Stannous Chloride → HCID 68153836, compound

HRID 2276283Notes

Reaction equation

HRID 2276283 reaction equation
Cl[Sn]Cl.[F:4][C:5]1[CH:24]=[CH:23][CH:22]=[C:21]([F:25])[C:6]=1/[CH:7]=[CH:8]/[C:9]1[CH:17]=[CH:16][C:12]([N:13]([CH3:15])[CH3:14])=[CH:11][C:10]=1[N+:18]([O-])=O>Cl.C(O)(=O)C>[F:4][C:5]1[CH:24]=[CH:23][CH:22]=[C:21]([F:25])[C:6]=1/[CH:7]=[CH:8]/[C:9]1[CH:17]=[CH:16][C:12]([N:13]([CH3:14])[CH3:15])=[CH:11][C:10]=1[NH2:18]

Participants

5

Reactant 2

HCID 24479Stannous ChlorideHCID 68153820HCID 68153820, compound

Product 1

HCID 68153836HCID 68153836, compoundYield 69.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 5 g (26.4 mmol, 8.5 equiv) of SnCl2 in 7 mL of conc HCl was added dropwise to a solution of 0.95 g (3.1 mmol) of 6 in 100 mL of glacial acetic acid. The mixture was stirred for ca. 12 h at 25° C. A precipitate was collected by filtration, washed with 5 mL of glacial acetic acid, and suspended in 200 mL of water. The aqueous suspension was adjusted to pH 9-10 with NaOH and was extracted with Et2O. The combined ethereal extracts were washed with water, dried over anhydrous MgSO4 and concentrated. The residue was recrystallized from ethanol to afford 590 mg (69%) of 7 as yellow crystals: mp 97-98° C. 1H NMR (DMSO-d6): δ 7.41 (d, 1H, J=16.4 Hz), 7.27 (d, 1H, J=8.8 Hz), 7.24-7.18 (m, 1H), 7.12-7.05 (m, 2H), 6.61 (d, 1H, J=16.4 Hz), 6.10 (dd, 1H, J1=8.8 Hz, J2=2.4 Hz), 6.03 (d, 1H, J=2.8 Hz), 5.05 (br.s, 2H), 2.87 (s, 6H). 13C NMR (DMSO-d6): δ 160.25 (dd, J1=246.0 Hz, J2=7.9 Hz, two C), 151.95, 147.98, 132.39 (t, J=7.1 Hz), 127.45 (t, J=11.1 Hz), 127.06, 116.11 (t, J=15.1 Hz), 112.20 (dd, J1=18.7 Hz, J2=6.8 Hz, two C), 111.39, 108.21, 103.52, 99.07, 40.28 (two C). MS: m/z (%) 275 (21), 274 (100), 273 (33), 257 (15), 211 (16). Anal. Calcd for C16H16F2N2: C, 70.06; H, 5.88. Found: C, 70.18; H, 5.94.

Workup

  1. filtrationA precipitate was collected by filtration
  2. washwashed with 5 mL of glacial acetic acid
  3. extractionwas extracted with Et2O
  4. washThe combined ethereal extracts were washed with water
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated
  7. customThe residue was recrystallized from ethanol

Sources & evidence

ORD record
ord-489702d616e24dc8bde34913e77a91f7
Source dataset
uspto-grants-2015_09
Patent number
US09132102B2

Reaction notes

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