Zur lokalisierung funktioneller gruppen in steroiden mit hilfe der massenspektrometrie—VII : 3,11-Dihydroxypregnan-20-one

The mass spectrometric degradation reactions of 3,11-dihydroxypregnan-20-ones concern mainly cleavage reactions in the D ring. Characteristic fragments are the ions of mass 43 combined with ions of mass 84 and 85. Equally, after single and double loss of water CH₃CO? is eliminated, as well as C 15–17, C20 and C21.All spectra of 3,11-dihydroxypregnan-20-ones are characterised by a key fragment of mass 190 produced by cleavage of bonds in the B ring.Ions with an 11α-OH group show important ions of mass 124 which are dominating if the A/B ring system is cis connected. In contrast the configuration of an OH group in position 3 can hardly be deduced by the spectra.     

Catalytic Reduction of Cyclic Ethers with Hydrosilanes

Catalytic reductive transformations of ethers as a synthetic building block are an important class of chemical reactions because a range of essential chemical feedstocks and fuels in contemporary life can be prepared through the key step of ethereal C?O bond cleavage of cellulosic biomass. Although conventional stoichiometric and catalytic methods for sp²‐ and sp³‐C?O bond cleavage of linear ethers and alcohols with hydrosilanes are well established, silylative ring opening of cyclic ethers has been less highlighted in this context. This review outlines catalytic systems for the silylative reduction of a range of cyclic ethers, including epoxides and sugars, leading to the corresponding alcohols and/or hydrocarbons. The chemical reactivity and selectivity of these ring‐opening catalytic processes are discussed with respect to the type of substrates; the representative catalytic working modes are also described.     

Stereochemical applications of mass spectrometry 4. Energy-resolved study of the fragmentation of esters of maleic and fumaric acids

The fragmentation of the dimethyl and diethyl esters of maleic and fumaric acids have been studied as a function of the internal energy of the molecular ions using charge exchange techniques and metastable ion studies in combination with isotopic labelling. The dimethyl ester molecular ions show distinctive behaviours at both low and high internal energies, indicating that interconversion of the molecular ions does not occur. The fumarate molecular ion fragments by elimination of CH₂O and (CO₂ + CH₃) in the metastable ion time-frame, while the maleate ester fragments primarily by loss of CH₃O. At higher internal energies both molecular ions fragment primarily by loss of CH₃O but the fragment ion from the maleate ester shows a greater stability, presumably because it assumes the cyclic cationated maleic anhydride structure. The diethyl maleate and diethyl fumarate molecular ions show identical metastable ion characteristics; in addition the [COS]⁺· charge exchange mass spectra are very similar. These results indicate that low-energy molecular ions interconvert. At higher internal energies interconversion does not occur, and, although both moiecular ions fragment by loss of C₂H₅O, the resultsint fragment ions show different stabilities and fragmentation reactions.     

Composition and temperature dependence of cesium-borate glasses by molecular dynamics

The structural aspects of xCs2O-(1-x)B2O3 glasses have been investigated by molecular dynamics as functions of Cs2O content (x=0.2, 0.3, and 0.4) and temperature (T=300 and 1250 K). The tetrahedral (B?4-) and triangular (B?3,B?2O-, and B?O2 (2-)) short-range order borate units were found to be the structure-building entities of the simulated glasses [?=bridging oxygen (BO) and O-=nonbridging oxygen (NBO) atom]. The increase of Cs2O content results in the progressive increase of the NBO-containing triangle population at the expense of the BO4- tetrahedral units. The same effect is caused by temperature increase at a fixed Cs2O content, and this was associated with the "fragile" characteristics of alkali borate glasses. A comparison of simulated Cs and Li borates showed very similar structures at x=0.2, but dissimilar ones when the alkali content exceeds this composition. In particular, for x>0.2 Cs borates exhibit a preference for NBO formation relative to Li borates. Differences in the microstructure of sites hosting Cs ions were found, and this permits their classification into bridging (b type) and nonbridging type (nb type) of sites. b-type sites consist exclusively of BO atoms, while both BO and NBO atoms participate in nb-type sites. These differences in Cs-site local bonding characteristics were found to be reflected on the Cs-O(site) vibration frequencies. Also, the computed Cs-O vibrational responses for simulated Cs borates were found to compare well with experimental far-infrared spectra.     

