FTIR analysis of dimethyl ether decomposition products following charge transfer ionization with Ar+ under matrix isolation conditions

Fourier transform infrared spectroscopic analysis has been performed on argon matrices formed following electron bombardment of argon/dimethyl ether mixtures. Products consistent with the ionization and subsequent fragmentation of dimethyl ether cation have been observed. Following ionization of dimethyl ether, fragmentation occurs that is consistent with ionization energy greater than 15 eV due to efficient charge transfer from dimethyl ether to Ar(+) as the major ionization process. Major products observed in the infrared spectra are methane, formaldehyde, HCO(*), CO, and Ar(2)H(+). These products are consistent with the known fragmentation of photoionized dimethyl ether in a 15-16 eV ionization energy range. However, the observation of dehydrogenated products is consistent with additional abstraction of hydrogen from proximally located species isolated within the matrix. Analogous experiments employing CD(3)OCH(3) give similar results, and the observed isotopically substituted products are consistent with the proposed fragmentation pathways.     

Influence of photo-Fries reaction products on the photodegradation of bisphenol-A polycarbonate

The photodegradation of BPA polycarbonate (PC) can be described as an autoaccelerating process initiated by the formation of biphenol products arising from a formal photo-Fries reaction pathway. Evidence comes from spiking PC films with model compounds of photo-Fries reaction products, pre-exposure of films to generate photo-Fries products, and kinetic analysis. Published data on products formed during natural PC weathering are consistent with this pathway.     

Structural Analysis of the Condensation Products of Xylan with Organotin Halides

Physical characterization of the products resulting from condensation of xylan with organostannanes halides is consistent with a tin-modified product. Results from elemental analysis shows the presence of tin consistent with the presence of the tin moiety. Results from control reactions are consistent with the product containing portions derived from both reactants. The presence of the Sn–O–R ether linkage is found by infrared spectroscopy. The presence of portions derived from both reactants is indicated by mass and infrared spectral results.     

The photochemical behaviour of bis aryl-1,3 triazenes

The photolysis of bis aryl-1,3 triazenes carried out in non-aromatic solvents gives products whose structures are consistent with a cage recombination process of homolytically formed radicals and the subsequent abstraction of hydrogen from the solvent molecules by these arylamino radicals.In aromatic solvents, a free-radical chain process leads to the formation of products resulting from the homolytic substitution on the solvent.     

The reactions of chlorine monofluoride with unsaturated compounds and the dehydrohalogenation of some of the derivatives

The reactions of chlorine monofluoride with benzene, toluene and nitrobenzene to give monochloro derivatives has been investigated and its addition reactions to various substituted olefins studied. The products from all these reactions are consistent with the participation of a chloronium ion as the reactive species, even in solvents of low dielectric constant. The chlorofluoro addition products formed from the olefins have been dehydrohalogenated and the mechanism of reactions discussed in terms of an E1 cb mechanism or paene-carbonium ion extreme.     

Products from enzymic oxidation of 2′,4,4′-trihydroxychalcone: structural reconsiderations

The enzymic products from peroxidase-catalysed oxidation of 2′,4,4′-trihydroxychalcone react with diphenylsulphide to form diastereoisomers of 4′,6-dihydroxy-2-(α-hydroxybenzyl)-coumaranone, consistent with their previously assigned dioxetane structure.     

Selectivity in the oxidative addition of C-S bonds of substituted thiophenes to the (C5Me5)Rh(PMe3) fragment: a comparison of theory with experiment

Theoretical studies were performed on the C-S bond activation reactions of 2-/3-cyanothiophene, 2-/3-methoxythiophene, and 2-/3-methylthiophene with the [Rh(PMe3)(C5Me5)] fragment to compare with the selectivity of these reactions observed in the experimental study, with the goal of determining whether the latter represent kinetic or thermodynamic products. Density functional theory (DFT) calculations have been used to optimize the ground-state structures of the two possible insertion products and the transition state structures leading to the formation of the products arising from the above cleavage reactions to address this question. With the 2-cyano and 2-methoxy substituents, the observed formation of one product resulting from the exclusive insertion of the rhodium into the more hindered substituted C-S bond was found to be consistent with the calculated energy differences between the ground states of the two possible products (7.6 and 2.6 kcal mol(-1)). With 2-methylthiophene, the product resulting from the activation of the unsubstituted C-S bond is calculated to be favored by 5.8 kcal mol(-1), in agreement with observed results. The approximately 1:1 ratio of products with 3-cyano and 3-methyl substituted thiophenes are also found to be consistent with the small calculated energy differences (0.4 and 0.8 kcal mol(-1)) between the ground states of the two insertion products. Although the observed high selectivity in the formation of a single C-S bond activation product with 3-methoxythiophene appears to be underestimated in the calculations, the observed products for all substituted thiophenes correlate with the calculated thermodynamic products. In addition, the kinetic selectivities predicted based on the calculated C-S bond activation barriers are different from those observed experimentally. Consequently, these investigations demonstrate that DFT calculations can be used reliably to differentiate if an experimentally observed C-S bond activation reaction proceeds under thermodynamic or kinetic control.     

