1.1- Diaryl derivatives ketones

Thioglycolic acid sulfuric acid 1,1-Diaryl derivatives from ketones s. 19, 837... 

Tiifluoromethyl derivatives of tetrahydrothiopyran-4-ols result from the Michael addition of hydrosulfide to a, -unsaturated trifluoromethyl ketones <96JOC1986> and tetrahydro-thiopyran-4-ones arise from the reaction of H2S with l,5-diaryl-2-chloropenta-l,4-dien-3-ones <96PS(108)93>. 

Benzoisothiazole-2,2-dioxides undergo autoxidation under basic conditions in the presence of TBA-Br to yield 2-aroylaniline derivatives (Scheme 10.6) and the more simple diarylmethylsulphones produce diaryl ketones (Table 10.29) [1],... 

Elba reaction org chem The formation of anthracene derivatives by dehydration and cycllzation of diaryl ketone compounds which have a methyl group or methylene group heating to an elevated temperature is usually required. elbs re.ak shan ( ELDOR See electron electron double resonance. ( el,dor or e el de o ar ( electrical calorimeter analy chem Device to measure heat evolved (from fusion or vaporization, for example) measured quantities of heat are added electrically to the sample, and the temperature rise is noted. a lek tra kal kal a rlm ad ar)... 

IV-acetyl pyrrolidines and -piperidines to the corresponding diones or ketones were similarly effected [405, 406], as were conversions of diacetyl and dibenzyl piperazines to diketo componnds by the same system (Table 5.1) [407]. Methylene groups adjacent to the N atom in tertiary polycyclic amines were oxidised by RuO /aq. NaCIO j/CCl (Fig. 5.5) [408]. A large-scale oxidation of l,4-bis(2-phenylethyl) piperazine to the dione was made by RnO /aq. Na(10 )/Et0Ac [409], and RuO /aq. Na(IO )/CCl converted dialkyl or diaryl A A -dimethyladenosines to the corresponding monoamido derivatives (Fig. 5.4) [410]. 

Two strategies for the synthesis of enantiomerically enriched diaryl methanols 27 are apparent first, asymmetric reductions of the corresponding diaryl ketones 36 [33], and, second, enantioselective aryl transfer reactions to the respective benzaldehyde derivatives 37 (Scheme 2.1.2.5) [34, 35]. 

However, these compounds are generally unstable. Most imines with a hydrogen on the nitrogen spontaneously polymerize.143 Stable hemiaminals can be prepared from polychlorinated and polyfluorinated aldehydes and ketones, and diaryl ketones do give stable imines Ar2C=NH.144 Aside from these, when stable compounds are prepared in this reaction, they are the result of combinations and condensations of one or more molecules of 12 and/or 13 with each other or with additional molecules of ammonia or carbonyl compound. The most important example of such a product is hexamethylenetetramine145 (11), prepared from ammonia and formaldehyde.146 Aromatic aldehydes give hydrobenzamides ArCH(N=CHAr)2 derived from three molecules of aldehyde and two of ammonia.147... 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

For related reasons, and because their excited-state energies are lower than for dialkyl ketones, diaryl ketones and simple alkyl aryl ketones do not fragment on irradiation in solution, even at higher temperatures. This leads to a photostability that is one factor contributing to the successful employment of ketones such as benzophe-none tPh-CO) or acetophenone (PhCOMe) as triplet sensitizers. a-Cleavage for ketones in solution at room temperature is promoted if structural factors cause the bond adjacent to the carbonyl group to be somewhat weaker than normal. Hence t-alkyl ketones give decar-borylation products readily (4.5), as do benzyl ketones (4.6 and benzoin derivatives (4.7). 

Pyrrole- and indole-carboxylic acid chlorides react with dialkyl- and diaryl-cadmium to yield the ketones and it is noteworthy that the reaction of the anhydride of indole-2,3-dicarboxylic acid with diphenylcadmium produces 3-benzoylindole-2-carboxylic acid and not its isomer (53JCS1889). The ability of l-methylindole-2-carboxylic acid to react with nucleophiles is enhanced by conversion into the mixed anhydride with methanesulfonic acid. The mixed anhydride reacts with carbanions derived from diethyl malonate and from methyl acetate to yield the indolyl (3- keto esters (80TL1957). 

Alkyl- or aryl-dibenzothiophenes are conveniently prepared from the 2-arylthio-cyclohexanones, which are readily cyclized and dehydrogenated to yield the respective 1-, 2-, 3- or 4-substituted dibenzothiophenes (382 equation 9 Section 3.15.2.3.2). More complex polycyclic systems are available, using suitable aryenethiols, such as naph-thalenethiols, and 2-bromo-l-tetralone to synthesize the appropriate 2-arylthio ketones. Diaryl sulfides can be converted to dibenzothiophene derivatives in satisfactory yields by photolysis in the presence of iodine (equation 10) (75S532). Several alkyldibenzothiophenes with substituents in the 2- and/or 3-positions were prepared in satisfactory yield by the condensation of dichloromethyl methyl ether with substituted allylbenzo[6]thiophenes (equation 11) (74JCS(P1)1744). 

FRIEDEL-CRAFTS REACTION. Aluminum chloride anhydrous, introduced by Friedcl and Crafts, is used as reagent, generally in CS solution to avoid rise in temperature, for the preparation of (I) aryl-alkyl hydrocarbons, (2) di- and triphenylmethane and derivatives, and (3) aryl-alkyl and diaryl ketones, Other chlorides, such as those of zinc, irun(lll), and liniiV), are often effective in certain cases. 

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