Reaction of spironaphthalenones with hydroxylamine: Part III. A novel mechanism for the formation of products and trapping of an intermediate.

A mechanism involving the intermediacy of nitrene 5, formed from the oxime of spironaphthalenone 1 by acid catalysed dehydration, has been proposed to explain the formation of pyrrolotropones/pyrrolo esters from spironaphthalenones. The initially formed nitrene rearranges to the isopyrrole 6, which either undergoes sigmatropic migration to the pyrrolotropone 2 or adds alcohol to form the pyrrolo ester depending on substitution at 1′ position. The isopyrrole intermediate 6 has been trapped as a Diels-Alder adduct 8.

Asymmetric Diels-Alder Reactions of Chiral Acrylates of Cholic Acid Derivatives

New steroid-based chiral auxiliaries 6, 9, and 12 have been synthesized from readily available cholic acid. These new chiral auxiliaries place the reactive and the shielding sites in a 1,5 relationship to each other. Diels-Alder reaction of cyclopentadiene with corresponding acrylate esters (7, 10, and 13) have been examined. Acrylates 7 and 10 yielded cycloadducts with 29-88% diastereomeric excess with excellent endo selectivity in the presence of an excess of Lewis acids such as AlCl3, BF3.OEt(2), FeCl3, SnCl4, TiCl4, and ZnCl2. Treatment of acrylate 7 with cyclopentadiene in the presence of BF3.OEt(2) at -80 degrees C gave the endo adduct (>99%) with 88% de. Lewis acid catalyzed and uncatalyzed reactions of acrylates 7 and 10 with cyclopentadiene yielded cycloadducts with opposite stereochemistry. The chiral auxiliary was recovered in a nondestructive manner only via iodolactonization. Acrylate ester of alcohol 12 did not show any selectivity in either catalyzed and uncatalyzed reactions with cyclopentadiene. The presence of a flat aromatic surface at C-7 of the steroid was found to be essential to effect high diastereoselection.

Dialkylaminopyridine catalysed esterolysis of p-nitrophenyl alkanoates in different cationic microemulsions

The reactions of p-nitrophenyl alkanoate esters with dialkylaminopyridine (DAAP) and its related mono- and di-anionic water-soluble derivatives have been studied separately in three different microemulsion (ME) media. These were (a) oil-in-water ME (O/W), (b) water-in-oil ME (W/O) and (c) a bicontinuous ME, where oil and water are in nearly comparable amounts. All the ME systems were stabilized by cationic surfactant, cetyltrimethylammonium bromide (CTABr) and butanol as a cosurfactant. The second-order rate constants (k(2)) in the microemulsion media were also determined : over a phase volume (phi) of approximately 0.13-0.46. In order to explain the contribution of effective concentration of the nucleophiles in the aqueous pseudophase, corrected rate constants k(2 phi) = k(2)(1 - phi) were obtained, The rate constants of the corresponding hydrolytic reactions were also examined in CTABr micelles. While the DAAP catalysts were partitioned between the micellar and aqueous pseudophases in ME, the hydrophobic substrates were found to be mainly confined to oil-rich phases, Present results indicate that the main effect of ME media on the hydrolysis reaction is due,to both electrostatic reasons and substrate partitioning.

The generation of carbonyl compounds from acetals and ketals by iodotrichlorosilane (ITCS)

Cheap and readily available iodotrichlorosilane (SiCl4 / NaI) readily regenerates aldehydes and ketones from cyclic and acyclic acetals and ketals, in 20–60 min at ambient temperature. The reaction is highly chemoselective as phenolic ethers and esters are not cleaved. The pathway for the process is unlike any previously proposed.

Thermodynamics of flow and vaporization processes in long-chain liquids

The flow and vaporization behaviors of long-chain esters of varying molecular weights (300-900) ana branching (linear, Y-shaped, and +-shaped molecules) have been studied. The flow behavior is found to depend on the structure as well as the molecular weight. Below a molecular weight of 600, the molecules flow wholly but above this, segmental motion occurs, and the flow becomes independent of the molecular weight which is explained from the blob model. The blob concept demonstrates that the hole of a size of about 11 angstrom is needed for the flow to occur and it is much less than the size of the molecule. The blob size is observed to slightly decrease along the series linear and Y- and +-branched esters. The heat of vaporization is found to be independent of the molecular structure since the molecules acquire a coiled spherical shape during vaporization and hence depends only on the molecular weight. A significant structural effect is observed for the esters on their glass transition temperature (T(g)). The T(g) vs molecular weight plot displays contrasting trend for linear and +-branched esters, with Y esters showing an intermediate behavior. It is explained from their molecular packing and entanglement as visualized by the blob model.

