Irradiation aliphatic compounds

It thus seemed that the origin of the various components in meat volatiles could best be established by analyzing irradiation-induced compounds in meat protein and meat fat separately. Accordingly, a 500-gram sample of meat, the same size of sample normally used in irradiation studies of whole meat, was separated into a protein, a lipid, and a lipoprotein fraction by means of a methanol-chloroform extraction of the fat. The dry, air-free, fractions were then irradiated separately with 6 megarads of gamma radiation in the manner used for whole meat. The analytical results (Table V) show clearly that mainly sulfur compounds and aromatic hydrocarbons are formed in the protein fraction, whereas mainly aliphatic hydrocarbons are formed from the lipid. The lipoprotein fraction produced, as expected, both aliphatic hydrocarbons and sulfur compounds. Only the lipoprotein fraction had a characteristic irradiation odor. 

Irradiation of saturated aliphatic compounds typically results in imsaturation, polymerization, and isomerization. The radiolysis of cyclohexane illustrates all three of these processes. If the radicals are very energetic, cyclohexene can be formed by the abstraction of hydrogen from a cyclohexyl radical either by a hydrogen atom or by another cyclohexyl radical. If the radicals become thermalized, recombination of radicals can occur to give bicyclohexyl. A less frequent process is rearrangement, followed by hydrogen atom capture to yield methylcyclopentane. 

The irradiation of aromatic compounds results in considerably lower yields of radiolysis products than does irradiation of aliphatic compounds of similar molecular weight and functional group composition. This has been attributed to effectiveness of the delocalized 7t-orbitals in accommodating excitation energy without permitting the molecule to dissociate. Nevertheless, some radiolysis does occur. Benzene is known to yield biphenyl, phenylcyclohexadiene, and a polymeric material of average composition (C6H7) which behaves as if it were an unsaturated hydrocarbon. Dimerization and polymer formation are also characteristic of the radiation... 

The ordinates represent the viscosity increase relative to that of the material before irradiation (mostly at 100°F), so that they give a general indication of the extent of decomposition due to radiation exposure. This figure illustrates that aromatic hydrocarbons (n-butyl benzene) are more resistant to radiation damage than are aliphatic compounds (hexadecane). The most resistant of all are the polyphenyls, of which diphenyl is the simplest example. 

The reaction products formed after the reaction of COf with the substituted benzenes were determined either by GC-MS or HPLC under the described experimental conditions. Products were analysed for different irradiation times up to 10 min and for <10% reactant consumption in order to avoid secondary reactions of the reaction products. The products formed from the substrates investigated and properly identified are listed in Table 1. Aliphatic compounds of low molecular weight, i.e. containing four carbon atoms or less, are eluted with the solvent and could not be detected with our chromatographic set-up. 

By changing from the simplest to larger aliphatic and cyclic ketones, structural factors may be introduced which favor alternative unimolecular primary photoprocesses or provide pathways to products not available to the simple model compound. In addition, both the increase in molecular size and irradiation in solution facilitate rapid vibrational relaxation of the electronically excited reactant as well as the primary products to thermally equilibrated species. In this way the course of primary and secondary reactions will also become increasingly structure-selective. In a,a -unsym-metrically substituted ketones, the more substituted bond undergoes a-cleavage preferentially. 

The irradiation is usually carried out with light of the near UV region, in order to activate only ihc n n transition of the carbonyl function," thus generating excited carbonyl species. Depending on the substrate, it can be a singlet or triplet excited state. With aromatic carbonyl compounds, the reactive species are usually in a Ti-state, while with aliphatic carbonyl compounds the reactive species are in a Si-state. An excited carbonyl species reacts with a ground state alkene molecule to form an exciplex, from which in turn diradical species can be formed—e.g. 4 and 5 in the following example ... 

The imidazole ring is a privileged structure in medicinal chemistry since it is found in the core structure of a wide range of pharmaceutically active compounds efficient methods for the preparation of substituted imidazole libraries are therefore of great interest. Recently, a rapid synthetic route to imidazole-4-carboxylic acids using Wang resin was reported by Henkel (Fig. 17) [64]. An excess aliphatic or aromatic amine was added to the commercially available Wang-resin-bound 3-Ar,M-(dimethylamino)isocyano-acrylate, and the mixture was heated in a sealed vial with microwave irradi-... 

Examples of the use of heterodienophiles under the action of microwave irradiation are not common. Soufiaoui [84] and Garrigues [37] used carbonyl compounds as die-nophiles. The first example employed solvent-free conditions the second is an example of the use of graphite as a susceptor. Cycloaddition of a carbonyl compound provided a 5,6-dihydro-2H-pyran derivative. These types of reaction proceed poorly with aliphatic and aromatic aldehydes and ketones unless highly reactive dienes and/or Lewis acid catalysts are used. Reaction of 2,3-dimethyl-l,3-butadiene (31) with ethyl glyoxylate (112) occurred in 75% yield in 20 min under the action of microwave irradiation. When conventional heating is used it is necessary to heat the mixture at 150 °C for 4 h in a sealed tube to obtain a satisfactory yield (Scheme 9.33). 

