1 -nonenes, addition

Acyl halides are intermediates of the carbonylations of alkenes and organic-halides. Decarbonylation of acyl halides as a reversible process of the carbo-nylation is possible with Pd catalyst. The decarbonylation of aliphatic acid chlorides proceeds with Pd(0) catalyst, such as Pd on carbon or PdC, at around 200 °C[109,753]. The product is a mixture of isomeric internal alkenes. For example, when decanoyl chloride is heated with PdCF at 200 C in a distillation flask, rapid evolution of CO and HCl stops after I h, during which time a mixture of nonene isomers was distilled off in a high yield. The decarbonylation of phenylpropionyl chloride (883) affords styrene (53%). In addition, l,5-diphenyl-l-penten-3-one (884) is obtained as a byproduct (10%). formed by the insertion of styrene into the acyl chloride. Formation of the latter supports the formation of acylpalladium species as an intermediate of the decarbonylation. Decarbonylation of the benzoyl chloride 885 can be carried out in good yields at 360 with Pd on carbon as a catalyst, yielding the aryl chloride 886[754]. 

Scheme 2.2 Cu-catalysed 1,4-additions of ZnEt2 and AlMe3 to ( )-3-nonen-2-one with 1,1 -binaphthalene-derived ligands.

Nitroxyl radicals as alkyl radical acceptors are known to be very weak antioxidants due to the extremely fast addition of dioxygen to alkyl radicals (see Chapter 2). They retard the oxidation of solid polymers due to specific features of free radical reactions in the solid polymer matrix (see Chapter 19). However, the combination of two inhibitors, one is the peroxyl radical acceptor (phenol, aromatic amine) and another is the alkyl radical acceptor (nitroxyl radical) showed the synergistic action [44-46]. The results of testing the combination of nitroxyl radical (>NO ) (2,2,6,6-tetramethyl-4-benzoylpiperidine-l-oxyl) + amine (phenol) in the autoxidation of nonene-1 at 393 K are given here ([>NO ]o + [InH]o = 1.5 x 10 4mol L 1 p02 98 kPa) [44]. 

Bicyclo[4.3.0]nonenes, thanks to their frequent appearance in natural products, are other important targets for novel annulation methodology. A six-membered ring-annulation to cyclopentenones has yet to be developed, the main reason for this being that, until very recently, the levels of enantioselectivity in catalytic 1,4-additions to 2-cyclopentenone were too low for a synthetically useful procedure. However, a highly enantioselective annulation of a five-membered ring to 2-cyclo-hexenone has been developed (Scheme 7.26) [80]. 

Crust volatiles were isolated immediately after baking by extraction with dichloromethane and sublimation in vacuo ( ). Application of aroma extract dilution analysis 6) to the acid-free crust extract led to the detection of 31 odorants. After separation and enrichment, these compounds were identified by comparison of the MS/EI, MS/Cl and retention data on two columns of different polarity to reference compounds. Aroma quality was also assessed. The results of the identification experiments (Table I) revealed that 2(E)-none-nal (No. 1), followed by 2(E),4(E)-decadienal (No. 2) and 3-methyl-butanal (No. 3) showed the highest FD-factors in the crust of the chemically leavened bread. Additionally l-octen-3-one, 2(Z)-nonenal, 2(E),4(E)-nonadienal and an unknown compound with a metallic odor contributed high FD-factors to the overall flavor (For a discussion of FD-factors, see Chapter by Schieberle and Grosch, this book). 

The flavor compounds of the crust from the chemically leavened model bread were then compared to those recently identified (6) in the crust of a standard wheat bread which was leavened by addition of yeast (Table I). One striking difference was that Acp (No. 16), which showed the highest FD-factor in the yeast-leavened bread showed a very low FD-factor in the chemically leavened bread. This indicated, that the flour contained only minor amounts of the precursor (s) for the formation of Acp. On the other hand, 2(E),4(E)-decadienal, 2(E),4(E)-nonadienal, l-octen-3-one and 2(Z)-nonenal, which are undoubtedly formed by a heat-induced oxidative degradation of the flour lipids, became predominant odorants in the chemically leavened compared to the yeast-leavened bread. 

Despite the above difficulties, several specific chemicals have been associated with specific off-flavors in dairy products. Forss et al. (1955a,b) reported that -hexanal, 2-octenal, 2-nonenal, 2,4-heptadienal and 2,4-nonadienal are the principal carbonyls contributing to the copper-induced cardboard off-flavor in milk. Hall and Lingnert (1986) associated this flavor defect with n-hexanal in spray-dried whole milk. l-Octen-3-one has been associated with a metallic off-flavor in dairy products (Stark and Forss, 1962), the metallic off-flavor being reproduced by addition of l-octen-3-one to milk or cream (Bassette et al., 1986). l-Octen-3-one has a threshold concentration of 1 pg/kg in butterfat (Shipe et al., 1978). 

The manufacturing processes for these materials are very similar to the one for cumene. When nonene is the desired product, additional fractionation is required, the extent of which is determined by product specifications. 

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