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Structure of 420-37-1
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CAS No. : | 420-37-1 |
Formula : | C3H9BF4O |
M.W : | 147.91 |
SMILES Code : | C[O+](C)C.F[B-](F)(F)F |
MDL No. : | MFCD00011798 |
InChI Key : | CZVZBKHWOFJNCR-UHFFFAOYSA-N |
Pubchem ID : | 2735153 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H314 |
Precautionary Statements: | P260-P264-P280-P301+P330+P331-P303+P361+P353-P304+P340+P310-P305+P351+P338+P310-P363-P405-P501 |
Class: | 8 |
UN#: | 3261 |
Packing Group: | Ⅱ |
* 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% | Stage #1: at 20℃; for 2 h; Stage #2: With sodium hydroxide In water; ethyl acetateCooling with ice |
Preparation 6 5-iodo-2-methyl-2H-indazole To a solution of 5-iodo-1H-indazole (500 g, 2.05 mol) in EtOAc (4 L) is added trimethyloxonium tetrafluoroborate (450 g, 3.04 mol). After the resulting white suspension is stirred at room temperature for 2 h, it is concentrated under vacuum. Ice water (1 L) is added to the residue, and it is basified to pH 12 with 10percent aqueous NaOH solution. The solids are collected by filtration, and redissolved in DCM (5 L). The insolubles are filtered off and the filtrate is washed with 10percent aqueous NaOH solution (2*100 mL). The organic layer is dried over anhydrous Na2SO4, filtered through a short silica gel column, and concentrated. Methyl tert-butyl ether is added to the residue to give a slurry and the product is collected by filtration to give the title compound (360 g, 68.0percent). MS (m/z): 259.0 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In dichloromethane; at 20℃;Inert atmosphere; Schlenk technique; | <strong>[1003-91-4]2,4,5-tribromo-1-methyl-imidazole</strong> (1) (0.5g, 1.56mmol) and trimethyloxonium tetrafluoroborate (0.25g, 1.72mmol) in a Schlenk flask was charged with dichloromethane (30mL). The mixture was stirred overnight at room temperature to afford a colorless solid. The volatiles were removed in vacuum and the resulted solid was washed with diethyl ether (2×15mL) and dried under vacuum to give 3 as colorless powder. Yield: 0.60g (91percent). Mp: 304°C. 1H NMR (DMSO-d6, 500MHz, delta, ppm): 3.78 (s, 6H, N?CH3). 13C NMR (DMSO-d6, 125MHz, delta, ppm): 38.1 (N?CH3), 112.0 (4,5-C?Br), 124.9 (C2?Br). IR (KBr, cm?1): 1637(m), 1554(m), 1504(s), 1445(m), 1396(m), 1329(m), 1295(m), 1056(vs), 1034(vs), 813(w), 641(w), 522(w). ESI MS: m/z 332.8081 [M?(BF4) ]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | In ethyl acetate; at 20℃; for 3h; | To a solution of 5-methoxy-indazole (1.0 g, 6.7 mmol) in ethyl acetate (10 ml) was added BF40(CH3)3(1.3 g, 8.9 mmol). The solution was stirred at rt for 3 h. Sat. NaHC03aq. (10 ml) was added and extracted with ethyl acetate (20 ml). Organics were dried over Na2S04, concentrated, and purified by flash chromatography on silica gel (PE /EA = 2/1) to afford 0.64 g (59%) of the title compound as a yellow solid. [M+H] Calc'd for C9H10N2O, 163; Found, 163. |
In ethyl acetate; at 20℃; for 2h; | 2-methyl-4-methoxyphenylamine (27.4 g, 200 mmol) was added to a solution of tetrafluoroboric acid (HBF4, 50% aqueous solution, 100 mL). The solution was stirred at room temperature for about 10 min, then cooled to 0~5C. A solution of sodium nitrite (13.9 g, 200 mmol) in water (20 mL) was dropped in. The mixture was warmed to room temperature and stirred 1 h. The reaction mixture was filtrated and the crude product was washed with diethyl ether (3 x 100 mL) and dried in air to provided 49.7 g of 2-methyl-4-methoxyphenyldiazonium tetrafluoroborate. 2-methyl-4-methoxyphenyldiazonium tetrafluoroborate (49.7 g, 21 1 mmol), 18-crown-6 (2.79 g, 10.6 mmol), potassium acetate (43.4 g, 422 mmol) were added to chloroform (300 mL). The reaction mixture was stirred at room temperature for 2 h. The solution was washed with brine (3 x 30 mL), dried over sodium sulphate, and the solvents evaporated under vacuum. The residue was purified by flash chromatography (ethyl acetate/petroleum ether 2:8 to 4:6) to provide 5-methoxy- lH-indazole (10.2 g). LC-MS (ESI) M+lfound= 149 (MWcalc= 148.1) To a stirred mixture of 5-methoxy-lH-indazole (9.5 g, 64.6 mmol) in ethyl acetate (200 mL), was added trimethyloxonium tetrafluoroborate (19.1 g, 129 mmol). The mixture was stirred at room temperature for 2 h. The reaction mixture was washed with saturated NaHCO3 solution (100 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and the solvents evaporated. Purification of the residue by flash chromatography (ethyl acetate/petroleum ether 2:3) gave 5-methoxy-2-methyl-2H-indazole (8.6 g). LC-MS (ESI) M+lfound= 163 (MWca,c= 162.1).To a mixture of 5-methoxy-2-methyl-2H-indazole (8.2 g, 50.6 mmol) in acetic acid (100 mL) was added N-bromosuccinimide (9.01 g, 50.6 mmol). The mixture