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  • 1965-1969  (322)
  • 1960-1964  (8)
  • 1920-1924
  • Analytical Chemistry and Spectroscopy  (318)
  • Fibers
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 4 (1969), S. 210-223 
    ISSN: 1432-0827
    Keywords: Invertebrate ; Tetracycline ; Growth ; Fibers ; Test
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La croissance de la carapace deStrongylocentrotus intermedius est étudiée à l'aide de la tétracycline. Des specimens de l'été ne présentent pas de fluorescence dans les plaques, sauf dans le système apical et les régions voisines. Un faisceau d'éléments fibreux, présentant une autofluorescence blanche laiteuse, est orienté perpendiculairement à chaque ligne de suture. Les spécimens de l'hiver ne présentent ces éléments qu'après décalcification des coupes. La croissance de chaque plaque, chez ces derniers s'effectue de la façon suivante: suture longitudinale » surface interne = mamelon et bosse du tubercule 〉 suture transversale 〉 surface externe de la base de l'épine dorsale 〉 surface externe de la plaque. La carapace adulte augmente de taille selon deux mécanismes de croissance: d'une part, par adjonction de nouvelles plaques au système apical et, d'autre part, par apposition sur des régions données de chaque plaque. Il apparait que des éléments fibreux sont intéressés par la croissance de la carapace et qu'un mécanisme différent de croissance s'observe dans les carapaces de l'été et de l'hiver. Le système apical semble se calcifier selon un mécanisme spécifique qui permet une formation active de plaques nouvelles pendant toute l'année.
    Abstract: Zusammenfassung Das Wachstum des Skeletes vonStrongylocentrotus intermedius wurde mit Hilfe von Tetracyclin untersucht. Bei Sommerexemplaren konnte die Tetracyclinfluorescenz in den Platten nicht beobachtet werden, außer im apicalen System und seiner anliegenden Umgebung. Eine Menge von fibrösen Elementen mit einer milchig-weißen Autofluorescenz war senkrecht zu jeder Nahtlinie angeordnet. Bei Winterexemplaren waren diese Elemente nur in demineralisierten Schnitten deutlich sichtbar. Der Wachstumsgradient jeder Platte war bei Winterexemplaren der folgende: Longitudinalnaht » innere Oberfläche = Terminalknopf und Hals der Tuberkel 〉 Latitudinalnaht 〉 Oberfläche der Basis des Stachels 〉 äußere Oberfläche der Platte selbst. Das ausgewachsene Skelet als Ganzes vergrößert seinen Umfang auf zwei Wachstumsarten, einerseits durch Zusatz von neuen Platten zum apikalen System, anderseits durch Zuwachs an bestimmten Stellen von jeder Platte. Die Resultate lassen vermuten, daß fibröse Elemente am Skeletwachstum beteiligt sind und daß der Mechanismus dieses Wachstums bei Sommer- und bei Winterexemplaren verschieden ist. Es wäre denkbar, daß das apikale System auf einen spezifischen Mechanismus der Verkalkung ansprechen würde, welcher eine aktive Bildung neuer Platten während des ganzen Jahres erlaubt.
    Notes: Abstract Growth of the test ofStrongylocentrotus intermedius was examined with the aid of tetracycline. In summer specimens, tetracycline fluorescence was not observable in the plates, except in the apical system and its adjacent area. An array of fibrous elements with a milky white autofluorescence was oriented perpendicularly to each suture line. In winter specimens the elements were evident only in demineralized sections. The growth gradient of each plate estimated on winter specimens was as follows: longitudinal sture » inner surface = mammelon and part of boss in tubercle 〉 latitudinal suture 〉 outer surface of base of spine shaft 〉 outer surface of plate itself. The mature test as a whole increases in size by two modes of growth, an addition of new plates to the apical system and an accretion on fixed sites of each plate. The results suggest that fibrous elements are involved in the test growth, and that there is a different mechanism of the test growth between summer and winter specimens. The apical system may be equipped with a specific mechanism of calcification which permits an active formation of new plates throughout the year.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 467-479 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms for the major fragmentations obtained with selected substituted uracils are discussed. Interpretation of data was facilitated by use of metastable peaks, high-resolution data, and low-voltage spectra.The major fragmentation obtained with N-alkyl substituted uracils, when the alkyl group contains 2 or more carbons, is due to cleavage of the alkyl substituent. This cleavage is accompanied by a rearrangement of 1 or 2 hydrogens from the alkyl group to the uracil ring. Possible mechanisms for the rearrangements are discussed. It was found that the molecular ion of 1- and 3-alkyl substituted uracils (where the alkyl group has 2 or more carbons) does not undergo the expected ‘retro Diels-Alder Reaction’. Instead, the odd-electron ion formed by loss of the alkyl substituent with a single hydrogen rearrangement undergoes this reaction (loses HNCO). Since it is formed as a secondary reaction product, the relative abundance of the ‘retro Diels-Alder’ fragment is low compared to what is obtained in the spectra of the simple uracils.The ‘retro Diels-Alder Reaction’ can be used to differentiate between 2- and 4-thiouracils, and between 1- and 3-methyl and phenyl substituted uracils. It was found that 1- and 3-alkyl substituted uracils (alkyl group of 2 or more carbons) can be differentiated by the mass of the M-alkyl fragment since the 3-substituted compounds give predominantly a double hydrogen rearrangement and the 1-substituted compound gives mainly a single hydrogen rearrangement. In addition the intensity of the molecular ion, relative to the M-alkyl ion, is considerably stronger in the 1-substituted uracils.