Arabidopsis thaliana LUP1 converts oxidosqualene to multiple triterpene alcohols and a triterpene diol

The Arabidopsis thaliana LUP1 gene encodes an enzyme that converts oxidosqualene to pentacyclic triterpenes. Lupeol and beta-amyrin were previously reported as LUP1 products. Further investigation described here uncovered the additional products germanicol, taraxasterol, psi-taraxasterol, and 3,20-dihydroxylupane. These results suggest that the 80 known C(30)H(50)O compounds that are structurally consistent with being oxidosqualene cyclase products may be derived from fewer than 80 enzymes and that some C(30)H(52)O(2) compounds may be direct cyclization products of oxidosqualene.     

Etude du Comportement Photochimique de quelques Diaryl-1,3-triazènes

Study of the Photochemical Behaviour of Some Diaryl-1,3-triazenes The photolysis of Diaryl-1,3-triazenes gives products whose structures are consistent with a cage recombination process of homolytically formed radicals and subsequent abstraction of hydrogen from the solvent molecules by arylamino radicals. In aromatic solvents, a free-radical chain process leads to the formation of products resulting from the homolytic substitution on the solvent. Quenching experiments show that singlet and triplet excited states are reactive but that intersystem crossing efficiency is low.     

Secondary organic aerosol from limona ketone: insights into terpene ozonolysis via synthesis of key intermediates

Limona ketone was synthesized to explore the secondary organic aerosol (SOA) formation mechanism from limonene ozonolysis and also to test group-additivity concepts describing the volatility distribution of ozonolysis products from similar precursors. Limona ketone SOA production is indistinguishable from alpha-pinene, confirming the expected similarity. However, limona ketone SOA production is significantly less intense than limonene SOA production. The very low vapor pressure of limonene ozonolysis products is consistent with full oxidation of both double bonds in limonene and furthermore with production of products other than ketones after oxidation of the exo double bond in limonene. Mass-balance constraints confirm that ketone products from exo double-bond ozonolysis have a minimal contribution to the ultimate product yield. These results serve as the foundation for an emerging framework to describe the effect on volatility of successive generations of organic compounds in the atmosphere.     

Intramolecular cyclization and subsequent rearrangements of alkyne-tethered N-heterocyclic carbenes

Alkyne-tethered imidazole and 1,2,4-triazole-based N-heterocyclic carbene precursors have been prepared and studies of the intramolecular reactions of carbenes are performed. Products consistent with intramolecular cyclizations and subsequent rearrangements were observed. Mechanistic studies using crossover experiments showed that the products did arise from intramolecular carbene additions. The reactions are proposed to go through vinylogous diaminocarbene intermediates similar to vinylogous dialkoxycarbenes formed during Boger cycloaddition reactions. Imidazole substituted dienes were observed to be the major products of tandem cyclization and elimination reactions that were observed for imidazole-based N-heterocyclic carbenes.     

Kinetic isotope effects implicate two electrophilic oxidants in cytochrome p450-catalyzed hydroxylations

Intramolecular kinetic isotope effects (KIEs) were determined for cytochrome P450-catalyzed hydroxylation reactions of methyl-dideuterated trans-2-phenylcyclopropylmethane-d2 (1-d2), which gives two products from oxidation of the methyl group, trans-2-phenylcyclopropylmethanol (2) and 1-phenyl-3-buten-1ol (3). In oxidations of each enantiomer of 1-d2 with three P450 enzymes (CYP2B1, CYPDelta2E1, and CYPDelta2E1 T303A), the apparent intramolecular KIEs were different for products 2 and 3 in all cases and different for each enzyme-substrate combination. In oxidations of each enantiomer of undeuterated 1-d0 and trideuteriomethyl 1-d3 by CYP2B1 and CYPDelta2E1, the ratio of products 2/3 decreased for 1-d3 in comparison to 1-d0 in all cases. The results require multiple pathways for P450-catalyzed hydroxylation and are consistent with the "two-oxidants" model, where hydroxylation is effected by both the hydroperoxy-iron species and the iron-oxo species. The results are not consistent with predictions of the "two-states" model for P450-catalyzed hydroxylations, where oxidations occur from a low-spin state and a high-spin state of iron-oxo.     

Use of high-resolution mass spectrometry to identify precursors and biodegradation products of perfluorinated and polyfluorinated compounds in end-user products

Structural identification of perfluoroalkyl and polyfluoroalkyl substances found in end-user products and their biodegradation products was performed using ultra-high resolution mass spectrometry. Little attention has so far been paid to the environmental burden of perfluorooctane sulfonate and perfluorooctanoic acid from compounds with a molar mass of ~2,000. Analysis of end-user waterproofing and stain repellent products revealed the presence of numerous ions with molar masses ranging from 1,000 to 2,000 and complex mass spectra. Ultra-high resolution mass spectrometry determined the accurate mass of the observed ions, allowing the cleavage position and fragment structure to be determined. The precursor structures were determined based on reconstitution of the retrieved fragments. Products of fluorochemical manufacturers before voluntary regulation comprised compounds with plural perfluorooctyl chains. In the current product lines, compounds comprising perfluorobutyl chains were detected. Biodegradation tests using activated sludge revealed that biodegradation products consistent with those reported previously were generated even from complex end-user products. For example, the biodegradation test revealed the formation of N-ethyl perfluorooctane sulfonamido acetic acid and various fluorotelomer acids in the samples. The results of the present study suggest that the environmental burden of these compounds should be reevaluated.     

