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CAS No. : | 2075-45-8 |
Formula : | C3H3BrN2 |
M.W : | 146.97 |
SMILES Code : | C1=N[NH]C=C1Br |
MDL No. : | MFCD00075602 |
InChI Key : | WVGCPEDBFHEHEZ-UHFFFAOYSA-N |
Pubchem ID : | 16375 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P305+P351+P338 |
* 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 |
---|---|---|
68% | With caesium carbonate In N,N-dimethyl-formamide at 180℃; for 1.5 h; Microwave irradiation | Step 1 : 4-Bromo- 1 -cyc A mixture of 4-bromo-lH-pyrrazole (1.0 g, 6.8 mmol), bromo cyclopropane (1.3 g, 10.7 mmol), cesium carbonate (3.5 g. 10.7 mmol), and DMF (6 mL) in a 30 mL microwave vial is heated to 180 °C under radiation for 1.5 hr. After cooled to room temperature, the reaction mixture is filtered. The filtrate is concentrated and the residue is purified on a silica gel flash chromatography with ethyl acetate/petroleum ether (1 :5) to get a brown liquid (0.87 g, 68percent yield). (MS: [M+l] 259) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 16h; | A sealable vessel was charged with potassium carbonate (3.76 g, 27.2 mmol), 4-bromo- lH-pyrazole (4.00 g, 27.2 mmol), and 10 mL DMF. To this mixture, 2-iodopropane (3.27 ml, 32.7 mmol) was added and the <n="115"/>vessel sealed. The mixture was heated at 80 C for 16 h and allowed to cool to rt . The mixture was diluted with EtOAc, extracted with water, water, sat NaHCO3, and the organic layer dried over Na2SO4, filtered and evaporated. The mixture was purified via flash chromatography using a EtOAc in CH2C12 gradient. The desired compound (as determined by TLC, 12 stain) was collected as a colorless liquid. | |
To a solution of 4-bromo-1H-pyrazole (20 g, 0.137 mol)in DMF (60 mL) was added NaH (60 wtin oil, 8.2 g, 0.203 mol) at 0 .The resulting mixture was stirred for 30 mins at 0 ,then a solution of 2-iodopropane (25.6 g, 0.15 mol) indioxane (10 mL) was added dropwise at 0 . Theresulting mixture was stirred at RT overnight, quenched with water (50 mL) ,and extracted with EtOAc (30 mL x 3) . The combined organic layers were washedwith brine, dried over Na2SO4, filtered, and concentratedin vacuo. The residue was purified by silica gel column chromatography (7EtOAc in petroleum ether) to give the title compound as a solid.LRMS m/z (M+H) 189.1, 191.1 found, 189.2, 191.2 required. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; n-butyllithium; In hexane; water; | 2. Preparation of Pyrazole -4-carboxylic acid (4): To a solution 4-bromopyrazole (3) (3.82 g, 0.026 m) in ether (30 ml) at -78° C., was added a solution of 2-4 M n-butyllithium in hexane (21.7 ml, 0.052 m) in drops over a period of 40 minutes. After stirring at -78° C. for 31/2 hours, the solution was warmed to ambient temperature and stirred for a further period of 5 hours. The solution was cooled again to -78° C. and excess dry ice was added. After stirring for 2 hours at -78° C., the reaction mixture was allowed to warm to ambient temperature overnight. Water was added to quench the reaction and the heterogeneous mixture was neutralized to ph 7 by the careful addition of concentrated HCl. The mixture was further diluted with water to dissolve all the solids and was washed with ether. Water was removed from the aqueous layer by distillation under vacuum to yield an off-white solid (4.38 g, crude 4). The product was not purified and was carried on for the subsequent reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With 1-methyl-pyrrolidin-2-one; caesium carbonate; at 80℃; for 12h;Large scale; | 2.08 kg of