was stirred at room temperature for 4 h. The reaction was quenched with ethyl acetate (200 mL) and washed with saturated NaHCO3 aqueous solution until stopped bubbling. The organic layer was separated and washed with brine, then dried over anhydrous sodium sulphate, filtered and concentrated under vacuum. Purification of the residue by flash chromatography (ethyl acetate/petroleum ether 1 :9) gave 3-bromo-5-methoxy- 2-methyl-2H-indazole (8.23 g). LC-MS (ESI) Mfound= 241 (MWcalc= 241.1) 3-Bromo-5-methoxy-2-methyl-2H-indazole (7.9 g, 32.7 mmol) was dissolved in dimethylacetamide (200 mL), and the following reagents were added: Pd2(dba)3 (1.2 g, 1.3 mmol, 4 mol%), Dppf (1.4 g, 2.6 mmol, 8 mol%), Zn powder (513 mg, 7.8 mmol, 24 mol%) and Zn(CN)2 (4.6 g, 39.2 mmol). The mixture was stirred at 170C for 6 h. The reaction mixture was quenched with water (400 mL) and extracted with ethyl acetate (3 x 200 mL). The organic extracts were dried over sodium sulphate and concentrated in vacuum. The crude product was purified by flash chromatography (ethyl acetate/petroleum ether 2:8) to give 5-methoxy-2-methyl-2H-indazole-3-carbonitrile as a white solid (5.9 g).5-Methoxy-2-methyl-2H-indazole-3-carbonitrile (4.67 g, 25 mmol) was dissolved in methanol (60 mL) and an aqueous solution of sodium hydroxide (10%, 60 mL) was added. The reaction mixture was refluxed for 4 h. Methanol was evaporated in vacuum. The residue was acidified to pH=4~5 EPO <DP n="72"/>and extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed with brine, dried and evaporated to provide 5-methoxy-2-methyl-2H-indazole-3-carboxylic acid (4.3 g) as a white powder.To a dichloromethane (400 mL) solution of 5-methoxy-2-methyl-2H-indazole-3-carboxylic acid (4.3 g, 20.6 mmol) were added methy lam ine (hydrochloride salt, 2.8 g, 41.3 mmol), 1- hydroxybenzotriazole hydrate (HOBt) (5.6 g, 41.3 mmol), 3-ethyl-l-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDCI) (11.9 g, 62 mmol) and triethylamine (17 mL, 124 mmol). The reaction mixture was stirred at room temperature for 3 h and then quenched with water (200 mL). The organic layer was separated and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were washed with diluted hydrochloric acid and brine, dried and evaporated to provide 5-methoxy-2-methyl-2H- indazole-3-carboxylic acid methylamide (3.03 g). LC-MS (ESI) Mfound= 219 (MWcalc= 219.2) To a solution of 5-methoxy-2-methyl-2H-indazole-3-carboxylic acid methylamide (2.9 g, 13.1 mmol) in dry dichloromethane (150 mL), Boron trifluoride-methyl sulfide complex (IM, 35 mL) was dropped in at O0C and the reaction mixture was warmed to room temperature and stirred overnight. The reaction was quenched with water, the water phase was extracted with dichloromethane (3 x 50 mL), and the combined organic phases were washed with brine, dried over sodium sulphate, and concentrated under vacuum to provide 5-hydroxy-2-methyl-2H-indazole-3- carboxylic acid methylamide (2.7 g). Yield from 2-methyl-4-methoxyphenylamine: 10%To a soluti... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
180 mg (85%) | In dichloromethane; ethyl acetate; | Step C 1-(tert-Butoxycarbonyl)-2,3,6,7-tetrahydro-5-methoxy-(1H)-1,4-diazepine Trimethyloxonium tetrafluoroborate (Meerwein's salt) (141 mg, 0.94 mmol) was added in one portion to a solution of <strong>[190900-21-1]1-(tert-butoxycarbonyl)hexahydro-(5H)-1,4-diazepin-5-one</strong> (200 mg, 0.94 mmol) in 2.0 mL of anhydrous methylene chloride. The mixture was stirred overnight at room temperature. The reaction mixture was partitioned between 10 mL of saturated aqueous sodium bicarbonate and 20 mL of ethyl acetate. The organic layer was separated and the aqueous layer was extracted with 3*10 mL of ethyl acetate. The combined ethyl acetate layers were washed with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride. After drying over anhydrous sodium sulfate, the organic solution was concentrated in vacuo to give 180 mg (85percent) of 1-(tert-butoxycarbonyl)-2,3,6,7-tetrahydro-5-methoxy-(1H)-1,4-diazepine as a yellow liquid. 1 H NMR(400 MHz, CD3 OD): delta3.58 (s, 3H), 3.53-3.45 (m, 6H), 2.63-2.59 (m, 2H), 1.46 (s, 9H). Mass spectrum: m/z=129. |
100 mg | In dichloromethane; at 0 - 20℃; | 6.01.22.05 5-Methoxy-2,3,6,7-tetrahydro-(1,4)-diazepine-1-carboxylic acid tert-butyl ester 77.5 mg trimethyloxonium tetrafluoroborate was added to 100 mg <strong>[190900-21-1]5-oxo-[1,4]diazepane-1-carboxylic acid tert-butyl ester</strong> in 2 mL dichlormethane at 0-5° C. The reaction mixture was stirred over night at RT. The reaction was washed with saturated sodium hydrogencarbonate solution and water and evaporated to yield 100 mg of the desired product. Rt: 0.79 min (method B), (M+H)+: 229 |
