Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 75415-03-1 | MDL No. : | MFCD00115151 |
Formula : | C8H7N3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | HKEWOTUTAYJWQJ-UHFFFAOYSA-N |
M.W : | 145.16 | Pubchem ID : | 2797657 |
Synonyms : |
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 11 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 41.82 |
TPSA : | 41.57 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.59 cm/s |
Log Po/w (iLOGP) : | 1.11 |
Log Po/w (XLOGP3) : | 0.84 |
Log Po/w (WLOGP) : | 1.47 |
Log Po/w (MLOGP) : | 0.27 |
Log Po/w (SILICOS-IT) : | 2.13 |
Consensus Log Po/w : | 1.16 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.94 |
Solubility : | 1.65 mg/ml ; 0.0114 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.3 |
Solubility : | 7.35 mg/ml ; 0.0506 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -3.36 |
Solubility : | 0.0638 mg/ml ; 0.00044 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.77 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.3% | With hydrazine hydrate In ethanol at 60℃; for 0.5 h; | Example 15 Synthesis of 2-(3-pyrazolyl)pyridine (17a) Compound 16a (1 g, 6.2 mmol) obtained from the aforesaid process and hydrazine hydrate (2 mL) were dissolved in ethanol (3.3 mL), and reacted at 60° C. for 0.5 hour. Then, the mixture was cooled to room temperature, and then the solvent was removed in vacuum to afford the product 17a (874.7 mg) as a faint yellow solid, with a yield of 97.3percent. 1H-NMR (400 MHz, CDCl3): δ 8.66 (d, J=4.8 Hz, 1H), 7.75 (d, J=3.6 Hz, 2H), 7.67 (d, J=2 Hz, 1H), 7.23-7.27 (m, 1H), 6.81 (d, J=2 Hz, 1H). |
97.3% | With hydrazine hydrate In ethanol at 60℃; for 0.5 h; | Example 15 Synthesis of 2-(3-pyrazolyl)pyridine (17a) Compound 16a (1 g, 6.2 mmol) obtained from the aforesaid process and hydrazine hydrate (2 mL) were dissolved in ethanol (3.3 mL), and reacted at 60 °C for 0.5 hour. Then, the mixture was cooled to room temperature, and then the solvent was removed in vacuum to afford the product 17a (874.7 mg) as a faint yellow solid, with a yield of 97.3percent. 1H-NMR (400MHz, CDCl3 ): δ 8.66 (d, J = 4.8 Hz, 1H), 7.75 (d, J = 3.6 Hz, 2H), 7.67 (d, J = 2 Hz, 1H), 7.23-7.27 (m, 1H), 6.81 (d, J = 2 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydrazine In ethanolHeating / reflux | To a solution of 10 g (56. 7 mmol) of 3-dimethylamino-1-pyridin-2-yl- propenone in 100 mL absolute ethanol was added 1. 96 mL (62. 4 mmol, 1. 1 equiv.) of anhydrous hydrazine with stirring to give a pale yellow solution. This solution was heated to reflux and stirred overnight, then concentrated to give a tan-colored solid. The solid was then crystallized from ethyl acetate/hexane to give 8. 06 g (55. 5 mmol, 98percent) of 2-(1H-pyrazol-3-yl)-pyridine as tan-colored CRYSTALS. 1H-NMR (300 MHz, CDCI3, 8) : 11. 69 (br s, 1 H), 8. 66 (dd, J = 1 Hz, 5 Hz, 1 H), 7. 76 (d, J = 3 Hz, 1 H), 7. 74 (s, 1 H), 7. 66 (d, J = 2 Hz, 1 H), 7. 23 (t, J = 9 HZ, 1 H), 6. 81 (d, J = 3 Hz, 1 H) ; M/Z : 146 [M + H] +. |
0.19 g | at 50℃; for 0.166667 h; Microwave irradiation | Its synthesis by conventional methods and some spectroscopic datahave been previously reported [15a,15b]. MW assisted method: A mixtureof 2-acetylpyridine (0.22 mL, 2 mmol) and DMF-dimethylacetal(0.27 mL, 2 mmol) was heated in a microwave oven for 2 h at 100 °C,and then the volatiles were removed in vacuo. The brown red solid wasmixed with hydrazine hydrate (0.2 mL, 4 mmol) and heated in a microwaveoven for 10 min at 50 °C. The volatiles were removed in vacuo,the red residue was washed with water (3×5 mL), and the ochre solidthus obtained was dried in vacuo, and recrystallized from CH2Cl2/hexane, yielding 0.19 g (65percent). IR (cm−1): 3124 m, 3058 m, 3023 m,2978 m, 2937 m, 2898 m, 2835 m, 2802 m, 2735 m, 2654 w, 2501 w,2324 w, 2165 w, 2051 w, 1981 w, 1704 w, 1590 s, 1567 m, 1536 w,1502 m, 1454 m, 1416 s, 1357 m, 1303 m, 1271 w, 1231 m, 1192 w,1144 m, 1129 w, 1088 m, 1059 m, 1048 m, 1036 w, 1000 w, 993 m,950 m, 924 w, 877 m, 843 m, 797 m, 757 vs, 704 s, 695 m, 627 m,615 m. 1H NMR (400 MHz, CDCl3) δ 11.70 (s, NH, 1H), 8.63 (dt, J=4.9and 1.2 Hz, H3′, 1H), 7.73 (dt, J=8.2 and 4.1 Hz, H6′ and H4′, 2H), 7.64(d, J=2.1 Hz, H4, 1H), 7.22 (dd, J=8.1, 4.9 Hz, H5′, 1H), 6.77 (s, H5,1H). 13C{1H} NMR (101 MHz, CDCl3) δ 206.95 (C2′), 192.18 (C3),149.43 (C3′), 136.45 (C4′ and C4), 122.80 (C5′), 120.03 (C6′), 103.32(C5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | Stage #1: at 100℃; for 16 h; Reflux Stage #2: With hydrazine hydrate In ethanol at 60℃; for 0.5 h; |
A mixture of N-dimethoxymethyl-N,N-dimethylamine(10 mL) and 2-acetylpyridine (40 mL) was refluxed at 100 °C for 16 h, then concentrated by rotating evaporationto give dark brown solid. This was washed with hexane(100 mL) and diethyl ether (100 mL) to give the pure and bright yellow crystalline product. Hydrazine monohydrate (40 mL) and ethanol (15 mL) were mixed with the previously obtained solid, and the mixture was stirred at 60 °C for 30 min. After cooling, distilled water (75 mL) was added to the solution, which was kept at 0 °C for 24 h to produce a light yellow precipitate. This was recrystallized from a mixture of dichloromethane and hexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydrazine; In ethanol;Heating / reflux; | To a solution of 10 g (56. 7 mmol) of 3-dimethylamino-1-pyridin-2-yl- propenone in 100 mL absolute ethanol was added 1. 96 mL (62. 4 mmol, 1. 1 equiv.) of anhydrous hydrazine with stirring to give a pale yellow solution. This solution was heated to reflux and stirred overnight, then concentrated to give a tan-colored solid. The solid was then crystallized from ethyl acetate/hexane to give 8. 06 g (55. 5 mmol, 98%) of 2-(1H-pyrazol-3-yl)-pyridine as tan-colored CRYSTALS. 1H-NMR (300 MHz, CDCI3, 8) : 11. 69 (br s, 1 H), 8. 66 (dd, J = 1 Hz, 5 Hz, 1 H), 7. 76 (d, J = 3 Hz, 1 H), 7. 74 (s, 1 H), 7. 66 (d, J = 2 Hz, 1 H), 7. 23 (t, J = 9 HZ, 1 H), 6. 81 (d, J = 3 Hz, 1 H) ; M/Z : 146 [M + H] +. |