Reactions of gaseous acylium ions with 1,3-dienes: further evidence for polar [4 + 2+] Diels-Alder cycloaddition

A novel reaction of acylium and thioacylium ions, polar [4 + 2(+)] Diels-Alder cycloaddition with 1,3-dienes and O-heterodienes, has been systematically investigated in the gas phase (Eberlin MN, Cooks RG. J. Am. Chem. Soc. 1993; 115: 9226). This polar cycloaddition, yet without precedent in solution, likely forms cyclic 2,5-dihydropyrylium ions. Here we report the reactions of gaseous acylium ions [(CH(3))(2)N-C(+)=O, Ph-C(+)=O, (CH(3))(2)N-C(+)=S, CH(3)-C(+)=O, CH(3)CH(2)-C(+)=O, and CH(2)=CH-C(+)=O] with several 1-oxy-substituted 1,3-dienes of the general formula RO-CH=CH-C(R(1))=CH(2), which were performed to collect further evidence for cycloaddition. In reactions with 1-methoxy and 1-(trimethylsilyloxy)-1,3-butadiene, adducts are formed to a great extent, but upon collision activation they mainly undergo structurally unspecific retro-addition dissociation. In reactions with Danishefsky's diene (trans-1-methoxy-3-(trimethylsilyloxy)-1,3-butadiene), adducts are also formed to great extents, but retro-addition is no longer their major dissociation; the ions dissociate instead mainly to a common fragment, the methoxyacryl cation of m/z 85. This fragment ion is most likely formed with the intermediacy of the acyclic adduct, which isomerizes prior to dissociation by a trimethylsilyl cation shift. Theoretical calculations predict that meta cycloadducts bearing 1-methoxy and 1-trimethylsilyloxy substituents are unstable, undergoing barrierless ring opening induced by the charge-stabilizing effect of the 1-oxy substituents. In contrast, for the reactions with 1-acetoxy-1,3-butadiene, both the experimental results and theoretical calculations point to the formation of intrinsically stable cycloadducts, but the intact cycloadducts are either not observed or observed in low abundances. Both the isomeric ortho and meta cycloadducts are likely formed, but the nascent ions dissociate to great extents owing to excess internal energy. The ortho cycloadducts dissociate by ketene loss; the meta cycloadducts undergo intramolecular proton transfer to the acetoxy group followed by dissociation by acetic acid loss to yield aromatic pyrylium ions. Either or both of these dissociations, ketene and/or acetic acid loss, dominate over the otherwise favored retro-Diels-Alder alternative. The pyrylium ion products therefore constitute compelling evidence for polar [4 + 2(+)] cycloaddition since their formation can only be rationalized with the intermediacy of cyclic adducts.     

Nitramine anion fragmentation: A mass spectrometric and Ab initio study

The fragment ion formation characteristics of the radical anions generated from hexahydro-1,3,5-trinitrotriazine (RDX) and its three nitroso metabolites were studied using GC/MS with negative chemical ionization (NCI) to understand the fragmentation mechanisms responsible for the formation of the most abundant ions observed in their NCI mass spectra. Ab initio and density functional theory calculations were used to calculate relative free energies for different fragment ion structures suggested by the m/z values of the most abundant ions observed in the NCI mass spectra. The NCI mass spectra of the four nitramines are dominated by ions formed by the cleavage of nitrogen-nitrogen and carbon-nitrogen bonds in the atrazine ring. The most abundant anions in the NCI mass spectra of these nitramines have the general formulas C(2)H(4)N(3)O (m/z 86) and C(2)H(4)N(3)O(2) (m/z 102). The analyses of isotope-labeled standards indicate that these two ions are formed by neutral losses that include two exocylic nitrogens and one atrazine ring nitrogen. Our calculations and observations of the nitramine mass spectra suggest that the m/z 86 and m/z 102 ions are formed from either the (M--NO)(-) or (M--NO(2))(-) fragment anions by a single fragmentation reaction producing neutral losses of CH(2)N(2)O or CH(2)N(2)O(2) rather than a set of sequential reactions involving neutral losses of HNO(2) or HNO and HCN.     