    Additional Material: 12 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 547-548 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Deuterium labelling has been utilised to elucidate the mechanism by which a molecule of water is eliminated from a heterocyclic nitro compound under electron-impact.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 175-194 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of ten dehydration and solvolysis products obtained from β-amyrin and glycyrrhetic acid were studied. With the exception of those resulting from ‘backbone’ rearrangement, they exhibited conventional fragmentation due to the ring C chromophore, like the parent alcohols. Only those products with a contracted ring A suffered loss of an isopropyl radical. In the latter type, special fragmentation features were exhibited by the isopropylcyclopentene and by the isopropylidene products. These differences enabled the assignment of probable structures for two unknown derivatives.
    Additional Material: 12 Ill.
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  • 5
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The C8H9+-ion, formed from the molecular ions of 2-phenyl-1-bromoethane, 1-phenyl-1-bromoethane and of 1-phenyl-1-nitroethane by loss of the bromine atom and of the nitro group, splits off a molecule of acetylene after an almost complete randomization of hydrogens, as proved by deuteration. An eight-membered ring structure for the C8H9+-ion is proposed to explain these results.By loss of the nitro group from the molecular ions of 1-phenyl-1-nitropropane and of 1-phenyl-2-nitropropane the well-known phenylated cyclopropane ion3 (C9H11)+ is generated. Mass spectra of analogues, specifically deuterated in the side-chain, show that in this ion a randomization of hydrogen atoms in the cyclopropane ring as well as a hydride transfer from the cyclopropane ring to the phenyl cation occur.
    Additional Material: 17 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 893-900 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main fragmentation sequences of glycollide and its homologues are initiated by fission of a CO—O bond, leading to the formation of fragment ions of low, m/e, such as [R1CO]+ and [CR1R2CCO]+. When a hydrogen atom is present on a ring carbon atom, 1,3 hydrogen migration occurs to produce [CHR2OH]+. In case where a ring carbon atom carries an alkylchain ≥ C2H5, a McLafferty rearrangement occurs with the adjacent carbonyl group. When both ring carbon atoms are dimethyl substituted, a 1,4 hydrogen migration must be invoked to account for the observed fragmentation sequence.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 907-914 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of ortho substituents in nitrobenzence radical cation decompositions are discussed for non-interacting halogen substituents. These effects are distinct from those of the same substituents in the meta and para positions, and support previous indications that ring position identity is retained in nitrobenzene molecular ions. More importantly, the steric effect of the halo substituents may be gauged from these data; it indicates that several previously suggested mechanisms for the loss of NO must be reconsidered. The existence of steric effect in very well defined systems may be used as a structural tool in organic mass spectrometry.
    Additional Material: 4 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 933-933 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 953-963 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of thirty sydnoes have been interpreted; the types investigated include 3-aryl, 3-alkyl-, substituted 3-alkylsydnones; and bis sydnones. A characteristic fragmentation mode involves initial loss of NO and CO from the molecular ion, but peaks corresponding to alkylcarbonium ions dominate the spectra of 3-alkylsydnones; a cyclic mechanism is suggested for weak transitions involving loss of sydnone neutral molecule from the molecular ion. A mechanism is proposed for loss of chlorine radical from the molecular ion of 3-(2,4-dichlorophenethyl)sydnone. An unusual feature in the mass spectrum of trimethylenebis sydnone is rationalised on the basis of a precursor 1,2,3-oxadiazole ion. The effect of substituents in the aryl ring on the fragmentation of 3-arylsydnones is discussed.