0.19 g | With hydrazine hydrate; at 50℃; for 0.166667h;Microwave irradiation; | Its synthesis by conventional methods and some spectroscopic datahave been previously reported [15a,15b]. MW assisted method: A mixtureof 2-acetylpyridine (0.22 mL, 2 mmol) and DMF-dimethylacetal(0.27 mL, 2 mmol) was heated in a microwave oven for 2 h at 100 C,and then the volatiles were removed in vacuo. The brown red solid wasmixed with hydrazine hydrate (0.2 mL, 4 mmol) and heated in a microwaveoven for 10 min at 50 C. The volatiles were removed in vacuo,the red residue was washed with water (3×5 mL), and the ochre solidthus obtained was dried in vacuo, and recrystallized from CH2Cl2/hexane, yielding 0.19 g (65%). IR (cm-1): 3124 m, 3058 m, 3023 m,2978 m, 2937 m, 2898 m, 2835 m, 2802 m, 2735 m, 2654 w, 2501 w,2324 w, 2165 w, 2051 w, 1981 w, 1704 w, 1590 s, 1567 m, 1536 w,1502 m, 1454 m, 1416 s, 1357 m, 1303 m, 1271 w, 1231 m, 1192 w,1144 m, 1129 w, 1088 m, 1059 m, 1048 m, 1036 w, 1000 w, 993 m,950 m, 924 w, 877 m, 843 m, 797 m, 757 vs, 704 s, 695 m, 627 m,615 m. 1H NMR (400 MHz, CDCl3) delta 11.70 (s, NH, 1H), 8.63 (dt, J=4.9and 1.2 Hz, H3?, 1H), 7.73 (dt, J=8.2 and 4.1 Hz, H6? and H4?, 2H), 7.64(d, J=2.1 Hz, H4, 1H), 7.22 (dd, J=8.1, 4.9 Hz, H5?, 1H), 6.77 (s, H5,1H). 13C{1H} NMR (101 MHz, CDCl3) delta 206.95 (C2?), 192.18 (C3),149.43 (C3?), 136.45 (C4? and C4), 122.80 (C5?), 120.03 (C6?), 103.32(C5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.3% | With hydrazine hydrate; In ethanol; at 60℃; for 0.5h; | Example 15 Synthesis of 2-(3-pyrazolyl)pyridine (17a) Compound 16a (1 g, 6.2 mmol) obtained from the aforesaid process and hydrazine hydrate (2 mL) were dissolved in ethanol (3.3 mL), and reacted at 60 C. for 0.5 hour. Then, the mixture was cooled to room temperature, and then the solvent was removed in vacuum to afford the product 17a (874.7 mg) as a faint yellow solid, with a yield of 97.3%. 1H-NMR (400 MHz, CDCl3): delta 8.66 (d, J=4.8 Hz, 1H), 7.75 (d, J=3.6 Hz, 2H), 7.67 (d, J=2 Hz, 1H), 7.23-7.27 (m, 1H), 6.81 (d, J=2 Hz, 1H). |
97.3% | With hydrazine hydrate; In ethanol; at 60℃; for 0.5h; | Example 15 Synthesis of 2-(3-pyrazolyl)pyridine (17a) Compound 16a (1 g, 6.2 mmol) obtained from the aforesaid process and hydrazine hydrate (2 mL) were dissolved in ethanol (3.3 mL), and reacted at 60 C for 0.5 hour. Then, the mixture was cooled to room temperature, and then the solvent was removed in vacuum to afford the product 17a (874.7 mg) as a faint yellow solid, with a yield of 97.3%. 1H-NMR (400MHz, CDCl3 ): delta 8.66 (d, J = 4.8 Hz, 1H), 7.75 (d, J = 3.6 Hz, 2H), 7.67 (d, J = 2 Hz, 1H), 7.23-7.27 (m, 1H), 6.81 (d, J = 2 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | To a solution of <strong>[75415-03-1]3-(2-pyridyl)pyrazol</strong>e (291 mg, 2 mmol) in THF (20 mL) was added NaH (0.3 g, 12.5 mmol). The mixture was stirred for lh and the Mel (568 mg, 4 mmol) was added in one portion. The reaction mixture was stirred for 18h at room temperature. The reaction was quenched with MeOH and the solvent was removed in vacuo. The residue was treated with water and EtOAc. The organic layer was separated and the aqueous layer was extracted with EtOAc. The combined organic phase was dried over Na2S04, filtered, and concentrated to give crude product. The crude product was purified on ISCO columns. Fractions containing pure product were combined and evaporated to give 3-(2-pyridyl)-l-methylpyrazole (300 mg, 94%) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | at 180℃; for 30h; | 1st step: adding to the reaction kettle 2.1g2 - (1H-pyrazol-3-yl) pyridine and 3.7g2- bromopyridine [2 - (1H-pyrazol-3-yl) pyridine and 2-polybromide pyridine mole ratio of 1 : 1.6], in the reactor is placed into an oven after heating to 190 C, reaction 24h;2nd step: after the reaction is ended, take the solid using saturated Na2CO3solution cleaning, separating out the solid;3rd step: the separate the solid is dried fully then dissolved in chloroform, using silica gel as stationary phase, the volume of the petroleum ether and ethyl acetate ratio of 1:1 as the eluting agent mixed solution of dry-column, collecting product, evaporation and concentration, drying, the obtained yellow solid powder is the target product, nuclear product resonating chart as shown in Figure 1, the yield of 70.1%. The eluting agent is added before the dissolving solid petroleum ether for use out of the chloroform solution. he basic steps of the embodiment 1 the same, but in 1st step 2 - (1H-pyrazol-3-yl) pyridine and 2-bromo pyridine molar ratio of 1 : 1.5, the heating temperature is 180 C, the reaction time is 30h, saturation, solid in 2nd step NaHCO3solution cleaning, the obtained yield of 71.0%. |
32.9 g (97%) | In water; | EXAMPLE 12 The synthesis of 1,3-di(2-pyridyl)pyrazole (13). A mixture of compound 11 (22.2 g, 153 mmol) and 2-bromopyridine (42.3 g, 268 mmol) was heated for 20 h at 190 C. The cooled mixture was dissolved in hot H2 O (200 ml) and the pH was adjusted to basic with solid Na2 CO3. After cooling, the precipitate was filtered and washed with cold H2 O. Yield: 32.9 g (97%). UV (EtOH): 294, 283, 224. IR (KBr): 1593, 1578 (arom). 1 H-NMR (CDCl3): 7.14 (d, J=2.6, 1H); 7.21 (ddd, J=1.0, 4.9, 7.3, 1H); 7.27 (ddd, J=1.1, 4.9, 7.3, 1H); 7.79 (dt, J=1.7, 7.3, 1H); 7.85 (dt, J=1.7, 7.3, 1H); 8.12-8.16 (m, 2H); 8.44 (dd, J=1.7, 4.9, 1H); 8.64 (d, J=2.6, 1H); 8.68 (bd, J=4.9, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With N-iodo-succinimide; In DMF (N,N-dimethyl-formamide); at 0 - 90℃; | To an ice-cold, stirred solution of 3. 0 g (20. 7 mmol) of 2-(LH-PYRAZOL-3-YL)- pyridine in 25 mL dry DMF was added 4. 66 g (20. 7 mmol) of N-iodosuccinimide (freshly recrystallized from dioxane/ether) in portions over 10 minutes. The resulting orange solution was warmed to room temperature, then heated to 90 C overnight with stirring, after which the solution turned dark orange. The solution was partitioned between CH2C12 and saturated NAHCO3 solution. The organic solution was washed twice with saturated NaHCO3, once with water, then brine, and dried with NA2SO4. The filtrate was concentrated and the residue was recrystallized twice from ETHANOL/WATER to give 3. 77 g (13. 9 mmol, 67%) OF 2-(4-IODO-LH-PYRAZOL-3-YL)-PYRIDINE as fine, beige-colored CRYSTALS. 1H-NMR (300 MHz, CDC13, #) : 11. 50 (br s, 1 H), 8. 64 (dd, J = 2 HZ, 6 HZ, 1 H), 8. 39 (d, J = 8 HZ, 1 H), 7. 82 (td, J = 2 Hz, 8 Hz, 1 H), 7. 69 (s, 1 H), 7. 30 (qd, J = 1 Hz, 5 Hz, 1 H) ; m/z : 272 [M + H] +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | In 1,4-dioxane; at 150℃; for 1h; | EXAMPLE 39 In a sealed tube dicarbonyl intermediate 10 (52 mg, 0.13 mmol), <strong>[75415-03-1]2-(1H-pyrazol-3-yl)pyridine</strong> (104 mg, 0.71 mmol) and 1,4-dioxane (2.0 mL) were combined and heated at 150 C. with microwaves for 1 h. The reaction mixture was concentrated, diluted with MeOH, filtered and purified by preparative HPLC to yield 54 (31 mg, 0.06 mmol, 47%) as an off-white solid. 1H NMR: (500 MHz, DMSO-d6) delta 12.60 (br s, 1H), 8.97 (d, J=1.8 Hz, 1H), 8.94 (s, 1H), 8.73-8.66 (m, 2H), 8.61 (br s, 1H), 8.02 (t, J=7.0 Hz, 1H), 7.54-7.38 (m, 6H), 7.31 (d, J=1.8 Hz, 1H), 3.92-3.13 (m, 8H); LC/MS: (ES+) m/z (M+H)+=507; HPLC Rt=1.19 min., column N. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sulfuric acid; nitric acid; In water; at 20℃; | 2-(1H-Pyrazol-3-yl)pyridine (10 g) was suspended in concentrated sulfonic acid (30 mL), then fuming nitric acid (6.5 mL, 2 eq.) was added to the solution dropwise while stirring. The reaction mixture was stirred overnight at room temperature. It was quenched by pouring into ice-water (500 mL). The aqueous solution was neutralized by adding solid sodium carbonate, until pH reached around 8. White precipitate was collected by filtration, washed with water and dried to give 2-(4-nitro-1H-pyrazol-3- yl)pyridine 102 (13 g, 99% yield). |
