Hydrochloric Acid → HCID 86658613, compound

HRID 1801362Notes

Reaction equation

HRID 1801362 reaction equation
[S:1](=[O:3])=[O:2].N[C:5]1[CH:6]=[C:7]([CH:11]2[C:20]([CH3:22])([CH3:21])[CH2:19][C:18]3[C:13](=[CH:14][CH:15]=[C:16]([C:23]([O:25][CH3:26])=[O:24])[CH:17]=3)[NH:12]2)[CH:8]=[CH:9][CH:10]=1.N([O-])=O.[Na+].[ClH:31]>C(O)(=O)C.O>[Cl:31][S:1]([C:5]1[CH:6]=[C:7]([C:11]2[C:20]([CH3:22])([CH3:21])[CH2:19][C:18]3[C:13](=[CH:14][CH:15]=[C:16]([C:23]([O:25][CH3:26])=[O:24])[CH:17]=3)[N:12]=2)[CH:8]=[CH:9][CH:10]=1)(=[O:3])=[O:2]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 23668193Sodium NitriteHCID 67442023HCID 67442023, compound

Product 1

HCID 86658613HCID 86658613, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
-10 °C

Procedure

To a stirred solution of cuprous chloride (90 mg, 0.91 mmol) in acetic acid (60 mL) was bubbled with sulfur dioxide gas for 6 h at room temperature. A mixture of methyl 2-(3-aminophenyl)-3,3-dimethyl-1,2,3,4-tetrahydroquinoline-6-carboxylate (992 mg, 3.20 mmol) in conc. hydrochloric acid (30 mL) and acetic acid (10 mL) was stirred for 1 hour. After cooling to −10° C., a solution of sodium nitrite (334 mg, 4.84 mmol) in water (7 mL) was added dropwise below −10° C. The resulting mixture was stirred for 1 h at −10° C. The prepared sulfur dioxide-salt solution was added to the solution above at −10° C. After addition, the mixture was stirred for 24 h at room temperature. The reaction mixture was quenched onto 100 g of crushed ice. The mixture was extracted with dichloromethane (40 mL, four times). The combined organic layers were washed with water (40 mL, twice), saturated aqueous Sodium bicarbonate solution (30 mL, twice), and saturated brine (40 mL) and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was removed by filtration, and the organic solvent was evaporated under reduced pressure to afford 1.0 g of methyl 2-(3-(chlorosulfonyl)phenyl)-3,3-dimethyl-3,4-dihydroquinoline-6-carboxylate. MS (ESI+APCI) M+1=394.

Workup

  1. stirringThe resulting mixture was stirred for 1 h at −10° C
  2. additionAfter addition
  3. stirringthe mixture was stirred for 24 h at room temperature
  4. customThe reaction mixture was quenched onto 100 g of crushed ice
  5. extractionThe mixture was extracted with dichloromethane (40 mL, four times)
  6. washThe combined organic layers were washed with water (40 mL
  7. dry with materialtwice), saturated aqueous Sodium bicarbonate solution (30 mL, twice), and saturated brine (40 mL) and dried over anhydrous magnesium sulfate
  8. customAnhydrous magnesium sulfate was removed by filtration
  9. customthe organic solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-60f7ecd1db4d4d04b3321eb74e1629f4
Source dataset
uspto-grants-2013_01
Patent number
US08344137B2

Reaction notes

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