    Additional Material: 5 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 997-1003 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of eight ferrocene derivatives containing C6F5, C6F5CO, C6F5CH2 or p-CH3OC6F4 groups attached to one or both cyclopentadienyl rings are described and discussed. In addition to features normally found in the mass spectra of ferrocene compounds, the migration of fluorine to the iron atom leads to the formation of ions such as [C5H4COFeF]+. The elimination of neutral FeF2 or C5H5FeF molecules is also found.
    Additional Material: 3 Tab.
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  • 11
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1039-1039 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1037-1038 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 13
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 337-345 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cracking patterns of twenty five toluene-p-sulphonamides have been studied. In certain cases an abundant [M — SO2] ion is detected: the structural features associated with this phenomenon are discussed.
    Additional Material: 1 Tab.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1175-1177 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 16
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron-impact induced fragmentation of eight aziridinones has been studied by conventional as well as by high resolution mass spectrometry. All α-lactams exhibit a molecular ion. The major primary step, in the fragmentation, is the ejection of carbon monoxide from the molecular ion. Ions of the general formula R1—NC and R2R3C=O were found in the mass spectra of all α-lactams investigated. A skeletal rearrangement to rationalize these ions is proposed. The fragmentation of the molecular ion is affected by the N-substituent. Exact mass measurement and specific deuterium labeling indicate the absence of McLafferty rearrangement from either the N- or C-substituent.
    Additional Material: 10 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 755-756 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectrum of CH3CH2CH2COOD shows no observable loss of C2H3D. This indicates for this compound that either the McLafferty rearrangement is concerted, or that the second step (olefin loss) is very fast in comparison to the reverse transfer of hydrogen back to the methylene radical.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A system is described in which computer techniques are used to carry out major steps in the procedure for interpretation of high-resolution mass spectral data. These steps include identification and evaluation of the molecular ion, neutral fragments lost from the molecular ion, and characteristic ion series, followed by elucidation of specific structural details using a sub-routine for the particular compound class selected. The technique shows promise of not only increasing the interpreter's efficiency, but of providing more specific and detailed structural information from the spectral data.
    Additional Material: 12 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 17-31 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of twenty-six commercially available medicinal phenothiazines have been determined at high resolution. In each compound, the side chain attached to the 10-position of the phenothiazine ring contains nitrogen and fission of the C—C bond α to this nitrogen gives in most cases the base peak. Some of the compounds are also substituted at the 2-position and this substituent generally remains intact, though some substituents such as acetyl, propionyl, methoxyl and methylthio can undergo fragmentation. Fragmentations fall into three groups; those which give ions representing a part of the side chain; those which give ions representing the intact phenothiazine ring with part of the side chain attached; those which give ions representing a partially fragmented ring system.
    Additional Material: 2 Tab.
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  • 21
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 209-212 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of deuterated species shows that both the isomeric ions [CH2=SH]+ and [CH3—S]+ are formed in the ratio 2:1 from CH3SH; the ions [CH3CH=SH]+ and [CH3CH2S]+ in the ratio 0·8:1 from CH3CH2SH; and [CH2=OH]+ and [CH3—O]+ in the ratio 6·7:1 from methanol.The heats of formation of [CH3S]+ and [C2H5S]+ are of the order of 222 and 203 Kcal.mole-1 respectively. The isomeric ions cannot be distinguished on thermodynamic grounds.
    Additional Material: 2 Tab.
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  • 22
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 355-365 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectra of five benzotriazinone derivatives are reported and the fragmentation mechanisms are discussed. That the first loss of 28 mass units is a nitrogen molecule appears to be characteristic of the molecules.