With sulfuric acid; nitric acid; at 20 - 100℃; for 1h; | 2-(lH-pyrazole-3-yl) pyridine (Maybridge) (0.63 g, 4.34 mmol) was dissolved in c. H2SO4 (10 ml) and treated with a mixture of c. H2SO4 (5 ml) and c. HNO3 (5 ml). This mixture was stirred at ambient temperature O/N, then heated at 100C for 1 h. cooled to ambient temperature, then poured onto ice and neutralized. The solid that formed was filtered and dried to give 2-(4-nitro-lH-pyrazol-3-yl)-pyridine (1.3 g) (LC/MS polar: Rt 2.12, [M+H]+ 192). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water N2 atmosphere; addn. of triflate to mixt. of Fe-salt and ligand (in warmH2O, crystn.); washing (cold H2O), drying (P2O5); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With 2,6-dimethylpyridine In methanol; water MeOH soln. of tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 3-(2-pyridyl)pyrazole, 2,6-dimethylpyridine excess layered on top of an aq. soln. ofCd(ClO4)2; crystd. after 2 wk at room temp.; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With thionyl chloride; triethylamine In benzene at 0℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | 2-(1H-Pyrazol-3-yl)pyridine15 (13.0 g, 90 mmol) and tetra-n-butylammonium bromide (1.4 g, 4.3mmol) were suspended in distilled water (219 ml). With vigorous stirring, sodium carbonate (60g, 0.56 mol) was added gradually to the reaction mixture. At room temperature chloroform (70ml) was added and the flask was equipped with a reflux condenser. This mixture was heated atreflux for three days during which it became a dark emulsion. The mixture was allowed to coolto room temperature and filtered to remove the solid sodium carbonate. The organic layer wasseparated from the aqueous layer and the latter was extracted with diethylether (3×100 ml). Thecombined organic layers were washed with distilled water (2×200 ml) and dried over sodiumsulphate. The solution was filtered and the solvent was removed under reduced pressure. Theresulting red-brown residue was dissolved in the minimum amount of hot toluene and pouredinto a flask containing a small amount of p-toluenesulfonic acid (0.18 g). The dark solution washeated at reflux temperature for one day. After it had cooled to room temperature, a darkprecipitate appeared that was filtered. The residue was suspended in water (100 ml) and stirredovernight. Then the red brown residue was filtered, washed with water, extensively with ethanoland hexane, to afford pure tris(3-(pyridin-2-yl)-1H-pyrazol-1-yl)methane (HC(3-Pypz)3, 1). Sandbrown powder, yield 45%, 6.0 g. 1H NMR (500 MHz, CDCl3, 25 C): deltaH 7.03 (3H, d, CHpz, 3JHH = 2.65 Hz), 7.23 (3H, m, CHpy),7.70 (6H, m, CHpz + CHpy), 7.96 (3H, d, CHpy, 3JHH = 8.0 Hz), 8.60 (1H, s, CH), 8.61 (3H, d,CHpy, 3JHH = 5.10 Hz). 13C NMR (125 MHz, CDCl3, 25 C): deltaC 84.0 (CH), 106.1 (CHpz), 120.6(CHpy), 123.0 (CHpy), 130.9 (CHpz), 136.6 (CHpy), 149.3 (CHpy), 151.2 (Cpy), 153.9 (Cpz). IR(KBr, ~[cm-1]): 3162 vw (nu(CHarom)), 3139 vw (nu(CHarom)), 3106 vw (nu(CHarom)), 3048 vw(nu(CHarom)), 2967 w (nu(CHaliph)), 2923 vw (nu(CHaliph)), 2852 vw (nu(CHaliph)), 1592 s, 1567 m,1482 vs, 1457 s, 1432 m, 1394 m, 1361 m, 1340 s, 1286 m, 1247 vs, 1213 vs, 1195 s, 1052 m,1033 m, 812 vs, 802 vs, 792 s, 774 s, 759 vs, 748 m. EI-MS (m/z, (%)): 445.1 (35) [M+ =C25H19N9], 303.1 (51) [M+-C8H6N3 + 2H], 302.1 (98) [M+-C8H6N3 + H], 301.1 (100) [M+-C8H6N3], 300.1 (98) [M+-C8H6N3 - H], 299.0 (28) [M+-C8H6N3 - 2H], 289.1 (5) [C15H11N7+],288.1 (16) [C15H11N7+ - H], 287 (14) [C15H11N7+ - H], 223.0 (10) [C12H9N5+], 157.0 (66)[C9H7N3+], 156.0 (81), 144.0 (13) [C8H6N3+], 143.0 (21), 142.0 (11), 141.0 (4), 80.0 (3), 79.0(46), 78.0 (94) [C5H4N+], 76.0 (6). Anal. Calcd for C25H19N9 (445.1 g/mol): C, 67.40; H, 4.30; N,28.30%. Found: C, 67.10; H, 4.31; N, 28.00%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetramethyl ammoniumhydroxide; sodium hydroxide; In water; toluene; at 120℃; for 24h; | 4.2.1 Ligand 1-[(5-methyl-2,2'-bipyridin-5'-yl)-methyl-1H-pyrazol-3-yl]-pyridine (L1) A mixture of 5-bromomethyl-5'-methyl-2,2'-bipyridine (3.00 g, 11.40 mmol), 3-(2-pyridyl)-pyrazole (1.81 g, 12.50 mmol), toluene (80 ml), (CH3)4NOH (1 ml of a 40% aqueous solution) and aqueous NaOH (6.5 g dissolved in 15 ml water) was heated to 120 C for 24 h with vigorous stirring. After the removal of the solvent, a light yellow solid was separated by filtration, washed with NaOH solution three times, recrystallized from CH2Cl2/hexane and dried. Yield: 2.65 g (71%). Mp 128-130 C, HRMS: m/z 164.5777 (L1H22+, main peak), 328.1556 (L1H+, middle peak), 350.1384(L1Na+, small peak), and 677.2844 (L12Na+, small peak). Anal. Calc. for C20H17N5: C, 73.37; H, 5.23; N, 21.39. Found: C, 73.31; H, 5.28; N, 21.41%. 1H NMR (400 MHz, CDCl3): delta 2.39 (s, 3H), 5.46 (s, 2H), 6.94 (d, 1H, J = 2.35 Hz), 7.22(dd, 1H, J = 4.70 Hz), 7.47 (d, 1H, J = 2.35 Hz), 7.62 (d, 1H, J = 8.06), 7.70(d, 1H, J = 7.8 Hz), 7.73(d, 1H, J = 7.80 Hz), 7.75(t, 1H, J = 7.80 Hz), 8.27(d, 1H, J = 8.06 Hz), 8.35(d, 1H, J = 8.06 Hz), 8.62(s, 1H), and 8.64 (d, 1 H, J = 4.7 Hz). (400 MHz, CD3CN): delta 2.36 (s, 3H), 5.44 (s, 2H), 6.89 (d, 1H, J = 2.35 Hz), 7.23(t, 1H, J = 7.80 Hz), 7.67 (dd, 1H, J = 7.80 Hz), 7.73 (d, 1H, J = 8.60), 7.75(t, 1H, J = 7.8 Hz), 7.92(d, 1H, J = 7.8 Hz), 8.27(d, 1H, J = 7.8 Hz), 8.33(d, 1H, J = 8.60 Hz), 8.47(s, 1H), 8.55(d, 1H, J = 4.7 Hz), and 8.69 (s, 1 H). (400 MHz, DMSO-d6): delta 2.35 (s, 3H), 5.54 (s, 2H), 6.86 (d, 1H, J = 2.35 Hz), 7.29(t, 1H, J = 7.80 Hz), 7.75 (dd, 1H, J = 7.80 Hz), 7.81 (d, 1H, J = 8.60), 7.91(d, 1H, J = 7.8 Hz), 8.02(d, 2H, J = 7.8 Hz), 8.27(d, 1H, J = 7.8 Hz), 8.34(d, 1H, J = 8.51 Hz), 8.47(s, 1H), 8.57(d, 1H, J = 4.7 Hz), and 8.65 (s, 1 H). 