alpha-diazoacetoacetate ( 0.25 mmol) was added in a 25 mL Schrocker tube at room temperature,[Cp * RhCl2] 2 (0·01 mmol), AgSbF6 (0.04 mmol) and tetrahydrofuran (2.00 mL) were added and argon was bubbled through argon for 2 minutes. Tighten the lid. Stir at 60 C for 24 hours. The reaction was stopped and concentrated under reduced pressure to give a crude product. The column was finally rinsed with a mixture of petroleum ether and ethyl acetate and subjected to rapid column chromatography (silica gel column) to give the corresponding nitrogen-containing fused heterocyclic compound (60 mg of white solid, 84% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In tetrahydrofuran; at 25℃; for 48h;Inert atmosphere; | A solution of ethyl 3,5-diphenyl-1-hydro-pyrazole (0.20 mmol ), alpha-benzyl diazoacetoacetate ( 0.25 mmol) was added in a 2 5 mL Schrocker tube at room temperature.[Cp * RhCl2] 2 (0·01 mmol), AgSbF6 (0.04 mmol) and tetrahydrofuran (2.00 mL) were added and argon was bubbled through argon for 2 minutes. Stir at 25 C for 48 hours. The reaction was stopped and concentrated under reduced pressure to give a crude product. Finally, the mixture was washed with a mixture of petroleum ether and ethyl acetate, and the corresponding nitrogen-containing fused heterocyclic compound (77 mg of white solid, 99% yield) was obtained by flash column chromatography (baby gel column). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In tetrahydrofuran; at 60℃; for 24h;Inert atmosphere; | A solution of ethyl 3,5-diphenyl-1-hydro-pyrazole (0.20 mmol ), alpha-diazo-1-phenyl-1,3-butanedione ( 0.25 mmol) was added in a 2 5 mL Schrocker tube at room temperature.[Cp * RhCl2] 2 (0·01 mmol), AgSbF6 (0.04 mmol) and tetrahydrofuran (2.00 mL) were added and argon was bubbled through argon for 2 minutes. Stir at 60 C for 24 hours. The reaction was stopped and concentrated under reduced pressure to give a crude product. Finally, rinsed with a mixture of petroleum ether and ethyl acetate, and the column chromatography was rapidly subjected to column chromatography to give the corresponding nitrogen-containing fused heterocyclic compound (83 mg in white, 92% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium carbonate / acetonitrile / 2 h / Inert atmosphere; Reflux 2: water; sodium hydroxide / 4 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: All the ligands and the corresponding complexes were synthesized in the similar manner; a typical synthesis of complex 3a is described as follows: in a 100mL flask, pyrazole (0.69g 10.09mmol) was dissolved in 50mL of DMF, and NaH (0.29g, 12.16mmol) was added to the solution, the reaction mixture was stirred for 30min. 2,8-Dichloroquinoline (2.0g, 10.09mmol) was then slowly added to the flask, after the reaction mixture was refluxed for 48h under a nitrogen atmosphere, the reaction was terminated with ice water after cooling to room temperature, and a white suspension was formed. The precipitate was filtered and recrystallized from ethanol, and dried under vacuum at 30C to give the desired product 1a as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With oxygen; copper diacetate; In dimethyl sulfoxide; at 85℃; under 760.051 Torr; | General procedure: The solution of pyrazoline (2 mmol) in DMSO (10 mL) is stirred at 85 ± 5 C under 1 atm of O2 gas for appropriate time. If thestarting material is consumed, the reaction solution is cooled to room temperature. After the reaction mixture is poured into thewater (200 mL) with stirring, flocculent solid is formed. After one hour, the solid is collected by filtration and washed with water.Then the solid is dried under vacuum at 45 C overnight to afford pyrazole. If no solid is formed the mixture is extracted three timeswith DCM. The combined organic layers are washed with water, dried over anhydrous Na2SO4, and concentrated under reducedpressure. The residue is purified by column chromatography on silica gel using heptane/ethyl acetate as eluent to afford the purepyrazole. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: thionyl chloride / dichloromethane / 0.5 h / 20 °C 1.2: 1 h 2.1: tetrakis(actonitrile)copper(I) hexafluorophosphate; [(4S)-4-[5-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphanyl-1,3-benzodioxol-4-yl]-4,5,6,7-tetrahydro-1,3-benzodioxol-5-yl]-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphane; triethylamine / tetrahydrofuran / 12 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3,5-Diphenylpyrazole With thionyl chloride In dichloromethane at 20℃; for 0.5h; Stage #2: cis-2-hexenoic acid for 1h; |
Tags: 1145-01-3 synthesis path| 1145-01-3 SDS| 1145-01-3 COA| 1145-01-3 purity| 1145-01-3 application| 1145-01-3 NMR| 1145-01-3 COA| 1145-01-3 structure
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P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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