100 mg | In dichloromethane; at 0 - 20℃; | 5-Methoxy-2, 3, 6, 7-tetrahydro-(l, 4)-diazepine-l-carboxylic acid tert-butyl ester 77.5 mg trimethyloxonium tetrafluoroborate was added to 100 mg 5-oxo-[l, 4] diazepane-1- carboxylic acid tert-butyl ester in 2 mL dichlormethane at 0-5 °C. The reaction mixture was stirred over night at RT. The reaction was washed with saturated sodium hydro gencarbonate solution and water and evaporated to yield 100 mg of the desired product. Rt: 0.79 min (method B), (M+H) : 229 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.4% | In ethyl acetate; at 25 - 30℃; for 20h; | Example 1 Trimethyloxonium tetrafluoroborate (125.2 g, 0.85 mol) was added to a stirred suspension of <strong>[6494-19-5]3-methyl-6-nitro-indazole</strong> (100 g, 0.56 mol) in ethyl acetate (2000 mL) over a period of 4 hours in four equal lots at 1 hour time intervals. The reaction mixture was stirred at 25° C. to 30° C. for 16 hours. The solvent was recovered under reduced pressure. A saturated sodium bicarbonate solution (3240 mL) was added to the mixture slowly, and the reaction mixture was extracted with 4:1 mixture of dichloromethane isopropyl alcohol (1080 mL*5). The solvent was recovered under reduced pressure. Methyl tert-butyl ether (800 mL) was added to the residue, and the reaction mixture was stirred for 30 minutes at 45° C. to 50° C. The reaction mixture was cooled to 25° C. to 30° C. and was stirred at this temperature for 30 minutes. The solid was filtered, washed with methyl tert-butyl ether (100 mL*2), and dried in an air oven at 50° C. for 12 hours to afford 2,3-dimethyl-6-nitro-2H-indazole as a yellow solid. Yield: 82.4percent w/w |
73% | In acetone; at 20℃; for 3h;Product distribution / selectivity; | To a stirred solution of 18.5 g (0.11 mol) of 3-methyl-6-nitro-7H-indazole in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of trimethyloxonium tetraflouroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added <n="26"/>saturated aqueous NaHCO3 (600 mL) and a 4:1 mixture of chloroform-isopropanol (200 ml), the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 mL) and the combined organic phase was dried (Na2SO4). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2,3-dimethyl-6-nitro- 2tf-indazole as a yellow solid (15.85 g, 73 percent). 1H NMR (300 MHz, DMSO-d6) delta 8.51 (s, 1H), 7.94 (d, J = 9.1 Hz, 1 H), 7.73 (d, J = 8.9 Hz, 1 H), 4.14 (s, 3H), 2.67 (s, 3H). MS (ES+, m/z) 192 (M+H). |
73% | In acetone; at 20℃; for 3h; | To a stirred solution of 18.5 g (0.11 mol) of [3-METHYL-6-NITRO-1H-INDAZOLE] in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of [TRIMETHYLOXONIUM] [TETRAFLOUROBORATE.] After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous [NAHC03] (600 mL) and a 4: 1 mixture of chloroform-isopropanol (200 [ML),] the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 mL) and the combined organic phase was dried [(NA2S04).] Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2, 3-dimethyl-6-nitro-2H-indazole as a yellow solid (15.85 [G,] 73 [percent).APOS;H] NMR (300 MHz, [DMSO-D6)] 8 8.51 (s, [1 H),] 7.94 (d, [J= 9.] 1 Hz, [1 H),] 7.73 (d, [J =] 8.9 Hz, [1 H),] 4.14 (s, 3H), 2.67 (s, 3H). MS [(ES+,] [M/Z)] 192 (M+H). |
73% | In acetone; at 20℃; for 3h;Product distribution / selectivity; | To a stirred solution of 18.5 g (0.11 mol) of 3-methyl-6-nitro- 7H-indazole in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of trimethyloxonium tetraflouroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous NaHCO3 (600 ml_) and a 4:1 mixture of chloroform-isopropanol (200 ml), the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 mL) and the combined organic phase was dried (Na2SO4). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2,3-dimethyl-6-nitro-2H-indazole as a yellow solid (15.85 g, 73 percent). 1H NMR (300 MHz, DMSO-d6) delta 8.51 (s, 1 H), 7.94 (d, J = 9.1 Hz, 1 H), 7.73 (d, J = 8.9 Hz, 1 H), 4.14 (s, 3H)1 2.67 (s, 3H). MS (ES+, m/z) 192 (M+H). |
73% | In acetone; at 20℃; for 3h;Inert atmosphere; | Intermediate Example 11 Preparation of 2,3-dimethyl-2H-indazol-6-amine To a stirred solution of 18.5 g (0.11 mol) of <strong>[6494-19-5]3-methyl-<strong>[6494-19-5]6-nitro-1H-indazole</strong></strong> in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of trimethyloxonium tetraflouroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous NaHCO3 (600 ml) and a 4:1 mixture of chloroform-isopropanol (200 ml), and the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 ml) and the combined organic phase was dried (Na2SO4). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 ml) to afford 2,3-dimethyl-6-nitro-2H-indazole as a yellow solid (15.85 g, 73 percent). 1H NMR (300 MHz, d6DMSO) delta 8.51 (s, 1H), 7.94 (d, J = 9.1 Hz, 1H), 7.73 (d, J = 8.9 Hz, 1H), 4.14 (s, 3H), 2.67 (s, 3H). MS (ES+, m/z) 192 (M+H).; To a stirred solution of 2,3-dimethyl-6-nitro-2H-indazole (1.13 g) in 2-methoxyethyl ether (12 ml), at 0 °C, was added a solution of 4.48 g of tin(II) chloride in 8.9 ml of concentrated HCl dropwise over 5 min. After the addition was complete, the ice bath was removed and the solution was allowed to stir for an additional 30 min. Approximately 40 ml of diethyl ether was added to reaction, resulting in precipitate formation. The resulting precipitate was isolated by filtration and washed with diethyl ether, and afforded a yellow solid (1.1 g, 95 percent), the HCl salt 2,3-dimethyl-2H-indazol-6-amine. 1H NMR (300 MHz, d6DMSO) delta 7.77 (d, J = 8.9 Hz, 1H), 7.18 (s, 1H), 7.88 (m, 1H), 4.04 (s, 3H), 2.61 (s, 3H). MS (ES+, m/z) 162 (M+H). |
