Photochemical transformations of pyridinium salts: mechanistic studies and applications in synthesis

The discovery, understanding and synthetic exploitation of the photochemical transformation of pyridinium salts are described. The investigations surrounding the remarkable transformation of pyridinium salts into a host of structurally complex motifs have helped extend the comprehension of aromatic and heteroaromatic photochemistry. The synthetic community has, in recent years, recognised the potential inherent in these compounds and has since exploited the irradiation of variously substituted pyridinium salts as key steps in the preparation of advanced intermediates in numerous synthetic programmes.     

Photochemical synthesis of diaza-steroids

N-Iminopyridinium ylides 12 and 13 readily undergo regio-specific photoinduced ring expansion to the isomeric 1,2-diazepines 14 and 15 respectively. Similarly UV irradiation of the steroidal N-iminopyridinium ylide 25, which can be obtained from 19-nortestosterone, leads quantitatively and in a regiospecific manner to the corresponding diazepine 26. In a second photochemical reaction 26 gives the cyclobutene derivative 27. Variable temperature ¹H NMR and OCD measurements of the optically active diazepine 26 indicate that one of the two possible diastereoisomeric conformations is preferred.     

Photochemical reactivity of 9-vinyladenine with diethyl fumarate

The photochemical reaction between 9-vinyladenine ( 2 ) and diethyl fumarate ( 4 ) gave an unusual photoadduct, epimers 4 and 5 , probably derived from attack of the vinyl group on N-3 and reaction of diethyl fumarate on N-9 and N-6.     

Photochemical synthesis of tetraaryl-substituted pentacenes

The syntheses of 1,4,8,11-tetraphenylpentacene and 1,4,8,11-tetra(2′-thienyl)pentacene are described via photodecarbonylation of the corresponding α-diketone precursors.     

Photochemical synthesis of colloidal metals

New photochemical method for preparation of colloidal metal particles (Cu, Ag, Au) as a films on the quartz surface and colloidal dispersion in different matrixes has been devised. Possibilities to control the properties of photogenerated colloidal metal particles are discussed.     

Photochemical generation of carbonate radicals and their reactivity with phenol

The reaction of carbonate radical with phenol in aqueous solution has been investigated in systems in which carbonate radicals were generated by UV irradiation of an aqueous solution of [Co(NH₃)₅CO₃]⁺ (pH 8.0 phosphate buffer). Both steady state and time resolved photolysis experiments were performed. Upon continuous irradiation of complex phenol mixtures, phenol was converted into benzoquinone and dihydroxybenzenes. Benzoquinone was the major by-product in the early stages of the reaction. Laser flash excitation (266 and 355 nm) of the cobalt complex clearly showed the formation of the carbonate radical. When phenol was added to the solution of the complex, a second species was observed which was assigned to the phenoxyl radical. The second-order rate constant of reaction between phenol and carbonate radical was found to be equal to 1.6 × 10⁷ M⁻¹ s⁻¹, in agreement with literature data of 2.2 × 10⁷ M⁻¹ s⁻¹.     

Photochemical synthesis of gold nanorods

Gold nanorods have been synthesized by photochemically reducing gold ions within a micellar solution. The aspect ratio of the rods can be controlled with the addition of silver ions. This process reported here is highly promising for producing uniform nanorods, and more importantly it will be useful in resolving the growth mechanism of anisotropic metal nanoparticles due to its simplicity and the relatively slow growth rate of the nanorods.     

A highly efficient olefin metathesis initiator: improved synthesis and reactivity studies

The synthesis of ligand 8, required for the preparation of catalyst 4c has been optimised. Ligand exchange studies indicate that biphenyl-based alkylidene 4c initiates considerably faster than its unsubstituted analogue 4a. The performance of 4c in ring-opening cross metathesis reactions involving substrates containing unprotected chelating atoms is also reported.     

Photochemical synthesis of pentacene and its derivatives

A novel alpha-diketone precursor of pentacene, 6,13-dihydro-6,13-ethanopentacene-15,16-dione, was prepared and converted successfully to pentacene in 74 % yield by photolysis of the precursor in toluene: Irradiation of the diketone solution in toluene with light of 460 nm under an Ar atmosphere caused the solution to change from yellow to fluorescent orange-pink within a few minutes, after which, purple precipitates appeared. After 35 min, the solution changed to colorless and the purple precipitates were filtered to give pentacene in 74 % yield. By contrast, in the presence of oxygen, the color of the solution changed from yellow to pale yellow, and only 6,13-endoperoxide of pentacene was quantitatively obtained. The rate of the reaction upon photolysis was measured by observing the decay of n-pi* absorption of the precursor at 460 nm, and was found to be similar in both the presence and absence of oxygen. Therefore, the photoreaction of the alpha-diketone precursor seemed to occur via the singlet excited state. Because the T-T absorption of pentacene was observed upon photolysis of the precursor in the nanosecond transient absorption measurement under an Ar atmosphere, the excited triplet state of the pentacene generated singlet oxygen by sensitization, and it reacted with the ground-state pentacene to give the 6,13-endoperoxide. The alpha-diketone deposited on glass was also converted successfully to pentacene film by photoirradiation. In addition, diketone precursors of a mixture of 2,8- and 2,9-dibromopentacene and 2,6-trianthrylene were also prepared and their photoconversion was performed.     

Photochemical synthesis and self-assembly of gold nanoparticles

Colloidal gold was prepared by UV light irradiation of the mixture of HAuCl₄ aqueous solution and poly(vinyl pyrrolidone) (PVP) ethanol solution in the presence of silver ions. The resulting sheet-like nanoparticles were found to self-assemble into nanoflowers by a centrifuging process. The results of control experiments reflected that only suitable size sheet-like nanoparticles could assemble into the flower-like structures. The presence of Ag ions and PVP are essential for the formation process of nanoflowers. They perform their function by serving as structure-directing agents to produce the sheet-like particles. The appearance of the flower-like assemblages is attributed to the combination of Van der Waals force and the anisotropic hydrophobic attraction between the nanoparticles. The flower-like assemblages films can be used as surface-enhanced Raman spectroscopy (SERS) substrates with 4-aminothiophenol (4-ATP) molecule as a test probe.     

Photochemical studies on xanthurenic acid

The tryptophan metabolite xanthurenic acid (Xan) has been isolated from aged human cataractous lenses. The photophysical properties of Xan were examined to determine if it is a potential chromophore for age-related cataractogenesis. We found that Xan produces singlet oxygen (psi delta = 0.17 in CD3OD) with the same efficiency as the lenticular chromophore N-formyl kynurenine and quenches singlet oxygen at a rate similar (2.1 x 10(7); CD3OD) to other tryptophan metabolites found in the eye. As the mechanisms of induction of cataracts may also involve redox reactions, the interactions of hydrated electrons (e(aq)-), the azide radical (N3*) and hydroxyl radical (OH*) with Xan were studied using the technique of pulse radiolysis. The reaction rate constants of e(aq)-, N3* and OH* with Xan were found to be of the same order of magnitude as other tryptophan metabolites. The rate constant for reaction of Xan with e(aq)- solvated electrons was found to be diffusion controlled (k = 1.43 x 10(10) M(-1) s(-1); the reaction with N3* was very fast (k = 4.0 x 10(9) M(-1) s(-1)); and with OH* was also near diffusion controlled (k = 1.0 x 10(10) M(-1) s(-1)). Superoxide O2*- production by irradiated Xan in methanol was detected by electron paramagnetic resonance and substantiated by determining that the enhanced rate of oxygen consumption of Xan irradiated in the presence of furfuryl alcohol was lowered by superoxide dismutase.     

Photochemical synthesis of cadmium sulfide nanoparticles

The formation of cadmium sulfide nanoparticles upon UV irradiation of aqueous solutions of cadmium thiosulfates was established on the basis of spectroscopic and macroscopic data. The yield and size of the cadmium sulfide nanoparticles depend on the ratio of cadmium to thiosulfate ions in solution, the concentration of the solution, and the irradiation duration. The cadmium sulfide nanoparticles with a diameter of 4 nm were obtained by the photolysis of solutions with a concentration of 10⁻³ mol L⁻¹ at the ratio S₂O₃ ²⁻: Cd²⁺ = 2: 1.     

Photochemical synthesis of 2-substituted benzothiazoles

The photochemical reaction of 1 -indolethiocarbanilides 1 , di- and tri-substituted thioureas 3–5 and 4,4 -di-methyl-2,6-dioxothiocyclohexanecarboxanilides 9 affording the respective benzothiazoles are described.     

Photochemical synthesis of α-oxygenated benzothiophenedioxides

The photochemical synthesis of 1-hydroxy[b]benzo-1,3-dihydrothiophene-2,2-dioxides from orthomethylbenzaldehyde and its analogs is described. Some of the chemistry of these α-oxygenated sulfones, including exchange of the 1-hydroxy group with various alkoxy groups and the thermal reversion of these oxygenated derivatives to trappable 1-alkoxy-substituted o-quinodimethanes has been investigated.     

Photochemical studies of thymine in ice

Abstract— Solutions containing various concentrations of thymine have been irradiated (254 nm) at — 196°, and the corresponding absorbance changes at 315 nm due to thymine-thymine adduct formation have been followed as a function of dose. The maximum yield of the adduct is about 3–2 per cent. Additional irradiation leads to a reduction in the yield of adduct and to an increase in the yield of the proposed trimer, which shows a sigmoid dose response curve. Not more than 10 per cent of the thymine is converted to trimer. Irradiation of the trimer in solution converts it into adduct plus thymine. Fluorescence due to the adduct does not appear directly after irradiation at — 196°, but comes about upon annealing at elevated temperatures (T > - 80°).     

Cyanocalix[4]arenes: synthesis,crystal structures and reactivity studies

Abstract

Herein, we describe an improved method to synthesise mono-, di- and tetra-cyanocalix[4]arene and report their crystal structure determinations. We also report our attempts to further functionalise the cyanocalix[4]arenes into dithiadiazolyl-calix[4]arenes, and propose a hypothesis as to why the cyano group on a calix[4]arene is an extremely challenging group to modify.