Biphenyl ketones

The question of whether it, it triplets of aromatic ketones have some intrinsic chemical property has been a controversial subject in organic photochemistry (130). Recently, the correlation of structure and reactivity of some excited triplet biphenyl ketones was approached by a combined esr, CIDEP, and CIDNP study (129). The low-temperature esr confirmed the assignment of the ir, ir triplet as the lowest triplet state in these biphenyl ketones. 

A general procedure for the preparation of alkyl biphenyl ketones has been described whereby the acyl halide is added to a mixture of biphenyl, aluminum chloride, and carbon disulfide (62-90%). Nitrobenzene or carbon disulfide is used as the solvent in the preparation of 2-acetyl-fluorene (83%) and the isomeric 2- and 3 acylphenanthrenes. ... 

Yeast and G. candidum acetone powder (APG4) are complementary to each other in the reduction of various trifluoromethyl biphenyl ketones. Yeast reduction affords the (Rj-alcohol, whereas G. candidum reduction affords the (Sj-alcohol (Fig. 15-32)>1811. 

Figure 15-32. Reduction of trifluoromethyl biphenyl ketones bakers yeast vs C. candidum acetone powder 181. ...

The 4-biphenyl ketone series was incorrectly referred to as "3-biphenyl by Willgerodt cf. Vorlander. Ber., 40, 4536 (1907). 

In this chapter, two general synthetic methods of poly (aryl ether ketone) copolymers were introduced, that is, (1) nucleophilic substitution step copolycondensation of at least two different monomers of bisphenol and at least one dihalobenzoid compound or at least one monomer of bisphenol and at least two different dihalobenzoid compounds (2) electrophilic Friedel-Crafts copolycondensation of at least two different monomer of diphenyl ether and terephthaloyl chloride or at least one monomer of diphenyl ether and terephthaloyl chloride as well as isophthaloyl chloride. Some representative monomers were included. By the method (1), the synthesis and characterization of structural poly (aryl ether ketone) copolymers—poly (ether ether ketone)-poly (ether ether ketone ketone) (PEEK-PEEKK), poly (ether ether ketone)-poly (ether biphenyl ether ketone) (PEEK-PEDEK), poly (ether ether ketone ketone)-poly (ether biphenyl ether ketone ketone) (PEEKK-PEDEKK), poly (ether ether ketone)-poly (ether ether ketone biphenyl ketone) (PEEK-PEEKDK) and poly (ether biphenyl ether ketone)-poly (ether biphenyl ether ketone biphenyl ketone) (PEDEK-PEDEKDK) were discussed. The s5mthesis and characterization of the functional PAEK copolymers, such as liquid crystal poly (aryl ether ketone) copol5oners, poly (aryl ether ketone) copolymers with pendent group of low dielectric constant and poly (aryl ether ketone) copolymers with crosslinking moieties were also discussed in details. These PAEK copolymers showed a lot of special performance and can maybe be applied in optical waveguides, microelectronics, display devices, membrane materials and so on. 

Poly (ether ether ketone)-poly (ether ether ketone biphenyl ketone) (PEEK-PEEKDK) copolymer... 

Ai -A-homo-4-ketones by reaction with lithium and biphenyl at The resulting dienone is transformed into the corresponding tropone by treatment with bromine. The Swiss chemists also found that base treatment of 19-mesyloxy-A " -3-oximes gives directly 4-oximino-A-homo-estra-l(10),2,4a-trienes in moderate yield. ... 

The chloromethylation can be generally employed in aromatic chemistry benzene, naphthaline, anthracene, phenanthrene, biphenyls and many derivatives thereof are appropriate substrates. The benzylic chlorides thus obtained can be further transformed, for example to aromatic aldehydes. Ketones like benzophe-none are not reactive enough. In contrast phenols are so reactive that polymeric products are obtained. ... 

Buchwtild and co-workers have developed highly aedve cattilysts consisting of bulky, electron-rich phosphine ligands v/ith a biphenyl backbone combined v/ith PdfOAci for the aryladon of ketones or niiroalkanes fEq 5 73 ... 

