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CAS No. : | 401-95-6 | MDL No. : | MFCD00010206 |
Formula : | C9H4F6O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LDWLIXZSDPXYDR-UHFFFAOYSA-N |
M.W : | 242.12 | Pubchem ID : | 136247 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H227-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 |
---|---|---|
90% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper diacetate; In water; acetonitrile; at 20℃; for 6h;Green chemistry; | General procedure: A mixture of alcohol (5.0 mmol), Cu(OAc)2 (9.1 mg, 0.05 mmol), and TEMPO (7.8 mg, 0.05 mmol) in CH3CN/H2O (5/10 mL) was stirred at room temperature for specified time. After completion of the reaction (monitored by TLC, eluents: petroleum ether/ethyl acetate = 4/1), dichloromethane (10 mL) was added to the resulting mixture. The dichloromethane phase was separated, and the aqueous phase was further extracted with dichloromethane (10 mL × 2). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by column chromatography (eluents: petroleum ether/ethyl acetate = 10/1) to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene; for 5h;Heating / reflux;Product distribution / selectivity; | Step 2:A crude mixture of 5-amino-2-methyltetrazole and 5-amino-1-methyltetrazole is treated with 3,5-bis(trifluoromethyl)benzaldehyde (48 ml_, 71g, 0.29 mol) in toluene (780 ml_), and the mixture is stirred and refluxed for 5 hours. The resulting mixture is filtered to remove off the insoluble solid (5-amino-1-methyltetrazole), and the residue is washed with hot toluene. The filtrate is concentrated to give crude 2-methyl-N-[3,5-bis(trifluoromethyl)phenylmethylene]- 2H-tetrazole-5-amine (70.1g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene; for 3h;Heating / reflux;Product distribution / selectivity; | <Method 2> <n="85"/>Step 1 :A mixture 5-amino-2-methyltetrazole (5.00 g, 50 mmol) and 3,5- bis(trifluoromethyl)benzaldehyde (19.5 g, 81 mmol) in toluene (100 ml.) is stirred and refluxed for 3 hours. The resulting mixture is concentrated to give crude 2-methyl-N-[3,5- bis(trifluoromethyl)phenylmethylene]-2/-/-tetrazole-5-amine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.5% | With hydrogen;aluminum nickel; In toluene; | Example 5 (not according to the invention) 37 g of 3,5-bis(trifluoromethyl)benzaldehyde and 4 g of Raney nickel together with 150 ml of toluene were placed in a reaction vessel at room temperature. The vessel was pressurized with 30 bar of hydrogen gas and the mixture was hydrogenated at 50 C. for 7.5 hours while stirring. The mixture was subsequently cooled to room temperature, depressurized and the catalyst was filtered off. The filtrate was evaporated and the crude product obtained in this way was distilled at 17 mbar. 3,5-bis(trifluoromethyl)benzyl alcohol having a boiling point of 97 C. was obtained in a yield of 31.5 g and a purity of 97.7%. This corresponds to a yield of 82.5% of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene; for 0.75h;Heating / reflux; | A mixture of the crude product and 3,5-bis(trifluoromethyl)benzaldehyde (43.0 g, 0.18 mol) in toluene (600 mL) is stirred and refluxed for 45 min. After cooling to room temperature, the resulting mixture is concentrated. NaBH4 (8.12 g, 0.22 mol) is added portionwise slowly to EtOH (500 mL) solution of the resulting residue, and the mixture is stirred at room temperature for 4 hours. After addition of sat. NH4CI aq. and water, the mixture is extracted with ethyl acetate. The combined organic layer is washed with brine, dried over magnesium sulfate, filtered and concentrated. The crude product is purified by crystallization (50 mL of /- PrOH:H2O. 3:7) to give [3,5-bis(trifluoromethyl)phenylmethyl](2-methyl-2H-tetrazol-5- yl)amine (12.4 g). | |
In toluene; for 4h;Heating / reflux; | The reaction solution was concentrated and the obtained residue was dissolved in ethanol (70 ml), and sodium borohydride (2.10 g) was added with stirring at room temperature. The reaction solution was stirred at room temperature for 30 min, and saturated aqueous ammonium chloride was added. The mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine. The organic layer was dried over sodium sulfate and sodium sulfate was filtered off. The filtrate was concentrated and the obtained residue was recrystallized from isopropanol-water (3:7, 50 ml) to give the title compound. 1H-NMR(CDCl3,300 MHz)delta: 4.16(s,3H), 4.66(d,J=6.3 Hz2H), 4.92(brs,1H), 7.79(s,1H), 7.83(s,2H). | |
