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Chemical Structure| 38875-76-2 Chemical Structure| 38875-76-2

Structure of 38875-76-2

Chemical Structure| 38875-76-2

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Product Details of [ 38875-76-2 ]

CAS No. :38875-76-2
Formula : C7H5ClN2
M.W : 152.58
SMILES Code : CC1=NC=C(C#N)C(Cl)=C1
MDL No. :MFCD01078061
InChI Key :WAYNDJKNBVJWPH-UHFFFAOYSA-N
Pubchem ID :17966217

Safety of [ 38875-76-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338

Application In Synthesis of [ 38875-76-2 ]

* 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 [ 38875-76-2 ]

[ 38875-76-2 ] Synthesis Path-Downstream   1~13

  • 1
  • [ 1184-85-6 ]
  • [ 38875-76-2 ]
  • [ 1073160-09-4 ]
YieldReaction ConditionsOperation in experiment
87% With caesium carbonate; In acetonitrile; at 60℃; for 20h; Step 8. Preparation of <strong>[38875-76-2]4-Chloro-6-methyl-nicotinonitrile</strong> (B17-8): A suspension of B17-7 (20 g, 131.5 mmol) in POCl3 (62 mL, 580 mmol) was heated at 110 C. for 15 minutes. The mixture was allowed to cool to 25 C. and treated portion-wise over 20 minutes with PCl5 (38.12 g, 183.4 mmol). The mixture was then heated at 110 C. for 1 hour and concentrated. The resultant residue was diluted with EtOAc (100 mL), cooled to 10 C., and quenched with aqueous Na2CO3 (200 mL). The mixture was then extracted with EtOAc (3×250 mL), and the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The resultant residue was purified by chromatography (silica gel; 4-5% EtOAc in petroleum ether as eluting solvent) to provide B17-8 as an off-white puffy solid. Yield: 7.5 g, 37%. 1H NMR (CDCl3): delta 8.75 (s, 1H), 7.38 (s, 1H), 2.65 (s, 3H). Mass: (M+1) 153 calculated for C7H5ClN2.
  • 2
  • [ 1073160-08-3 ]
  • [ 38875-76-2 ]
YieldReaction ConditionsOperation in experiment
37% Step 8. Preparation of 4-Chloro-6-methyl-nicotinonitrile (B17-8): A suspension of B17-7 (20 g, 131.5 mmol) in POCl3 (62 mL, 580 mmol) was heated at 110 C. for 15 minutes. The mixture was allowed to cool to 25 C. and treated portion-wise over 20 minutes with PCl5 (38.12 g, 183.4 mmol). The mixture was then heated at 110 C. for 1 hour and concentrated. The resultant residue was diluted with EtOAc (100 mL), cooled to 10 C., and quenched with aqueous Na2CO3 (200 mL). The mixture was then extracted with EtOAc (3×250 mL), and the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The resultant residue was purified by chromatography (silica gel; 4-5% EtOAc in petroleum ether as eluting solvent) to provide B17-8 as an off-white puffy solid. Yield: 7.5 g, 37%. 1H NMR (CDCl3): delta 8.75 (s, 1H), 7.38 (s, 1H), 2.65 (s, 3H). Mass: (M+1) 153 calculated for C7H5ClN2.
  • 3
  • [ 38875-76-2 ]
  • 6-(bromomethyl)-4-chloronicotinonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 12h;Inert atmosphere; Reflux; A mixture of <strong>[38875-76-2]4-chloro-6-methylnicotinonitrile</strong> (3.2 g, 21 mmol), NBS (3.7 g, 21 mmol), and benzoyl peroxide (968 mg, 4 mmol) in CCI4 (50 mL) under nitrogen was heated to reflux for 12 hours. The mixture was cooled to 25C, filtered and the filtrate was concentrated under reduced pressure. The residue was use in the next step without further purification. MS (ESI) m/z: 231 [M+H]+.
  • 4
  • [ 38875-76-2 ]
  • C14H9ClN4 [ No CAS ]
  • 5
  • [ 1073160-08-3 ]
  • [ 38875-76-2 ]
YieldReaction ConditionsOperation in experiment
64% With phosphorus pentachloride; trichlorophosphate; for 20h;Reflux; A solution of 4-hydroxy-6-methylnicotinamide (5 g, 32 mmol) and PCI5 (10.3 g, 50 mmol) in POCI3 (50 mL) was heated to reflux for 20 hours. The reaction mixture was cooled to 25C and concentrated under reduced pressure. The residue was purified by silica gel chromatography using Petroleum ether:EtOAc (3: 1 ) as eluting solvents to afford 4-chloro-6-methylnicotinonitrile as white solid (3.2 g, 64%). MS (ESI) m/z: 153 [M+H]+
