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[ CAS No. 97483-77-7 ]

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2D
Chemical Structure| 97483-77-7
Chemical Structure| 97483-77-7
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Product Details of [ 97483-77-7 ]

CAS No. :97483-77-7MDL No. :MFCD00234144
Formula : C6H3BrN2 Boiling Point : -
Linear Structure Formula :-InChI Key :-
M.W :183.01Pubchem ID :817154
Synonyms :

Computed Properties of [ 97483-77-7 ]

TPSA : 36.7 H-Bond Acceptor Count : 2
XLogP3 : 1.6 H-Bond Donor Count : 0
SP3 : 0.00 Rotatable Bond Count : 0

Safety of [ 97483-77-7 ]

Signal Word:DangerClass:8,6.1
Precautionary Statements:P261-P280-P301+P310-P305+P351+P338UN#:2923
Hazard Statements:H301-H315-H318-H335Packing Group:
GHS Pictogram:

Application In Synthesis of [ 97483-77-7 ]

  • Upstream synthesis route of [ 97483-77-7 ]
  • Downstream synthetic route of [ 97483-77-7 ]

[ 97483-77-7 ] Synthesis Path-Upstream   1~9

  • 1
  • [ 97483-77-7 ]
  • [ 30766-11-1 ]
YieldReaction ConditionsOperation in experiment
64% With hydrogenchloride In waterReflux Preparation 245-Bromopyridine-2-carboxylic acidAdd 5-bromopicolinonitrile (1 g, 5.46 mmol) to concentrated HC1 (13.4 mL, 139.66 mmol) in a round bottomed flask. Heat the mixture to reflux with stirring overnight. Cool the mixture to room temperature. Filter the resulting white solid, washing with water. Dry the solid under reduced pressure to give 5-bromopyridine-2- carboxylic acid (0.707 g, 64percent) as a white solid. LC-ES/MS m/z 202 [M+H]+.
Reference: [1] Patent: WO2013/66640, 2013, A1, . Location in patent: Page/Page column 21
[2] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 7, p. 2074 - 2079
[3] Patent: WO2008/729, 2008, A1, . Location in patent: Page/Page column 74-75
[4] Patent: WO2005/14571, 2005, A1, . Location in patent: Page/Page column 23
[5] Patent: WO2005/14571, 2005, A1, . Location in patent: Page/Page column 27
[6] Patent: WO2005/40144, 2005, A1, . Location in patent: Page/Page column 12-13
[7] Patent: WO2006/40192, 2006, A1, . Location in patent: Page/Page column 39
[8] Patent: WO2006/29906, 2006, A1, . Location in patent: Page/Page column 16
  • 2
  • [ 626-55-1 ]
  • [ 7677-24-9 ]
  • [ 55758-02-6 ]
  • [ 13958-98-0 ]
  • [ 97483-77-7 ]
Reference: [1] Chemistry - A European Journal, 2017, vol. 23, # 59, p. 14733 - 14737
  • 3
  • [ 97483-77-7 ]
  • [ 31181-90-5 ]
YieldReaction ConditionsOperation in experiment
60% With diisobutylaluminium hydride In tetrahydrofuran at -78℃; for 4 h; To a stirred solution of 5-bromopicolinonitrile (0.5 g, 2.732 mmol, 1.0 eq) in tetrahydrofuran (10 mL) at -78 °C DIBAL (4 mL, 4.98 mmol, 1.5 eq) was added and reaction mixture was stirred for 4 h at -78 °C. The reaction mixture was monitored by TLC, and quenched with 2N HCI (2 mL) and extracted with dichloromethane (10 mL), dried over sodium sulphate and evaporated to provide fairly pure 5-bromopicolinaldehyde (0.3 g, ~ 60 percent) which was used to the next stage without further purification.
Reference: [1] Patent: WO2013/13815, 2013, A1, . Location in patent: Page/Page column 228
[2] Patent: US2010/222345, 2010, A1, . Location in patent: Page/Page column 96
[3] Patent: US2013/29962, 2013, A1, . Location in patent: Paragraph 1101
[4] Patent: WO2016/82930, 2016, A1, . Location in patent: Page/Page column 37
  • 4
  • [ 75-16-1 ]
  • [ 97483-77-7 ]
  • [ 214701-49-2 ]
YieldReaction ConditionsOperation in experiment
65%
Stage #1: at -20 - -10℃; for 3 h;
Stage #2: With hydrogenchloride; water In tetrahydrofuran at -40 - -35℃; for 0.166667 h;
