The photochemistry of polymers containing anthrylmethyl vinyl ketone

The photolysis of copolymers of anthrylmethyl vinyl ketone (AMVK) with styrene and methyl methacrylate has been studied, both in solution and in the solid phase. Quantum yields of the order of 0.01 were observed in both cases for release of the major product, methyl anthracene (MA). Photolysis of an aqueous emulsion of a styrene-AMVK copolymer showed similar yields of MA. The results indicate the possibility of using the Norrish type I process as a means of releasing drugs or other biologically active compounds from polymeric matrices. © 1995 John Wiley & Sons, Inc.     

O-nitrobenzyl photochemistry: Solution vs. solid-state behavior

The efficiency of various 2-nitrobenzyl groups in the photogeneration of carboxylic acid from nitrobenzyl esters has been determined, and the solution vs. solid polymer matrix photochemistry is compared. Generally, the quantum yield for photoreaction is lower in the solid state, probably due to decreased conformational mobility. The substitution that affords the largest increase in quantum yield (?) is at the α-carbon atom. The value of ? for α-methyl-2-nitrobenzyl trimethylacetate in solution is 0.65 vs. 0.13 for the parent 2-nitrobenzyl ester.     

Unusual annulation reaction of an α,β-unsaturated ketone

An unsusual 2,3 cyclopentaindanone (III) was obtained, presumably as a result of a mixed Michael and Stobbe condensation, in the course of an attempted Robinson annulation.     

The photochemistry of methyl cyclobutyl ketone. Part 2. Temperature dependence and the acetyl radical decomposition

Following earlier room-temperature studies, gaseous mixtures of methyl cyclobutyl ketone (MCK) diluted in argon have been photolyzed at temperatures up to 205°C. Experiments have been carried out at a variety of pressures (up to ca. 2 atm) at wavelengths of 313 nm (steady state conditions) and 308 nm (pulsed photolysis). The results are consistent with a mechanism dominated by radical-radical reactions involving acetyl, methyl, and cyclobutyl radicals. Acetyl radical processes predominate at lower temperatures while methyl radical reactions are more important at high temperatures. The results are interpreted via kinetic modelling of a mechanism in which a key role is played by the acetyl radical decomposition reaction Values for k₃ have been obtained and its temperature and pressure dependence are fitted by RRKM theory and a weak-collisional activation model to yield This high-pressure limiting Arrhenius equation is consistent with other studies in the same temperature range, but is difficult to reconcile with higher temperature investigations.     

Oligoazobenzenophanes--synthesis, photochemistry and properties

The possibility to modulate molecules reversibly by light has been fascinating chemists early on. One of the most powerful photochromic classes of compounds are azobenzenes, which have been incorporated in multiple molecular systems to alter their functionality. Recently, the incorporation of azobenzenes into macrocyclic scaffolds, azobenzenophanes, revealed a novel aspect of this interesting photoswitch. Especially, the build-in of more than one azobenzene moiety into the structure creates photochromic compounds with multiple accessible states. The cyclic arrangement also leads to a change in the photochemical properties, which offer new opportunities for functional molecular devices. In this article the synthesis as well as the photochemistry including applications of macrocyclic azobenzenes, containing more than one azobenzene unit, oligoazobenzenophanes, are reviewed.     

Unexpected photochemistry and charge-transfer complexes of [CB(11)H(12)](-) carborane

Although the [CB(11)H(12)](-) carborane does not exhibit an absorption band in UV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation.     

Characterization,processing, and properties of an aromatic poly (ether ketone)

Poly(oxy-1,3-phenylenecarbonyl-1,4-phenylene), mPEK, was synthesized in a methane sulfonic acid/phosphorus pentoxide medium through the polycondensation of 3-phenoxybenzoic acid. The polymer was soluble at room temperature in strong acids and common organic solvents. Differential scanning calorimetry on mPEK indicated a glass transition temperature of 132°C and no detectable crystal melting behavior. The polymer was thermo-oxidatively stable up to 420°C in air as determined by thermogravimetric analysis. Thermal degradation resulted in a crosslinked polymer. Compression molding was successfully applied to consolidate mPEK powder into bulk specimens without causing degradation. Tensilefractured surfaces of the consolidated specimens were examined by scanning electron microscopy which strongly indicated adequate fusion of mPEK powder but also disclosed microvoids of uniform size, shape, and distribution. X-ray scattering revealed that mPEK powder was amorphous and that the consolidated mPEK specimens were structurally isotropic as well as amorphous. The bulk specimen density was determined to be 1.29 ± 0.01 g/cm³ and the three-dimensionally isotropic bulk tensile properties were shown to be 4.10 ± 0.10 GPa (modulus), 0.07 ± 0.01 GPa (strength), and 0.021 ± 0.006 (elongation at break). Tensile properties of the amorphous mPEK specimens compared favourably with literature values of state-of-the-art semicrystalline thermoplastics. Crystaline phases could be realized for mPEK by melt-processing, or precipitating from a solvent.     

