Isobutylene → HCID 86747051, compound

HRID 484465Notes

Reaction equation

HRID 484465 reaction equation
[C:1]([C@H:4]1[CH2:13][C@H:12]([CH2:14][C:15]([O:17][CH3:18])=[O:16])[C:11]2[C:6](=[CH:7][C:8]([Cl:20])=[CH:9][C:10]=2[Cl:19])[NH:5]1)([OH:3])=[O:2].[CH3:21][C:22](=[CH2:24])[CH3:23].C(=O)([O-])O.[Na+]>ClCCl.S(=O)(=O)(O)O>[CH3:18][O:17][C:15]([CH2:14][C@@H:12]1[C:11]2[C:6](=[CH:7][C:8]([Cl:20])=[CH:9][C:10]=2[Cl:19])[NH:5][C@@H:4]([C:1]([O:3][C:22]([CH3:24])([CH3:23])[CH3:21])=[O:2])[CH2:13]1)=[O:16]

Participants

6

Reactant 3

HCID 8255IsobutyleneHCID 516892Sodium BicarbonateHCID 15168488HCID 15168488, compound

Product 1

HCID 86747051HCID 86747051, compound

Reagents, catalysts & solvents 2

HCID 1118Sulfuric AcidCatalystHCID 6344DichloromethaneSolvent2×

Procedure

Trans-2-carboxy-4-methoxycarbonylmethyl-5,7-dichloro-1,2,3,4-tetrahydroquinoline (Example 156) (4 g) was suspended in dichloromethane (50 ml) and isobutylene (50 ml) was condensed at 0° C. Concentrated sulphuric acid (10 drops) was added and the reaction mixture was shaken for 3 days under a nitrogen atmosphere of 30 p.s.i. The solution was poured into saturated sodium hydrogen carbonate solution and diluted with a further amount of dichloromethane (100 ml). The organic layer was separated and the aqueous solution was washed with diethyl ether (100 ml). The combined organic layers were dried (Na2SO4), filtered and concentrated under vacuum. The residue obtained was purified by chromatography on silica gel with 20% hexane in dichloromethane as eluent to give the title compound as a colourless oil (4.07 g); δ (250 MHz, DMSO) 1.45 (9H, s, (CH3)3C), 1.64 (1H, ddd, J=13.0, 12.4 and 4.0 Hz, CHACHBHCCHD), 2.10 (1H, dm, J=13.0 Hz, CHACHBHCCHD), 2.49 (2H, m, CHECHFCO2CH3), 3.44 (1H, m, CHACHBHCCHDCHEHFCO2CH3), 3.65 (3H, s, CO2CH3), 3.97 (1H, dd, J=12.4 and 3.4 Hz, CHACHBHCCHD), 6.63 (2H, m, 6-H or 8-H and NH), 6.79 (1H, d, J=2.0 Hz, 6-H or 8-H); m/e (FAB) 374 (M+1); Found C, 54.93; H, 5.67; N, 3.69. C17H21Cl2NO4 requires C, 54.56; H, 5.66; N, 3.74%.

Workup

  1. customcondensed at 0° C
  2. customThe organic layer was separated
  3. washthe aqueous solution was washed with diethyl ether (100 ml)
  4. dry with materialThe combined organic layers were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe residue obtained
  8. customwas purified by chromatography on silica gel with 20% hexane in dichloromethane as eluent

Sources & evidence

ORD record
ord-975d2b28e5c54d4b99377e613c2a158e
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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