Intermediate 10: 1-(5-Bromopyridin-2-yl)ethanone; see W098/46605; 5-Bromo-2-cyanopyridine (Markevitch, David Y.; Rapta, Miroslav; Hecker, Scott J. ; Renau, Thomas E. ; Synth. Commun.; 33; 19; 2003; 3285 - 3290) (8 g, 43.7 mmol) was dissolved in dry THF (200 mL) and cooled to - 20°C. Methylmagnesium bromide (43.7 mL, 3M) was added drop wise and the temperature was held between -20°C and -10°C for 3 hours. The reaction mixture was cooled to -40°C and conc. HCI (4.5 mL) in water (15 mL) was added dropwise. It was stirred for 10 minutes at -35°C and then poured into a beaker with potassium phosphate buffer (300 mL, 1M, pH 7), under stirring. Ethyl acetate (300 mL) was added and the organic phase was dried over sodium sulfate. Upon concentration at room temperature under reduced pressure to - 50 mL the product crystallized, 2.4 g, mp 112°C. The mother liquor was further concentrated and chromatographed on silica gel with dichloromethane/ ethylacetate (100:1) to give another 3.25 g product (65percent combined yield). 1H-NMR (DMSO-d6) No.: 2.60 (s, 3H) ; 7.88 (dd, 1H); 8.25 (dd, 1H); 8.86 (d, 1H).
65%
Stage #1: at -20 - -10℃; for 3 h;
Stage #2: With hydrogenchloride; water In tetrahydrofuran at -40 - -35℃; for 0.166667 h;
Stage #3: potassium phosphate buffer
Intermediate 10: 1-(5-Bromopyridin-2-yl)ethanone; See W098/46605; 5-Bromo-2-cyanopyridine (Markevitch, David Y. ; Rapta, Miroslav; Hecker, Scott J. ; Renau, Thomas E. ; Synth. Commun.; 33; 19; 2003; 3285 - 3290) (8 g, 43.7 mmol) was dissolved in dry THF (200 mL) and cooled to - 20°C. Methylmagnesium bromide (43.7 mL, 3M) was added drop wise and the temperature was held between -20°C and -10°C for 3 hours. The reaction mixture was cooled to -40°C and concentrated HCl (4.5 mL) in water (15 mL) was added dropwise. It was stirred for 10 minutes at -35°C and then poured into a beaker with potassium phosphate buffer (300 mL, 1M, pH 7), under stirring. Ethyl acetate (300 mL) was added and the organic phase was dried over sodium sulfate. Upon concentration at room temperature under reduced pressure to - 50 mL the product crystallized, 2.4 g, mp 112°C. The mother liquor was further concentrated and chromatographed on silica gel with dichloromethane/ ethylacetate (100:1) to give another 3.25 g product (65percent combined yield). (at)H-NMR (DMSO-d(at)) No.: 2.60 (s, 3H) ; 7.88 (dd, 1H) ; 8.25 (dd, 1H) ; 8.86 (d, 1H).
30%
Stage #1: at -20℃; for 3 h;
Stage #2: With hydrogenchloride; water In tetrahydrofuran; diethyl ether at -40℃;
5-Bromopicolinonitrile (5.4 g, 29.7 mmol) was dissolved in anhydrous THF (120 mL) and cooled to -200C. MeMgBr (35 mL, IM in Et2O) was added dropwise, and the reaction mixture was stirred at -200C for 3 h. The reaction mixture was cooled to -40 0C, and neutralized with cone. HCl. The solvent was removed under reduced pressure. The residue was dissolved in EtOAc and washed with water. The aqueous layer was extracted with EtOAc. The combined organic phase was dried (Na2SO4) and evaporated under vacuum. The crude product was purified by column chromatography on silica gel (EtOAc - hexanes) to give l-(5-bromopyridin-2-yl)ethanone (1.9 g, 30percent yield).
Reference: [1] Journal of Medicinal Chemistry, 2007, vol. 50, # 20, p. 4868 - 4881
[2] Patent: WO2005/116022, 2005, A1, . Location in patent: Page/Page column 44
[3] Patent: WO2005/116023, 2005, A1, . Location in patent: Page/Page column 44-45
[4] Organic and Biomolecular Chemistry, 2015, vol. 13, # 36, p. 9418 - 9426
[5] Patent: WO2008/108988, 2008, A1, . Location in patent: Page/Page column 67
[6] Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 22, p. 5909 - 5915
  • 5
  • [ 676-58-4 ]
  • [ 97483-77-7 ]
  • [ 214701-49-2 ]