13C NMR (100 MHz, CDCl3): delta 18.6, 53.9, 105.4, 120.4, 120.9, 121.0, 122.7, 131.1, 131.9, 133.8, 136.5, 136.8, 137.7, 148.6, 149.7, 149.9, 152.3, 152.7, 153.3, 156.5. UV-Vis spectrum in CH3CN, lambdamax = 285 nm (epsilon = 34520 M-1 cm-1, pi?pi? transitions), and 250 nm (epsilon = 36390 M-1 cm-1, pi?pi? transitions). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.4% | With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 4h; | Example 16 Synthesis of 2-(1-(2-fluoro-4-nitrophenyl)-3-pyrazolyl)pyridine (18a) Compound 17a (1 g, 6.9 mmol) obtained from the aforesaid process and 3,4-difluoro-nitrobenzene (0.74 mL) were dissolved in N,N-dimethylformamide (20 mL), and then anhydrous potassium carbonate (1.9 g) was added thereto. The mixture was reacted at 100 C. for 4 hours. After completion of the reaction, the reactant mixture was cooled to room temperature. Water was added to the mixture, resulting in a substantial amount of precipitate. |
93.4% | With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 4h; | Example 16 Synthesis of 2-(1-(2-fluoro-4-nitrophenyl)-3-pyrazolyl)pyridine (18a) Compound 17a (1 g, 6.9 mmol) obtained from the aforesaid process and 3,4-difluoronitrobenzene (0.74 mL) were dissolved in N,N-dimethylformamide (20 mL), and then anhydrous potassium carbonate (1.9 g) was added thereto. The mixture was reacted at 100 C for 4 hours. After completion of the reaction, the reactant mixture was cooled to room temperature. Water was added to the mixture, resulting in a substantial amount of precipitate. Then, the precipitate wassuction-filtered, and the filter cake was recrystallized with acetone to get the product 18a as a white powder (1.7 g), witha yield of 93.4%.[0110] 1H-NMR (400 MHz, CDCl3 ): delta 8.69-8.70 (m, 1H), 8.39-8.44 (m, 1H), 8.26-8.27 (m, 1H), 8.15-8.21 (m, 2H),8.11-8.13 (m, 1H), 7.78-7.82 (m, 1H), 7.30-7.32 (m, 1H), 7.22 (d, J= 2.4 Hz, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | In water; at 139.84℃; for 72h;Autoclave; High pressure; | A mixture containing Cd(OAc)2*3H2O (OAc is acetate; 23.1 mg, 0.10 mmol), L (14.5 mg, 0.10 mmol), fumaric acid (11.6 mg, 0.10 mmol) and water (10 ml) was sealed in a Teflon lined stainless steel vessel (20 ml), which was heated at 413 K for 3 d and then cooled to room temperature at a rate of 5 K h-1. Colourless block-shaped crystals suitable for X-ray analysis were obtained in a yield of 45%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With potassium hydroxide; at 139.84℃; for 72h;High pressure; | General procedure: A mixture of 2,3',5,5'-biphenyl tetracarboxylic acid (33.0 mg,0.1 mmol), 2,2'-bipy (17.6 mg, 0.1 mmol), Cd(OAc)2*2H2O(26.6 mg, 0.1 mmol), and KOH (5.6 mg, 0.1 mmol) were added to water (12 mL) in a 25 mL Teflon-lined stainless steel vessel. Themixture was heated at 413 K for 3 days, and then slowly cooled down to room temperature. Colorless block crystals of 2 were obtained (yield: 47% based on cadmium). Anal. Calc. for C36H26Cd2-N4O10: C, 48.07; H, 2.91; N, 6.23. Found: C, 48.16; H, 2.87; N, 6.29%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tetrabutylammomium bromide; potassium carbonate; In water; acetone; for 40h;Reflux; | 2,3-Dichloroquinoxaline (400 mg, 2.01 mmol), 3-(2-pyridyl)-1H-pyrazole (pypz) (640 mg, 4.41 mmol), K2(CO)3 (760 mg,5.49 mmol) and tetra butyl ammonium bromide (TBAB) (800 mg,2.48 mmol) (Scheme 1) were taken in 30 ml of freshly distilled acetoneand refluxed for 40 h. Reaction mixture changed to reddishcolor during reaction, after completion of the reaction 100 ml ofdistilled water was added drop by drop to the reaction mixtureuntil that precipitate appeared. The precipitate was separatedand washed two to three times with water, and an off whiteproduct was obtained which was further dried in vacuum. Yield: 420 mg (68%); IR (KBr): m 3400 (w), 3157 (w), 3135 (w),3043 (w), 2923 (w), 2852 (w), 1591 (w), 1558(w), 1486 (m),1436 (m), 1371 (m), 1291 (w), 1272 (w), 1180 (w), 1125 (m),1096 (m), 992 (w), 767 (m), 756 (m), 599 (w) cm1; 1H NMR(400 MHz, CDCl3, 25 C): d 8.48 (d, 1H, J = 4.4 Hz, CH(pyridine)), 8.20(d, 1H, J = 2.4 Hz, CH(quinoxaline)), 8.09-8.07 (m, 2H, CH(pyrazole,pyridine)), 7.78-7.75 (m, 2H, CH(quinoxaline)), 7.63 (d, 1H, J = 8.0 Hz,CH(pyridine)), 7.47 (t, 1H, CH(quinoxaline)), 7.12 (d, 1H, J = 2.4 Hz,CH(pyrazole)), 7.06 (t, 1H, CH(pyridine)) ppm. ESI-MS (m/z): 309.02(M+H); UV-Vis {Acetonitrile, kmax, nm (e/104 M1 cm1)}: 211(2.12), 244 (2.42), 281 (1.53), 336 (1.32); Anal. Calc. for C16H10ClN5(307.74): C, 62.45; H, 3.28; N, 22.76. Found: C, 62.91; H, 3.61; N,22.91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36.7% | In ethanol; water; at 140℃; for 72h;Autoclave; | A mixture of HL (0.2 mmol, 29 mg), Zn(NO3)26H2O (0.2 mmol, 59 mg),ethanol (1 ml), and H2O (10 ml) was stirred for 0.5 h in air, then the resulting mixture was transferred in a Teflon-linedstainless reactor and heated to 140 C for 3 days under autogenous pressure and cooled to room temperature at a rate of10 C/h. Consequently, the colorless block-shaped crystals suitable for X-ray single crystal diffraction were obtained witha yield of 36.7 % (based on Zn(NO3)26H2O) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32.7% | In ethanol; water; at 140℃; for 72h;Autoclave; | HL (0.2 mmol, 29 mg), Cu(NO3)23H2O (0.2 mmol,48 mg), 4,4?-dibromobiphenyl (0.01 mmol, 31 mg), ethanol (3 ml) were added to 12 ml H2O, subsequently, the mixture wasplaced in a Teflon-lined stainless reactor and heated to 140 C for 3 days under autogenous pressure. Finally, the blue blockshapedcrystals suitable for X-ray single crystal diffraction were obtained with a yield of 32.7 % (based on Cu(NO3)23H2O) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; In water; benzene; at 80℃; | 2-(1H-Pyrazol-3-yl)pyridine (0.339 g, 2.33 mmol) and 3-bromomethylbenzoic acid (0.500 g, 2.33 mmol) were added to a solution of 40% aqueous NaOH (3.5 mL), benzene (10 mL), and Bu4NOH (4 drops), and the resulting solution was refluxed at 80 C overnight. After cooling to room temperature, the colourless organic layer was separated from the yellow aqueous layer. The aqueous layer was then washed with ethyl acetate (2 * 10 mL) before being acidified to pH 3 using aqueous HCl (6 M), at which point a yellow precipitate formed. This precipitate was extracted into ethyl acetate (3 * 60 mL) that was then washed with water (2 * 50 mL) and brine (50 mL). The organic layer was then dried over magnesium sulfate before having the solvent removed under reduced pressure. Recrystallization from ethyl acetate/petroleum ether (40-60 C) gave L2 as a pale brown solid (0.224 g, 34%). Anal. Calc. for C16H13N3O2·0.25H2O C, 67.71; H, 4.80; N, 14.80. Found: C, 67.94; H, 4.67; N, 14.72%. 