Collision cell pressure effect on CID spectra pattern using triple quadrupole instruments: a RRKM modeling

Control of the ion internal energy in mass spectrometry is needed to establish a workable mass spectral library. The purpose of this study is to understand and to compare the pressure effects on the collision‐induced dissociation (CID) spectrum pattern recorded using triple quadrupole instruments. The monoprotonated Leucine enkephalin [YGGFL, H⁺] was used as a thermometer molecule to calibrate the electrospray ionization (ESI) and the CID internal energies deposited on the molecular species and the time scale of ion decompositions. The survival yield and the ratio of a₄/b₄ fragment ions were mainly monitored. The energy uptake for the ESI source geometry used in our study has no impact on the CID spectrum fingerprint. The collision cell pressure for the [YGGFL, H⁺] has a major influence on the SY curves slope and on the experimental time scale. To demonstrate the pressure effect on internal energy distribution, three models (threshold, thermal and collisional) based on RRKM theory were built using the Masskinetics software. As a result, the limit of each model is discussed, and the investigation demonstrates that the thermal model, using truncated Maxwell‐Boltzmann internal energy distribution, is well‐suited for simulating the experimental data at high pressure widely used in the analytical conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Identification tree based on fragmentation rules for structure elucidation of organophosphorus esters by electrospray mass spectrometry

Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non‐volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI‐MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MSⁿ) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision‐induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an ‘identification tree’ based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the ‘identification tree’. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and evaluation of new phosphonated δ-lactam and glutarimide derivatives as angiotensin converting enzyme inhibitors

An efficient synthesis of new γ,δ-insaturated δ-lactam and glutarimide derivatives bearing a phosphonomethyl group from a common allylphosphonate precursor is described. Our approach is based on a two-step procedure involving the preparation of phosphonated-1,5-ketoester and −1,5-diester followed by an amidation–heterocyclization sequence. The first step proceeds via Michael's addition of ethyl acetoacetate and diethyl malonate on an allylphosphonate starting material. The second step consists of a base-promoted intramolecular amidation-cyclization sequence with primary amines, which accounts for the construction of δ-lactams and glutarimide skeletons. We performed the evaluation of angiotensin I-converting enzyme (ACE) inhibition using an in vitro enzyme assay on six new compounds. Five compounds showed potent ACE inhibitory activity, with IC₅₀ values ranging from 0.02 to 0.27 mg/ml. Compared with Captopril, used as a reference drug, two new glutarimide derivatives exhibited higher efficiency ACE inhibition activity.     

Photochemical Processes of Superbase Generation in Xanthone Carboxylic Salts

Photobase generators are species that allow the photocatalysis of various reactions, such as thiol-Michael, thiol-isocyanate, and ring-opening polymerization reactions. However, existing compounds have complex syntheses and low quantum yields. To overcome these problems, photobase generators based on the photodecarboxylation reaction were developed. We synthesized and studied the photochemistry and photophysics of two xanthone photobase, their carboxylic acid precursors, and their photoproducts to understand the photobase generation mechanism. We determined accurate quantum yields of triplet states and photobase generation. The effect of the intermediate radical preceding the base release was demonstrated. We characterized the photophysics of the photobase by femtosecond spectroscopy and showed that the photodecarboxylation process occurred from the second excited triplet state with a rate constant of 2.2×10⁹ s⁻¹.     

Decarboxylative Mannich Reactions with N-Alkyl Imines

The use of N-alkyl imines in decarboxylative Mannich reaction with substituted malonic acids half oxyesters (SMAHOs) has been developed to afford a direct access to secondary β^2,3-aminoesters. The transformation occurs under very practical conditions (DABCO as a catalyst in bulk toluene and open to air) and can be performed with a broad range of each substrate in yields of 36 to 97 %. Importantly, the reaction was found to require the use of acidic additives in combination with the organocatalyst to limit the competitive olefination reaction.     

Crystal structure oftrans-ethyl(1,5,6-trimethylbenzimidazole)-bis(dimethylglyoximato)cobalt(III). Relationships between structural and spectroscopic properties in compounds of the general formulae [Co(dmgH)2(R)(1,5,6-Me3Bzm)]

Summary The synthesis and x-ray crystal structure oftrans-[Co(dmgH)₂(Et)(1,5,6-Me₃Bzm)] where dmgH=dimethylglyoximate(–1), and 1,5,6-Me₃Bzm=1,5,6-trimethylbenzimidazole, is reported. The compound C₁₉H₂₆N₆O₄Co is monoclinic, space group P2₁/n;a=11.700(4);b=24.205(6);c=8.500(3) Å and =101.63(3)°. D(calcd) 1.299 g cm^–3; Z=4 and R=0.066 for 2359 independent reflections. Comparison of Co-N(axial ligand) bond lengths for compounds of general formulaetrans-[Co(dmgH)₂(R)(L)], with L=pyridine or 1,5,6-trimethylbenzimidazole and R=CH(CN)Cl, CH₂NO₂, Me, Et,i-Pr, cyclo-hexyl or adamantyl is made. The Co–N(1,5,6-Me₃Bzm) bond lengths of the trimethylbenzimidazole derivatives show a fairly linear relationship with the electronic parameter of the axial R group, derived from the¹³C-n.m.r. spectra of their pyridine analogues. The influence of steric effects on the properties of these Co^III compounds is discussed.     

Photooxidation of ABS of long-wavelengths

The evolution of the photochemical degradation of ABS has been studied in conditions of long wavelength irradiation (λ's> 300 nm). The main photoproducts involved in the oxidative evolution have been identified by using FTIR spectroscopy and chemical titrations. A particular attention has been devoted to α–β unsaturated ketones that appear as secondary photoproducts. Those ketones present a low photochemical stability when exposed in the range 300–400 nm. Conditions for their formation have been experimentally studied. Formation of oxidation photoproducts has been also studied at the macroscopic level and it has been shown that their repartition in the polymer is heterogeneous. The origins of the heterogenities have been studied.     

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.