With molecular sieves 5-10 A; In toluene; for 4h;Heating / reflux; | Preparation 5 N-(3,5-Bis(trifluoromethyl)benzyl)-<strong>[6154-04-7]2-methyl-2H-tetrazol-5-amine</strong> A mixture of 3,5-bis(trifluoromethyl)benzaldehyde (4 g, 16.5 mmol), <strong>[6154-04-7]2-methyl-2H-tetrazol-5-amine</strong> (1.96 g, 19.8 mmol) and molecular sieves (5-10 A beads) in toluene (50 mL) was heated at reflux for 4 hours, after which time the solvent was removed. Ethanol (50 mL) and sodium borohydride (1.25 g, 33 mmol) were added. The resulting mixture was stirred at room temperature for 30 minutes and then partitioned between saturated NH4Cl (50 mL) and ethyl acetate (2*50 mL). The combined organic layers were washed with saturated NaCl (50 mL), dried (MgSO4), filtered and concentrated to yield the title compound as a white solid (4.7 g). 1H NMR (400 MHz, CDCl3) delta 4.2 (s, 3H) 4.7 (s, 1H) 4.7 (s, 1H) 5.0 (t, J=6.0 Hz, 1H) 7.8 (s, 1H) 7.9 (s, 2H). MS (ES+) Calc: 325.08, Found: 325.8 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of 3,.5-bis(trifluoromethyl)benzaldehyde (4 g, 16.5 mmol), <strong>[6154-04-7]2-methyl-2H-tetrazol-5-amine</strong> (1.96 g, 19.8 mmol) and Molecular Sieves (5-10A beads) in toluene (50 ml.) was heated at reflux for 4 hours, after which time the solvent was removed. Ethanol (50 mL) and sodium borohydride (1.25 g, 33 mmol) were added. The resulting mixture was stirred at room temperature for 30 minutes, and then partitioned between saturated ammonium chloride (50 mL) and ethyl acetate (twice at 50 mL). The combine organic layers were washed with saturated NaCI (50 mL), dried (magnesium sulfate), filtered and concentrated to yield the title compound as a white solid (4.7 g). 1H NMR (300 MHz, CHLOROFORM-D) delta ppm 4.2 (s, 3 H) 4.7 (s, 1 H) 4.7 (s, 1 H) 5.0 (t, J=6.0 Hz, 1 H) 7.8 (s, 1 H) 7.9 (s, 2 H); MS (ES+) CaIc: 325.08, Found: 325.8 (M+1). | ||
A stirred solution of 3,5~bis(trifluoromethyl)benzaldehyde (877 muL, 5.29 mmol) and 2-methyl-2H- tetrazol-5 -amine (628 mg, 6.35 mmol) in toluene (15 mL) was heated at reflux for 2.5 h. The reaction was concentrated in vacuo and the residue was redissolved in EtOH (15 mL). Sodium borohydride (400 mg, 10.58 mmol) was added and the mixture was stirred at room temperature for 14 h. The reaction was quenched with sat. NH4Cl and was partitioned between H2O (25 mL) and EtOAC (25 mL). The aqueous layer was re-extracted with EtOAc (3 x 25 mL) and the combined extracts were washed with brine (50 mL), dried (Na2SO4), filtered and concentrated in vacuo. The residue was recrystallized from IPAiH2O (3:7) and cooled at 4C for 14 h. A precipitate formed and was collected by filtration and dried in a vacuum oven to afford N-[3,5-bis(trifluoromethyl)benzyl]-2-methyl-2H-tetrazol-5-amme as a white solid. LCMS = 326.1 (M+l)+. lEta NuMR (CDCI3, 500 MHz): delta 7.86 (s, 2 H), 7.82 (s, 1 H), 4.69 (s, 2 H), 4.19(s, 3 H). | ||
Preparation 5 N-(3,5-Bis(trifluoromethyl)benzyl)-<strong>[6154-04-7]2-methyl-2H-tetrazol-5-amine</strong> A mixture of 3,5-bis(trifluoromethyl)benzaldehyde (4 g, 16.5 mmol), <strong>[6154-04-7]2-methyl-2H-tetrazol-5-amine</strong> (1.96 g, 19.8 mmol) and molecular sieves (5-10 A beads) in toluene (50 mL) was heated at reflux for 4 hours, after which time the solvent was removed. Ethanol (50 mL) and sodium borohydride (1.25 g, 33 mmol) were added. The resulting mixture was stirred at room temperature for 30 minutes and then partitioned between saturated NH4Cl (50 mL) and ethyl acetate (2*50 mL). The combined organic layers were washed with saturated NaCl (50 mL), dried (MgSO4), filtered and concentrated to yield the title compound as a white solid (4.7 g). 1H NMR (400 MHz, CDCl3) delta 4.2 (s, 3H) 4.7 (s, 1H) 4.7 (s, 1H) 5.0 (t, J=6.0 Hz, 1H) 7.8 (s, 1H) 7.9 (s, 2H). MS (ES+) Calc: 325.08, Found: 325.8 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of the crude product and 3,5-bis(trifluoromethyl)benzaldehyde (43.0 g, 0.18 mol) in toluene (600 mL) is stirred and refluxed for 45 min. After cooling to room temperature, the resulting mixture is concentrated. NaBH4 (8.12 g, 0.22 mol) is added portionwise slowly to <n="47"/>Case 50508EtOH (500 ml_) solution of the resulting residue, and the mixture is stirred at room temperature for 4 hours. After addition of sat. NH4CI aq. and water, the mixture is extracted with ethyl acetate. The combined organic layer is washed with brine, dried over magnesium sulfate, filtered and concentrated. The crude product is purified by crystallization (50 mL of /- PrOHiH2O. 3:7) to give [3,5-bis(trifluoromethyl)phenylmethyl](2-methyl-2H-tetrazol-5- yl)amine. | ||
A mixture of the crude product and 3,5-bis(trifluoromethyl)benzaldehyde (43.0 g, 0.18 mol) in toluene (600 mL) is stirred and refluxed for 45 min. After cooling to room temperature, the resulting mixture is concentrated. NaBH4 (8.12 g, 0.22 mol) is added portionwise slowly to EtOH (500 mL) solution of the resulting residue, and the mixture is stirred at room temperature for 4 hours. After addition of sat. NH4CI aq. and water, the mixture is extracted with ethyl acetate. The combined organic layer is washed with brine, dried over magnesium sulfate, filtered and concentrated. The crude product is purified by crystallization (50 mL of /- PrOH:H2O. 3:7) to give [3,5-bis(trifluoromethyl)phenylmethyl](2-methyl-2tf-tetrazol-5- yl)amine . |
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