1H NMR (400 MHz, dmf-d7): delta (ppm) = 5.61 (2H, s, Hg), 6.95 (1H, d, J = 2.3 Hz, He), 7.30 (1H, ddd, J = 7.4, 4.8, 1.2 Hz, Hb), 7.54 (1H, t, J = 7.7 Hz, Hh), 7.64 (1H, dt, J = 7.7, 1.5 Hz, Hk), 7.83 (1H, td, J = 7.7, 1.8 Hz, Hc), 8.01-7.95 (3H, m, Hd, Hj and Hi), 8.05 (1H, d, J = 2.3 Hz, Hf), 8.60 (1H, dt, J = 4.9, 1.3 Hz, Ha). HRESI-MS (dmf/MeOH): m/z calcd for C16H12N3O2-: 278.0935 [L2-H]-: found: 278.0930. Selected IR numax/cm-1: 2415, 1690, 1598, 1566, 1492, 1294, 768. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; In water; benzene; at 80℃; | <strong>[75415-03-1]2-(1H-pyrazol-3-yl)pyridine</strong> (0.500 g, 3.45 mmol) and 1,3-dimethyl-5-(bromomethyl)benzene-1,3-dicarboxylate (0.990 g, 3.45 mmol) were added to a solution of 40% aqueous NaOH (5 mL), benzene (15 mL), and Bu4NOH (5 drops), and the resulting solution was refluxed at 80 C overnight. After cooling to room temperature, the colourless organic layer was separated from the yellow aqueous layer. The aqueous layer was then washed with ethyl acetate (2 * 10 mL) before being acidified to pH 3 using aqueous HCl (6 M), at which point a white precipitate formed. The solvents were then removed in vacuo and the residue dissolved in ca. 1 mL of dmf. Addition of ethyl acetate gave a pale yellow solid, which was filtered off, washed with ethyl acetate and diethyl ether and dried (0.354 g, 32%). Anal. Calc. for C17H13N3O4·2H2O: C, 56.83; H, 4.77; N, 11.69. Found: C, 56.78; H, 3.82; N, 11.55%. 1H NMR (400 MHz, dmf-d7): delta (ppm) = 5.71 (2H, s, Hg), 6.96 (1H, d, J = 2.3 Hz, He), 7.30 (1H, ddd, J = 7.5, 4.9, 1.2 Hz, Hb), 7.83 (1H, td, J = 7.7, 1.8 Hz, Hc), 7.97 (1H, dt, J = 7.7, 1.8 Hz, Hd), 8.12 (1H, d, J = 2.3 Hz, Hf), 8.21 (2H, m, Hh), 8.63-8.56 (2H, m, Ha, Hi). HRESI-MS (dmf/MeOH): m/z calcd for C17H12N3O4-: 322.0833 [L3-H]-; found: 322.0826 (100%). Selected IR numax/cm-1: 2415, 1703, 1599, 1463, 1278, 766. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium hydroxide; tetra(n-butyl)ammonium hydroxide / benzene; water / 80 °C 2: methanol / 0.5 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | The L ligand was synthesized by following the known method [42]. Typically, <strong>[75415-03-1]3-(2-pyridyl)pyrazol</strong>e (15mmol, 2.18g), DMSO (40mL) and NaOH (15mmol, 0.60g) were stirred at 80C for 1h. Then 1,4-dibromobutane (2.5mmol, 0.54g) was added to the mixture with stirring at 100C for 10h. After DMSO was removed, the crude product was achieved. After washing with methanol, the L ligand was achieved as a yellowish powder in 65% yield. Anal. calcd for C20H20N6 (Mr=344.41): C, 69.74; H, 5.85; N, 24.40%. Found: C, 69.63; H, 5.91; N, 24.46%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With N-iodo-succinimide; In ethyl acetate; at 25℃; for 12h; | In a dry test tube, add 72.5mg of 3-pyridyl pyrazole and 178mg of methyl benzene sulfinateSodium, was added under stirring, 336mg of NIS 12 hours. After completion of the reaction, ethyl acetate and water extraction, the resulting organic phase was concentrated on a rotary evaporator, silica gel column (ethyl acetate and petroleum ether, the volume ratio of 1: 3) to give the product 200mg, yield 94% , the following reaction formula: |
94% | With N-iodo-succinimide; In ethyl acetate; at 25℃; for 12h; | General procedure: Pyrazoles 4 (0.5 mmol), sodium sulfinate 2 (1.0 mmol) and NBS or NIS (1.5 mmol) were dissolved in 2 mL of EtOAc solvent. the reaction mixture was stirred at room temperature under air for 12 h. After the reaction, the resulting mixture was extracted with EtOAc. The combined organic phase was dried over anhydrous Na2SO4 and the solvent was then removed under vacuum. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate, 3:1) to afford the corresponding product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Under an argon atmosphere, copper hexahydrate perchlorate [Cu [C104] 2 · 6H20] (167 mg,0.45 mmol) and excess copper powder (230 mg, 3.62 mmol) were stirred in 8 mL of acetonitrile for 20 minutes,After which a solution of 1,4-bis [diphenylphosphine] butane (384 mg, 0.90 mmol) in 12 mL of dichloromethane was added,After stirring for 1 hour, a solution of 3- [2-pyridyl] pyrazole ligand (131 mg, 0.90 mmol) was added,The reaction was continued for 3 hours at room temperature. After filtration, the solvent was evaporated to dryness on a rotary evaporator,And recrystallized from a mixed solvent of dichloromethane (2 mL) and diethyl ether (20 mL) at a volume ratio of 1:10.Filtered and recrystallized to give colorless crystalline product which was washed 3-4 times with 25 mL of diethyl ether,After drying in vacuo, a white solid product was obtained as perchlorate ? bis [3- [2-Pyridyl] pyrazole] bis [mu-Mu-bis [diphenylphosphine] butane] bis [copper (II) complex] (456 mg, 0.31 mmol)was 69%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | [MeCN] 4] [Cl04] (186 mg, 0.57 mmol) and 1,4-bis [diphenylphosphine] in an argon atmosphere,Butane (244 mg, 0.57 mmol) in 20 mL of methylene chloride was stirred at room temperature for 0.5 hour,Pyridyl] pyrazole ligand (8311 ^, 0.571111111) was added to the colorless, transparent reaction liquid,The reaction was stirred at room temperature for 4 hours,After evaporation of the solvent on a rotary evaporator,And recrystallized from a mixed solvent of dichloromethane (2 mL) and diethyl ether (20 mL) at a volume ratio of 1:10.Filtered and recrystallized to give colorless crystalline product which was washed 3-4 times with 20 mL of diethyl ether,After vacuum drying, a white solid product was obtained as perchlorateBis [3- [2-pyridyl] pyrazole] ? bis [mu-1,4-bis [diphenylphosphine] butane]Complex (309 mg, 0.21 mmol) in 74% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-Bromosuccinimide; In ethyl acetate; at 25℃; for 12h; | General procedure: Pyrazoles 4 (0.5 mmol), sodium sulfinate 2 (1.0 mmol) and NBS or NIS (1.5 mmol) were dissolved in 2 mL of EtOAc solvent. the reaction mixture was stirred at room temperature under air for 12 h. After the reaction, the resulting mixture was extracted with EtOAc. The combined organic phase was dried over anhydrous Na2SO4 and the solvent was then removed under vacuum. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate, 3:1) to afford the corresponding product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | A mixture of <strong>[75415-03-1]3-(2-pyridyl)pyrazol</strong>e (0.92 g, 6.36 mmol) andsodium hydride [60% dispersion in mineral oil; 1.58 g, 66.00 mmol]in dry THF (30 cm3) was stirred for 10 min under N2. To this wasadded a solution of 2,7-bis(bromomethyl)naphthalene (1.00 g,3.18 mmol) and tetrabutylammonium iodide (20 mg, catalytic) indry THF (20 cm3). The mixture was heated to 75 C for 24 h. Aftercooling and filtration, the solvent was removed by rotary evaporation.The residue was purified by column chromatography on silicagel eluting with DCM/MeOH (95:5 v/v) to give L27naph as an offwhitesolid in 69% yield. ESMS: m/z 443 (M+H)+. 1H NMR(400 MHz, CDCl3): delta (ppm) 8.46 (1H, d, J 4.8); 7.81 (1H, d, J 7.9);7.51 (1H, d, J 8.3); 7.42 (1H, td, J 7.8, 1.6); 7.35 (1H, s); 7.24 (1H,d, J 2.2); 7.12 (1H, d, J 8.5); 6.92 (1H, m); 6.82 (1H, d, J 2.2); 5.23(2H, s). Analysis: found C, 74.6; H, 55; N, 18.7%. C28H22N60.5H2Orequires: C, 74.5; H, 5.1; N, 18.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In acetone; at 160℃; for 72h;Sealed tube; | CuCl2 · 2H2O, 2- (1H-pyrazol-3-yl) pyridine in a molar ratio of 1: 0.5Were added to the reactor liner,And add 17ml of acetone to the reactor tank, sealed,The reaction at a temperature of 160 72h. Naturally cooled to room temperature,Get the chemical formula C16H12N6C14Cu2 crystal, yield:70% (calculated as CuCl2 · 2H2O).After the complex is excited by the light of lambdaex = 325nm,A strong characteristic fluorescence appears at lambdaem = 365 nm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 57% | With sodium methylate; In methanol; water; at 120℃; for 72h;Autoclave; High pressure; | A mixture of ZnCl2·4H2O (20.84 mg, 0.1 mmol), Hpzpy(28.84 mg, 0.2 mmol), MeOH (3 mL) and H2O(1 mL) wassealed in a 25-ml Teflon-lined stainless container and heatedat 120 C for 72 h. After cooling to room temperature at arate of 5 C/h, colorless block crystals were obtained in ca.57% yield based on Zn. Anal. Calcd. for C32H24N12Zn4Cl4:C 39.22%, H 2.47%, N 17.15%; found C 39.28%, H 2.57%,N 17.18%. IR (KBr, cm-1): 3208 w, 2040 s, 1580 s, 1506 w,1438 m, 1372 w, 1245 w, 1089 s, 1028 w, 777 m, 723 m,705 w, 692 w, 623 m. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 62% | With sodium methylate; In water; at 130℃; for 72h;Autoclave; High pressure; | A mixture of CuCl2·4H2O (20.84 mg, 0.1 mmol), Hpzpy(28.84 mg, 0.2 mmol), DMF (3 mL) and H2O(1 mL) wassealed in a 25-ml Teflon-lined stainless container and heatedat 130 C for 72 h. After cooling to room temperature at arate of 5 C/h, colorless block crystals were obtained in ca.62% yield based on Cu. Anal. Calcd. for C18H18Cu2N6O6:C 39.93%, H 3.35%, N 15.52%; found C 39.84%, H 3.24%,N 15.48%. IR (KBr, cm-1): 3138 w, 2040 s, 1584 s, 1512 w,1438 m, 1372 w, 1245 w, 1089 s, 1028 w, 777 m, 723 m,705 w, 692 w, 623 m. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With triethylamine; In acetonitrile; for 336h; | A solution of Cu(NO3)2·3H2O (24.0 mg, 0.10 mmol) in acetonitrile or acetone was put in one arm of an H-tube and anacetonitrile or acetone solution of HL (14.5 mg, 0.10 mmol) plus NEt3 (14 muL, 0.1 mmol) was put in the other arm ofthe H-tube. The H-tube was left standing for two weeks to produce brown block-shaped crystals of 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With triethylamine; In acetonitrile; at 140℃; for 72h;High pressure; Autoclave; | Complex 3 was obtained by solvothermal methods. Cu(CH3COO)2·H2O (39.8 mg, 0.20 mmol), HL (39.8 mg,0.20 mmol) and Et3N (28 uL, 0.20 mmol) plus acetonitrile (10 mL) were transferred into a Teflon autoclave and heated at 140 C for three days to give blue needle-shaped crystals of complex 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With sodium ethanolate; In ethanol; water; acetonitrile; for 168h; | Solid HL (14.5 mg, 0.10 mmol) and NaOEt (6.8 mg,0.10 mmol) were dissolved in ethanol (8 mL). Cu(HCOO)2·4H2O (15.4 mg, 0.10 mmol) was dissolved in a mixture of acetonitrile (4 mL) and water (2 mL). The two solutions were mixed together and stirred for 10 min. The resulting green solution was filtered and evaporated for one week to give dark green rod-shaped crystals of 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | A mixture of N-dimethoxymethyl-N,N-dimethylamine(10 mL) and 2-acetylpyridine (40 mL) was refluxed at 100 C for 16 h, then concentrated by rotating evaporationto give dark brown solid. This was washed with hexane(100 mL) and diethyl ether (100 mL) to give the pure and bright yellow crystalline product. Hydrazine monohydrate (40 mL) and ethanol (15 mL) were mixed with the previously obtained solid, and the mixture was stirred at 60 C for 30 min. After cooling, distilled water (75 mL) was added to the solution, which was kept at 0 C for 24 h to produce a light yellow precipitate. This was recrystallized from a mixture of dichloromethane and hexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | A solution of 2-(1-H-Pyrazol-3-yl) pyridine (23.52 g ; 0.162 mol) in 200 ml of anhydrous 2-methoxyethyl ether was stirred with potassium (6.0 g, 0.153 mol) at 70Cuntil the metal dissolved. To this solution was added of 2, 6-dibromopyridine (11.8 g, 0.0496 mol) in one portion. The resulting mixture was stirred at 110C for 4 days. The solvent was removed on a rotary evaporator using efficient water aspirator. Final traces of solvent were removed by adding water to the resulting oil and reducing the volume on a rotary evaporator. Water was added, and the resulting white solid was collected by suction filtration.Washed with NaOHsolution several times. The compound was purified by recrystallizingfrom dichloromethane-hexane, yield 23.06 g (65%). Mp 128-130 C, HRMS (Fig. S4): m/z 183.5726 (L1H22+, main peak),366.1461 (L1H+, small peak), 388.1282 (L1Na+, small peak). 1HNMR (600 MHz, CDCl3) delta 8.68 (d, J = 4.4 Hz, 2H), 8.62 (d,J = 2.6 Hz, 2H), 8.12 (d, J = 7.9 Hz, 1H), 8.00-7.97 (m, 2H), 7.95(dd, J = 9.3, 6.0 Hz, 1H), 7.76 (td, J = 7.7, 1.6 Hz, 2H), 7.26-7.23(m, 2H), 7.15 (d, J = 2.6 Hz, 2H). 13C NMR (151 MHz, CDCl3) delta 154.33 (s), 151.59 (s), 149.87 (s), 149.69 (d, J = 54.4 Hz), 141.27(s), 136.61 (s), 128.43 (s), 123.04 (s), 120.47 (s), 109.58 (s),106.85 (s). 1H NMR (400 MHz, DMSO-d6) delta 9.12 (d, J = 2.5 Hz,2H), 8.71 (d, J = 4.2 Hz, 2H), 8.26 (t, J = 8.0 Hz, 1H), 8.18 (d,J = 7.7 Hz, 2H), 8.03 (d, J = 7.9 Hz, 2H), 7.98 (t, J = 7.5 Hz, 2H),7.46-7.41 (m, 2H), 7.23 (d, J = 2.4 Hz, 2H). Found: C, 69.06; H,4.16; N, 26.78%. Calc. for C21H15N7: C, 69.03; H, 4.14; N, 26.83. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41.1% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.3% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49.8% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43.3% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With sodium hydride; In N,N-dimethyl-formamide; at 25℃; for 12h; | General procedure: Compound 4a (2 mmol), NaH (2.4 mmol) and indole were dissolved in DMF (10 mL). The reaction mixture was stirred at room temperature for 12h before diluted with water (20 mL) and extracted with ethyl acetate (30 mL × 3). The organic layer was concentrated in vacuum. Purication by ash column chromatography gave the target product 5h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70%; 90% | With sodium hydroxide; In tetrahydrofuran; at 75℃; for 72h; | A mixture of 3 (1.88 g, 5.0 mmol), <strong>[75415-03-1]3-(2-pyridyl)pyrazol</strong>e(1.54 g, 10.6 mmol), THF (50 cm3) and aqueous NaOH(17.5 M, 6 cm3) was stirred at 75 C for 3 days. The organiclayer was separated, dried over MgSO4 and concentratedbefore purification by silica column. Elution with EtOAc/CH2Cl2 (4:1) ? 100% EtOAc yielded two fractions. The firstfraction collected yielded 4 as an off-white solid (Yield:1.78 g, 3.5 mmol, 70%), and the second fraction yieldedthe Boc-deprotected Lan as an off-white solid (yield: 0.41 g,1.0 mmol, 20%; total yield 90%). 1H-NMR (400 MHz, CDCl3):delta 8.57 (2H, ddd; pyridyl H6), 7.87 (2H, dt; pyridyl H3), 7.63(2H, td; pyridyl H4), 7.37 (1H, s; ArH), 7.35 (2H, d; pyrazolylH5), 7.20 (2H, s; ArH), 7.14 (2H, ddd; pyridyl H5), 6.84 (2H, d;pyrazolyl H4), 6.71 (1H, bs; NH), 5.22 (4H, s; CH2), 1.41 (9H,s; tBu). ESMS: m/z 530 [M + Na]+, 508 [M + H]+, 452 [M -tBu+2H]+, 255 [M + 2H]2+, 227 [M - tBu+3H]2+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In water; at 150℃; for 0.166667h;Microwave irradiation; | MW assisted method: A mixture of [Ru(bipy)2Cl2]·2H2O (0.052 g,0.1 mmol), pypzH (0.015 g, 0.1 mmol), NH4PF6 (0.033 g, 0.2 mmol),and H2O (0.5 mL) was heated in a microwave oven for 10 min at 150 C.The orange solid obtained was filtered off and washed thoroughly withwater (5×5 mL), and then with Et2O (2×5 mL), and vacuum dried.Yield: 0.070 g (82%). IR (cm-1): 3656 wm, 3364 m, 3115 w, 2164 w,2051 w, 1981 w, 1606 w, 1568 w, 1516 w, 1464 m, 1447 m, 1377 w,1313 w, 1270 w, 1244 w, 1164 w, 1126 w, 1111 w, 1090 w, 1070 w,1028 w, 975 w, 929 w, 893 w, 880 w, 827 vs, 756 vs, 729 s, 660 m,649 m, 612 w. 1H NMR (500 MHz, Me2CO-d6): 7.43 (ddd, J=7.7, 5.7,and 1.5 Hz, H5? pypzH, 1H), 7.50 (ddd, J=7.7, 5.6, and 1.3 Hz, H5bipy1, 1H), 7.54 (d, J=2.9 Hz, H4 pypzH, 1H), 7.57 (ddd, J=7.7, 5.6,and 1.4 Hz, H5? bipy2, 1H), 7.61 (ddd, J=7.7, 5.7, and 1.4 Hz, H5bipy2, 1H), 7.64 (ddd, J=7.7, 5.6, and 1.4 Hz, H5? bipy1, 1H), 7.89(ddd, J=5.7, 1.5, and 0.8 Hz, H4? pypzH, 1H), 8.01 (ddd, J=5.6, 1.5,and 0.7 Hz, H4? bipy1, 1H), 8.03-8.07 (m, H4 bipy1 and H4? bipy2, 2H),8.11 (ddd, J=5.7, 1.5, and 0.7 Hz, H4 bipy2, 1H), 8.15 (d, J=2.9 Hz,H5 pypzH, 1H), 8.11-8.17 (m, H6? pypzH and H6 bipy1, 2H), 8.17-8.25(m, H6 and H6? bipy2, and H6? bipy1, 3H), 8.47 (ddd, J=8.0, 1.5, and0.8 Hz, H3? pypzH, 1H), 8.75 (ddd, J=8.2, 1.3, and 0.7 Hz, H3 bipy1,1H), 8.78-8.82 (m, H3 and H3? bipy2, and H3? bipy1, 3H), 13.52 (s, NHpypzH, 1H). 13C{1H} NMR (126 MHz, Me2CO-d6): 105.6 (C4 pypzH),123.0 (C3? pypzH), 123.9 (C3? bipy2), 124.0 (C3 bipy1), 124.3 (C3?bipy1), 124.4 (C3 bipy2), 125.7 (C5? pypzH), 127.3 (C5 bipy1), 127.7 (C5bipy2), 127.8 (C5? bipy2), 127.9 (C5? bipy1), 134.8 (C5 pypzH), 137.7 (C6bipy1), 137.8 (C6? bipy1), 138.0 (C6? bipy2), 138.2 (C6 bipy2), 151.7 (C4?pypzH), 151.8 (C3 pypzH), 152.0 (C4? bipy2), 152.0 (C4 bipy2), 152.3(C4? bipy1), 152.5 (C4 bipy1), 153.4 (C2? pypzH), 157.3 (C2? bipy1),157.6 (C3? bipy1), 157.9 (C2 bipy1), 157.9 (C2? bipy2). Anal. Calcd forC28H23F12N7P2Ru: C, 39.63; H, 2.73; N, 11.56. Found: C, 39.70; H,2.67; N, 11.64. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In hexane; at 200℃; for 0.0833333h;Microwave irradiation; | Its synthesis by conventional methods and complete spectroscopicdata have been previously reported [9c]. MW assisted method: A mixtureof [ReBr(CO)5] (0.041 g, 0.1 mmol), pypzH (0.015 g, 0.1 mmol), andhexane (2 mL) was heated in a microwave oven for 5 min at 200 C. Thesolvent was removed and dried in vacuo and the pale yellow solidobtained was spectroscopically pure. Analytical data were consistentwith those reported previously. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With [bis(acetoxy)iodo]benzene In 1,2-dichloro-ethane at 20 - 80℃; for 6h; Schlenk technique; | 1-(3,4-Dihydro-1H-isochromen-1-yl)-1H-benzimidazole(3aa; Ref. 6); Typical Procedure General procedure: PhI(OAc)2 (0.5 mmol) was added to a mixture of 1H-benzimidazole(1a; 0.5 mmol), isochroman (2a; 2.0 mmol), and DCE (2.0mL) in a Schlenk tube at r.t. The mixture was stirred at 80 °C for6 h then cooled. H2O (10 mL) was added, and the mixture wasextracted with CH2Cl2 (3 × 10 mL). The combined organic layerwas dried (Na2SO4) and concentrated under reduced pressure.The residues were purified by flash column chromatography(silica gel, hexane-EtOAc) to give a colorless oil; yield: 115 mg(92%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 2h; | A solution of 2-(1H-pyrazole-3-yl)pyridine (3.02 g, 20.80 mmol) and NBS (3.72 g, 20.90 mmol) in DMF (30 mL) was stirred for 2 h in an ice bath. The reaction mixture was poured into ice water, filtered, and dried in vacuo. The residue (4.38 g, 95% yield) as a white solid was reacted without further purification. 1H-NMR (270 MHz, CDCl3) delta: 11.46 (1H, br s), 8.63-8.65 (1H, m), 8.29 (1H, d, J = 8.4 Hz), 7.78-7.85 (1H, m), 7.64 (1H, s), 7.28-7.33 (1H, m). LC/MS (ESI): m/z 223 [M + H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In methanol; at 20℃; for 4h; | General procedure: To a methanolic (5 mL) solution of pyrazole based ligand (L1-L3,134-150 mg, 1 mmol), was added a methanolic (5 mL) solution of [RuCl2(eta6-p-cymene)]2 (30.6 mg, 0.5 mmol), and the reaction mixturewas allowed to stir for 4 h at room temperature. The solution wasconcentrated to 3 mL under reduced pressure, and addition of petroleumether (10-12 mL) gave a clear orange/yellowish orange solid. Thesolid was collected by filtration, washed with petroleum ether manytimes and air dried. The complexes were recrystallized from chloroform-acetonitrile mixture. 