cesium carbonate,0.78 kg of 4-bromopyrazole was dissolved in 4 liters of N-methylpyrrolidone,Heated to 80 degrees,A 5 liter solution of N-methylpyrrolidone was added to 1.8 kg of compound (CZT-7)Reaction for 12 hours.Cooled to room temperature,Add 50 litersMethyl tert-butyl etherwith50 liters of water,Stir for 1 hour.After dispensing,The organic phase was washed with 20 liters of * 4 water and dried 50percentLiter of hexane and stirred at room temperature for 2 hours. Filtered and dried to give 1.35 kg of compound (CZT-8) in a yield of 77percent |
58% | B. To a cold solution (0 °C) of 4-bromo-lH-pyrazole (14.9 g, 0.10 mol) in 80 mL of dichloromethane was added sodium hydride (8.13 g, 0.20 mol) portion wise. The mixture was stirred at 0 °C for 1 hour, followed by the addition of a solution of tert-butyl 4-((methylsulfonyl)oxy)piperidine-l-carboxylate (34.0 g, 0.12 mol) in 30 mL of N,N-dimethylformamide. The resulting mixture was heated at 110 °C overnight. Purification by column chromatography afforded tert-butyl 4-(4-bromo-lH- pyrazol-l-yl)piperidine-l-carboxylate as a yellow oil in 58percent yield (19.5 g). 1H NMR (400 MHz, CDC13) delta 7.48 (s, 1H), 7.44 (s 1H), 4.35-4.20 (m, 3H), 2.95-2.85 (m, 2H), 2.15-2.05 (m, 2H), 1.92-1.81 (m, 2H), 1.48 (s, 9H). | |
45% | To a stirred solution of 4-bromo-pyrazole (10.44 g, 71.03 mmol) in anhydrous DMF (96 mL), cooled to 0° C., was slowly added NaH (60percent in mineral oil) (3.13 g, 78.133 mmol). The solution was stirred for 1 hour at 0° C. 4-Methanesulfonyloxy-piperidine-1-carboxylic acid tert-butyl ester (19.82 g, 71.03 mmol) was added slowly and the reaction was heated to 100° C. overnight or until consumption of the pyrazole by NMR. The reaction was cooled to room temperature and water added (20 mL) followed by extraction with EtOAc. The combined extracts were washed with saturated aqueous NaCl (4*20 mL), dried with Na2SO4 and concentrated to afford 4-(4-bromo-pyrazol-1-yl)-piperidine-1-carboxylic acid tert-butyl ester as an orange oil. The oil was purified using silica gel chromatography eluding with 10percent EtOAc/hexanes to 25percent EtOAc/hexanes to provide 4-(4-bromo-pyrazol-1-yl)-piperidine-1-carboxylic acid tert-butyl ester as a white solid (10.55 g, 45percent yield) with a Rf=0.4 (25percent EtOAc/hexanes, using iodine as the stain). 1H NMR (CDCl3, 400 MHz) delta 7.46 (s, 1H), 7.43 (s, 1H), 4.23 (m, 3H), 2.88 (m, 2H), 2.10 (m, 2H), 1.88 (m, 2H), 1.47 (s, 9H). |
45% | To a stirred solution of 4-bromo-pyrazole (10.44 g, 71.03 mmol) in anhydrous DMF (96 mL), cooled to 0°C, was slowly added NaH (60percent in mineral oil) (3.13 g, 78.133 mmol). The solution was stirred for 1 hour at 0°C. 4-Methanesulfonyloxy-piperidine-1-carboxylic acid tert-butyl ester (19.82 g , 71.03 mmol) was added slowly and the reaction was heated to 100°C overnight or until consumption of the pyrazole by NMR. The reaction was cooled to room temperature and water added (20 mL) followed by extraction with EtOAc. The combined extracts were washed with saturated aqueous NaCI (4 x 20 mL), dried with Na2SO4 and concentrated to afford 4-(4-bromo-pyrazol-1-yl)-piperidine-1-carboxylic acid tert-butyl ester as an orange oil. The oil was purified using silica gel chromatography eluting with 10percent EtOAc/hexanes to 25percent EtOAc/hexanes to provide 4-(4-bromo-pyrazol-1-yl)-piperidine-1-carboxylic acid tert-butyl ester as a white solid (10.55 g, 45percent yield) with a R^= 0.4 (25percent EtOAc/hexanes, using iodine as the stain). 1H NMR (CDCI3, 400 MHz) 8 7.46 (s, 1H), 7.43 (s, 1H), 4.23 (m, 3H), 2.88 (m, 2H), 2.10 (m, 2H), 1.88(m, 2H), 1.47(s, 9H). | |
