Dimerization ketone

Lediglich beim Methylsulfon (R3 = CH3) entstehen nennenswerte Mengen dimere Ketone (bis zu 20% bei einer Keton-Ausbeute von 57-95% d.Th.). 

Tetroxans ( dimeric ketone or aldehyde peroxides ) (7) are readily obtainable from carbonyl compounds and Caro s acid or hydrogen peroxide and sulfuric acid by the method described by Baeyer and Villiger.28,20 However, aromatic ketones undergo a Baeyer-Villiger rearrangement under these conditions to form esters of carboxylic acids.30... 

Whereas dimeric ketone peroxides (7) liberate the equivalent quantity of iodine when heated with acidic potassium iodide solution, trimeric ketone peroxides (13, 14, and 15) do not react quantitatively with iodide.16 The same behavior of the two types of ketone... 

The carbonation of polymeric carbanions using carbon dioxide is one of the simplest, most useful, and widely used functionalization reactions. However, there are special problems associated with the simple carbonation of polymeric organolithium compounds. Eor example, when carbonations with high-purity, gaseous carbon dioxide are carried out in benzene solution at room temperature using standard high vacuum techniques, the carboxylated polymer is obtained in only 27-66% yield for PSLi, PILi, and poly(styrene-b-isopre-nyl)lithium. The functionalized polymer is contaminated with dimeric ketone (23-27%) and trimeric alcohol (7-50%)... 

A rather specialized solid-state carbonation procedure can be used to carbonate PSLi and other living polymers with backbones which have glass transition temperatures significantly above room temperature. Thus, freeze-drying of benzene solutions of PSLi generates a porous solid which can be carbonated in the solid state to give minimal amounts of dimeric ketone products (1-2%). In addition, essentially quantitative yields of carboxylated polystyrene were obtained from freeze-dried solutions of PSLi that were complexed with 1-2 molar equivalents of TMEDA. No dimer was detected by SEC or TLC analyses. A freeze-dried sample of poly... 

Figure 4.9 Formation of dimeric ketones of maleopimaric-type adducts [26].

Carboxyl End Groups. Termination of bifimctional living polystyrene by solid CO2 yields polymers with carboxyl end groups (169). Because of its commercial potential, this reaction has been studied in depth. In addition to carboxyl groups (60%), dimeric ketones (30%) and trimeric carbinols (10%) are formed with gaseous CO2 (170). 

By contrast, in the system propionic acid d) - methyl isobutyl ketone (2), (fi and are very much different when y 1, Propionic acid has a strong tendency to dimerize with itself and only a weak tendency to dimerize with ketone also,the ketone has only a weak tendency to dimerize with itself. At acid-rich compositions, therefore, many acid molecules have dimerized but most ketone molecules are monomers. Acid-acid dimerization lowers the fugacity of acid and thus is well below unity. Because of acid-acid dimerization, the true mole fraction of ketone is signi-... 

Pyridyl)hydrazine (Aldrich), 4-acetylpyridine (Acros), N,N,N -trimethylethylenediamine (Aldrich), methylrhenium trioxide (Aldrich), InQj (Aldrich), Cu(N0j)2-3H20 (Merck), Ni(N03)2-6Il20 (Merck), Yb(OTf)3(Fluka), Sc(OTf)3 (Fluka), 2-(aminomethyl)pyridine (Acros), benzylideneacetone (Aldrich), and chalcone (Aldrich) were of the highest purity available. Borane dimethyl sulfide (2M solution in THE) was obtained from Aldrich. Methyl vinyl ketone was distilled prior to use. Cyclopentadiene was prepared from its dimer immediately before use. (R)-l-acetyl-5-isopropoxy-3-pyrrolin-2-one (4.15) has been kindly provided by Prof H. Hiemstra (University of Amsterdam). 

The 3.8-nonadienoate 91, obtained by dimerization-carbonylation, has been converted into several natural products. The synthesis of brevicomin is described in Chapter 3, Section 2.3. Another royal jelly acid [2-decenedioic acid (149)] was prepared by cobalt carbonyl-catalyzed carbonylation of the terminal double bond, followed by isomerization of the double bond to the conjugated position to afford 149[122], Hexadecane-2,15-dione (150) can be prepared by Pd-catalyzed oxidation of the terminal double bond, hydrogenation of the internal double bond, and coupling by Kolbe electrolysis. Aldol condensation mediated by an organoaluminum reagent gave the unsaturated cyclic ketone 151 in 65% yield. Finally, the reduction of 151 afforded muscone (152)[123]. n-Octanol is produced commercially as described beforc[32]. 

Reactions with Aldehydes and Ketones. The base-catalyzed self-addition of acetaldehyde leads to formation of the dimer, acetaldol [107-89-1/, which can be hydrogenated to form 1,3-butanediol [107-88-0] or dehydrated to form crotonaldehyde [4170-30-3]. Crotonaldehyde can also be made directiy by the vapor-phase condensation of acetaldehyde over a catalyst (53). 