Synthesis and esterolytic chemistry of some (dialkylamino) pyridine-functionalized micellar aggregates. Evidence of catalytic turnover

Four new (dialkylamino)pyridine-functionalized surfactants have been synthesized. Micelles were generated either from the surfactant alone in aqueous buffer (pH 8.5 or 9.0) or by comicellization in 1 x 10(-3)-1 x 10(-4) M aqueous micellar cetyltrimethylammonium bromide (CTABr) solution at pH 8.5 or 9.0. Such aggregates were used to cleave p-nitrophenyl alkanoates or p-nitrophenyl diphenylphosphate. The nucleophilic reagents and the second-order ''catalytic'' rate constants toward esterolysis of the substrate p-nitrophenyl octanoate (at 25 degrees C, pH 9.0) were [cat.] = 1 x 10(-4) M, [CTABr] = 1 x 10(-3) M, and k(cat.) = 440.13 M(-1) s(-1) for 1b, [cat.] = 5 x 10(-4) M, [CTABr] = 5 x 10(-4) M, and k(cat.) = 30.8 M(-1) s(-1) for 1c, [cat.] = 5 x 10(-4) M, [CTABr] = 5 x 10(-3) M, and k(cat.) = 183.64 M(-1) s(-1) for 2a, and [cat.] = 3 x 10(-4) M and k(cat.) = 54.1 M(-1) s(-1) for 2b. The catalytic systems, especially 1b/CTABr and 2a/CTABr, also conferred significantly greater reactivity toward the esters derived from alkanoic acids of moderate chain length (C-6-C-10) during hydrolytic cleavages relative to their shorter and longer counterparts. Importantly, the catalytic systems comprising the coaggregates of either neutral 1b and CTABr (1:10) or anionic 2a and CTABr (1:10) conformed to the Michaelis-Menten kinetic scheme and demonstrated turnover behavior in the presence of excess substrate.

A new strategy for the alpha-vinylation of ketones: Application to an enantioselective synthesis of sesquiterpene (+)-alpha-elemene

A new, simple and preparatively useful protocol for the construction of a-vinyl ketones, particularly those bearing a quaternary carbon centre, from the corresponding alkenes has been devised. Our four-step strategy consists of dichloroketene addition, base catalysed ring contraction to 'push-pull' cyclopropane esters, reduction and eliminative cyclopropane fragmentation to unravel the a-vinyl ketone moiety. The generality of this approach has been demonstrated with a few representative olefins and good regio- and stereocontrol has been observed. As an application of this methodology, an enantioselective synthesis of sesquiterpene hydrocarbon (+)-alpha-elemene (42) from R-(+)-limonene (43) has been accomplished.

Chiral Mitsunobu reactions with (1S)-(+)-ketopinic acid: kinetic resolutions of secondary alcohols

Several secondary alcohols undergo the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and (1S)-(+)-ketopinic acid (0.5 equiv. each relative to alcohol) in CH2Cl2 solution at -23degreesC, to furnish the chiral secondary alcohol and its ketopinate ester (d.e. >95%,). Chromatographic separation of these and subsequent hydrolysis of the ketopinate ester (KOH EtOH/0degreesC) provides the chiral secondary alcohol in overall yields of similar to75% and e.e. of similar to80%. When the above Mitsunobu reaction is performed with 1 equiv. of all the reactants. an effective dynamic kinetic resolution of the alcohol is observed in two cases, the ketopinate esters being isolated in 63 and 75% yields and >95% d.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

Enzymatic synthesis of flavors in supercritical carbon dioxide

Commercially important flavor esters of isoamyl alcohol, catalyzed by crude hog pancreas lipase (HPL), were synthesized under solvent-free conditions and in supercritical carbon dioxide. The esters synthesized were isoamyl acetate, isoamyl propionate, isoamyl butyrate, and isoamyl octanoate. Very low yields (3-4%) of isoamyl acetate were obtained, but high yields for the other three esters were obtained under both supercritical and solvent-free conditions. The yields of esters of the even-carbon acids, isoamyl acetate, butyrate, and octanoate, increased with increasing chain length, whereas the yield of isoamyl propionate was higher than that of isoamyl butyrate. The optimum temperature of the reaction was higher under supercritical conditions (45 degreesC) than under solvent-free conditions (35-40 degreesC). The effects of other parameters such as alcohol concentration, water concentration, and enzyme loading were investigated. An increase in the water concentration decreased the conversion significantly in supercritical carbon dioxide but not under solvent-free conditions. The optimum ratio of alcohol to acid was dependent on the extent of inhibition by the acid. Although providing a higher apparent yield by being run in a highly concentrated medium, the overall conversion under solvent-free conditions was lower than that under supercritical conditions for similar enzyme concentrations, indicating that the synthesis of esters in supercritical carbon dioxide might be a viable option.

Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites: Role of cation-guest binding

Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenyleylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20% ee and 55% de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum similar to10% ee).

Michael addition of masked thiolates to conjugated systems in aqueous media promoted by ammonium tetrathiomolybdate

Thiolates generated in situ by the action of ammonium tetrathiomolybdate on alkyl halides, thiocyanates and disulfides undergo Michael addition to alpha,beta-unsaturated esters, nitriles :and ketones in water under neutral conditions.