NaH (60percent in mineral oil, 1.36 g, 34 mmol) is added portionwise to a stirred solution of 4- bromopyrazole (4.58 g, 30.9 mmol) in DMF (20 ml). The resulting mixture is stirred for 1h at O0C and 4-Methanesulfonyloxy-piperidine-1-carboxylic acid tert-butyl ester (as obtained in preparation 61 , 8.62 g, 30.9 mmol) is added. The resulting pale suspension is heated at 1000C for 1h. The reaction is quenched with water and extracted with EtOAc several times. The combined organic layers are washed with brine, dried over Na2SO4, filtered and the filtrate is concentrated in vacuo. The residue is purified by chromatography on a 120 g silica gel column on a Combiflash Companion.(TM). (Isco Inc.) apparatus ( gradient hexanes: TBDME from 1 :0 => 0:1) to afford the title compound as a colorless solid, Rt = 1.213 min (Acquity UPLC BEH C18, 2.1x50mm, 1.7 micron, detection 215nM, 0.1 min 2percent CH3CN in H2O , 2percent to 100percent CH3CN in H2O in 1.5min, 0.4 min 100percent CH3CN + 0.1 percent TFA, flow rate 1.0ml/min); MS: 330 (M+1, 79Br)+. | ||
As shown in step 3-ii of Scheme 3, to a solution of 4-bromopyrazole (4.68 g, 31.83 mmol) in DMF (300 mL) at 00C was added sodium hydride (60percent on mineral oil, 1.27 g, 31.83 mmol). The solution was stirred at 00C for one hour, at which point a solution of Compound 1013 (9.78 g, 31.83 mmol) in DMF (50 mL) was added dropwise. The reaction mixture was stirred at room temperature for 1 hour and then refluxed for 16 hours. Disappearance of both starting materials was observed by TLC (1 : 1 EtOAc/hexanes). The reaction was cooled to room temperature, quenched by the addition of brine (300 mL), and extracted with ethyl acetate (3 x 200 mL). The combined organics were washed with 1percent aqueous LiCl (3 x 200 mL), dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude bromide was purified by silica gel chromatography (0 - 25percent EtOAc/hexanes) to give Compound 1014. | ||
With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 80℃; for 12h; | c) tert-Butyl 4-(4-bromo- 1 H-pyrazol- 1 -yl)piperidine- 1 -carboxylateTo a cooled solution of the compound of Intermediate Example 5(b) (6.7 g, 23.9 mmol) in DMF (50 ml) was added NaH (2.8 g, 1 19 mmol, 5 eq.) and 4-bromo-lH-pyra- zole (2.8 g, 19.1 mmol, 0.8 eq.) and stirred at 80 °C for 12 h. The mixture was quenched and extracted with ethyl acetate (3 chi 100 ml). The combined organic layer was washed with water, brine and dried over sodium sulphate. The solvent was distilled off to afford the crude product (8.0 g). | |
General procedure: To an ice-cooled solution of 4-bromo-1H-pyrazole (1.19 g, 8.07 mmol) in 10 mL of DMF was added portionwise sodium hydride (355 mg, 8.88 mmol, 60percent in oil). The resulting mixture was stirred for additional 1 h. Then to the mixture was added oxan-4-yl methanesulfonate (1.60 g, 8.88 mmol), which was prepared in a similar manner as described for 12. The resulting mixture was gradually heated to 100 °C and stirred for 10 h. After cooled to room temperature, the reaction was quenched with water. The mixture was extracted with EA. The organic layer was washed with brine, dried over anhydrous Na2SO4 and concentrated under vacuum. The crude product was purified by silica gel column chromatography (EA/PE, 1:6) to afford 26a as a white solid in 61percent yield. | ||