Reference: [1] Patent: WO2008/91681, 2008, A2, . Location in patent: Page/Page column 239
[2] Patent: US2010/16298, 2010, A1, . Location in patent: Page/Page column 202
  • 6
  • [ 97483-77-7 ]
  • [ 137178-88-2 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 7, p. 2074 - 2079
  • 7
  • [ 97483-77-7 ]
  • [ 327056-62-2 ]
Reference: [1] Patent: WO2006/12374, 2006, A1, . Location in patent: Page/Page column 214
[2] Patent: US2003/225106, 2003, A1, . Location in patent: Page 95
  • 8
  • [ 97483-77-7 ]
  • [ 1056039-83-8 ]
Reference: [1] European Journal of Organic Chemistry, 2016, vol. 2016, # 7, p. 1305 - 1313
[2] Patent: WO2008/108988, 2008, A1,
  • 9
  • [ 24424-99-5 ]
  • [ 97483-77-7 ]
  • [ 1188477-11-3 ]
YieldReaction ConditionsOperation in experiment
47% With sodium tetrahydroborate; nickel(II) chloride hexahydrate In methanol at 0 - 15℃; for 3 h; To a mixture of 5- bromopicolinonitrile (3.0 g, 16.4 mmol) in MeOH (60 mL) was added di-tert-butyl dicarbonate (7.2 g, 32.8 mmol) and nickel chloride hexahydrate (0.33 g, 1.64 mmol). The mixture was cooled to 0°C, followed by portion wise addition of NaBH4 (4.3 g, 0.115 mol) over 2 hr. The mixture was stirred at 15°C for 1 hr then poured into ice- water (200 g) and extracted with EtOAc. The combined organic layers were washed with brine, dried over anhydrous Na2SC>4, and concentrated under reduced pressure. The residue was purified by flash column chromatography to give the desired product (2.2 g, 47percent yield) as a yellow solid. LC-MS: m/z 287,289 (M+H)+.
650 mg With sodium tetrahydroborate; nickel(II) chloride hexahydrate In methanol at 0 - 20℃; for 14 h; Step 1
Preparation of (5-Bromo-pyridin-2-ylmethyl)-carbamic acid tert-butyl ester
To a solution of 5-Bromo-pyridine-2-carbonitrile (1.0 g, 5.46 mmol) in methanol (10 mL) at 0° C. is added NiCl2.6H2O (0.12 g, 0.54 mmol), Di-tert-butyl dicarbonate (2.38 g, 0.010 mmol) and NaBH4 (0.413 g, 0.010 mmol) at 0° C. then stirred at room temperature for 14 hours.
The reaction solvent is removed under reduced pressure and crude is diluted with water and ethyl acetate.
The organic layer was separated, dried over sodium sulphate and concentrated in vacuum.
The crude is purified by column chromatography eluting with 30percent ethyl acetate in hexane to afford the title compound (650 mg).
1H-NMR (400 MHz, CDCl3) δ: 1.44 (s, 9H), 4.37 (d, J=5.44 Hz, 2H), 5.41 (bs, 1H), 7.18 (d, J=8.28 Hz, 1H), 7.75-7.78 (dd, J1=8.32 Hz, J2=2.28 Hz, 1H), 8.57 (d, J=2.08 Hz, 1H). LC-MS (m/z): [M+H]=289.0.
1 g at 0 - 20℃; for 18 h; To a solution of 5-bromo-2-cyanopyridine (5.0 g, 27.32 mmol) in methanol (50 mL) at 0 °C were added nickel (II) chloride hexahydrate (649 mg, 27.32 mmol), di-tert-butyl dicarbonate (11.9 g, 54.64 mmol) and sodium borohydride (2.06 g, 54.64 mmol). The reaction mixture was stirred at RT for 18 h. The mixture was concentrated under reduced pressure and the residue was diluted with ethyl acetate and water. The layers were separated and the aqueous layer was extracted twice with ethyl acetate. The combined organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated. The residue thus obtained was purified by silica gel column chromatography to afford 1.0 g of the titled product. 1H NMR (300 MHz, CDCl3) δ 1.45 (s, 9H), 4.39 (d, = 5.4 Hz, 2H), 5.47 (br s, 1H), 7.21 (d, = 8.1 Hz, 1H), 7.79 (d, = 8.1 Hz, 1H), 8.59 (s, 1H); APCI-MS (m/z) 289 (M+H)+.
Reference: [1] Patent: WO2016/112088, 2016, A1, . Location in patent: Paragraph 0660
[2] Patent: US2013/237502, 2013, A1, . Location in patent: Paragraph 0367
[3] Patent: WO2018/42342, 2018, A1, . Location in patent: Page/Page column 53
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