2-Phenyl-1,3-thiazol-5(4H)-one → HCID 178479882, compound

HRID 2398435Notes

Reaction equation

HRID 2398435 reaction equation
C[N:2]1C2[C:6](=[C:7]([OH:12])C=CC=2)[C:5](=[O:13])[CH2:4][CH:3]1CC#N.CN1C2C(=C([OH:28])C=CC=2)C(=O)CC1CC=O.C1(C2SC(=O)CN=2)C=CC=CC=1.[C:45]1([C:51]2[S:52][C:53](=[O:71])[C:54](=[CH:56][CH2:57][CH:58]3[CH2:67][C:66](=[O:68])[C:65]4[C:60](=[CH:61][CH:62]=[CH:63][C:64]=4[OH:69])[N:59]3[CH3:70])[N:55]=2)[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=1>[Ni].N1C=CC=CC=1>[C:51]([NH:55][CH:54]1[CH:56]2[CH:6]([CH:7]([OH:12])[CH:67]3[CH:58]([CH2:57]2)[N:59]([CH3:70])[C:60]2[C:65](=[C:64]([OH:69])[CH:63]=[CH:62][CH:61]=2)[C:66]3=[O:68])[C:5](=[O:13])[C:4]([C:3]([NH2:2])=[O:28])=[C:53]1[OH:71])(=[S:52])[C:45]1[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=1

Participants

7

Reactant 4

HCID 125499042-Phenyl-1,3-thiazol-5(4H)-oneHCID 21435228HCID 21435228, compoundHCID 53860035HCID 53860035, compoundHCID 54159451HCID 54159451, compound

Product 1

HCID 178479882HCID 178479882, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 1049PyridineSolvent

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

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Sources & evidence

ORD record
ord-2b57045cdd6b41dfab2914ba9a8d8113
Source dataset
uspto-grants-1977_05
Patent number
US04024272

Reaction notes

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