With sodium hydride; In N,N-dimethyl-formamide; at 80℃; for 12h; | To a cooled solution of the compound of Intermediate Example 5(b) (6.7 g, 23.9 mmol) in DMF (50 ml) was added NaH (2.8 g, 119 mmol, 5 eq.) and 4-bromo-1H-pyrazole (2.8 g, 19.1 mmol, 0.8 eq.) and stirred at 80° C. for 12 h. The mixture was quenched and extracted with ethyl acetate (3*100 ml). The combined organic layer was washed with water, brine and dried over sodium sulphate. The solvent was distilled off to afford the crude product (8.0 g). | |
With sodium hydride; In N,N-dimethyl-formamide; at 20 - 110℃;Inert atmosphere; | Sodium hydride (400 mg, 60percent dispersion, 10 mmol) was added to a stirred solution of the bromopyrazole (1.47g, lOmmol) and 4-Methanesulfonyloxy-pipehdine-1-carboxylic acid tert-butyl ester (2.4 g, 8.6 mmol) in dry DMF (10 ml) at room temperature. After gas evolution had ceased, the reaction was stirred and heated at 110 0C under N2 for 4 h. The reaction mixture was allowed to cool to room temperature and stand at for 18 h before being partitioned between EtOAc and H2O. The organic layer was separated, washed with water H2O (x2), brine (x1 ), then dried (Na2SO4), filtered and the solvent removed in vacuo.The residue was purified using silica column chromatography running a 10-25percentEtOAc/petrol gradient to give a colourless oil (1.7 g, 5.15 mmol). 1 H NMR (400 MHz,CDCI3): 7.48 (1 H, s), 7.45 (1 H, s), 4.45-4.07 (3H, m), 2.90 (2H, t), 2.12 (2H, d), 1.97-1.79(2H, m), 1.50 (9H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Step 1: 4-Bromo-1-(3-methyl-oxetan-3-ylmethyl)-1H-pyrazole To a suspension of NaH (98 mg, 55% in mineral oil, 2.25 mmol) in DMF (1.2 ml) was added a solution of 4-bromopyrazole (300 mg, 2.04 mmol) in DMF (2 ml). The reaction mixture was stirred at room temperature for 15 minutes before a solution of <strong>[78385-26-9]3-bromomethyl-3-methyloxetane</strong> (404 mg, 2.45 mmol) in DMF (2 ml) was added slowly. The mixture was stirred at room temperature for 1.5 h, then diluted with saturated NaHCO3 solution and extracted with 3 times with EtOAc. The combined organic layers were washed 2 times with water and with brine, dried (Na2SO4) and evaporated. The remaining colorless oil was purified by silica gel chromatography (heptane/EtOAc 80:20-50:50) to obtain the title compound (444 mg, 94%) as colorless oil. MS (EI): 231.2 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 16h; | b) 4-(4-Bromo- 1 H-pyrazol- 1 -yl)-2-methylbutan-2-olTo a solution of 4-bromo-lH-pyrazole (1 g, 6.84 mmol, 1.0 eq) in DMF were added K2C03 (2.3 g, 17.1 mmol, 2.5 eq.) and <strong>[35979-69-2]4-bromo-2-methylbutan-2-ol</strong> (1.7 g, 10.27 mmol, 1.5 eq.). The mixture was stirred at RT for 16 h. The mixture was quenched and extracted as in Intermediate Example 5(a). The solvent was distilled off to afford the product in 60 % yield (0.9 g). LC-MS (ESI): Calculated mass 233.0; Observed mass 235.0.[M+H]+ (rt: 0.64 min). |
60% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 16h; | To a solution of 4-bromo-1H-pyrazole (1 g, 6.84 mmol, 1.0 eq) in DMF were added K2CO3 (2.3 g, 17.1 mmol, 2.5 eq.) and <strong>[35979-69-2]4-bromo-2-methylbutan-2-ol</strong> (1.7 g, 10.27 mmol, 1.5 eq.). The mixture was stirred at RT for 16 h. The mixture was quenched and extracted as in Intermediate Example 5(a). The solvent was distilled off to afford the product in 60% yield (0.9 g). LC-MS (ESI): Calculated mass 233.0; Observed mass 235.0. [M+H]+ (rt: 0.64 min). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h; | a) 4-Bromo- 1 -isopropyl- 1 H-pyrazoleTo a solution of 4-bromo-l H-pyrazole (5 g, 34 mmol) in DMF (70 ml) were added 2C03 (11.83 g, 85.6 mmol, 2.5 eq.) and 2-bromopropane (6.3 g, 51.36 mmol, 1.5 eq.) and the mixture was stirred at RT for 12 h. The mixture was quenched and extracted as in Intermediate Example 5(a). The solvent was distilled off and the crude residue was purified by column chromatography (60-120 silica gel, 20 % ethyl acetate in hexane) to afford the product in 89 % yield (5.8 g). 1H NMR (300 MHz, DMSO-i¾): delta 8.01 (s, 1H), 7.50 (s, 1H), 4.49-4.43 (m, 1H), 1.38 (d, 6H). |
89% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h; | To a solution of 4-bromo-1H-pyrazole (5 g, 34 mmol) in DMF (70 ml) were added K2CO3 (11.83 g, 85.6 mmol, 2.5 eq.) and 2-bromopropane (6.3 g, 51.36 mmol, 1.5 eq.) and the mixture was stirred at RT for 12 h. The mixture was quenched and extracted as in Intermediate Example 5(a). The solvent was distilled off and the crude residue was purified by column chromatography (60-120 silica gel, 20% ethyl acetate in hexane) to afford the product in 89% yield (5.8 g). 1H NMR (300 MHz, DMSO-d6): delta 8.01 (s, 1H), 7.50 (s, 1H), 4.49-4.43 (m, 1H), 1.38 (d, 6H). |
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 10h; | [0001187] To a solution of 4-bromo-lH-pyrazole (2.92 g, 20.0 mmol) in anhydrous DMF (50 mL) was added 2-bromopropane (3.69 g, 30.0 mmol) and potassium carbonate (6.90 g, 50 mmol) at room temperature. The reaction mixture was stirred for 10 h. The mixture was diluted with water (100 mL) and extracted with ethyl acetate (150 mL x 3). The combined organic extracts were washed with brine (150 mL x 2) and dried over anhydrous sodium sulfate. After filtration, the solvent was removed in vacuo and the residue was purified with flash column chromatography on silica gel to give Compound 330A. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3300 mg | Step 1 : 4-(Methylthio)-1H-pyrazole A suspension of 4-bromopyrazole (4 g, 27 mmol) in tetrahydrofuran (68 mL) was cooled to 0C and n-butyllithium (2.5 M in hexanes, 35.9 mL, 90 mmol) was added dropwise over a period of 20 min. The reaction mixture was stirred at room temperature for 1 h and then was cooled to 0C. 1 ,2-Dimethyldisulfide (2.66 mL, 30.0 mmol) was added dropwise. The reaction mixture was stirred at 0C for 1.5 h. The reaction mixture was poured into water (150 mL) and then it was acidified to pH~8 with a saturated aqueous solution of ammonium chloride and a solution of aqueous hydrochloric acid (1 N). The mixture was extracted with ethyl acetate (150 mL x 3) and the combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 4-(methylthio)-1 H-pyrazole (3300 mg). 1H NMR (500 MHz, CDCI3) delta 2.36 (s, 3H), 7.63 (s, 2H). | |
To a solution of 4-bromo-lH-pyrazole (200 mg, 1.361 mmol) in anhydrous THF (5 mL) was added n-BuLi (2.5 M, 1.8 mL, 4.5 mmol) at 0C. The solution was stirred at room temperature for 1 hour. The MeSSMe (128 mg, 0.12 mL, 1.361 mmol) was added at 0C and reaction solution was stirred at room temperature for 2 hours. The reaction was poured into ethyl acetate (50 mL) and water (50 mL). The separated organic layer was washed brine (50 mL), dried over magnesium sulfate and concentrated in vacuo. Due to its smell, the crude product was used in next oxidation reaction without further purification |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tetrakis(triphenylphosphine) palladium(0); tetraethylammonium hydroxide; In tetrahydrofuran; water; toluene; at 120℃; for 35h; | 4- bromo -1H- pyrazole 3 g (20.41mmol), thecompound 2-1 7.09 g (20mmol), and the tetrakis triphenylphosphine palladium (0) (Pd(PPh3)4) 1.18 g (1.02mmol) and tetraethylammonium hydroxide ((n-Et) 4 NOH) aqueous