The importance of tertiary amines in the photochemically induced electron transfer reactions has also been addressed5. Direct irradiation of aromatic or aliphatic amines often leads to the scission of C—N, N—H or C—H bonds that lead to the subsequent chemical reactions by radical pathways6. In this section, photochemical reactions of amines reported since 1978 will be considered with emphasis on photoinduced electron transfer. Photochemical reactions of inorganic and organometallic compounds will not be included unless photochemistry of amine moieties is the primary interest. 

An economical, practical, and environmentally acceptable procedure was elaborated for oxidative deprotection of trimethylsilyl ethers to their corresponding carbonyl compounds. The reaction proceeded in a solventless system, within a short period of time, and yields were good. On irradiation in a conventional microwave for 30 s, trimethylsilyl ether of benzyl alcohol in the presence of mont-morilonite KIO and finely grounded Fe(N03)3 9H2O gave rise to benzaldehyde in 95% yield. The applicability of this method was tested with several aromatic, alicyclic, and aliphatic trimethylsilyl ethers. Duration did not exceed 1 min, and yields were not lower than 80% (Mojtahedi et al. 1999). 

The photochemistry of a number of long chain aliphatic a-diketones has been reported.46 68 Included in the study were 2,3-pentanedione, 3,4-hexane-dione, 4,5-octanedione, 5,6-decanedione, 2,7-dimethyl-4,5-octanedione, and 1,2-cyclodecanedione. Without exception, irradiation of these compounds in cyclohexane or benzene yielded cyclobutanols, presumably by an internal abstraction-cyclization mechanism. The reaction is quite selective, producing... 

The most recent published report of a photochemical transformation of a substituted ferrocene is by this reviewer.45 Compound 12 is irradiated in an aliphatic hydrocarbon and one of the products is benzoylferrocene. This trans-... 

Monocyclic 1,3-oxazepines (325) with aryl substituents at the 2-, 4- and 7-positions can be prepared in moderate yield (20-40%) by the reaction of aliphatic diazo compounds with 1,3-oxazinium perchlorates (324) (74S187). Tetra- and penta-phenyl-l,3-oxazepines (328 R = H or Ph) have been obtained via the reaction of azide with pyrylium salts (326) (78H(l 1)331). This principle had earlier been applied to the preparation of 1,3-benzoxazepines (74CR(C)(278)1389> and more recently to 3,1-benzoxazepines (81JHC847). The preparation of 2-phenyl-1,3-oxazepine.(331) by the UV irradiation of (329) is mechanistically interesting in that it apparently involves an intermediate (330) of the same type as (327) (73TL1835), but the method has only been used in this one case. One of the few examples of a dihydro-1,3-oxazepine (333) has been prepared by the thermolysis of the aziridine (332) (68JOC4547). 

Extender oils were foxmd to cause a considerable increase in the dose required to attain the optimum cure. This can be explained by reaction of transienf infermediafes formed on the irradiated polymer chain with the oil and with the energy transfer, which is particularly effective when the oil contains aromatic groups. Thus, the ranking of oils as to their cure inhibition is aromatic > naphtenic > aliphatic. This aspect is very important because many carbon-black-reinforced EPDM compounds contain frequently 100 phr or more oil. 

Organic azides (RNS) are isoelectronic with diazo-compounds, and like them are yellow in colour. On irradiation azides lose nitrogen to produce monovalent nitrogen species, nitrenes lRN . In the absence of an addend, aliphatic nitrenes generally undergoa shift of hydrogen to give an imine (5.34), whereas aromatic nitrenes can dimerize to yield an azo-compound (S.3SI. 

The first report on a successful microwave-assisted one-step reduction of ketones to their respective hydrocarbons via the hydrazones appeared in 20 0 265. This so called Huang-Minlon variant of the Wolff-Kishner reduction was successfully applied to some aromatic and aliphatic aldehydes and ketones, including intermediates in the synthesis of the alkaloid flavopereirine. The reactions were performed by mixing the carbonyl compound with 2 equiv of hydrazine hydrate and an excess of powdered KOH in a commercial microwave oven. The mixtures were irradiated at 150 W for a few minutes before 250-350 W irradiations were applied (Scheme 4.39). The reaction was shown... 

Most of the other products found in irradiated meat volatiles except those containing sulfur or aromatic rings may also be accounted for by mechanisms associated with alkyl free radical formation in the fat. Oxygenated compounds are far less abundant than hydrocarbons, but appreciable amounts of a homologous series of n-aliphatic alcohols up to hexanol are found. Of these, only ethanol is detected in the unirradiated controls. Since the water content of meat averages nearly 60%, the formation of alcohols may be thought to occur by reaction of the alkyl free radical with water. Such a mechanism is supported by the fact that only traces of alcohols are found in irradiated dry butterfat and were undetected in irradiated triglycerides or methyl esters of fatty acids. 

The most common routes to carbenes27 are also the major ones to generate silylcar-benes, namely dediazoniation of aliphatic diazo compounds and a-elimination reactions (Scheme 1). The extrusion of N2 from silyl-substituted diazo compounds can be achieved by UV-irradiation or thermally. The thermal decomposition, however, is of less importance since these diazo compounds are thermally much more stable than their nonsilylated counterparts, so that thermal impact may stimulate noncarbene pathways. 

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