73% | In acetone; at 20℃; for 3h;Inert atmosphere; | 18.5 g (0.11 mol) of <strong>[6494-19-5]3-methyl-<strong>[6494-19-5]6-nitro-1H-indazole</strong></strong> was dissolved in 350 ml of acetone,20 g (0.14 mol) of trimethyloxonium tetrafluoroborate was added with stirring at room temperature,The reaction solution was filled with argon for 3 h,The solvent was removed under reduced pressure,The solid was added with 600 ml of aqueous NaHCO3 solution,200 ml of a mixture of chloroform and isopropanol (4: 1)The organic phase was dried over anhydrous sodium sulfate,filter,The solvent was distilled off,To give a brown solid,Washed with ether,15.85 g of 2,3-dimethyl-6-nitro-2H-indazole was obtained in a yield of 73percent. |
73% | Intermediate Example 1 Preparation of 2,3-dimethyl-6-nitro-2H-indazole Procedure 1: To a stirred solution of 18.5 g (0.11 mol) of <strong>[6494-19-5]3-methyl-<strong>[6494-19-5]6-nitro-1H-indazole</strong></strong> in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of trimethyloxonium tetrafluoroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous NaHCO3 (600 mL) and a 4:1 mixture of chloroform-isopropanol (200 ml), the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4*200 mL) and the combined organic phase was dried (Na2SO4). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2,3-dimethyl-6-nitro-2H-indazole as a yellow solid (15.85 g, 73percent). 1H NMR (300 MHz, DMSO-d6) delta 8.51 (s, 1H), 7.94 (d, J=9.1 Hz, 1H), 7.73 (d, J=8.9 Hz, 1H), 4.14 (s, 3H), 2.67 (s, 3H). MS (ES+, m/z) 192 (M+H). | |
73% | In acetone; at 20℃; for 3h;Product distribution / selectivity; | Intermediate Example 1 Preparation of 2,3-dimethyl-6-nitro-2H-indazole Procedure 1: To a stirred solution of 18.5 g (0.11 mol) of 3-methyl-6-nitro-1H- indazole in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of trimethyloxonium tetraflouroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous NaHC03 (600 mL) and a 4: 1 mixture of chloroform-isopropanol (200 ml), the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 mL) and the combined organic phase was dried (Na2S04). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2,3-dimethyl-6-nitro-2H-indazole as a yellow solid (15.85 g, 73 percent). |
73% | In acetone; at 20℃; for 3h;Product distribution / selectivity; | To a stirred solution of 18.5 g (0.1 1 mol) of 3-methyl-6-nitro-7/-/-indazole in 350 ml acetone, at room temperature, was added 20 g (0.14 mol) of thmethyloxonium tetraflouroborate. After the solution was allowed to stir under argon for 3 hours, the solvent was removed under reduced pressure. To the resulting solid was added saturated aqueous NaHCO3 (600 ml_) and a 4:1 mixture of chloroform-isopropanol (200 ml), the mixture was agitated and the layers were separated. The aqueous phase was washed with additional chloroform: isopropanol (4 x 200 mL) and the combined organic phase was dried (Na2SO4). Filtration and removal of solvent gave a tan solid. The solid was washed with ether (200 mL) to afford 2,3-dimethyl-6-nitro-2/-/-indazole as a yellow solid (15.85 g, 73 percent). 1H NMR (300 MHz, DMSOd6) delta 8.51 (s, 1 H), 7.94 (d, J = 9.1 Hz, 1 H), 7.73 (d, J = 8.9 Hz, 1 H), 4.14 (s, 3H), 2.67 (s, 3H). MS (ES+, m/z) 192 (M+H). |
32% | Example 50: Process for preparation of DMND[000167] To a stirred solution of 3-methyl-6-nitro- l H-indazole (MNID) (5.0 g, 28.2 mmol) in acetone (95 mL, 19V) at ambient temperature was added trimethyloxonium tetrafluoroborate (5.3 g, 35.8 mmol, 1 .27 eq). Stirring was continued under nitrogen and the reaction was monitored by TLC. After 5.5 h another 1 g of trimethyloxonium tetrafluoroborate was added to the reaction in an attempt to push it to completion. After 7.5 h total reaction time the solvent was removed and saturated sodium bicarbonate ( 162 mL) was added to the residue, followed by a 4: 1 mixture of CHC : IPA (54 mL). The resulting mixture was agitated and the layers were separated. The aqueous phase was washed with additional CHCI3: IPA 4: 1 (4x54 mL) and the combined organic phases were dried ( a2SO,)), filtered and evaporated to dryness. The