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Chemical Structure| 144873-99-4 Chemical Structure| 144873-99-4

Structure of 144873-99-4

Chemical Structure| 144873-99-4

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Product Details of [ 144873-99-4 ]

CAS No. :144873-99-4
Formula : C7H5BrN2
M.W : 197.03
SMILES Code : N#CCC1=CC=C(Br)N=C1
MDL No. :MFCD08706175
InChI Key :CTBARTMXUVSCRR-UHFFFAOYSA-N
Pubchem ID :17749976

Safety of [ 144873-99-4 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H301-H315-H318-H335
Precautionary Statements:P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P310-P330-P332+P313-P362-P403+P233-P405-P501
Class:8(6.1)
UN#:2923
Packing Group:

Application In Synthesis of [ 144873-99-4 ]

* 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 [ 144873-99-4 ]

[ 144873-99-4 ] Synthesis Path-Downstream   1~9

  • 1
  • [ 101990-45-8 ]
  • [ 143-33-9 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
49% In 1,3-dioxane; water; at 20℃; for 15h; Step 3: (6-Bromopyridin-3-yl) acetonitrile To a stirred solution [OF NACN (117G,] 2. [38MOL)] in dioxane (1L) and water (1L), was added the above crude <strong>[101990-45-8]2-bromo-5-bromomethylpyridine</strong> (275g) and the mixture was stirred at rt for 15h. The reaction mixture was quenched with cold water [(15L)] and extracted with EtOAc [(3X1L).] The organic layer was washed with water [(3X1 L),] brine [(2X1 L),] dried with [NA2S04] and concentrated under reduced pressure to give crude title compound. The crude residue was purified by column chromatography over silica gel (pet. [ETHER/ETHYLACETATE,] 7: 3) to give 95g [(6-BROMOPYRIDIN-3-YL)] acetonitrile as a pale yellow solid (49%). [TLC, [RF=] 0.5, pet. [ETHER/ETHYLACETATE] 7: 3]
  • 2
  • [ 101990-45-8 ]
  • [ 151-50-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
61% In N,N-dimethyl-formamide; at 60℃; for 0.5h; (Referential Example 10) Synthesis of 2-bromo-5-(cyanomethyl)pyridine (referential compound 10-1) Potassium cyanide (7.80 g, 120 mmol) was added to a solution of 15.0 g (60.0 mmol) of <strong>[101990-45-8]2-bromo-5-bromomethylpyridine</strong>(referential compound 8) in 150 ml of N,N-dimethylformamide and the mixture was slowly stirred at 60C for 15 minutes. After that, water was added thereto little by little until potassium cyanide was completely dissolved and then the mixture was stirred at 60C for 15 minutes. After the reaction was finished, the reaction solution was poured into ethyl acetate/saturated aqueous solution of ammonium chloride and the organic layer was separated therefrom. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo. The resulting residue was subjected to a silica gel column chromatography (eluding solvent: n-hexane: ethyl acetate = 9:1 to 7:3 (v/v)) and the fraction containing the aimed substance was concentrated in vacuo to give 9.24 g of the title compound as pale yellow powder (yield: 61%). Rf value: 0.15 (n-hexane: ethyl acetate = 4:1 (v/v)) Mass spectrum (CI, m/z): 197, 199 (M+ + 1) IR spectrum (KBr, cm-1): 2253 1H-NMR spectrum (CDCl3, δ ppm): 3.74 (s, 2H), 7.61-7.53 (m, 2H), 8.36-8.35 (m, 1H)
  • 3
  • 2-bromo-S-bromomethylpyridine [ No CAS ]
  • [ 101990-45-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
109 g (32% from 2-bromo-5-picoline) In N-methyl-acetamide; water; Step 5. Preparation of 2-bromo-5-cyanomethyl-pyridine The 476 g of crude <strong>[101990-45-8]2-bromo-5-bromomethylpyridine</strong> from step 4 was dissolved in 4000 mL of dimethylformamide (DMF)/water (7:1) and treated with 168 g (2.58 mol) of potassium cyanide. The reaction was allowed to stir at ambient temperature for 72 h, concentrated in vacuo, and partitioned between ethyl acetate and water; the organic layer was washed with water, washed with brine, dried (MgSO4), and reconcentrated in vacuo to provide the crude nitrile. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (25:75) gave 109 g (32% from 2-bromo-5-picoline) of 2-bromo-5-cyanomethylpyridine as a yellowish orange solid: mp 55.5-57.5 C.; NMR (CDCl3) δ 3.74 (s, 2H), 7.54 (d, J=8 Hz, 1H), 7.59 (dd, J=8 and 2 HZ, 1H), 8.35 (d, J=2 Hz, 1H); MS (FAB) m/e (rel intensity) 199 (85), 197 (100).
  • 4
  • [ 101990-45-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
109 g (32% from 2-bromo-5-picoline) In N-methyl-acetamide; water; Step 5: Preparation of 2-bromo-5-cyanomethyl-pyridine. The 476 g of crude <strong>[101990-45-8]2-bromo-5-bromomethylpyridine</strong> from step 4 was dissolved in 4000 mL of dimethylformamide (DMF)/water (7:1) and treated with 168 g (2.58 mol) of potassium cyanide. The reaction was allowed to stir at ambient temperature for 72 h, concentrated in vacuo, and partitioned between ethyl acetate and water; the organic layer was washed with water, washed with brine, dried (MgSO4), and reconcentrated in vacuo to provide the crude nitrile. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (25:75) gave 109 g (32% from 2-bromo-5-picoline) of 2-bromo-5-cyanomethylpyridine as a yellowish orange solid: mp 55.5-57.5 C.; NMR (CDCl3)δ3.74 (s, 2 H), 7.54 (d, J=8 Hz, 1 H), 7.59 (dd, J=8 and 2 HZ, 1 H), 8.35 (d, J=2 Hz, 1 H); MS (FAB) m/e (rel intensity) 199 (85), 197 (100).