    Additional Material: 6 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 387-399 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC5H4CH2Fe(CO)2C5H5, NC5H4CH2COMo(CO)2C5H5, NC5H4CH2W(CO)3C5H5, NC5H4CH2COMn(CO)4, C5H10NCH2CH2Fe(CO)2C5H5, (CH3)2NCH2CH2COFeCOC5H5 and (CH3)2NCH2CH2COMn(CO)4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C5H5Mo(CO)3CH2NCO; (iii) The arylazomolybdenum derivatives RN2Mo(CO)2C5H5 (R = phenyl, p-tolyl, or p-anisyl); (iv) The compound (C6H5N)2COFe2(CO)6 obtained from Fe3(CO)12 and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH3)2NCH2CH2N(CH3)2W(CO)4. Further examples of eliminations of hydrogen, CO, and C2H2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC5H4CH2MC5H5]+ to give the ions [(C5H5)2M]+ (M = Fe, Mo and W); (ii) Conversion of C5H5Mo(CO)3CH2NCO to C5H5Mo(CO)2CH2NCO within the mass spectrometer; (iii) Elimination of N2 from [RN2MoC5H5]+ to give [RMoC5H5]+; (iv) Novel eliminations of HNCO, FeNCO, and C6H5NC fragments in the mass spectrum of (C6H5N)2COFe2(CO)6; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH3)2NCH2CH2N(CH3)2W(CO)4.
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  • 24
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1033-1035 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigation of metastable ion transitions shows, that spontaneous charge separations (loss of an electron from a cation) and ion-pair formations (loss of negative ions from positive ones)are taking place in conventional mass spectrometry. Such processes may be important factors in formation of doubly charged ions.
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  • 25
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1042-1042 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1067-1072 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes a direct appearance potential difference method, which is employed to determine, qualitatively, relative free radical stabilities. The method appears to be of general value since the starting materials (β-substituted N-ethylanilines) are relatively simple to prepare and because the dominant electron-impact reaction is the one which releases the free radical under investigation.
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  • 27
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of ion structure and energy is discussed briefly and attention directed to the existence of two types of structural information. Studies of ion formation reactions bear on the initial structure of the ion, whereas decomposition reactions relate to the ion at a later time, after structural rearrangement has had chance to occur. The desirability of conducting both types of investigation concurrently is emphasized. Of the available experimental methods at this time, kinetic measurements for formation studies and metastablel ion relative abundances for decomposition studies have been utilized, although other techniques may eventually prove preferable in the future. The [M - Y] reaction of a series of substituted benzyl substrates XC6H4CH2Y, where Y = OC6H5 and H, has been examined, and the present results are compared with previous work on ion structure and energy in this area, with the aim of evaluating the potential of the newer techniques.
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  • 28
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 1117-1133 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The fragmentation behavior of derivatives of benzisothiazole-S-dioxide is discussed. A series of degradation processes typical for this class of compounds is observed whose relative importance, however, largely depends upon substituents present. Provided it is energetically favorable fragmentation of the substituents (frequently followed by expulsion of SO2) prevails, otherwise degradation of the heteroaromatic ring is observed (sometimes with rearrangements involving the SO2 group). No parallels between thermal and electron-impact induced rearrangements have been observed.
    Notes: Das Fragmentierungsverhalten von Derivaten des Benzisothiazol-S-dioxids wird diskutiert. Es läßt sich für die Verbindungsklasse eine Reihe von typischen Zerfallsreaktionen erkennen, deren relatives Gewicht jedoch stark von der Art der substitution abhängt. Soweit dies energetisch günstig ist, tritt bevorzugt Abbau des Substituenten (evtl. gefolgt von Verlust von SO2) auf, Anderenfalls Zerfall des heteroaromatischen Ringes. (u.U. erst nach Umlagerung im Bereich der SO2-Gruppe). parallelität zwischen thermischen und elektronenstoßinduzierten Umlagerungen wird nicht beobachtet.
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  • 29
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    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 2 (1969), S. 136-136 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 30
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the α-cleavage processes of aliphatic amines (using RLCH2N(R)CH2Rs and RLCH(NR)RsRL represents the larger Rs the smaller alkyl group throughout this paper and both, unless indicated to the contrary, have similar degrees of lsubstitution on the α-carbon atom. as typical substrates) at several ionizing voltages indicates that the loss ratio of large and small alkyl radicals, [M — RL]/[M — Rs], decreases with ionizing voltage. This ratio, greater than 1·0 at 70 eV, may become less than unity at low voltage (15 eV, 10 eV) in some cases. Comparison of similarly structured compounds with nitrogen or oxygen as the heteroatom suggests that the effects of ionizing voltage are lessened when the fragment is of greater stability (e.g. amine vs. ether or imine vs. ketone). The effects of lowering the ionizing voltage became much less pronounced as the alkyl groups become larger or similar in size.
