Quinolyl Ketones

In 1912, Rabe described the reaction of ethyl cinchoninate with benzylmagnesium chloride, from which benzyl-(4-quinolyl)-ketone (CLXXIII) was obtained in small amounts (206), accompanied by the... 

In connection with their work on the synthesis of quininio acid and of cinchoninic acid, Kaufmann and his collaborators (178-180, 184) had prepared 4-cyano- methoxyquinoline and 4-cyanoquinoline, obtained earlier by dehydration of cinchoninamide with thionyl chloride or with phosphorus pentoxide (209). Both products reacted with methylmag-nesium iodide in anisole solution and furnished methyl-(6-methoxy-4-quinolyl)-ketone and methyl-(4-quinolyl)-ketone respectively (210, 211). Like Rabe (206), these investigators were cognizant of the synthetic... 

The important role played by the quinicines (rubatoxanones, quina-toxines) in the syntheses of the dihydrocinchona alkaloids and the possibility that such substances might be used for the preparation of products approaching quinine in therapeutical interest, has led to the production of a large number of quinolyl ketones of various types and the corresponding secondary alcohols, and other derivatives obtainable from them, of which mention may be made of Rubtzov s syntheses of several isomerides of dihydroquinine. ... 

Exchange of the pyridine ligand of the C-C cleaved complex 26 with soft ligands such as phosphines, phosphites, or CO brings about reductive elimination to regenerate the 8-quinolyl ketone 22 [45]. 

Quinolyl cyclobutylmethyl ketone 72 undergoes C-C bond cleavage by rho-dium(I) to form the inserted intermediate 73, as mentioned in Eq. 21. Sequential (3-carbon elimination leads to ring-opening of the cyclobutane ring. Addition of pyridine and P(OMe)3 induces reductive elimination to give a mixture of linear 8-quinolyl ketones 74 and 75 [86]. 

The hydrogenation of quinolyl ketones is worthy of considerable discussion because of the variety of results. Selective reduction, as compared with pyridyl ketones reported in Section XVI, B, is complicated by the benzenoid portion of the molecule. 

The reduction of quinolyl ketones of the following type produces results that require some explanation ... 

C,H,N,0]- Anion radical from di-p-quinolyl ketone 69Morl 246 ... 

In addition to the benzothiaphenyl system, indolyl ketones, pyridyl ketones, quinolyl ketones,and dibenzofuryl ketones have all provided Elbs products when subjected to pyrolysis conditions. Typically, yields have been in the 5-30% range. 

Quinolylfluorone, see T-00320 2-Quinolyl ketone, see D-01101 (2-Quinolyl)methyl-A-2-quinolylhydrazone, see Q-00026... 

Cabarrocas G, Ventura M, Maestro M, Mahia J, Villalgordo JM (2001) Synthesis of novel optically pure quinolyl-P-amino alcohol derivatives from 2-amino thiophenol and chiral a-acetylenic ketones and their IBX-mediated oxidative cleavage to IV-Boc quinolyl carboxamides. Tetrahedron Asymmetry 12 1851-1863... 

It has recently been found that the rearrangement of 19 and 20 to 2-acyl quinolines, such as 35, and 1-acylisoquinolines can be conveniently carried out in dimethylformamide at room temperature. A number of quinolyl and isoquinolyl ketones have been prepared in this manner. Use of dimethylsulfoxide as solvent also allows rearrangement to proceed at room temperature but the initially formed ketones reacted further with the solvent anion to give products such as 37. ... 

KETONE, METHYL 5-METHYL-l-(2-QUINOLYL)-4-PYRAZOLYL see MLW600 KETONE, METHYL 5-METHYL-l-(2-QLTNOXALINYL)-4-PYRAZOLYL see MLW630 KETONE, METHYL 5-METHYL-2-THIENYL see MPR300... 

C11H9N02 8-hydroxy-5-quinolyl methyl ketone 2598-31-4 396.65 34.050 1,2 21725 C11H11N 4-methyl-1 -naphthalenamine 4523-45-9 537.36 47.485 2... 

Suggs and Jun exploited 8-quinolyl alkyl ketones 19-22 as substrates for C-C bond cleavage, as shown in Eq. 21. The formation of complexes 23-26 by insertion between the carbonyl carbon and the a-carbon is favored due to the general preference for five-membered chelate rings observed for cyclometalated complexes [42]. No deuterium is lost in the reaction of 8-quinolyl alkyl ketone 20, which has both benzylic positions deuterated. Interestingly, the chirality of the... 

Carbonyl groups are also utilized in catalytic C-C bond cleaving reactions. Under catalytic conditions, 8-quinolyl phenyl ketone 85 reacts with ethylene to give 8-quinolyl ethyl ketone 86 and styrene in quantitative yield [105]. Styrene is formed by cleavage of the phenyl-carbonyl bond, followed by ethylene insertion into the resultant phenyl-rhodium bond, and (3-hydride elimination. The accompanying formation of a rhodium-hydride complex is followed by incorporation of ethylene to furnish the ethyl ketone 86. 

Asymmetric dihydroxylation of the side-chain of Z-1-(4-meth-oxyphenyl)-1-(tert-butyldimethylsiloxy)-1-propene to give (R)-l-hydroxyethyl 4-methoxyphenyl ketone in 94% yield (99% e.e.) was effected by addition of the alkene to a stirred mixture of osmium tetroxide, potassium ferricyanide, potassium carbonate, a 9-0-(9 -phenanthryl)ether(PHN) of dihydroquinidine and 1 mole of methanesulphonamide in aqueous tert-butanol (1 1), with reaction during 16 hours at ambient temperature. Then treatment with sodium sulphite prior to work-up to gave the product (ref. 130). Other best ligands were the 9-0-(4 -methyl-2 -quinolyl) ethers (MEQ) of dihydroquinine. 

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