  • 5
  • 2-bromo-5-romomethylpyridine [ No CAS ]
  • [ 101990-45-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
109 g (32% from 2-bromo-5-picoline) In N-methyl-acetamide; water; Step 5: Preparation of 2-bromo-5-cyanomethyl-pyridine The 476 g of crude <strong>[101990-45-8]2-bromo-5-bromomethylpyridine</strong> from step 4 was dissolved in 4000 mL of dimethylformamide (DMF)/water (7:1) and treated with 168 g (2.58 mol) of potassium cyanide. The reaction was allowed to stir at ambient temperature for 72 h, concentrated in vacuo, and partitioned between ethyl acetate and water; the organic layer was washed with water, washed with brine, dried (MgSO4), and reconcentrated in vacuo to provide the crude nitrile. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (25:75) gave 109 g (32% from 2-bromo-5-picoline) of 2-bromo-5-cyanomethylpyridine as a yellowish orange solid: mp 55.5-57.5 C.; NMR (CDCl3) δ3.74 (s, 2H), 7.54 (d, J=8Hz, 1H), 7.59 (dd, J=8 and 2 HZ, 1H), 8.35 (d, J=2Hz, 1H); MS (FAB) m/e (rel intensity) 199 (85), 197 (100).
  • 6
  • [ 168173-56-6 ]
  • [ 143-33-9 ]
  • [ 144873-99-4 ]
  • 7
  • potassium cyanide [ No CAS ]
  • [ 101990-45-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
12.2 g With tetrabutylammomium bromide; In dichloromethane; water; at 20℃; for 16h; To a mixture of 2-bromo-5-bromomethyl-pyridine 140 (29.4 g, 1 16.96 mmol) and KCN (22 g, 350.88 mmol) in DCM/water (v:v = 1 :2, 300 mL) was added TBAB (3.77 g, 1 1.7 mmol). The mixture was stirred at r.t. for 16 hr. The mixture was diluted with DCM (100 mL) and the layers were separated. The aqueous layer was extracted with DCM (3x200 mL), The organic layers were combined , washed with brine (2x200 mL), dried over Na2S04, filtered and concentrated to afford the crude product. The crude product was purified by silica gel column chromatography (PE/EtOAc =10: 1→5 : 1 ) to afford the desired compound 141 ( 12.2 g, 53%). LCMS: m/z 199 (M+l )+.
  • 8
  • [ 101990-45-8 ]
  • [ 7677-24-9 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
48.6% Trimethylsilyl cyanide (7.1g, 71.57mmol) was dissolved in acetonitrile (200mL),Add tetrabutylammonium fluoride (18.7g, 71.52mmol) at room temperature,Stir for 10 minutes,A solution of compound 19b (12 g, 47.82 mmol) in acetonitrile (100 mL) was added.The reaction was carried out at room temperature for 2 hours, and TLC showed that the reaction was complete.The reaction solution was added with saturated sodium bicarbonate solution, extracted with ethyl acetate,Combine the organic phases, wash with saturated brine, and dry with anhydrous sodium sulfate,After concentration, the crude product was purified by silica gel column chromatography to obtain the title compound 19c (4.58 g, yield 48.6%).
To a solution of trimethylsilyl cyanide (2.37 g, 23.9 mmol) in acetonitrile (30 mL) was added tetrabutyl ammonium fluoride (1 M in tetrahydrofuran, 6.25 g, 23.9 mmol), and the mixture was stirred at it for 0.1 hr. Then 2-bromo-5-(bromomethyl)pyridine (4.00 g, 15.9 mmol) in acetonitrile (20 mL) was added, and the mixture was stirred at rt for 0.2 hr. On completion, the reaction was concentrated to remove acetonitrile and then diluted with water (30 mL). The mixture was extracted with ethyl acetate (3 X 80 mL), washed with brine (3 X 30 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to give a residue. The residue was purified by chromatography on silica gel (petroleum ether: ethyl acetate = 50: 1 to 5: 1) to give the title compound. NMR (400MHz, CDC13) δ = 8.34 (d, J = 1.8 Hz, 1H), 7.61 - 7.56 (m, 1H), 7.55 - 7.51 (m, 1H), 3.74 (s, 2H).
  • 9
  • [ 773837-37-9 ]
  • [ 101990-45-8 ]
  • [ 144873-99-4 ]
YieldReaction ConditionsOperation in experiment
87% With tetrabutylammomium bromide; In aq. phosphate buffer; acetonitrile; at 60℃; for 5h;pH 7.0;Inert atmosphere; To a CH 3 CN: phosphate buffer solution (pH 7) = 3: 1 solution (100 ml) of 2-bromo-5- (bromomethyl) pyridine (630 mg, 2.46 mmol) at room temperature under a nitrogen atmosphere was added sodium cyanide (366 mg, 7.38 mmol) and tetrabutylammonium bromide (90 mg, 0.24 mmol), and the mixture was stirred at 60 C. for 5 hours.Thereafter, the mixture was cooled to 0 C., phosphate buffer (pH 7) was added, and the mixture was extracted with dichloromethane. The extract was washed with saturated saline and dried over anhydrous sodium sulfate.The anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by column chromatography (hexane: ethyl acetate = 2: 1) to obtain (6-bromopyridin-3-yl) acetonitrile.Yield 432 mg, yield 87%, white solid.
 

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