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  • 31
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    Biological Mass Spectrometry 2 (1969), S. 655-656 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 32
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on the element maps of twenty-two gibberellin methyl esters fragmentations are discussed, which are characteristic of the common structural features as well as structural modification in gibberellin homologues.
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  • 33
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    Biological Mass Spectrometry 2 (1969), S. 865-876 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: In contrast to the olefins I and II, olefins alkylsubstituted at the double-bond(III to IX) suffer no isomerization by hydrogen migration before fragmentation occurs. Almost the only degradation-reaction of the molecular ions of the olefins III to VIII is the McLafferty-rearrangement. From the isomers III and IV, respectively V and VI, the same McLafferty-rearrangement product is formed, therefore the spectra are nearly identical.A general scheme for the occurrence of identical mass spectra of isomeric compounds is given.The olefin IX in which the McLafferty-rearrangement is not possible shows preferential cleavage of the ally1 bond. If the chain contains a futher alky-substituent, bond-rupture at the branched c-atom competes with the McLafferty-rearrangement.
    Notes: Im Gegensatz zu den Olefinen I und II unterliegen die an der Doppelbindung alkylsubstituierten Olefine II bis IX keiner der Bruchstückbildung vorausgehenden Isomerisierung unter Wasserstoffwanderung. Bei den Olefinen III bis VIII ist die McLafferty-Umlagerung die nahezu einzige Abbaureaktion der Molekülionen. Aus den Isomeren III und IV bzw. V und VI entsteht das gleiche McLaffetty-Abbauprodukt, so daß die Spektren praktisch identisch sind.Es wird ein allgemeingültiges Schema für das Auftreten identischer Massenspektren isomerer Verbindungen angegeben.Ein Olefin der Struktur IX, bei dem die McLaffetty-Umlagerung nicht möglich ist, zeigt bei Electronenbeschuß vorzugsweise. Befindet sich ein weiterer Alkylsubstitutent in der Kette, so tritt als Konkurrenzreaktion zur McLaffety-Umlagerung der Bindungsbruch an der Verzweigungsstelle ein.
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  • 34
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photoionization, as well as the electron-impact, mass spectra of exo-and endo-norbornyl bromide and of exo-and endo-8-bromobicyclo[3.2.1]octane show that exo-Br loss is more facile than endo-Br loss in formation of C7H11⊕ and C8H13⊕, respectively. The relative intensity values are compared with solvolysis data from the same systems.
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  • 35
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    Biological Mass Spectrometry 2 (1969), S. 985-995 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation of competing metastable transitions in the mass spectra of ethylene ketals RSRLC(OCH2)2 (where RL is a larger n-alkyl group than RS) has established that in most cases RS is lost with a lower activation energy than RL. This technique has also been applied to ketones RSRLC=O, to show again that RS is usually lost with the lower activation energy (thus supporting earlier data based on relative daughter ion abundances at the threshold). In the classes of compounds so far investigated, although [M+ - RS] ions are formed with lower activation energies than [M+ - RL] ions, the ion yield of [M+ - RS] ions is anomalously low from ions of high internal energy. Factors which may influence the [M+ - RS]/[M+ - RL] ratio of daughter ion intensities are examined. It is suggested that at the threshold [M+ - RS] and [M+ - RL] ions may be formed with rearrangement, or from an electronic state that cannot be effectively populated from molecular ions of high internal energies.
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  • 36
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The major fragmentation paths of the 1-(2-thienyl)alkylalkanones ionized by electron impact are delineated by means of isotopically labeled molecules, metastable ion peaks and low ionization voltage data. A prominent process is cleavage of the bond beta to the carbonyl group with the concurrent rearrangement of a hydrogen atom. Another important process is cleavage alpha to the carbonyl group to produce the thienoylium ion analogous to the benzoylium ion. As expected, the data show that increasing the chain length by two methylene groups increases the total ion current. The bulk of this increase is found in the increased ion current of the rearrangement ion with the remainder being associated with alkyl fragments and oxygenated ion species.
