Phosphorus oxychloride → 6,9-Dichloro-1,2,3,4-tetrahydro-2-acridinecarboxylic acid methyl ester
Reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH2:11])[C:5](=[CH:9][CH:10]=1)[C:6](O)=O.P(Cl)(Cl)([Cl:14])=O.O=[C:18]1[CH2:23][CH2:22][CH:21]([C:24]([O:26][CH3:27])=[O:25])[CH2:20][CH2:19]1>>[CH3:27][O:26][C:24]([CH:21]1[CH2:22][CH2:23][C:18]2[C:19](=[C:6]([Cl:14])[C:5]3[C:4]([N:11]=2)=[CH:3][C:2]([Cl:1])=[CH:10][CH:9]=3)[CH2:20]1)=[O:25]Participants
Procedure
To a slurry of 16.5 g (0.096 mol) of 4-chloroanthranilic acid and 166 ml of phosphorous oxychloride is added portionwise 15 g (0.096 mol) of methyl 4-ketocyclohexane carboxylate. The reaction mixture is refluxed for 3 h, cooled, and concentrated in vacuo. The residue is dissolved in methylene chloride and poured into an ice-NH4OH mixture. The aqueous phase is separated and extracted with methylene chloride. The combined organic phases are dried over Na2SO4 and concentrated in vacuo. The residue is triturated with ethyl ether to give 21.7 g (73%) of the title compound: IR (KBr) 1730, 1605, 1580, and 1550 cm-1 ; NMR (DMSO-d6) δ8.14-8.08 (m, 1H), 8.0-7.96 (m, 1H), 7.70-7.64 (m, 1H), 3.70 (s, 3H), 3.30-3.16 (m, 1H), 3.12-2.96 (m, 4H), 2.32-2.20 (m, 1H), and 2.04-1.86 (m, 1H).
Workup
- temperatureThe reaction mixture is refluxed for 3 h
- temperaturecooled
- concentrationconcentrated in vacuo
- dissolutionThe residue is dissolved in methylene chloride
- additionpoured into an ice-NH4OH mixture
- customThe aqueous phase is separated
- extractionextracted with methylene chloride
- dry with materialThe combined organic phases are dried over Na2SO4
- concentrationconcentrated in vacuo
- customThe residue is triturated with ethyl ether
Sources & evidence
- ORD record
- ord-cc5ec8267d0c4a1aafe7b440ca989ebf
- Source dataset
- uspto-grants-1990_11
- Patent number
- US04970316
Reaction notes
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