Kinetic energy release and position of transition state during the intramolecular substitution of ionized 2-benzoyl pyridines

The loss of substituents X from molecular ions of ortho substituted 2-benzoyl pyridines has been investigated as a function of the dissociation energy of the C? X bond. Comparison of unimolecular and collisional induced decompositions of the resulting [M ? X]⁺ ions and reference ions arising from 3-hydroxypyrido[1,2-α]indole shows that cyclic fragment ions are formed in every case by an intramolecular substitution reaction with the exception of the parent compound (X = H), which gives rise to a mixture of [M ? H]⁺ ions with different structures. The heat of formation of the cyclic ion has been estimated experimentally and by calculation using thermochemical data, and from this value and the appearance energies, the activation energies of the reverse reactions have been evaluated for the different reaction systems. Measurement of the kinetic energy release during the substitution reactions shows that only part of the reverse activation energy is released as kinetic energy. The energy partitioning quotient varies from 0.37 to 0.08 depending on the dissociation energy of the C? X bond or the reaction enthalpy. A sudden change in the energy partitioning quotient is observed with increasing exothermicity of the reaction, paralleling the behaviour of similar reaction systems. These results are interpreted as a demonstration of the influence of the variation of transition state position on the energy partitioning quotient.     

Collision-induced dissociation of ring-opened cyclic depsipeptides with a guanidino group by electrospray ionization/ion trap mass spectrometry

The characteristics shown in the electrospray ionization/ion trap mass spectra of ring-opened LI-F antibiotics (cyclic depsihexapeptides with a 15-guanidino-3-hydroxypentadecanoic group as a side-chain) were examined. Collision-induced dissociation (CID) MS of protonated molecules of the depsipeptides produced many fragment ions. Most of these fragment ions contained information for determining the amino acid sequences of antifungal antibiotics. The fragment ions were classified into six groups (b(n'), B(n'), B'(n'), beta(n'), y(n) and Y(n)). According to MS(3) spectra, the B(n'), B'(n) and beta(n) ions can be considered to be derived with a cleavage at each CO--NH in the peptide bonds of [MH--NH(3)](+),[MH--NH(3)--OH](+) and [MH--NH(3)--2H(2)O](+), respectively, in ion trap MS. Losses of NH(3) and H(2)O from the amino acid residues of the depsipeptides in ion trap MS are likely to be smaller than those from the side-chain. The measurements with electrospray ionization (ESI)/ion trap MS of depsipeptides with a side chain containing polar groups may provide useful information for structural determination.     

Fragmentation of valine and proline in resonant free electron capture reactions

The processes of resonant electron capture by molecules of valine and proline were studied. The main dissociative decay channels of molecular ions and the structures of fragment ions were established. The reactions of simple bond cleavage and H-shift rearrangement processes were revealed. The dissociative electron attachment cross-sections for [M - H]^? ions were measured in the region of 1.25 eV. The metastable decay of [M - H]^? ions were found in the energy region of 4.5?C8 eV. The structures of decomposing parent ions were determined using the statistical model of metastable fragmentation.     

Ortho effect in the fragmentation of 2-acetoxychalcones under electron impact

2-Acetoxychalcones decompose under electron impact conditions by loss of an acetoxy fragment to form flavylium ions. The effect is restricted to the ortho position and is reduced after hydrogenation of the chalcone double bond. The intense flavylium ion originates—as shown by specific labelling with ¹⁸O—from two different fragmentation lines: (a) direct loss of an acetoxy radical by cleavage of the phenolic Ar? O bond and (b) sequential elimination of ketene and a hydroxy radical.     

