Carbon Tetrachloride → HCID 86706035, compound

HRID 2280261Notes

Reaction equation

HRID 2280261 reaction equation
C[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][N:8]=2)[N:3]=1.C1C(=O)N(Cl)C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.CCOC(C)=O.[C:44]([Cl:48])(Cl)(Cl)[Cl:45]>>[Cl:45][CH:44]([Cl:48])[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][N:8]=2)[N:3]=1

Participants

6

Reactant 5

HCID 5943Carbon TetrachlorideHCID 7187Benzoyl PeroxideHCID 8857Ethyl AcetateHCID 31398ChlorosuccinimideHCID 5890332-Methyl-1,5-naphthyridine

Product 1

HCID 86706035HCID 86706035, compound

Procedure

A mixture of 2-methyl-1,5-naphthyridine (CAS#7675-32-3, Synchem-OHG #CDP146FP1, 998 mg, 6.92 mmol), NCS (1109 mg, 8.31 mmol), and benzoyl peroxide (84 mg, 0.347 mmol) in CCl4 (34 mL) was stirred at reflux for 17 h. The reaction mixture was checked by TLC (100% EtOAc). Volatiles were removed under reduced pressure and the residue was partitioned between EtOAc and saturated aqueous sodium bicarbonate. The organic layer was washed with brine, dried (MgSO4), and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography on an Analogix IF-280 (Agilent SF15-24 g, 7:3 to 3:7 hexane/EtOAc). Fractions #7-8 were combined and concentrated under reduced pressure to give the undesired byproduct, 2-(dichloromethyl)-1,5-naphthyridine, as an off-white solid (113 mg, 7.7% yield). Fractions #12-18 were combined and concentrated under reduced pressure to give the desired 2-(chloromethyl)-1,5-naphthyridine as an off-white solid (472 mg, 38.2%). 1H NMR (300 MHz, CDCl3) δ 8.99 (dd, J=4.2, 1.6, 1H), 8.45 (d, J=8.8, 1H), 8.38 (ddd, J=8.5, 1.5, 0.8, 1H), 7.85 (d, J=8.7, 1H), 7.66 (dd, J=8.6, 4.2, 1H), 4.86 (s, 2H). MS (DCI—NH3) m/z=179 (M+H)+, m/z=196 (M+NH4)+, m/z=213 (M+NH4+NH3)+.

Workup

  1. temperatureat reflux for 17 h
  2. customVolatiles were removed under reduced pressure
  3. customthe residue was partitioned between EtOAc and saturated aqueous sodium bicarbonate
  4. washThe organic layer was washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. customthe residue was purified by column chromatography on an Analogix IF-280 (Agilent SF15-24 g, 7:3 to 3:7 hexane/EtOAc)
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-743dcacd10d849c0a1d57e804f298b8f
Source dataset
uspto-grants-2015_09
Patent number
US09138494B2

Reaction notes

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