Pyrene appended bile acid conjugates: Synthesis and a structure-gelation property study

A wide variety of novel compounds obtained by combining two types of known organogelators, viz., bile acid alkyl amides and pyrene alkanoic acids, were synthesized and screened for their gelation ability. The 3 alpha esters of 1-pyrene butyric acid (PBA) of alkylamides of deoxycholic acid (DCA) turned out to be effective in the gel formation with many organic solvents although the gelation has to be triggered by the addition of a charge transfer (CT) agent 2,4,7-trinitrofluorenone (TNF). The special feature of these molecules is that the organogelation is achieved only after derivatizing the acid moiety of the 1-pyrenealkanoic acids. Additionally, the gelation properties can be fine-tuned by inserting different functional groups at the bile acid side chain. The gels obtained are deep red in colour and optically transparent up to 2% w/v. The SEM studies of the obtained xerogels revealed bundled rod-like morphology without specialized branching.

Dispersion and vaporization of biofuels and conventional fuels in a crossflow pre-mixer

In lean premixed pre-vaporized (LPP) combustion, controlled atomization, dispersion and vaporization of different types of liquid fuel in the premixer are the key factors required to stabilize the combustion process and improve the efficiency. The dispersion and vaporization process for biofuels and conventional fuels sprayed into a crossflow pre-mixer have been simulated and analyzed with respect to vaporization rate, degree of mixedness and homogeneity. Two major biofuels under investigation are Ethanol and Rapeseed Methyl Esters (RME), while conventional fuels are gasoline and jet-A. First, the numerical code is validated by comparing with the experimental data of single n-heptane and decane droplet evaporating under both moderate and high temperature convective air now. Next, the spray simulations were conducted with monodispersed droplets with an initial diameter of 80 mu m injected into a turbulent crossflow of air with a typical velocity of 10 m/s and temperature of around 800K. Vaporization time scales of different fuels are found to be very different. The droplet diameter reduction and surface temperature rise were found to be strongly dependent on the fuel properties. Gasoline droplet exhibited a much faster vaporization due a combination of higher vapor pressure and smaller latent heat of vaporization compared to other fuels. Mono-dispersed spray was adopted with the expectation of achieving more homogeneous fuel droplet size than poly-dispersed spray. However, the diameter histogram in the zone near the pre-mixer exit shows a large range of droplet diameter distributions for all the fuels. In order to improve the vaporization performance, fuels were pre-heated before injection. Results show that the Sauter mean diameter of ethanol improved from 52.8% of the initial injection size to 48.2%, while jet-A improved from 48.4% to 18.6% and RME improved from 63.5% to 31.3%. The diameter histogram showed improved vaporization performance of jet-A. (C) 2011 Elsevier Ltd. All rights reserved.

When should fig fruit produce volatiles? Pattern in a ripening process

Ripe fruit need to signal their presence to attract dispersal agents. Plants may employ visual and/or olfactory sensory channels to signal the presence of ripe fruit. Visual signals of ripe fruit have been extensively investigated. However, the volatile signatures of ripe fruit that use olfactorily-oriented dispersers have been scarcely investigated. Moreover, as in flowers, where floral scents are produced at times when pollinators are active (diurnal versus nocturnal), whether plants can modulate the olfactory signal to produce fruit odours when dispersers are active in the diel cycle is completely unknown. We investigated day night differences in fruit odours in two species of figs, Ficus racemosa and Ficus benghalensis. The volatile bouquet of fruit of F.racemosa that are largely dispersed by bats and other mammals was dominated by fatty acid derivatives such as esters. In this species in which the ripe fig phase is very short, and where the figs drop off soon after ripening, there were no differences between day and night in fruit volatile signature. The volatile bouquet of fruit of F. benghalensis that has a long ripening period, however, and that remain attached to the tree for extended periods when ripe, showed an increase in fatty acid derivatives such as esters and of benzenoids such as benzaldehyde at night when they are dispersed by bats, and an elevation of sesquiterpenes during the day when they are dispersed by birds. For the first time we provide data that suggest that the volatile signal produced by fruit can show did l differences based on the activity period of the dispersal agent. (C) 2011 Elsevier Masson SAS. All rights reserved.

Dioxomolybdenum reagents in organic synthesis: utility of redox capability to design reduction and oxidation

The usefulness of dioxomolybdenum reagents in oxo-transfer reactions have been reviewed. The redox ability of dioxomolybdenum reagent has been utilized in designing several synthetic methods, which are useful in organic synthesis. Several reactions such as oxidation of alcohols, sulfides, amines, azides olefins etc are accomplished by using dioxomolybdenum reagents. Similarly, it is also demonstrated that dioxomolybdenum complex is useful in performing reduction of aldehydes, ketones, esters, azides etc. A fine tuning of reaction conditions provides suitable conditions to perform either oxidation or reduction by using catalytic amount of reagents. The oxidation reactions are further simplified by employing the polymer supported molybdenum reagents.