resulting brown solid was washed with diethylether (about 160 mL) and dried on the filter under nitrogen/vacuum to afford crude DMND (3.2 g, 87.5percent purity). The crude material (2.9 g) was then dissolved in EtOH (50 mL) at reflux and the solution was gradually cooled to ambient temperature and then to 5 °C, and was kept at this temperature for 1 h. The resulting precipitate was isolated by filtration and the filter cake was washed with cold EtOH ( 10 mL) and dried in a vacuum oven (35 mbar) at 55°C for 4 h to give 2,3-dimethyl-6-nitro-2H-indazole ( 1 .57g, ca 32percent) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,2-dichloro-ethane; | EXAMPLE 64(3) To a solution of (R)-N-(3,4-dimethoxybenzyl)-2-(2-hydroxy-1-methylethylamino)-5-nitrobenzamide (200 mg) in 1,2-dichloroethane (10 mL) were added trimethyloxonium tetrafluoroborate (91.2 mg) and <strong>[38222-83-2]2,6-di-tert-butyl-4-methylpyridine</strong> (158 mg), and the mixture was heated for 3 hours under reflux. The mixture was washed with 1N-hydrochloric acid, water, an aqueous saturated sodium bicarbonate solution and brine. Then, the resultant was dried over magnesium sulfate and evaporated in vacuo. The residue was purified by a silica gel column chromatography eluding with a mixture of hexane and ethyl acetate (3:1 to 1:1). The obtained product was triturated with diisopropyl ether to give (R)-N-(3,4-dimethoxybenzyl)-2-(2-methoxy-1-methylethylamino)-5-nitrobenzamide as yellow powders (145 mg). NMR (DMSO-d6, delta): 1.17 (3H, d, J=7 Hz), 3.29 (3H, s), 3.42 (2H, br), 3.73 (3H, s), 3.74 (3H, s), 3.88-4.00 (1H, br), 4.37 (2H, d, J=7 Hz), 6.85-6.96 (4H, m), 8.12 (1H, dd, J=4, 8 Hz), 8.59 (1H, d, J=4 Hz), 9.09 (1H, d, J=8 Hz), 9.29 (1H, br); Mass m/z: 402(M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; | PREPARATION 108 Methyl 2-O-Benzyl-3-O-p-methoxybenzyl-6-O-methyl-alpha-D-glucopyranoside (122) Compound 121 (26.4 g) is dissolved in dichloromethane (263 ml) under a nitrogen atmosphere. Trimethyloxonium tetrafluoroborate (11.6 g) and <strong>[38222-83-2]2,6-di-tert-butyl-4-methylpyridine</strong> (17.4 g) are added at room temperature. After 4 hours, the mixture is poured onto ice-water and extracted with dichloromethane. The organic phase is washed with sodium hydrogen carbonate and concentrated. Purification of the crude product by chromatography on a column of silica gel allows 18.5 g of compound 122 to be obtained. TLC: Rf=0.25, silica gel, 7/3 v/v toluene/ethyl acetate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; | 2. The starting material was prepared by reaction of <strong>[1532-71-4]1-<strong>[1532-71-4]bromoisoquinoline</strong></strong> with trimethyloxonium tetrafluoroborate in CH2 Cl2 to give 1-bromo-2-methylisoquinolinium tetrafluoroborate, m.p. 162°. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydrogencarbonate; In methanol; dichloromethane; | Synthesis Example 6 To a solution of ethyl thioxamidate (1.0 g) in dichloromethane (10 ml), trimethyloxonium tetrafluoroborate (1.17 g) was added, and the resultant mixture was stirred at room temperature for 30 minutes. <strong>[443-86-7]3-Fluoro-2-methylaniline</strong> (0.94 g) was added thereto, followed by stirring for 10 minutes. The reaction mixture was concentrated. The mixture was dissolved in methanol (10 ml), 1N sodium bicarbonate (8 ml) was added thereto, and the resultant mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated, and the residue was chromatographed on silica gel column using a mixture of dichloromethane and methanol (10: 1 by volume) as an eluding solvent to give ethyl N-(3-fluoro-2-methylphenyl)amidinoformate (Compound No. 26) (0.8 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; In methanol; dichloromethane; | Synthesis Example 1 To a solution of ethyl thioxamidate (1.0 g) in dichloromethane (10 ml), trimethyloxonium tetrafluoroborate (1.17 g) was added, and the resultant mixture was stirred at room temperature for 30 minutes. <strong>[443-86-7]3-Fluoro-2-methylaniline</strong> (0.94 g) was added thereto, followed by stirring for 10 minutes. The reaction mixture was concentrated. The residue was dissolved in methanol (10 ml), an aqueous solution (5 ml) of potassium hydroxide (1.05 g) was added thereto, and the resultant mixture was stirred for 30 minutes. The reaction mixture was neutralized with acetic acid (0.5 g) and concentrated under reduced pressure. The solid residue was dissolved in a mixture of dichloromethane and methanol (4: 1 by volume) (100 ml), followed by filtration. The filtrate was concentrated under reduced pressure, and the oily residue was crystallized from acetone to give N-(3-fluoro-2-methylphenyl)amidinoformic acid (Compound No. 1) (1.15 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In dichloromethane; | Reference Example 51 Allyl 