40% With trichlorophosphate; at 110℃; for 5h; A suspension of product 4-hydroxy-6- methylnicotinamide (20.0 g, 131.5 mmol, 1.0 eq) in POCb (62 mL, 580 mmol, 4.4 eq) was heated at 110C for 5 hours. The mixture was allowed to cool to 10C, and quenched with aqueous NaiCC (200 ml). The mixture was then extracted with EtOAc (250 mL> 3), and the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The resultant residue was purified by chromatography (silica gel; 4-5% EtOAc in petroleum ether as eluting solvent) to provide product 4-chloro-6-methylnicotinonitrile as an off-white puffy solid (8.0 g, 40%). NMR (300 MHz, DMSO-tfc): delta 8.96 (s, 1H), 7.79 (s, 1H), 2.50 (s, 3H). ESI-MS (m/z): 153.0 (M+H)+.
  • 6
  • [ 473255-51-5 ]
  • [ 38875-76-2 ]
YieldReaction ConditionsOperation in experiment
A suspension of 4-chloro-6-methylnicotinamide (29.7 g, 195 mmol) in POC (80.2 mL, 860 mmol) is heated at 110 C for 15 min (gas development). The mixture is allowed to cool to rt, and is treated with PCI5 (57.0 g, 274 mmol) over 20 min. The mixture is heated again at 110 C for 1 h. The mixture is allowed to cool to rt, and is evaporated under reduced pressure. The residue is diluted with EtOAc, and cooled to 0 C. Aq. 10% Na2C03 is added. The mixture is extracted with EtOAc (3x). The combined org. layers are washed with brine, dried over Na2S04, filtered, and the solvents are removed under reduced pressure. Purification of the crude by automated FC (Biotage, EtOAc / heptane 2:98? 30:70) yields the title compound. LC-MS: tR = 0.55 min, MH+ = 194.15 (conditions 4).
  • 7
  • [ 38875-76-2 ]
  • 4-chloro-5-cyano-2-methylpyridine 1-oxide [ No CAS ]
YieldReaction ConditionsOperation in experiment
With urea hydrogen peroxide adduct; trifluoroacetic anhydride; In dichloromethane; at 0 - 20℃; for 3.5h; To a sol. of <strong>[38875-76-2]4-chloro-6-methylnicotinonitrile</strong> (10.0 g, 65.5 mmol) and H202-H2NCONH2 (18.5 g, 197 mmol) in CH2CI2 (80 mL) at 0 C is added trifluoroacetic acid anhydride (27.9 mL, 197 mmol) dropwise. The mixture is stirred at rt for 3.5 h. Aq. 10% Kl (800mL) is carefully added. The phases are separated, and the aq. Layer is extracted with CH2CI2. The combined org. layers are washed with aq. sat. Na2S203 and brine. The org. layer is dried over Na2S04, filtered, and the solvents are removed under reduced pressure to yield the crude title compound. LC-MS: tR = 0.34 min, MH+ = 210.22 (conditions 4).
  • 8
  • [ 38875-76-2 ]
  • 4-chloro-6-(hydroxymethyl)nicotinonitrile [ No CAS ]
  • 9
  • [ 38875-76-2 ]
  • (4-chloro-5-cyanopyridin-2-yl)methyl methanesulfonate [ No CAS ]
  • 10
  • methyl 4-hydroxy-6-methylnicotinate [ No CAS ]
  • [ 38875-76-2 ]
  • 11
  • [ 38875-76-2 ]
  • [ 1313709-87-3 ]
YieldReaction ConditionsOperation in experiment
64% With hydrazine hydrate; In butan-1-ol; for 12h;Reflux; Inert atmosphere; To a mixture of compound 4-chloro-6- methylnicotinonitrile (8.0 g, 52.6 mmol, 1.0 eq) in n-butanol (80 mL) was added hydrazine hydrate (7.9 g, 158 mmol, 3.0 eq), the mixture was heated to reflux under nitrogen for 12 h. The reaction mixture was allowed to cool to room temperature, the solid was collected by filtration and washed with ethyl acetate (30 mL> 2). Dried to give compound 3-amino-6-methyl-lH- pyrazolo[4,3-c]pyridine (5.0 g, 64%). NMR (300 MHz, DMSO- e) delta 11.61 (br, 1H), 8.80 (s, 1H), 6.97 (s, 1H), 5.69 (s, 2H), 2.46 (s, 3H). ESI-MS (m/z): 149.0 (M+H)+.
  • 12
  • [ 38875-76-2 ]
  • 2-chloro-4-(3-amino-6-methylpyrazolo[4,3-c]pyridin-1-yl)pyrimidine [ No CAS ]
  • 13
  • [ 67367-33-3 ]
  • [ 38875-76-2 ]
 

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