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  • 37
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    Springer
    Cell & tissue research 101 (1969), S. 323-337 
    ISSN: 1432-0878
    Keywords: Vitreous body ; Hyalocytes ; Three-dimensional network ; Fibers ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The vitreous body of the rat eye was studied by scanning electron microscopy. The freeze-dried specimens were either unfixed, freshly frozen or fixed and rinsed before being frozen. The vitreous body is surrounded by a coat of intercellular material covering a thin sheath of chiefly parallel fibers. The latter forms the base for a regularly organized three-dimensional network of fibers. The interfibrillar spaces are filled with ground substance and also contain a few cells. The shape of the cells varies from bipolar to polyhedronal. Their interconnected processes are usually undivided. The functional importance of this complex regular organization of the fibers and cells in the vitreous body is stressed.
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  • 38
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    Organic Magnetic Resonance 1 (1969), S. 279-280 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 39
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    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
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    Organic Magnetic Resonance 1 (1969), S. 295-303 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-precision line measurements and tickling were shown to yield information, often not accessible, on the assignment and signs of spin coupling constants. For pentafluorothiophenol-d, this information was obtained for the three meta-JFF's. Relative to C6F5SH, the 19F resonances in C6F5SD experienced an upfield ‘isotope’ shift.
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  • 41
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    Organic Magnetic Resonance 1 (1969), S. 281-293 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined the 19F NMR spectra of a number of oxygen-containing fluorocarbon products and obtained a comprehensive set of 19F chemical shift values, which enabled us to determine the influence of an oxygen atom bonded to a fluorocarbon group on the 19F chemical shift. The influence of neighbouring fluorocarbon groups, either directly connected or separated by an oxygen atom, was also considered.Our results may be summarized as follows. An oxygen atom bonded by a single bond (ether type bond) to a fluorine substituted carbon atom decreases the 19F chemical shift, as does the introduction of a further fluorine atom. Considering two adjacent fluorocarbon groups, a variation of x ppm in the 19F chemical shift of one of the two groups gives a variation of 0·12 x ppm in the opposite sense on the 19F chemical shift of the other group. If the two groups are connected by an ether oxygen atom, the effect is only about 0·06 x ppm.
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  • 42
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR spectral parameters are reported for benzofurazan, 1,2,3- and 2,1,3-benzothiadiazole, and 1-methyl- and 2-methyl-benzotriazole. The coupling constants are discussed in connection with the aromaticity of these compounds and the occurrence of partial bond fixation.
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  • 43
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    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 44
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    Organic Magnetic Resonance 1 (1969), S. 1-1 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Organic Magnetic Resonance 1 (1969), S. 2-2 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 46
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    Organic Magnetic Resonance 1 (1969), S. 344-344 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 47
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    Organic Magnetic Resonance 1 (1969), S. 343-344 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 48
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    Organic Magnetic Resonance 1 (1969) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 49
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    Organic Magnetic Resonance 1 (1969), S. 345-349 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to determine the effect of a single methyl group on the chemical shifts of protons in a cyclohexane ring, methylcyclohexane-1,2,3,3,5,5,-d6 has been synthesized. The protons in the 4-position and the 2,6-equatorial protons are not significantly different from those in ring-frozen cyclohexane. The 2,6-axial protons, however, experience an up-field shift of about 15 Hz from the position of the other axial protons. These observations are discussed in terms of the structure of methylcyclohexane.
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  • 50
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    Organic Magnetic Resonance 1 (1969), S. 375-388 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorine nuclear magnetic resonance (F-NMR) has been used to determine dissociation constants for multipolar complexes formed by several p-substituted fluorobenzenes in CCl4 and cyclohexane at 25°. Data in CCl4 were also obtained at -20°. The results are interpreted in simplified terms as dipole-dipole interactions which lead to a complex of net zero dipole moment. Although the dissociation constants are not of high accuracy, the values obtained do indicate that both polarity and steric effects are important in the presumed multipolar complexes.
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  • 51
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The proton magnetic resonance spectrum of acetyl-cyclobutadiene-irontricarbonyl has been measured including all observable 13C—H-coupling constants. The couplings are assigned and discussed with respect to structure and bonding properties of the molecule. The results exclude the structure of a cyclic conjugated diene with alternating double and single bonds.