AsH3 ultraviolet photochemistry: an ab initio view

Multireference configuration interaction calculations have been carried out for low-lying electronic states of AsH(3). Bending potentials for the nine lowest states of AsH(3) are obtained in C(3v) symmetry for As-H distances fixed at the ground state equilibrium value of 2.850 a(0), as well as for the minimum energy path constrained to R(1) = R(2) = R(3). The calculated equilibrium geometry and bond energy for the X (1)A(1) ground state agree very well with the previous experimental and theoretical data. It is shown that the lowest excited singlet state belongs to the (1)A(1) symmetry (in C(3v)), in contradiction to the previous calculations. This state is characterized by a planar equilibrium geometry. Asymmetric stretch potential energy surface (PES) cuts along the H(2)As-H recoil coordinate (at R(1) = R(2) = 2.850 a(0), θ = 123.9° and 90°) for numerous excited states and two-dimensional PESs for the X and ? states up to the dissociation limits are obtained for the first time. The ? (1)A(1), B(1)E-X (1)A(1) transition moments are calculated as well and used together with the PES data for the analysis of possible photodecay channels of arsine in its first absorption band.     

The near-infrared photochemistry of porphine imbedded in an N-hexane matrix

The near-infrared induced tautomerization of free-base porphine incorporated in a n-hexane-d₁₄ matrix is reported. Nernst glower irradiation on the NH stretch fundamental does not induce tautomerization, but irradiation in the regions 4000 < ν < 5100 cm⁻¹ and 5630 < ν < 7700 cm⁻¹ does induce tautomerization. Narrowband (8 cm⁻¹ fwhm) laser irradiation studies in the NH symmetric plus antisymmetric stretch combination band region (6300 < ν < 6600 cm⁻¹) show that the near-infrared induced tautomerization occurs at select wavelengths. Tautomer conversion in absence of site conversion is strong evidence that the observed photochemistry is due to porphine absorption and not hexane absorption. The estimated quantum yield of 3×10⁻⁵ for 6530 cm⁻¹ irradiation is at least one order of magnitude larger than the quantum yield expected from RRKM theory.     

聚醚酮醚酮酮/含萘环聚醚酮醚酮酮无规共聚物的合成与性能

在无水AlCl3及N－甲基吡咯烷酮（NMP）存在下，以4,4′-二（α－萘氧基）二苯酮（DNBP）作为第三单体，将其与4，4′－二苯氧基二苯酮（DPBP）和对苯二甲酰氯（TPC）在1，2－二氯乙烷（DCE）中进行低温溶液共缩聚反应，合成了一系列聚醚酮醚酮酮／含萘环聚醚酮酮醚酮酮无规共聚物，用IR、DSC、TG及WAXD等方法对其结构和性能进行了表征与测试。研究结果表明共聚物的玻璃化转变温度（Tg)要比纯PEKEKK的高，而其熔融温度（Tm)和结晶度（Xc)则随共聚物中含萘环PEKEKK结构单元含量的增加而逐渐降低。共聚物具有优异的耐热性能及抗腐蚀性能。     

Lingshuine,an Unexpected Passerini Product from the Hainan Sponge Axinyssa variabilis

Lingshuine ( 1 ), a novel sesquiterpene amide, along with three known N‐containing compounds, 2 – 4 , have been isolated from the Hainan sponge Axinyssa variabilis. The structure of 1 was elucidated by detailed analysis of the spectroscopic data and by chemical methods. Lingshuine represents the first example of a Passerini product formed during the isolation process.     

High intensity,argon ion laser-jet photochemistry

A new technique for the study of high intensity solution photochemistry has been developed. With this laser-jet technique, a high velocity microjet is irradiated with the focussed output of an argon ion laser. Under these extremely high intensity conditions, photochemically generated transient species with suitable absorption properties are excited further and produce relatively large amounts of photoproducts which are not observed under low intensity conditions. The application of this laser-jet technique in the study of the photochemistry of radicals, biradicals, photoenols and the higher excited states of carbonyl and polycyclic aromatic compounds is described.     

Aza-Baylis-Hillman reaction of salicyl N-tosylimines with methyl vinyl ketone, ethyl vinyl ketone or phenyl vinyl ketone

Reactions of salicyl N-tosylimines with methyl vinyl ketone, ethyl vinyl ketone or phenyl vinyl ketone proceeded smoothly under mild conditions to give the corresponding chromanes or aza-Baylis-Hillman adducts in moderate to excellent yields in the presence of phosphine or nitrogen Lewis base.     

A transannular reaction during lithium ammonia reduction of an α,β-unsaturated ketone

The lithium-ammonia reduction of the α,β-unsaturated bicyclic dione 2-methyl-Δ^1,6-bicyclo[6,4,0]cyclododecene-5,9-dione 1 has been found to give two isomeric products 2α-methyl-5-oxo-6β-tricyclo[6,4,0,0^1,9] dodecan-9α-ol 2 and 2-β-methyl-5-oxo-6β-tricyclo[6,4,0,0^1,9]dodecan-9α-ol 3 involving a transannular reaction. Chemical and spectral evidence are presented to support the assigned structures. The stereochemistry of 2 arid 3 is also discussed.