Simple olefins do not usually add well to ketenes except to ketoketenes and halogenated ketenes. Mild Lewis acids as well as bases often increase the rate of the cyclo addition. The cycloaddition of ketenes to acetylenes yields cyclobutenones. The cycloaddition of ketenes to aldehydes and ketones yields oxetanones. The reaction can also be base-cataly2ed if the reactant contains electron-poor carbonyl bonds. Optically active bases lead to chiral lactones (41—43). The dimerization of the ketene itself is the main competing reaction. This process precludes the parent compound ketene from many [2 + 2] cyclo additions. Intramolecular cycloaddition reactions of ketenes are known and have been reviewed (7). 

Diketones are intermediates for synthesis of perfumes and natural products, and several preparative methods have been developed (327) in the simplest preparative methods, ketone enolates ate oxidatively dimerized (328) ... 

Bond dissociation energies (BDEs) for the oxygen—oxygen and oxygen— hydrogen bonds are 167—184 kj/mol (40.0—44.0 kcal/mol) and 375 kj/mol (89.6 kcal/mol), respectively (10,45). Heats of formation, entropies, andheat capacities of hydroperoxides have been summarized (9). Hydroperoxides exist as hydrogen-bonded dimers in nonpolar solvents and readily form hydrogen-bonded associations with ethers, alcohols, amines, ketones, sulfoxides, and carboxyhc acids (46). Other physical properties of hydroperoxides have been reported (46). 

The a-oxygen-substituted hydroperoxides and dialkyl peroxides comprise a great variety as shown in Figure 1. When discussing peroxides derived from ketones and hydrogen peroxide, (1) is often referred to as a ketone peroxide monomer and (2) as a ketone peroxide dimer. 

Addition compounds form with those organics that contain a donor atom, eg, ketonic oxygen, nitrogen, and sulfur. Thus, adducts form with amides, amines, and A/-heterocycles, as well as acid chlorides and ethers. Addition compounds also form with a number of inorganic compounds, eg, POCl (6,120). In many cases, the addition compounds are dimeric, eg, with ethyl acetate, in titanium tetrachloride-rich systems. By using ammonia, a series of amidodichlorides, Ti(NH2) Cl4, is formed (133). 

AEyl chloride reacts with sodamide in Hquid ammonia to produce benzene when sodamide is in excess, hexadiene dimer is the principal product, with some trimer and tetramer (C24, six double bonds). AEylation at carbon atoms alpha to polar groups is used in the preparation of a-aEyl-substituted ketones and nittiles. Preparation of P-diketone derivatives, methionic acid derivatives, and malonic ester, cyanoacetic ester, and P-keto-ester derivatives, etc, involving substitution on an alpha carbon between two polar carbonyl groups, is particularly facEe. 

With l,3-dimethyl-2,l-benzisoxazolium salts, however, considerable reactivity has been reported. Condensation occurs readily with aldehydes, ketones, orthoesters and diazonium salts to yield styryl, cyanine and azo compounds, respectively (78JOC1233). In the presence of triethylamine, dimerization was observed, and the reactions of the cation were considered to involve the intermediacy of the anhydro base (77JOC3929). 

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... 

Homolytic cleavage of dlazonlum salts to produce aryl radicals is induced by titan1um(III) salt, which is also effective in reducing the a-carbonylalkyl radical adduct to olefins, telotnerization of methyl vinyl ketone, and dimerization of the adduct radicals. The reaction can be used with other electron-deficient olefins, but telomerization or dimerization are important side reactions. 

A more detailed representation of the reaction requires more intimate knowledge of the enolate structure. Studies of ketone enolates in solution indicate that both tetrameric and dimeric clusters can exist Tetrahydrofliran, a solvent in which many synthetic reactions are performed, favors tetrameric structures for the lithium enolate of isobutyr-ophenone, for example. ... 

Fig. 7.3. Crystal structures of some lithium etiolates of ketones. (A) Unsolvated hexameric enolate of methyl t-butyl ketone (B) tetrahydrofuran solvate of tetramer of enolate of methyl r-butyl ketone (C) tetrahydrofuran solvate of tetramer of enolate of cyclopentanone (D) dimeric enolate of 3,3-dimethyl-4-(r-butyldimethylsiloxy)-2-pentanone. (Structural diagrams are reproduced from Refs. 66-69.) by permission of the American Chemical Society and Verlag Helvetica Chimica Acta AG.

Two classes of charged radicals derived from ketones have been well studied. Ketyls are radical anions formed by one-electron reduction of carbonyl compounds. The formation of the benzophenone radical anion by reduction with sodium metal is an example. This radical anion is deep blue in color and is veiy reactive toward both oxygen and protons. Many detailed studies on the structure and spectral properties of this and related radical anions have been carried out. A common chemical reaction of the ketyl radicals is coupling to form a diamagnetic dianion. This occurs reversibly for simple aromatic ketyls. The dimerization is promoted by protonation of one or both of the ketyls because the electrostatic repulsion is then removed. The coupling process leads to reductive dimerization of carbonyl compounds, a reaction that will be discussed in detail in Section 5.5.3 of Part B. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide... 

The reactions of A -steroids with nitrosyl fluoride parallel those of their A -isomers. Thus, 17 -acetoxyandrost-4-ene (37) is converted to the nitrimine (38), in 67 % yield and thence to the 4-ketone (39), which can be dehydrofluorinated to the A -4-ketone (40) with lithium bromide in di-methylformamide. In the corresponding 19-nor series the nitroso dimer is also formed. 

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