Die Massenspektren einiger Arsen- und Arsenigsäureester – Kinetische Untersuchung ihres Fragmentierungsverhaltens

Mass Spectra of some Arsenic and Arsenious Esters. Kinetic Study of their Fragmentation Reactions The mass spectra of some arsenic and arsenious esters are reported. Based on a mechanistic interpretation of the kinetic of competitive and consecutive reactions correlations between mass spectra and molecular structure have been found. Conclusions: (a) molecular ions are not or very small observable; (b) fragment ions with trivalent and fivevalent arsenic (e.g. As(OCH₃)) are very abundant; (c) the first fragmentation reaction of the molecular ion is usually a simple cleavage, the second is elimination of a neutral by a rearrangement; (d) rearrangement reactions exhibit less activation energies and less frequency factors than simple cleavages, this is the reason for the differences between 70 eV and 9 eV spectra; (e) C? C cleavage in the ethoxy compounds is favoured because of the formation of mesomeric onium ions; (f) some fragmentations by electron impact are analogous to pyrolytic decompositions; (g) in the fragment ions of OAs(OCH₂C₆H₅)₃ the charge is placed on the aromatic ring.     

Side-chain effects on the fragmentation behaviour of alkylthiophenes

The processes leading to the fragment ions formed from alkylthiophene molecule ions by benzylic cleavage without and with transfer of one hydrogen from the side-chain to the ring and the influence of additional methyl groups on the relative importance of these two fragmentation reactions were investigated.     

在空气下制备掺二价稀土的硼酸盐及二价稀土离子(RE2+=Sm,Eu,Tm,Yb)的光谱特征

本文讨论了Sm2 、Eu2 、Tm2 、Yb2 等二价稀土离子的光谱特征 ,特别是在一些含四面体硼酸根的硼酸盐如SrB4 O7、SrB6 O10 和BaB8O13中它们的光谱性质。当以三价稀土离子取代化合物中的二价碱土离子时 ,利用不等价取代而产生的缺陷所带的电荷 ,可在高温的空气下使上述的稀土离子还原成二价 ,不需加入化学还原剂 ,从而提出了一个简便、安全的制备含二价稀土离子发光材料的方法     

Doubly charged fragment ions in the field ionization mass spectra of alkylbenzenes

It is shown that the radical [C₆H₅C_mH_2m]²⁺ fragment ions found in the field ionization mass spectra of alkylbenzenes are formed via a different adsorption state of the singly charged species than in the case of the formation of [M]²⁺ molecular ions. It is further demonstrated that the primary fragmentation of molecules by the cleavage of C? C bonds results not only from decompositions of molecular ions in the gas phase but also from surface reactions.     

Unimolecular decompositions of even-electron ions

Fragmentations of even-electron ions of lifetimes ≥10^?5s caused by electron and chemical ionization and by collisional activation have been correlated. Proposed reaction classifications include: cleavage of one bond with charge migration; cleavage of one bond through cyclization-displacement; cleavage of two bonds in a cyclic ion with charge retention; and cleavage of two bonds in an acyclic ion with rearrangement and charge retention. Such reactions are compared with those of odd-electron ions; despite a higher tendency for rearrangement, the decompositions of a positive even-electron ion, in particular as displayed in its collisional activation spectrum, have substantial utility for characterizing its structure.     

Comparative studies of 193-nm photodissociation and TOF-TOFMS analysis of bradykinin analogues: The effects of charge site(s) and fragmentation timescales

The dissociation reactions of [M + H]+, [M + Na]+, and [M + Cu]+ ions of bradykinin (amino acid sequence RPPGFSPFR) and three bradykinin analogues (RPPGF, RPPGFSPF, PPGFSPFR) are examined by using 193-nm photodissociation and post-source decay (PSD) TOF-TOF-MS techniques. The photodissociation apparatus is equipped with a biased activation cell, which allows us to detect fragment ions that are formed by dissociation of short-lived (<1 mus) photo-excited ions. In our previously reported photodissociation studies, the fragment ions were formed from ions dissociating with lifetimes that exceeded 10 mus; thus these earlier photofragment ion spectra and post-source decay (PSD) spectra [composite of both metastable ion (MI) and collision-induced dissociation (CID)] were quite similar. On the other hand, short-lived photo-excited ions dissociate by simple bond cleavage reactions and other high-energy dissociation channels. We also show that product ion types and abundances vary with the location of the charge on the peptide ion. For example, H+ and Na+ cations can bind to multiple polar functional groups (basic amino acid side chains) of the peptide, whereas Cu+ ions preferentially bind to the guanidino group of the arginine side-chain and the N-terminal amine group. Furthermore, when Cu+ is the charge carrier, the abundances of non-sequence informative ions, especially loss of small neutral molecules (H2O and NH3) is decreased for both photofragment ion and PSD spectra relative to that observed for [M + H]+ and [M + Na]+ peptide ions.     

