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Chemical Structure| 380380-63-2 Chemical Structure| 380380-63-2

Structure of 380380-63-2

Chemical Structure| 380380-63-2

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Product Details of [ 380380-63-2 ]

CAS No. :380380-63-2
Formula : C7H6BrN5
M.W : 240.06
SMILES Code : CN1N=NN=C1C2=NC=C(Br)C=C2
MDL No. :MFCD08436170

Safety of [ 380380-63-2 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H315-H319-H228
Precautionary Statements:P240-P210-P241-P264-P280-P302+P352-P370+P378-P337+P313-P305+P351+P338-P362+P364-P332+P313
Class:4.1
UN#:1325
Packing Group:

Application In Synthesis of [ 380380-63-2 ]

* 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.

  • Downstream synthetic route of [ 380380-63-2 ]

[ 380380-63-2 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 380380-60-9 ]
  • [ 74-88-4 ]
  • [ 380380-64-3 ]
  • [ 380380-63-2 ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide; In DMF (N,N-dimethyl-formamide); at 0 - 20℃; for 2h; 5-Bromo-2-(2-methyl-2H-tetrazol-5-yl) pyridine and 5-bromo-2- (1-methyl-1H-tetrazol-5- yl) pyridine. 5-Bromo-2-(2-methyl-2H-tetrazol-5-yl)pyridine and 5-bromo-2-(1-methyl-1H-tetrazol-5- yl) pyridine were prepared according to the procedure described by Dong A Pharmaceuticals (WO 01/94342). A mixture of 6.5 g unpurified 5-bromo-2-tetrazol-5-ylpyridine [Dong A Pharmaceuticals (WO 01/94342) ] (~28 mmol) and sodium hydroxide (9 g, 125 mmol) in dry dmf was evaporated to dryness under reduced pressure. A stirred solution of the involatile residue in dry DMF (50 mL) was treated dropwise at ice-bath temperature with iodomethane (3.0 ML, 48 mmol). The stirred reaction mixture was allowed to warm and then maintained at room temperature for 2 hours. The reaction mixture was partitioned between iced water and ethyl acetate. The organic phase was washed with water, dried over magnesium sulfate, and tehn evaporated under reduced pressure to give a residue that was purified by chromatography on silica gel [elution with dichloromethane : ethyl acetate (60: 1) ] to give: 1. 5-bromo-2- (1-methyl-1H-tetrazol-5-yl)pyridine (1.397 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 3), 1H-NMR (DMSO-d6) (300 MHz) 8 : 4.38 (s, 3H); 8.17 (d, 1H); 8.35 (dd, 1H); 8.96 (d, 1H). 2. 5-bromo-2-(2-methyl-2H-tetrazol-5-yl)pyridine (1.07 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf : 0. 1). 1H-NMR (DMSO-d6) (300 MHz) No. : 4.46 (s, 3H); 8.09 (d, 1H) ; 8.28 (dd, 1H) ; 8.88 (d, 1H).
With sodium hydroxide; In DMF (N,N-dimethyl-formamide); at 0 - 20℃; for 2h; 5-BROMO-2- (2-METHYL-2H-TETRAZOL-5-YL) PYRIDINE AND 5-BROMO-2- (L-METHYL-LH-TETRAZOL-5- YL) pyridine 5-Bromo-2-(2-methyl-2H-tetrazol-5-yl) pyridine and 5-BROMO-2- (1-METHYL-LH-TETRAZOL-5- YL) pyridine were prepared according to the procedure described by Dong A Pharmaceuticals (WO 01/94342). A mixture of 6.5 g unpurified <strong>[380380-60-9]5-BROMO-2-TETRAZOL-5-YLPYRIDINE</strong> [Dong A Pharmaceuticals (WO 01/94342)] (-28 mmol) and sodium hydroxide (9 g, 125 mmol) in dry DMF was evaporated to dryness under reduced pressure. A stirred solution of the involatile residue in dry DMF (50 ML) was treated dropwise at ice-bath temperature with iodomethane (3.0 mL, 48 mmol). The stirred reaction mixture was allowed to warm and then maintained at room temperature for 2 hours. The reaction mixture was partitioned between iced water and ethyl acetate. The organic phase was washed with water, dried over magnesium sulfate, and tehn evaporated under reduced pressure to give a residue that was purified by chromatography on silica gel [elution with dichloromethane : ethyl acetate (60: 1) ] to give: 1. 5-bromo-2-(1-methyl-1H-tetrazol-5-yl) pyridine (1.397 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0.3),'H-NMR (DMSO-D) (300 MHz) 8 : 4.38 (s, 3H); 8.17 (d, 1H); 8.35 (dd, 1H); 8.96 (d, 1H). 2. 5-bromo-2-(2-methyl-2H-tetrazol-5-yl) pyridine (1.07 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 1). LH-NMR (DMSO-DSLT300 MHz) 8 4.46 (s, 3H); 8.09 (d, 1H); 8.28 (dd, 1H) ; 8.88 (d, 1H). Structure assignment based on nmr HMBC experiments, in which long range coupling of the protons of CH3 to the C5 of the tetrazole ring is observed in the 1-methyl-1H-isomer of Rf 0.3, but not in the 2-methyl-2H-isomer of Rf 0.1). The compound referred to as 5-bromo-2- (1-METHYL-LH-TETRAZOL-5-YL) pyridine is thus the isomer of Rf 0.3 and the compound referred to as 5-BROMO-2-(2-METHYL-2H-TETRAZOL-5-YL) PYRIDINE is thus the ISOMER OF RF 0. 1
