Dimethyl Sulfate → HCID 21435240, compound
Reaction equation
C[O:2][C:3](=[O:18])[CH2:4][C:5]1[NH:6][C:7]2[C:12]([C:13](=[O:15])[CH:14]=1)=[C:11]([O:16][CH3:17])[CH:10]=[CH:9][CH:8]=2.S(OC)(O[CH3:23])(=O)=O>[OH-].[Na+].CO>[CH3:23][N:6]1[C:7]2[C:12](=[C:11]([O:16][CH3:17])[CH:10]=[CH:9][CH:8]=2)[C:13](=[O:15])[CH:14]=[C:5]1[CH2:4][C:3]([OH:2])=[O:18]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 2
Procedure
The starting material can be obtained by condensation of 3-amino-4-chloroanisole with acetonedicarboxylic acid dimethyl ester to give 4-oxo-5-methoxy-8-chloro-1,4-dihydro-quinoline-2-acetic acid methyl ester, hydrogenation on 5% Pd-on-charcoal in dioxan at 6 atmospheres and 60° to give 4-oxo-5-methoxy-1,4-dihydroquinoline-2-acetic acid methyl ester, reaction with dimethyl sulphate in sodium hydroxide solution to give 1-methyl-4-oxo-5-methoxy-1,4-dihydroquinoline-2-acetic acid, hydrogenation on PtO2 in methanol at 20° and normal pressure to give 1-methyl-4-oxo-5-methoxy-1,2,3,4-tetrahydroquinoline-2-acetic acid, reaction, via the chloride and the amide, to give the nitrile, ether splitting by means of BBr3 to give 1-methyl-4-oxo-5-hydroxy-1,2,3,4-tetrahydroquinoline-2-acetonitrile, reaction with Raney nickel to give 1-methyl-4-oxo-5-hydroxy-1,2,3,4-tetrahydroquinoline-2-acetaldehyde, condensation with 2-phenyl-2-thiazolin-5-one to give 2-phenyl-4-[2-(1-methyl-4-oxo-5-hydroxy-1,2,3,4-tetrahydro-2-quinolyl)-ethylidene]-2-thiazolin-5-one, condensation with acetone dicarboxylic acid monomethyl ester-monoamide to give 4-thiobenzamido-1,4,4a,5,5a,6,11,12-octahydro-3,10,12-trihydroxy-6-methyl-1,11-dioxo-6-aza-naphthacene-2-carboxamide (mixture of stereoisomers), epimerization with pyridine to give 4-de-dimethylamino-4-thiobenzamido-6-methyl-12a-dehydroxy-6-aza-tetracycline and hydroxylation.
Workup
- customto give
Sources & evidence
- ORD record
- ord-8cdbd038b6dd4c009ac69d6b9829db4a
- Source dataset
- uspto-grants-1977_05
- Patent number
- US04024272
Reaction notes
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