4-O-diphenylphosphono-2-deoxy-3-O-{(R)-3-dodecyloxytetradecyl}-6-O-methyl-2-(2,2,2-trichloroethoxycarbonylamino)-alpha-D-glucopyranoside To a solution of the compound of Reference Example 50 (385 mg, 0.382 =mol) in methylene chloride (5 ml) were added <strong>[38222-83-2]2,6-di-tert-butyl-4-methylpyridine</strong> (91 mg, 0.441 mmol) and trimethyloxonium tetrafluoroborate (64 mg, 0.435 mmol) and the mixture was stirred at room temperature for 20 hours. The reaction mixture was diluted with ethyl acetate. The ethyl acetate layer was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution, dried over magnesium sulfate and then concentrated in vacuo. The residue was purified by chromatography on a silica gel column using hexane:ethyl acetate=7:3 as the eluant to give the desired product (357 mg, yield 91percent). IR spectrum (CHCl3): 3436, 2928, 2855, 1744 cm-1 NMR spectrum (400 MHz, CDCl3) delta: 7.35-7.15 (10H, m), 5.90 (1H, m), 5.33-5.23 (3H, m, containing NH), 4.93 (1H, d, J=3.7 Hz), 4.77, 4.69 (2H, ABq, J=1 1.7 Hz), 4.67 (1H, m), 4.21 (1H, dd, J=5.1, 13.2 Hz), 4.04-3.98 (2H, m), 3.89-3.65 (4H, m), 3.54 (1H, dd, J=4.4, 11.0 Hz), 3.48 (1H, dd, J=2.2, 11.0 Hz), 3.26-3.19 (6H, m, containing 3H, s, delta3.24), 1.64-1.62 (2H, m), 1.44-1.43 (2H, m), 1.32-1.17 (38H, m), 0.88 (6H, t, J=6.6 Hz) Mass spectrum (m/z): 1020.4669 (M+H)+ Analyses for: C51 H81Cl3NO11P (Molecular weight: 1021.5) Calculated: C, 59.97; H, 7.99; N, 1.37; Cl, 10.41; P, 3.03. Found: C, 59.10; H, 7.85; N, 1.29; Cl, 10.51; P, 3.27. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Preparation 1 Synthesis of 5-bromo-2-methyl-2H-indazole Add at room temperature under nitrogen, trimethyloxonium tetrafluoroborate (229.34 g, 1.52 mol) portion wise to a mixture of 5-bromo-1H-indazole (199.6 g, 1.01 mol) in ethyl acetate (3.04 L, 31.06 mol), stir 2.5 h and filter to give a white solid. Wash the recovered solid twice with ethyl acetate (500 mL) and then add it portion wise to a cooled aqueous solution of 2 M sodium hydroxide (3.80 L, 7.60 mol) in an ice bath. Stir the mixture for 1 h, sonicate for 15 min., filter and wash the recovered solid twice with water (200 mL). Dry the solid overnight under vacuum, slurry in dichloromethane (1 L) and filter. Concentrate the filtrate and purify by silica gel chromatography eluding with dichloromethane to give the title compound as a yellow solid (149.77 g, 70%). MS (m/z): 211, 213 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | In dichloromethane; at 20℃; | To a solution of <strong>[109-11-5]3-morpholone</strong> (2.0 g, 20 mmol) in dichloromethane (40 mL) in a 100 mL single neck flask was added trimethyloxonium tetrafluoroborate (4.0 g, 27 mmol), the mixture was stirred at room temperature overnight. The mixture was quenched with saturated aqueous sodium bicarbonate solution (50 mL) under ice bath, and then adjusted pH to neutral. The mixture was extracted with dichloromethane (50 mL x 2). The combined organic layers were washed with saturated brine (50 mL x 2), dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum to give the title compound as a transparent oil (1.0 g, 44%).‘H NIVIR (400 1VIFIz5 CDC13) 4.01 (d, J 1.2 H4 2H’), 3.65 (d, J 2.3 H4 3H), 3.62 (dd, J 6.5, 3.2 Hz; 2H’), 3.51 (dd, J 6.5, 2.9 Hz, 2H). |
Example 9A5 -Methoxy-3 ,6-dihydro-2H- 1 ,4-oxazineA solution of 1.2 g (11.9 mmol) <strong>[109-11-5]morpholine-3-one</strong> in dichloromethane (70 ml) was cooled to 00C and treated with 25 g (238 mmol) dry sodium carbonate. After stirring for 10 min at 00C, 6.14 g (41.5 mmol) trimethyloxonium tetrafluoroborate were added at 00C. The mixture was allowed to warm to room temperature and stirred for 6 h. Water (100 ml) was added, and the organic layer was separated. The aqueous phase was extracted several times with dichloromethane, and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude product thus obtained was used in the next step without further purification.GC-MS (method 3): R1 = 3.36 min; MS (ESIpos): m/z = 116 (M+H)+. | ||
A solution of 1.2 g (1 1.9 mmol) <strong>[109-11-5]morpholine-3-one</strong> in dichloromethane (70 ml) was cooled to 0C and treated with 25 g (238 mmol) dry sodium carbonate. After stirring for 10 min at 0C, 6.14 g (41.5 mmol) trimethyloxonium tetrafluorob orate were added at 0C. The mixture was allowed to warm to room temperature and stirred for 6 h. Water (100 ml) was added, and the organic layer was separated. The aqueous phase was extracted several times with dichloromethane, and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude product thus obtained was used in the next step without further purification.GC-MS (method 5): Rt = 3.36 min; MS (ESIpos): m/z = 1 16 (M+H)+. |