With sodium hydroxide; In DMF (N,N-dimethyl-formamide); at 0 - 20℃; for 2h; 5-BROMO-2-(2-METHYL-2H-TETRAZOL-5-YL) PENDINE AND 5-BROMO-2-(1-METHEL-LH-TETRAZOL-5- 1 pyridine 5-BROMO-2- (2-METHYL-2H-TETRAZOL-5-YL) PYRIDINE AND 5-BROMO-2- (L-METHYL-LH-TETRAZOL-5- yl) pyridine were prepared according to the procedure described by Dong A Pharmaceuticals (WO 01/94342). A mixture of 6.5 g unpurified <strong>[380380-60-9]5-BROMO-2-TETRAZOL-5-YLPYRIDINE</strong> [Dong A Pharmaceuticals (WO 01/94342)] (-28 mmol) and sodium hydroxide (9 g, 125 mmol) in dry DMF was evaporated to dryness under reduced pressure. A stirred solution of the involatile residue in dry DMF (50 ML) was treated dropwise at ice-bath temperature with iodomethane (3.0 mL, 48 mmol). The stirred reaction mixture was allowed to warm and then maintained at room temperature for 2 hours. The reaction mixture was partitioned between iced water and ethyl acetate. The organic phase was washed with water, dried over magnesium sulfate, and tehn evaporated under reduced pressure to give a residue that was purified by chromatography on silica gel [ELUTION WITH DICHLOROMETHANE: ETHYL ACETATE (60: 1) ] TO GIVE: 1. 5-BROMO-2-(1-METHYL-LH-TETRAZOL-5-YL) pyridine (1.397 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 3), 1H-NMR (DMSO-D6) (300 MHZ) 8 : 4.38 (s, 3H); 8.17 (d, 1H); 8.35 (dd, 1H); 8.96 (d, 1H). 2. 5-BROMO-2- (2-METHYL-2H-TETRAZOL-5-YL) pyridine (1.07 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 1). LH-NMR (DMSO-D) (300 MHZ) 8 4.46 (s, 3H); 8.09 (d, 1H) ; 8.28 (dd, 1H); 8.88 (d, 1H). Structure assignment based on HMBC experiments, in which long range coupling of the protons of CH3 to the C5 of the tetrazole ring is observed in the 1-METHYL-LH-ISOMER of Rf 0.3, but not in the 2-methyl-2H-isomer of Rf 0.1). The compound referred to as 5-bromo-2- (1-METHYL-1H-TETRAZOL-5-YL) PYRIDINE is thus the isomer of Rf 0.3 and the compound referred to as 5-BROMO-2-(2-METHYL-2H-TETRAZOL-5-YL) PYRIDINE is thus the isomer OF RF 0. 1
A mixture of 6.5 g unpurified 5-bromo-2-tetrazol-5-ylpyridine [Dong A Pharmaceuticals (WO 01/94342)] (-28 mmol) and sodium hydroxide (9 g, 125 mmol) in dry DMF was evaporated to dryness under reduced pressure. A stirred solution of the involatile residue in dry DMF (50 ML) was treated dropwise at ice-bath temperature with iodomethane (3.0 mL, 48 mmol). The stirred reaction mixture was allowed to warm and then maintained at room temperature for 2 hours. The reaction mixture was partitioned between iced water and ethyl acetate. The organic phase was washed with water, dried over magnesium sulfate, and tehn evaporated under reduced pressure to give a residue that was purified by chromatography on silica gel [elution with dichloromethane: ethyl acetate (60: 1) ] to give: 1. 5-BROMO-2- (L-METHYL-LH-TETRAZOL-5-YL) pyridine (1.397 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 3), (DMSO-D6) (300 MHZ) 8 : 4.38 (s, 3H); 8.17 (d, 1H) ; 8.35 (dd, 1H); 8.96 (d, 1H). 2. 5-BROMO-2- (2-METHYL-2H-TETRAZOL-5-YL) pyridine (1.07 g), a colorless solid, (TLC: silica-gel, hexanes: ethyl acetate (4: 1), Rf: 0. 1). 1H-NMR (DMSO-D6) (300 MHZ) 8 4.46 (s, 3H); 8.09 (d, 1H); 8.28 (dd, 1H); 8.88 (d, 1H). Structure assignment based on HMBC experiments, in which long range coupling of the protons of CH3 to the C5 of the tetrazole ring is observed in the 1-METHYL-LH-ISOMER of Rf 0.3, but not in the 2-methyl-2H-isomer of Rf 0.1). The compound referred to as 5-bromo-2- (1-METHYL-LH-TETRAZOL-5-YL) pyridine is thus the isomer of Rf 0.3 and the compound referred to as 5-BROMO-2- (2-METHYL-2H-TETRAZOL-5-YL) pyridine is thus the isomer OF RF 0. 1
With potassium hydroxide; In N,N-dimethyl-formamide; at 20℃; for 23h; To the solution of crude <strong>[380380-60-9]5-bromo-2-(2H-tetrazol-5-yl)pyridine</strong>(3.15 g,.13.9 mmol) in DMF (32 mL) was added MeI (7.92 g, 55.8 mmol) and KOH (1.95 g, 34.8 mmol) at room temperature. The mixture was stirred for 23 h at r.t.. The reaction mixture was poured into ice water (100 mL) and extracted with EtOAc. The organic layer was washed with brine, dried (Na2SO4), and evaporated under vacuum to give a residue, further purified by flash column chromatography (hexanes - EtOAc from 50: 1 to 10:1) to give 5-bromo-2- (2-methyl-2H-tetrazol-5-yl)pyridine as yellow solid (1.32 g, 43% yield over 2 steps) and 5- bromo-2-(l-methyl-lH-tetrazol-5-yl)pyridine as a white solid (0.97 g, 32% yield, 2 steps).

 

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