Although the sulfone activated biphenyl and the ketone activated naphthalene moiety for the displacement polymerization have been reported by Attwood et al. [11], these were rediscovered by Cummings et al. [12] and Hergenrother et al. [13], respectively, for the synthesis of poly(aryl ethers). Recently, Singh and Hay [14] reported polymers containing 0-dibenzoyl benzene (1,2,3) moiety by reaction between bis(O-fluorobenzoyl) benzene or substituted benzene with bisphenates of alkali metal salt in DMAC as follows ... 

Man isoliert z. B. beim Vcrhaltnis a-Brom-keton Octacarbonyl-dikobalt =1 1 4-Acetyl-biphenyl (98°/ d.Th.) sowie 2-Acetyl-naphthalin (97% d.Th.). 

Copper-catalyzed systems have been developed that reduce ketones directly to silyl ethers. The reactions involve chiral biphenyl diphosphine type ligands and silane or siloxane hydride donors.187... 

The photodecarbonylation of a series of dibenzyl ketones was studied by Robbins and Eastman/63 The results of this study are presented in Table 4.5. The data in Table 4.5 indicate that the presence of a p-methyl or a p-methoxy group has little effect on the quantum yield for this reaction. p-Cyano groups, on the other hand, essentially totally eliminated the decarbonylation. Since the reaction could also be quenched (inefficiently) by benzonitrile or biphenyl, it was concluded that the decarbonylation occurs from a short-lived triplet state. The effect of the p-cyano groups then could result from internal triplet quenching. 

The present method is successful with a wide variety of ketones (see Table). Cyclic ketones (entries 1-4, 8) produce benzoannelated products in excellent overall yields. There is no need to purify the intermediate both the nucleophilic addition of methallylmagnesium chloride and the aromatic cyclization take place cleanly. Acyclic ketones (entries 5-7) also provide high yields of benzoannelated product. Aromatic ketones are particularly interesting substrates for this reaction since they provide substituted biphenyls, which are potentially useful materials for liquid crystal synthesis and whose preparation through classical methodology is often not straightforward. The conditions for the cationic cyclization step can be modified to accommodate acid-sensitive functionality. For example, cyclization of 3 to 4, the latter a precursor for 3-methyl-8,14-dehydromorphinan, was accomplished in 77% yield by treatment of 3 at... 

Binaphthol- and biphenyl-derived ketones (9 and 10) were reported by Song and coworkers in 1997 to epoxidize unfunctionalized alkenes in up to 59% ee (Fig. 3, Table 1, entries 9, 10) [37, 38]. Ketones 9 and 10 were intended to have a rigid conformation and a stereogenic center close to the reacting carbonyl group. The reactivity of ketones 9 and 10 is lower than that of 8, presumably due to the weaker electron-withdrawing ability of the ether compared to the ester. In the same year, Adam and coworkers reported ketones 11 and 12 to be epoxidation catalysts for several trans- and trisubstituted alkenes (Table 1, entries 11,12). Up to 81% ee was obtained for phenylstilbene oxide (Table 1, entry 25) [39]. 

Several substances alter the toxicity of chloroform in animals— most probably by modifying the metabolism to a reactive intermediate. Factors that potentiate chloroform s toxic effects include ethanol, polybrominated biphenyls, steroids, and ketones. Disulfiram, its metabolites, and a high-carbohydrate diet... 

Cyclization of a thiocarbonyl ylide with the C=C-bond of an aromatic ring was observed in the reaction of aryl biphenyl-2-yl ketones with di(tosyl)diazomethane in the presence of Rh2(OAc)4 (189). In the case where the aryl ring contains a 4-methoxy group, benzo[c]thiophene (164) was the only product formed. In contrast, when the aryl ring consists of a 2,4,6-trimethylphenyl group, compounds 165 and 166 were produced. It would seem that after 1,5-dipolar electrocyclization of the intermediate thiocarbonyl ylide occurs, aromatization then takes place by elimination of toluenesulfinic acid or methyl toluenesulfinate. 

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