Example 3A5-Methoxy-3,6-dihydro-2H-l ,4-oxazine A solution of 1.2 g (11.9 mmol) <strong>[109-11-5]morpholine-3-one</strong> in dichloromethane (70 ml) was cooled to 00C and treated with 25 g (238 mmol) dry sodium carbonate. After stirring for 10 min at 0C, 6.14 g (41.5 mmol) trimethyloxonium tetrafluoroborate were added at 0C. The mixture was allowed to warm to room temperature and stirred for 6 h. Water (100 ml) was added, and the organic layer was separated. The aqueous phase was extracted several times with dichloromethane, and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude product thus obtained was used in the next step without further purification.GC-MS (method 3): R, = 3.36 min; MS (ESIpos): m/z = 116 (M+?)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In ethyl acetate; at 20℃; for 12h;Inert atmosphere; | Reference Example 2 methyl 2-methyl-2H-indazole-4-carboxylate To a solution of <strong>[192945-49-6]methyl 1H-indazole-4-carboxylate</strong> (63.0 g, 358 mmol) in ethyl acetate (1.19 L) was added trimethyloxonium tetrafluoroborate (68.8 g, 465 mmol), and the mixture was stirred under nitrogen atmosphere at room temperature for 12 hr. The reaction solution was diluted with ethyl acetate, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The residue was purified by recrystallization (ethyl acetate/hexane) to give the title compound (57.0 g, yield 84%). 1H-NMR (CDCl3) delta: 3.98 (3H, s), 4.27 (3H, s), 7.34 (1H, dd, J = 8.4, 7.2 Hz), 7.91 (1H, d, J = 6.4 Hz), 7.93 (1H, d, J = 8.4 Hz), 8.42 (1H, s), MS (ESI+): 191 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.25 g (72%) | In dichloromethane; ethyl acetate; | Example 184c (E)-2-(4-Methoxybut-2-enyloxy)-6-nitrobenzonitrile To a solution of (E)-2-(4-hydroxybut-2-enyloxy)-6-nitrobenzonitrile (Example 184d) (0.50 g, 2.13 mmol) and <strong>[38222-83-2]2,6-di-tert-butyl-4-methylpyridine</strong> (2.18 g, 10.65 mmol) in CH2Cl2 (15.0 mL) at rt, was added trimethyloxonium tetrafluoroborate (1.58 g, 10.65 mmol) under a nitrogen atmosphere. After 1 h at rt, the reaction was quenched with water (50 mL) and extracted with EtOAc (4*50 mL). The combined extract was washed with water, 1.5M HCl, saturated aqueous NaHCO3 and brine, and was dried over anhydrous MgSO4. The filtrate was evaporated and the residue was purified by chromatography on silica gel using the solvent gradient hexanes?hexanes/EtOAc (3:7), to give 0.25 g (72%) of the title compound as a yellow solid. 1H-NMR (400 MHz, DMSO-d6) delta 7.84-7.92 (m, 2H), 7.68-7.73 (m, 1H), 5.82-6.03 (m, 2H), 4.82-4.88 (m, 2H), 3.87-3.93 (m, 2H), 3.21 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethyl acetate; at 20℃; for 6h; | (Step 1) Trimethyloxonium tetrafluoroborate (1.5 g) was added to a solution of <strong>[685109-10-8]7-bromo-5-nitro-1H-indazole</strong> (1.21 g) in ethyl acetate (12 mL), and the reaction solution was stirred at room temperature for 6 hours. After dilution with ethyl acetate, the reaction solution was washed successively with water and a saturated saline solution and then dried over anhydrous sodium sulfate. The solvent was evaporated under vacuum, ethyl acetate and isopropyl ether were added to the resultant residue, and the deposited precipitate was filtrated to obtain 7-bromo-2-methyl-5-nitro-2H-indazole as a light yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With pyridine; In dichloromethane; at 20℃; for 17h; | 3 mL glass vial was equipped with a rubber septum and magnetic stir bar. The vial was brought into a glove box and charged with trimethyloxonium tetrafluoroborate (198 mg, 1.33 mmol). The vial was sealed and removed from the glove box. A separate 3 mL vial was charged with <strong>[54221-96-4]2-methoxy-6-pyridinecarboxaldehyde</strong> (Aldrich 662933, 184 mg, 1.34 mmol) and was dissolved in CH2Cl2 (1.5 mL). The solution of pyridine was added via syringe onto the solid trimethoxonium tetrafluoroborate at room temperature. The vial which contained the pyridine was rinsed with CH2Cl2 (1 mL) and the rinse solution was injected into the reaction vial. The reaction vial was kept at room temperature and stirring was maintained at ca. 400-600 rpm. Over the course of the reaction (17 h), the solid trimethoxonium tetrafluoroborate gradually dissolved, the solution clarified, and an oil gradually formed. At the end of the reaction, hexanes (2 mL) were added after which stirring was stopped. Any solid or oil was allowed to settle and the solvent was removed by glass pipette. The solid or oil was then rinsed with several portions of hexanes followed by diethyl ether. Residual solvent was then removed in vacuo to provide the compound N-methyl-<strong>[54221-96-4]6-methoxy-2-pyridinecarboxaldehyde</strong> tetrafluoroborate. This oil was used for oxime formation without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; lithium hydroxide; trimethylsilyl trifluoromethanesulfonate; potassium