solution 43mL were put into 250 mL round bottom flask (round-bottomed flask)and after the anhydrous toluene (160mL) and anhydrous tetrahydrofuran (40mL) were added and the solid content was dissolved it reacted at 120 for 35 hours. After reaction was completed it extracted using the mixedsolvent (water chloroform: = 1 1: volume ratio) of chloroform and water and extracted organic layer were dried to the MgSO 4 . The outcome was decompressed andis distillated and the organic solvent was removed andsolid was obtained and it refined with the separation byit refined with the separation by this being refined using the n-hexane and tetrahydrofuran mixed solvent (N-hexane tetrahydrofuran: = 5 1) using the silica gel column chromatography with the separation and using and using and the compound 12-2 3.8 g (yield : 63%). |
63% | With tetrakis(triphenylphosphine) palladium(0); tetraethylammonium hydroxide; In tetrahydrofuran; toluene; at 120℃; for 35h; | 250 mL round bottom flask (round-bottomed flask) for 4-bromo-1H-pyrazol-3g (20.41mmol), compound 2-17.09g (20mmol), tetrakis triphenylphosphine palladium(0) (Pd (PPh3 ) 4) 1.18g (1.02mmol) and tetraethylammonium hydroxide ((n-Et) 4NOH) aqueous solution 43mL the flask, and anhydrous toluene (160mL) and anhydrous THF (40mL) was added to the solid component was dissolved and then, at 120 C was reacted for 35 hours. After the reaction was completed, a mixture of water and chloroform, the solvent was extracted by using the (water: chloroform = 1: 1 by volume), dry the organic layer was extracted with MgSO4. Obtaining a solid by removing the organic solvent by distillation under reduced pressure and the resultant product, it n- hexane and tetrahydrofuran mixed solvent (n- hexane: tetrahydrofuran = 5: 1) using a silica gel column using a chromatographic separation, and to give compound 12-2 3.8g (yield: 63%) was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With di-tert-butyl-diazodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 0 - 150℃; for 0.25h;Microwave irradiation; | To a mixture of 4-bromo-1H-pyrazole (200 mg, 1.36 mmol), <strong>[1007-03-0]cyclopropyl(phenyl)methanol</strong> (405 mg, 2.72 mmol) and PPh3 (720 mg, 2.72 mmol) in anhydrous THF (6 ml) cooled to 0 C. was added di-t-butyl azodicarboxylate (0.4 ml, 2.72 mmol) dropwise. The reaction was heated at 150 C. in a microwave reactor for 15 minutes. It was then cooled to room temperature and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (0-30% EtOAc/Hex) to afford the title compound (160 mg, 42%) as a clear oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25 g | To a solution of 4-bromo-1H-pyrazole (50 g, 340 mmol, 1.0 equiv) in sodium hydroxide (3.7 N, 555 mL) was added (aminooxy)sulfonic acid (116 g, 1.0 mol, 3.0 equiv). The mixture was stirred for 30 min and extracted with DCM (500 mL). The organic layer was washed with brine (200 mL) twice, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and poured into DCM (400 mL) and water (200 mL). To the resulting solution was added NaIO4 (147 g, 685 mmol, 2.0 equiv) at 0 oC. The mixture was stirred overnight, diluted with DCM (500 mL), washed with brine (200 mL) twice, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford 25 g of 5- bromo-1,2,3-triazine as brown oil. |
Tags: 4-Bromopyrazole | Pyrazoles | Bromides | Organic Building Blocks | Heterocyclic Building Blocks | 2075-45-8
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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.
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