Thionyl Chloride → HCID 71547128, compound

HRID 1476791Notes

Reaction equation

HRID 1476791 reaction equation
S(Cl)(Cl)=O.[Br:5][CH2:6][CH2:7][CH2:8][N:9]1[C@@H:18]([C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([O:25][CH3:26])[CH:20]=2)[C@@H:17]([C:27](O)=[O:28])[C:16]2[C:11](=[CH:12][C:13]([N+:30]([O-:32])=[O:31])=[CH:14][CH:15]=2)[C:10]1=[O:33].[Cl-].[Al+3].[Cl-].[Cl-]>C1C=CC=CC=1>[Br:5][CH2:6][CH2:7][CH2:8][N:9]1[C:18]2[C:19]3[CH:20]=[C:21]([O:25][CH3:26])[CH:22]=[CH:23][C:24]=3[C:27](=[O:28])[C:17]=2[C:16]2[C:11](=[CH:12][C:13]([N+:30]([O-:32])=[O:31])=[CH:14][CH:15]=2)[C:10]1=[O:33]

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 6451240Aluminum(III) ChlorideHCID 86706714HCID 86706714, compound

Product 1

HCID 71547128HCID 71547128, compoundYield 55.1%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Thionyl chloride (10 mL) was slowly added to a solution of cis-4-carboxy-N-(3-chloropropyl)-3,4-dihydro-3-(4-methoxyphenyl)-7-nitro-1(2H)isoquinolone (48, 1.94 g, 4.18 mmol) in benzene (60 mL). The reaction mixture was heated at reflux for 30 min, allowed to cool to room temperature, and concentrated. The residue was diluted with nitrobenzene (80 mL), chilled in an ice bath, and aluminum chloride (3.00 g, 22.5 mmol) was added. The reaction mixture was removed from the bath and heated at 100° C. for 1 h. Water (200 mL) was added, and the solution was extracted with CHCl3 (3×70 mL). The combined organic layers were washed with sodium bicarbonate (3×75 mL) and brine (75 mL), and dried over sodium sulfate. The solution was concentrated, hexanes (250 mL) were added, and the liquid was decanted. The solid was washed with hexanes (100 mL) and the liquid was decanted again. The solid was purified by silica gel column chromatography, eluting with chloroform-methanol, 20:1, to provide a red-orange solid (1.02 g, 55%): mp 282-284° C. (dec). IR (Film) 1699, 1667, 1612, 1555, 1499, 1332, 1159, 1078, 840, 785, 688, 662 cm−1; 1H NMR (CDCl3, 300 MHz) δ 8.85 (d, J=2.5 Hz, 1H), 8.70 (d, J=8.9 Hz, 1H), 8.55 (d, J=8.9 Hz, 1H), 7.60 (d, J=8.5 Hz, 1H), 7.38 (s, 1H), 7.06 (d, J=8.3 Hz, 1H), 4.60 (t, J=7.3 Hz, 2H), 3.91 (s, 3H), 3.75 (t, J=6.4 Hz, 2H), 2.36 (t, J=7.0 Hz, 2H); EIMS m/z (rel intensity) 444 (M+, 100), 442 (M+, 100), 363 [(M-Br)+, 69]; HRESIMS calcd for C20H15BrN2O5 442.0164 (MH+). found 442.0158 (MH+); Anal. Calcd for C20H15BrN2O5.0.8H2O: C, 52.49; H, 3.66; N, 6.12; Br, 17.46. Found: C, 52.20; H, 3.54; N, 5.96; Br, 17.46.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 30 min
  3. concentrationconcentrated
  4. additionThe residue was diluted with nitrobenzene (80 mL)
  5. temperaturechilled in an ice bath
  6. customThe reaction mixture was removed from the bath
  7. temperatureheated at 100° C. for 1 h
  8. additionWater (200 mL) was added
  9. extractionthe solution was extracted with CHCl3 (3×70 mL)
  10. washThe combined organic layers were washed with sodium bicarbonate (3×75 mL) and brine (75 mL)
  11. dry with materialdried over sodium sulfate
  12. concentrationThe solution was concentrated
  13. additionhexanes (250 mL) were added
  14. customthe liquid was decanted
  15. washThe solid was washed with hexanes (100 mL)
  16. customthe liquid was decanted again
  17. customThe solid was purified by silica gel column chromatography
  18. washeluting with chloroform-methanol, 20:1

Sources & evidence

ORD record
ord-fafb88bf522b4a0e93626d6b99d079d7
Source dataset
uspto-grants-2016_08
Patent number
US09402842B2

Reaction notes

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