2.3. [(eta6-p-cymene)Ru(eta2-N,N-L1)Cl]Cl (1)<strong>[75415-03-1]2-(1H-pyrazol-3-yl)pyridine</strong> ligand (L1, 145 mg, 1 mmol) was utilized.Yield: 90%. Color: Orange solid. UV-Vis (CH3OH): lambdamax, nm (epsilon,dm 3 mol-1 cm-1) 421 (1000), 324 (4500), 290 (8700). FT-IR (KBr): nu,cm-1 3402 (NeH), 1613 (C=C), 1433 (C=N). 1H NMR (400 MHz,DMSO-d6): delta, ppm 15.73 (s, 1H, NH), 9.43 (dd, J=4.6, 0.9 Hz, 1H,aromatic-H), 8.31 (d, J=2.8 Hz, 1H, aromatic-H), 8.24-8.12 (m, 2H,aromatic-H), 7.60 (ddd, J=7.3, 5.7, 1.8 Hz, 1H, aromatic-H), 7.26 (d,J=2.8 Hz, 1H, aromatic-H), 6.38 (d, J=6.1 Hz, 1H, p-cymene aromatic-H), 6.16 (d, J=6.1 Hz, 1H, p-cymene aromatic-H), 6.07 (d,J=6.1 Hz, 1H, p-cymene aromatic-H), 5.95 (d, J=6.1 Hz, 1H, pcymenearomatic-H), 2.62-2.52 (m, 1H, p-cymene CH(CH3)2), 2.18 (s,3H, p-cymene CH3), 0.90 (dd, J=6.6, 2.9 Hz, 6H, p-cymene CH(CH3)2). 13C NMR (100 MHz, DMSO-d6): delta, ppm 155.45, 150.31 (C=N),149.50, 139.76, 135.22, 125.04, 122.13, 104.34 (aromatic carbons),103.07, 102.77, 85.00, 83.91, 83.01, 81.56 (aromatic carbons of pcymene),30.41, 21.70, 21.44, 18.45 (aliphatic carbons of p-cymene).ESI+: m/z Found (Calcd.) 415.94 (416.05) [M-Cl]+. Anal. Calc.C18H21Cl2N3Ru·0.5H2O (%): C, 46.96; H, 4.82; N, 9.13. Found: C, 46.78; H, 4.91; N, 9.00. Mp (C): 258. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sodium hydroxide; In water; at 160℃; for 120h;pH Ca. 6.13;High pressure; Autoclave; | [Zn2(pzdc)(L)2(H2O)]2n2nH2O (1): A mixture of H2pzdc (0.068 g, 0.4 mmol), HL (0.028 g, 0.2 mmol), Zn(OAc)2*2H2O (0.088 g, 0.4 mmol), and 18mL H2O was adjusted to the pH ~6.13 with 0.5 mol/L NaOH, sealed in a Teflon-lined stainless steel vessel, heated to 160C for five days, and followed by slow cooling (a descent rate of 10C/h) to room temperature. Pale yellow block crystals were obtained. Yield of 32% (based on Zn). Anal. Calcd. For C44H32N16O11Zn4: C, 43.23; H, 2.64; N, 18.33. Found C, 42.97; H, 2.15; N, 17.89. IR (cm-1): 3286(w), 2989(w), 1752(m), 1637(m), 1605(m), 1567(w), 1473(w), 1434(w), 1375(m), 1357(m), 1255(w), 1159(w), 1118(w), 1060(w), 1013(m), 890(w), 783(w), 765(w), 636(w), 481(w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With sodium hydroxide; In water; at 140℃; for 168h;pH Ca. 7;High pressure; Autoclave; | [Mn(m2-O)(H2O)2(HL)]2n2nNIPH (2): A mixture of Mn(OAc)24H2O (0.10 g, 0.4 mmol), H2NIPH (0.084 g, 0.4 mmol), L (0.058 g, 0.4 mmol), and 18 mL H2O was placed in a Teflon reactor (30 mL) and the pH value was adjusted to about 7 with 0.5 mol/L NaOH solution. Then the mixture was heated at 140C for 7 days. After cooling to room temperature at a rate of 10C/h, brown crystals of 1 were collected in 45% yield. Anal. Calcd. for C32H30Mn2N8O18 (%): C, 41.57; H, 3.27; N, 12.12. Found (%): 41.36; H, 3.01; N, 11.98. IR (KBr, cm-1): 3413(m), 3102(w), 1630(s), 1606(s), 1583(m), 1533(m), 1495(w), 1443(w), 1334(s), 1101(w), 998(w), 788(w), 720(m), 537(w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | In water; N,N-dimethyl-formamide; at 130℃; for 50h;Sealed tube; | General procedure: A mixture of H4tptc (0.81mg, 0.002mmol), ZnCl2·4H2O (0.55mg, 0.004mmol), bpy (0.63mg, 0.004mmol), and DMF/H2O=1:1 (V=1mL) was transferred into a glass tube, which was pumped into a near-vacuum, sealed and heated at 130C for 3000min, and then cooled to 25C with a descent rate of 10C/h. The colorless crystals of 1 were collected by filtration with the yield of 39% (based on H4tptc). Anal. (%) calcd. C84H52N8O16Zn4: C, 59.66; H, 3.10; N, 6.63. Found: C, 59.27; H, 3.16; N, 6.67. IR (KBr pellet, cm-1): 3444 (m), 1695 (s), 1558 (vs), 1453 (m), 1379 (s), 1317 (s), 1256 (w), 1169 (s), 1021 (w), 916 (w), 842 (m), 774 (s), 694 (w), 651 (w), 583 (w) (Fig.S1). The synthetic method of 2 was similar to that of 1 except that pyp was replaced by bpy. And the block crystals of 2 were obtained with the yield of 48% (based on H4tptc). Anal. (%) calcd. C19H12N3O4Zn: C, 55.38; H, 2.91; N, 10.20. Found: C, 55.52; H, 3.04; N, 10.38; IR (KBr pellet, cm-1) for 2: 3186 (m), 3035 (w), 2964 (w), 1601 (s), 1398 (s), 1136 (m), 1091 (s), 966 (w), 901 (w), 848 (m), 776 (vs), 684 (m), 613 (m), 573 (m) (Fig.S1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With sodium hydride; In N,N-dimethyl-formamide; at 70℃; for 18h;Inert atmosphere; | Under the protection of argon, 5,15-bis (4-bromomethylbenzene) -10,20-bis (trimethylbenzene) porphyrin zinc (0.948g, 0.2equiv.), Pyridylpyrazole (0.726 g, 1.0equiv.), sodium hydride (0.4g, 2.0equiv.), dissolved in N, N-dimethylformamide (200mL) solvent, and reacted at 70 C for 18h; after that, dichloromethane was added to the reaction solution, The organic phase was washed with water and dried, and the solvent was removed under reduced pressure. The crude product was separated and purified using a 200-300 mesh alumina column. Dichloromethane / petroleum ether (2: 1) was used as the eluent to collect 5,15-di { 4- (Pyridine-pyrazolyl) methylbenzene} -10,20-bis (trimethylbenzene) porphyrin zinc, yield 39%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | In N,N-dimethyl-formamide; at 130℃; for 72h;Sealed tube; | A mixture of H4tptc (0.81 mg, 0.002 mmol), Cd(NO3)2·4H2O(1.3 mg, 0.004 mmol), bpz (0.63 mg, 0.004 mmol), and 1 mL DMF/H2O (v/v = 1/1) was transferred into a glass tube, which was pumpedinto a near-vacuum, sealed and heated at 130 C for 3 days, and thencooled to room temperature with a descent rate of 5 C/h. The colorlesscrystals were achieved with a yield of 37% (based on H4tptc). Anal. (%)calcd. for C38H30Cd2N6O11: C, 46.98; H, 3.11; N, 8.65, found (%): C,46.61; H, 3.19; N, 8.67. IR (KBr pellet, cm-1): 3432 (m), 1588 (vs),1539 (vs), 1477 (m), 1391 (vs), 1335 (s), 1243 (m), 1150 (m), 1008(w), 904 (w), 842 (m), 750 (s), 694 (m), 644 (w), 577 (w). |
Tags: 75415-03-1 synthesis path| 75415-03-1 SDS| 75415-03-1 COA| 75415-03-1 purity| 75415-03-1 application| 75415-03-1 NMR| 75415-03-1 COA| 75415-03-1 structure
[ 19959-77-4 ]
2-(5-Methyl-1H-pyrazol-3-yl)pyridine
Similarity: 0.89
[ 446880-81-5 ]
2-Bromo-4-(3-(pyridin-2-yl)-1H-pyrazol-4-yl)pyridine
Similarity: 0.81
[ 149246-87-7 ]
5-(Pyridin-3-yl)-1H-pyrazol-3-amine
Similarity: 0.74
[ 19959-77-4 ]
2-(5-Methyl-1H-pyrazol-3-yl)pyridine
Similarity: 0.89
[ 446880-81-5 ]
2-Bromo-4-(3-(pyridin-2-yl)-1H-pyrazol-4-yl)pyridine
Similarity: 0.81
[ 149246-87-7 ]
5-(Pyridin-3-yl)-1H-pyrazol-3-amine
Similarity: 0.74
[ 74173-48-1 ]
4-Methyl-4'-vinyl-2,2'-bipyridine
Similarity: 0.72
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :