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Chemical Structure| 742100-75-0 Chemical Structure| 742100-75-0

Structure of 742100-75-0

Chemical Structure| 742100-75-0

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Product Details of [ 742100-75-0 ]

CAS No. :742100-75-0
Formula : C6H5BrClNO
M.W : 222.47
SMILES Code : OCC1=CC(Br)=CN=C1Cl
MDL No. :MFCD08688594
InChI Key :ZZGSPGXWLOYKFH-UHFFFAOYSA-N
Pubchem ID :23091039

Safety of [ 742100-75-0 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H302-H315-H318-H335
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312+P330-P302+P352-P304+P340+P312-P305+P351+P338+P310-P332+P313-P362-P403+P233-P405-P501
Class:8
UN#:3261
Packing Group:

Application In Synthesis of [ 742100-75-0 ]

* 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 [ 742100-75-0 ]

[ 742100-75-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 742100-75-0 ]
  • [ 228251-24-9 ]
YieldReaction ConditionsOperation in experiment
With pyridinium chlorochromate; In dichloromethane; at 18 - 25℃; for 2h; (5-Bromo-2-chloropyridin-3-yl)methanol (Intermediate 3, 0.67 g, 3.01 mmol) and pyridinium chlorochromate (0.779 g, 3.61 mmol) were combined in anhydrous dichloromethane (10 ml) and stirred at room temperature. The reaction was stirred for 2 hours. The reaction mixture was diluted with diethyl ether and filtered. The filtrate was concentrated to a tan solid. The solid was suspended in methanol and deposited onto Isolute and dried. Purification by normal phase Isco column (40%- 100% dichloromethane/hexane) afforded the desired compound as a white solid(0.24g).MS (ES) MH+: 220 for C6H3BrClNO.1H NMR: 8.40 (s, IH), 8.85 (s, IH), 10.18 (s, IH)
Reference Example 154 To a solution of oxalyl chloride (1.98 ml) in dichloromethane (20 ml) was added dropwise a solution of DMSO (3.45 ml) in dichloromethane (30 ml) at -78C under a nitrogen atmosphere. The mixture was stirred as such for 10 minutes, and then a solution of 5-bromo-2-chloropyridin-3-yl)methanol (3.6 g) in dichloromethane (35 ml) was added dropwise thereto. The mixture was stirred as such for 10 minutes, and then triethylamine (13.5 ml) was added dropwise thereto. After stirring as such for 10 minutes, the resulting mixture was returned to room temperature and stirred for 1 hour. To the reaction solution was added water, followed by separation. The organic layer was washed with water and saturated brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and then the resulting residue was purified by silica gel column chromatography (hexane: ethyl acetate = 6: 1) to give 5-bromo-2-chloronicotinaldehyde (3.4 g) as colorless crystals. m.p. 88.0-89.0C. 1H-NMR (300 MHz, CDCl3) delta 8.33 (1H, d, J=2.7 Hz), 8.67 (1H, d, J=2.7 Hz), 10.38 (1H, s). Elementary analysis C6H3NOClBr, Calcd. C, 32.69; H, 1.37; N, 6.35: Found C, 32.51; H, 1.33; N, 6.18.
With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 12h; To a solution of (5-bromo-2-chloropyridin-3-yl)methanol (6.8 g, 30.6 mmol) in DCM (200 mL), was added Dess-Martin periodinane (32.4 g, 76.6 mmol) at 0C. The resulting mixture was stirred at room temperature for 12h. The reaction mixture was concentrated in vacuo and the residue was purified by column chromatography on silica gel (0 to 30% EtOAc in petroleum ether) to afford 5.05 g of 5-bromo-2-chloronicotinaldehyde. LCMS [M+H]+ 221.1.
With manganese(IV) oxide; In dichloromethane; at 20℃; for 9h;Inert atmosphere; To (5-bromo-2-choropyridin-3-y)methano (5.24 g, 22.1 mmo) in DCM (250 m) under N2 atmosphere was added Mn02 (19.2 g, 22.1 mmo). After 2h of stirring at RT, Mn02 (3.85 g, 44.2 mmo) was added, the reaction mixture was stirred for 3h at RT. Then Mn02 (1.92 g, 22.1 mmo) was added and the mixture was stirred at RT for 4h. Mn02 was coHected by fi?tration through a pad of cehte, washed with DCM and the fitrate was evaporated. The residue was purified by flash co?umn chromatography on siHca g& (hexane/TBME 1/0 to 3/7) to afford 5-bromo-2-choronicotinadehyde. Rt = 1.02 mm (UPLC Method B2), 1H NMR (400 MHz, DMSO-d5) O ppm: 10.19 (s, IH), 8.85 (d, IH), 8.39(d, IH).
To a solution of(COC1)2 (2.95 mL, 34.84 mmol) in dried DCM (26 mL) at -78 C was added a solution of DMSO (4.94 mL, 69.7mmol) in DCM (45 mL) dropwise, and stirred at-78C for 10 mm. Then a solution of (5-bromo-2-chloropyridin-3-yl)methanol (B-2) in DCM (45 mL) was added dropwise. The mixture was stirred at -78C for 10 mm. TEA (18.2 mL, 131 mmol) was added dropwise, and stirred for 1 h at -78C. The mixture was warmed to r.t. and stirred for 1 h. The mixture was diluted with water (100 mL). Layers were separated. The organic layer was washed with water and brine, dried over MgSO4, and concentrated. The residue was purified by column chromatography on silica gel eluting with 3-5% EA in hexane to give 5-bromo-2-chloronicotinaldehyde (B-3) as a white solid. MS-ESI (m/z): 220 [M + 1]

 

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