Removal of 3'-phosphate group by bacterial alkaline phosphatase improves oligonucleotide sequence coverage of RNase digestion products analyzed by collision-induced dissociation mass spectrometry

RNase mapping by nucleobase-specific endonucleases combined with liquid chromatography/tandem mass spectrometry (LC/MS/MS) is a powerful analytical method for characterizing ribonucleic acids (RNAs). Endonuclease digestion of RNA yields products that contain a 3'-terminal phosphate group. MS/MS via collision-induced dissociation (CID) of these digestion products on a linear ion trap generates fragmentation pathways that include the loss of phosphoric acid (-H(3)PO(4); -98 u), which does not provide information about the sequence of the digestion products and can reduce ion abundance from other pathways that provide sequence information. Here we investigate the use of bacterial alkaline phosphatase (BAP) after RNase digestion to remove the 3'-terminal phosphate from all RNase digestion products prior to LC/MS/MS analysis. RNase digestion products lacking the 3'-phosphate were found to produce CID spectra with more consistent, high-abundance c- and y-type fragment ions as well as significantly more a-Base and w-type ions than digestion products retaining the 3'-phosphate. In this manner, RNase mapping with LC/MS/MS can provide more complete RNA sequence information from fragment ions of higher abundance that are easier to interpret and identify.     

Zirconium-mediated SN2' substitution of allylic ethers: regio- and stereospecific formation of protected allylic amines

A new zirconium-mediated, regio- and stereospecific SN2' substitution of allylic ethers with a nitrogen nucleophile has been developed. Cbz-protected amine products were isolated in high yield from reactions with a wide range of Z allylic ethers. A mechanism of the allylic substitution consistent with the results of the kinetics and kinetic isotope effect studies was proposed.     

Efficient Photodecarboxylation of Trifluoromethyl-substituted Phenylacetic and Mandelic Acids

A total of eight CF₃-substituted phenylacetic and mandelic acids are shown to undergo efficient photodecarboxylation (PDC; Φ = 0.37–0.74) in basic aqueous solution to give the corresponding trifluoromethyltoluenes or trifluoromethylbenzyl alcohols. The products are consistent with the almost exclusive formation of benzylic carbanions that subsequently react with water, with minor amounts (≤5%) of radical-derived products detected. Quenching studies indicate that the reaction likely proceeds from the singlet excited state. This work demonstrates that the CF₃ group greatly facilitates the excited state ionic PDC of phenylacetic acids.     

Classical photodissociation dynamics with Bohr quantization

The standard classical expression of the state-resolved photodissociation cross section is not consistent with an efficient Bohr quantization of product internal motions. A new and strictly equivalent expression not suffering from this drawback is proposed. This expression opens the way to more realistic classical simulations of direct polyatomic photodissociations in the quantum regime where only a few states are available to the products.     

Stereocontrolled synthesis of bicyclic ureas and sulfamides via Pd-catalyzed alkene carboamination reactions

The synthesis of bicyclic ureas and sulfamides via palladium-catalyzed alkene carboamination reactions between aryl/alkenyl halides/triflates and alkenes bearing pendant cyclic sulfamides and ureas is described. The substrates for these reactions are generated in 3–5 steps from commercially available materials, and products are obtained in good yield with up to >20:1 diastereoselectivity. The stereochemical outcome of the sulfamide alkene addition is consistent with a mechanism involving anti-aminopalladation of the alkene, whereas the stereochemical outcome of the urea alkene addition is consistent with a syn-aminopalladation mechanism.     

Methane activation over zeolite catalysts: The methylation of benzene

The methylation of benzene with methane over ZSM-5 zeolite catalysts in a high pressure static reactor is shown to require oxygen as a reactant, implicating methanol as a key intermediate species. In the case of zeolite H-beta, methyl aromatics can be formed in the absence of oxygen, consistent with an earlier report that these products are formed from cracking of benzene over the acid zeolite.     

Thermal degradation of bromine-containing polymers. Part 9—Copolymers of 2,3-dibromopropyl methacrylate and 2,3-dibromopropyl acrylate with styrene

The products of the thermal degradation of copolymers of styrene (S) with 2,3-dibromopropyl methacrylate (2,3-DBPM) and 2,3-dibromopropyl acrylate (2,3-DBPA) have been analysed quantitatively using thermal analysis, infra-red spectroscopy, mass spectrometry and gas-liquid chromatography. The products are generally similar to those which result from the degradation of the two homopolymers and no significant interaction occurs between the two types of units in the polymer chains. The only abnormal feature is the fact that the yield of 2,3-DBPA increases as the 2,3-DBPA content of copolymers of 2,3-DBPA and S decreases but this is consistent with previous observations in related copolymer systems.