Extrusion from ketones

The carbanion generated from deprotonation of the w-carbon atom of sulpholene reacts with aldehydes and ketones to give alcohols. Sulphur dioxide extrusion from the products results in (E)-a-hydroxy-l,3-dienes (equation 72), or dehydration followed by thermal desulphonylation results in trienes117. Dienones can be obtained if the initial condensation is conducted with an aldehyde, followed by oxidation and sulphur dioxide removal117. 

Compared to the time scale of their formation, the carbonyl oxides are quite long lived (10 -10 s), and so their subsequent reactions can be monitored kinetically. For most of the carbonyl oxides, the decay is best fit to a second-order rate law, indicating a bimolecular decomposition pathway. For benzophenone oxide, the ketone is the major product at room temperature, and no dimer can be detected. A bimolecular process involving O2 extrusion from two molecules of the oxides is suggested under these conditions. 

Silylene extrusion from siliranes in the presence of alkynes, notably bis(trimethyl-siiyl)acetylene, gives the silirene (35) in good yield (Scheme 41) (76JA6382). Compound (35) is more stable thermally than hexamethylsilirane and shows 2 Si NMR absorptions for the ring atom at 5 = 106.2 p.p.m., some 50 p.p.m. downfieid from those of silacyclopropanes, and about 100 p.p.m. downfieid from normal cyclic and acyclic tetraalkylsilanes. Notable reactions include alcoholysis and the insertion of aldehydes and ketones, dimethylsilylene... 

Norrish Type I cleavage reactions dominate in the gas phase photochemistry of many acyclic aldehydes and ketones, whereas in the liquid phase this process is less common and alternative pathways (ii, iii, v) dominate. When no suitable C-H bonds are present to allow hydrogen abstraction reactions, however, this process will also constitute an important synthetic method for the cleavage of a-C-C bonds in solution. One important subsequent reaction of the resulting acyl and alkyl radicals is carbon monoxide formation and radical combination. Overall CO extrusion results which represents a versatile method for the formation of C-C single bonds from ketones. When cyclic substrates (cycloalkanones but not conjugated cycloalkenones which exhibit a different photochemistry) are used, ring... 

Although the enolate of ketone (179) may be prepared and O-alkylated, the ketone itself is not reported to enolize in solution <77X2i5i>. Acetoxy-1,4-dithiocin (176 R = Ac) is thermally unstable, decomposing when heated above 50 °C with extrusion of sulfur. By analogy with related studies of other 1,4-diheterocins and with the failure of attempts to prepare the parent 1,4-dithiocin via the valence tautomerization of benzene disulfides <74AG818>, it is proposed that this thermal decomposition occurs via thermal valence tautomerization in the reverse direction, followed by sulfur extrusion from the so-formed arene disulfide (Scheme 58) <78X363i>. 

Polyaryl ether ketones may be processed on conventional injection moulding and extrusion equipment, providing sufficiently high temperatures can be achieved. Melt temperatures required are typically 370°C for unreinforced PEEK, 390°C for reinforced PEEK and both unreinforced and reinforced PEK and unreinforced PEEKK, and 410°C for reinforced PEEKK. For the latter material a temperature profile from feed zone to nozzle would be... 

This group has also developed two ring-contraction systems of potential use in crown synthesis. In the first of these, extrusion of a phenylphosphine oxide unit results from treatment with alkoxide ion. In the second, similar conditions initiated decarbonyla-tion of a bis-pyridyl ketone Despite the apparent potential of these methods for crown synthesis, direct formation of crowns by processes which involve them do not appear to have enjoyed great success thus far. 

When 3,4-dichlorothiophene 1,1-dioxide (186) is treated with 2,5-dimethylfuran (187) at 50 °C, the adduct 188 can be obtained in 68% yield. Treatment of the reaction mixture at 93 °C gives the ketone 190 in 77% yield via extrusion of S02 from 188 a,nd the rearrangement of 189 (equation 124)117. Other examples are listed in Table 14. 

Diazaphospholes are known to undergo facile 1,3-dipolar cycloaddditions with a variety of dipoles [2, 4, 7, 98], During recent years, some interesting [2+3] cycloaddition reactions have been reported. 2-Acyl-[l,2,3]diazaphospholes 6 were reported to undergo [2+3] cycloaddition with diazocumulene 92, the minor equilibrium isomer of a-diazo-a-silyl ketones 91, to form a bicyclic cycloadduct 93 (Scheme 29). Thermolysis of the cycloadduct results in the formation of tricyclic phosphorus heterocycle 94, which can be explained due to the possibility of two parallel reactions of cycloadduct. On the one hand, extrusion of molecular nitrogen from 93... 

Three types of photoextrusion reactions have been identified in the irradiation of aryl-substituted 1,3,2-dioxathiolane 2-oxides [5 1-1-2 4-2] cycloelimination to produce a carbonyl compound, a carbene and sulfur dioxide extrusion of sulfur dioxide accompanied by a pinacol-like rearrangement to yield an aldehyde or ketone and extrusion of sulfur trioxide to give an alkene <72JOC2589>. Sensitization and quenching experiments indicate that a singlet state is responsible for the cycloelimination reaction, whereas the rearrangement and sulfur trioxide extrusion reactions arise from a triplet state <82JCR(S)175>. 

An enantioselective synthesis of (+)-estradiol has been accomplished from 1,3-dihy-drobenzo[c]thiophene 2,2-dioxide (306) by successive thermal S02-extrusion and cycloaddition (80HCA1703). Treatment of the optically active iodide (307) with two mole equivalents of the masked quinodimethane (306) in the presence of two mole equivalents of sodium hydride gave (308) as a 1 1 mixture of diastereoisomers. Thermolysis of this alkenic sulfone in 1,2,4-trichlorobenzene furnished the trans-anti-trans steroid (309) in 80% yield. Treatment of (309) with methyllithium gave the methyl ketone, which was subjected to a Baeyer-Villiger oxidation and then silyl ether-acetate cleavage to afford (-l-)-estradiol (310 Scheme 66). 

Two of these ketones, 2-heptanone and 2-octanone, have been identified among the thermal decomposition products of corn oil, and their quantities were found to increase when corn oil was oxidized in the presence of zein (4). The effect of an increased surface area for reaction between zein and corn oil during extrusion is hard to determine from these data. 

Tomboulian et al. (2002) has reported that butylated hydroxytoluene (BHT) can impart a "burnt plastic" odor and is an additive in HDPE pipes. Quinone may be derived from BHT due to interactions with residual chlorine in pipes (Anselme et al., 1985). Yam et al. (1996) reported that antioxidants, such as vitamin E, Irganox 1010, and BHT, contributed to off-flavors in water. Vitamin E yielded less off-flavor, possibly due to lower aldehyde and ketone concentrations. Extrusion temperatures over 280 °C and exposure time for melt contributed to more oxidation of LDPE films and higher intensities of off-flavors in water in contact with LDPE with different antioxidants (Andersson et al., 2005). 

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