carbonate; triethylamine; N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; methanol; propan-1-ol; dichloromethane; water; ethyl acetate; | Example 28 Potassium carbonate (647 mg, 4.68 mmol) and di-tert-butyl dicarbonate (716 mg, 3.28 mmol) were added to 2-(3-bromo-phenyl)-piperidine (750 mg, 3.12 mmol) in dichloromethane (10 mL). After overnight stirring at RT water (20 mL) was added to the solution. The resulting biphasic solution was separated into organic and aqueous phases. The aqueous phase was back extracted with dichloromethane (20 mL). The combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated to afford the title compound (1.03 g, 97percent) as a pale yellow oil. To a solution of 28a (1.03 g, 3.03 mmol) and potassium vinyltrifluoroborate (488 mg, 3.64 mmol) in n-propanol (30 mL), under an atmosphere of nitrogen was added 1,1' bis(diphenylphosphino)ferrocenedichloropalladium(II), dichloromethane adduct (49 mg, 0.06 mmol) and triethylamine (306 mg, 422 muL, 3.03 mmol). The reaction was heated to reflux and left to stir for 3 h before cooling to RT. The reaction mixture poured onto water and the resultant solution was extracted with diethyl ether (3*30 mL). The combined organics were dried over anhydrous sodium sulfate, filtered and concentrated. The resultant residue was purified by silica gel chromatography using a stepwise gradient of iso-hexanes/ethyl acetate 1:0 to 4:1 to afford the title compound (652 mg, 75percent) as a pale yellow oil. A solution of (2R,3R)-1-((1R,5S)-10,10-dimethyl-3,3-dioxo-3lambda*6*-thia-4-aza-tricyclo[5.2.1.0*1,5*]dec-4-yl)-3-hydroxy-2-methyl-hept-6-en-1-one (250 mg, 0.703 mmol) in anhydrous dichloromethane (7 mL) was prepared and trimethyloxonium tetrafluoroborate (208 mg, 1.406 mmol) was added. The reaction mixture was stirred at RT for 15 h. The reaction mixture was treated with methanol (1 mL), then 2 M hydrochloric acid (20 mL) and saturated brine (20 mL). The mixture was extracted with ethyl acetate (3*15 mL) and the extract was dried over sodium sulfate, filtered and evaporated to give a yellow gum. The gum was purified by silica gel chromatography using iso-hexanes/ethyl acetate 4:1 to give the title compound (223 mg, 86percent) as a colorless gum. A solution of 2 M lithium hydroxide in water (5 mL, 10 mmol) was added to a stirred solution of 28c (223 mg, 0.60 mmol) in tetrahydrofuran (15 mL). The stirred mixture was heated to 60° C. for 15 h. The reaction mixture was partially evaporated before adding 2 M hydrochloric acid (20 mL). The solution was extracted with ethyl acetate (3*15 mL). The extract was dried over sodium sulfate, filtered and evaporated to give a yellow gum (209 mg). The gum was purified by silica gel chromatography using iso-hexanes/ethyl acetate 3:1 to yield the title compound (68 mg, 66percent) as a yellow gum. A solution of (S)-1-[(S)-2-((S)-2-tert-butoxycarbonylamino-3-methylbutyrylamino)-propionyl]-hexahydropyridazine-3-carboxylic acid 2,2,2-trichloroethyl ester (316 mg, 0.59 mmol) in anhydrous dichloromethane (10 mL) was cooled to 0° C. under a nitrogen atmosphere before adding trimethylsilyl trifluoromethanesulfonate (160 muL, 0.885 mmol). The reaction mixture was stirred at 0° C. for 2 h before adding N,N-diisopropylethylamine (413 muL, 2.36 mmol) to afford (S)-1-[(S)-2-((S)-2-amino-3-methyl-butyrylamino)-propionyl]-hexahydro-pyridazine-3-carboxylic acid 2,2,2-trichloroethyl ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃; for 48h;Inert atmosphere; | General procedure: Me3O+BF4- (20 mmol) was added to a solution of 1,3,4,5-tetrahydro-2H-1-benzazepin-2-ones 1a-k (5 mmol) in CH2Cl2 (30 ml), and the resulting mixture was stirred at room temperature under an argon atmosphere for 48 h. The reaction mixture was diluted with saturated aqueous KHCO3 (30 ml), and the mixture was extracted with CH2Cl2 (2×20 ml). The organic phase was separated, dried over anhydrous Na2SO4, filtered, and the solvent was evaporated. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20.0℃; for 48.0h;Inert atmosphere; | General procedure: Me3O+BF4- (20 mmol) was added to a solution of 1,3,4,5-tetrahydro-2H-1-benzazepin-2-ones 1a-k (5 mmol) in CH2Cl2 (30 ml), and the resulting mixture was stirred at room temperature under an argon atmosphere for 48 h. The reaction mixture was diluted with saturated aqueous KHCO3 (30 ml), and the mixture was extracted with CH2Cl2 (2×20 ml). The organic phase was separated, dried over anhydrous Na2SO4, filtered, and the solvent was evaporated. |
Tags: 420-37-1 synthesis path| 420-37-1 SDS| 420-37-1 COA| 420-37-1 purity| 420-37-1 application| 420-37-1 NMR| 420-37-1 COA| 420-37-1 structure
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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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