Acetophenone, degradation

Our recent studies on effective bromination and oxidation using benzyltrimethylammonium tribromide (BTMA Br3), stable solid, are described. Those involve electrophilic bromination of aromatic compounds such as phenols, aromatic amines, aromatic ethers, acetanilides, arenes, and thiophene, a-bromination of arenes and acetophenones, and also bromo-addition to alkenes by the use of BTMA Br3. Furthermore, oxidation of alcohols, ethers, 1,4-benzenediols, hindered phenols, primary amines, hydrazo compounds, sulfides, and thiols, haloform reaction of methylketones, N-bromination of amides, Hofmann degradation of amides, and preparation of acylureas and carbamates by the use of BTMA Br3 are also presented. 

The phenylacetaldehyde reductase involved in the degradation of styrene is also able to accept long-chain aliphatic aldehydes and ketones, and halogenated acetophenones (Itoh et al. 1997). 

Havel J, W Reineke (1993) Microbial degradation of chlorinated acetophenones. Appl Environ Microbiol 59 2706-2712. 

Higson FK, DD Focht (1990) Bacterial degradation of ring-chlorinated acetophenones. Appl Environ Microbiol 56 3678-3685. 

Several pathways are used for the aerobic degradation of aromatic compounds with an oxygenated C2 or C3 side chain. These include acetophenones and reduced compounds that may be oxidized to acetophenones, and compounds including tropic acid, styrene, and phenylethylamine that can be metabolized to phenylacetate, which has already been discussed. 

FIGURE 8.35 Degradation of (a) mandelate, (b) 4-hydroxyacetophenone by side-chain oxidation pathways, (c) acetophenone by Baeyer-Villiger monooxygenation. 

Control experiments do not provide evidence for oxidation of the secondary alcohol groups in the glycoside or for degradation of the ligand backbone. A similar regioselectivity was also observed in a benzyl alcohol/1-phenylethanol model system that showed no proof for the oxidation of the secondary alcohol by formation of acetophenone (18, 23,26). 

In the later work, low optical activity (<30% ee) was observed for the products [e.g. 5] and the high asymmetric induction of the earlier work was attributed to carry over of the catalyst or chiral degradation derivatives (oxiranes) of the catalysts. Although the reported stereoselective reduction of acetophenone has been discredited, it has been suggested that the use of a chiral solvent, such as menthyl methyl ether, enhances the asymmetric reduction [7], The veracity of this claim has not been proven. 

The most direct route towards functionalized aliphatic polyesters is based on the functionalization of polyester chains. This approach is a very appealing because a wide range of functionalized aliphatic polyesters could then be made available from a single precursor. This approach was implemented by Vert and coworkers using a two-step process. Eirst, PCL was metallated by lithium diisopropylamide with formation of a poly(enolate). Second, the poly(enolate) was reacted with an electrophile such as naphthoyl chloride [101], benzylchloroformate [101] acetophenone [101], benzaldehyde [101], carbon dioxide [102] tritiated water [103], ot-bromoacetoxy-co-methoxy-poly(ethylene oxide) [104], or iodine [105] (Fig. 26). The implementation of this strategy is, however, difficult because of a severe competition between chain metallation and chain degradation. Moreover, the content of functionalization is quite low (<30%), even under optimized conditions. 

Table I shows that in either dioxane or acetonitrile the quantum yield for degradation of I, is unaffected by the presence of 0.1 M of triplet quencher, either sorbic acid, naphthalene or cyclohexadiene. In ethanol, triplet quenchers reduce < >d from 0.34 to 0.14. Quantum yields for intersystem crossing, as determined by a laser opto-acoustic technique ( ), were 0.36 in ethanol and 0.59 in dioxane. These results agree with our earlier report (3), and indicate that significant reactivity occurs from St of I in protic solvents, and that reaction occurs exclusively from Sx in aprotic solvents. While triplet quenching experiments cannot rigorously exclude participation by short-lived higher triplet states, Palm et al (9) have obtained conclusive evidence from CIDNP experiments for singlet-state participation in a series of aryloxy-acetophenones. Note that the triplet state of I is formed in aprotic solvents, and that in deaerated solutions at room temperature it decays by first-order kinetics with a lifetime of 200 ns (3). Remarkably, despite having lifetimes about 100 times longer than other, differently-substituted, aryloxyacetophenones (the longer lifetimes may...

In contrast to polymerisates, polycondensates can not be depolymerized under inert conditions. Decomposition usually leads to the destruction of the chemical structure and the monomers. The thermal decomposition of PET starts at about 300°C in an inert atmosphere [25]. Between 320 and 380°C the main products are acetaldehyde, terephthalic acid, and carbon oxides under liquefaction conditions. The amounts of benzene, benzoic acid, acetophenone, C1-C4 hydrocarbons, and carbon oxides increase with the temperature. This led to the conclusion that a P-CH hydrogen transfer takes place as shown in Eigure 25.8 [26]. Today the P-CH-hydrogen transfer is replaced as a main reaction in PET degradation by several analytic methods to be described in the following sections. The most important are thermogravimetry (TG) and differential scanning calorimetry (DSC) coupled with mass spectroscopy and infrared spectroscopy. 

Thermal degradation led to the oxo compounds including [(N02)N0)][Ti0(F3CS03)4], Tilv triflate complexes efFiciently catalyze a variety of reactions including the conversion of acetophenones to 1,3,5-triarylbenzenes,658 the nucleophilic ring opening of epoxides,659 Diels—Alder reactions,660 selective Claisen and Dieckmann ester condensations,661 esterification reactions,662 Fries rearrangements,663 homoaldol reactions,664 sequential cationic and anionic polymerizations,641 and the stereoselective synthesis of m-arabinofuranosides.606... 

The fate of diazirines on decomposition can be influenced by the addition of y -cyclodextrin (j6-CD). When 3-methyl-3-phenyl-3jf/-diazirine (3) was thermolyzed under argon, 1 -methyl-1,2-diphenylcyclopropane (4) was obtained as an isomeric mixture in close to 20% yield the main product (43% yield) was acetophenone azine (5). Cyclodextrin complexation prior to pyrolysis, however, increased the yield of 4 tremendously. The carbohydrate, therefore, facilitates both styrene (6) and cyclopropane formation.It is also interesting to note that the trans-41 cis-4 ratio increased concomitantly and that styrene appears as an isolable product after photochemical, but not after thermal degradation of the 3 /(-CD complex. 

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