二氯二乙烯——μú——二氯二铂络合物的质谱测定

本文报导了二氯二乙烯—μμ′—二氯二铂络合物的质谱,并基于各种同位素组合的质量及其相对丰度的计算,对其质谱做了归属。该络合物在电子轰击下的碎裂行为,我们提出两个主要的碎裂历程:端基配位基C_2H_4和C1的竞争失去,形成一系列含有稳定的四元环结构单元(Pt_2C1_2)的碎片离子,以及端基配位基和桥联氯的逐步断裂,形成另一系列含有Pt—Pt键的碎片离子。     

Intramolecular single and double hydrogen migrations in the mass spectra of substituted tetrahydro-1,3,2-oxazaphosphorin-2-oxides

The mass spectral fragmentation of substituted tetrahydro-1,3,2-oxazaphosphorin-2-oxides occurs by the cleavage of ring bonds. The ions due to simple cleavage, single and double hydrogen migration, seem to be triggered by C O bond cleavage of the oxazaphosphorin ring. The variations in the relative abundance of ions arising due to similar fragmentation modes have been found to depend on the nature of the substituent and the stability of the particular fragment. The single hydrogen transfer process is supported by metastable ion and shift techniques.     

Mass spectral characterization of tetracyclines by electrospray ionization,H/D exchange,and multiple stage mass spectrometry

Electrospray ionization (ESI) and collisionally induced dissociation (CID) mass spectra were obtained for five tetracyclines and the corresponding compounds in which the labile hydrogens were replaced by deuterium by either gas phase or liquid phase exchange. The number of labile hydrogens, x, could easily be determined from a comparison of ESI spectra obtained with N2 and with ND3 as the nebulizer gas. CID mass spectra were obtained for [M + H]+ and [M - H]- ions and the exchanged analogs, [M(Dx) + D]+ and [M(Dx) - D]- , and produced by ESI using a Sciex API-III(plus) and a Finnigan LCQ ion trap mass spectrometer. Compositions of product ions and mechanisms of decomposition were determined by comparison of the MS(N) spectra of the un-deuterated and deuterated species. Protonated tetracyclines dissociate initially by loss of H2O (D2O) and NH3 (ND3) if there is a tertiary OH at C-6. The loss of H2O (D2O) is the lower energy process. Tetracyclines without the tertiary OH at C-6 lose only NH3 (ND3) initially. MSN experiments showed easily understandable losses of HDO, HN(CH3)2, CH3 - N=CH2, and CO from fragment ions. The major fragment ions do not come from cleavage reactions of the species protonated at the most basic site. Deprotonated tetracyclines had similar CID spectra, with less fragmentation than those observed for the protonated tetracyclines. The lowest energy decomposition paths for the deprotonated tetracyclines are the competitive loss of NH3 (ND3) or HNCO (DNCO). Product ions appear to be formed by charge remote decompositions of species de-protonated at the C-10 phenol.     

Electron impact studies. CXXIV—Negative ion mass spectra of organic functional groups. Thioacetanilides

The thioacetanilide negative molecular ion (produced by secondary electron capture) is stable, but it fragments after collisional activation to yield [C₆H₅NH]^? by cleavage α to the C?S grouping. The negative molecular ions of (substituted) o-nitrothioacetanilides undergo a series of extremely complex rearrangement reactions. For example, the molecular anion derived from o-nitro-N-methylthioacetanilide yields both acetate and thioacetate anions as major fragment ions.