    Notes: Das Protonenresonanz-Spektrum des Acetyl-cyclobutadien-eisentricarbonyls wurde einschließlich aller beobachtbaren 13C—H-Kopplungskonstanten vermessen. Die Kopplungen warden zugeordnet und im Hinblick auf Molekülstruktur und Bindungsverhältnisse diskutiert. Auf Grund der Messungen kann die Struktur eines cyclisch-konjugierten Diens mit alternierenden Doppel- und Eingachbindungen ausgeschlossen warden.
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  • 52
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ΔH
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  • 53
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    Organic Magnetic Resonance 1 (1969), S. 481-489 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of line width and chemical shift vs. temperature for amide and hydroxyl proton magnetic resonance signals from: barbituric acid, dialuric acid, parabanic acid, alloxan and alloxan monohydrate dissolved in anhydrous dimethyl sulfoxide-d6 are reported. The behavior of the amide signals shows that, between 20 and 65°C, none of the compounds listed exhibits lactim-lactam tautomerism. The amide proton resonance in uracil has also been investigated. The signal is a closely spaced, equal intensity, doublet due to the non-equivalence of H(1) and H(3). Again, no evidence of tautomerism is observed. Activation energies for the hydroxyl resonances in dialuric acid and alloxan monohydrate indicate hydrogen bonding between solute and solvent. The results of simple LCAO-MO calculations are in accord with the experimental conclusions concerning tautomeric equilibria.
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  • 54
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    Biological Mass Spectrometry 2 (1969), S. 121-134 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: As a result of high resolution mass measurements, calculation of metastable ions, and investigation of specifically deuterated compounds the fragmentation is discussed of some α-substituted N-methyl benzylamides containing different N-acyl groups. α-Cleavage leads to the formation of N-methyl α-acylamino carbon ions which show skeletal rearrangement. The intensity of the rearranged ions depends on the structure of the N-acyl group. Migration of the α-methyl group is observed in the mass spectra of N-acetyl and N-p-Cl-benzoyl N-methyl-α-phenylethylamide.
    Notes: Der massenspektrometrische Zerfall einiger α-substituierter N-Methylbenzylamide mit verschiedenen N-Acylgruppen wird anhand der Ergebnisse aus hochauflösender Massenbestimmung, Berechnung der metastabilen Ionen Untersuchung spezifisch deuterierter Verbindungen diskutitert. Dabei wird die Strukturumlagerung der durch α-Spaltung entstandenen N-Methyl-α-acylaminocarboniu-Ionen nachgewiesen. Sie ist von der Art der N-Acylgruppe abhängig. In den Massenspektren von N-Acetyl-bzw. N-p-Cl-Benzoyl-methyl-α-phenyläthylamid wird die Wanderung der α-Methylgruppen beobachtet.
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  • 55
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    Biological Mass Spectrometry 2 (1969), S. 331-333 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a series of straight chain aliphatic ketones which has been studied, it has been shown that the structural requirement for loss of water from the molecular ions produced by electron-impact is an alkyl group of seven or more carbon atoms attached to the carbonyl function.
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  • 56
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    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    Biological Mass Spectrometry 2 (1969), S. 367-373 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of dunnione (II) from 2-hydroxynaphtha-1,4-quinone has been improved and used to prepare three deuteriated analogues. The mass spectra of these compounds and of the products of their reductive acetylation and deuterioacetylation have been measured and used to interpret the mass spectrum of atrovenetin.
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  • 58
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of thioglycollic acids and esters are reported and discussed. The spectra of compounds of the type X·CH(Y)·S·CH2·COOR(X 〉 Y) contain skeletal rearrangement fragments with the composition R·Y·C2H3SO+. Ions produced by simple cleavage processes may be usefully correlated with structure.
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  • 59
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    Biological Mass Spectrometry 2 (1969) 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    Biological Mass Spectrometry 2 (1969), S. 591-601 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of maleic acid, maleic acid-2,3-d, fumaric acid and fumaric acid-2,3-d have been examined and fragmentation mechanisms are proposed for these compounds. The molecular ion of the cis-acid fragments via H atom transfer from one carboxyl group to the other followed by loss of CO2. The trans acid does not fragment significantly by this route and the former effect may be characteristic of molecules containing two carboxyl groups cis-oriented to each other. This hypothesis was successfully tested by examining the mass spectra of citraconic, itaconic and phthalic acids. Itaconic and mesaconic acids show some of the fragmentation characteristics of fumaric acid.
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  • 61
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  • 62
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    Biological Mass Spectrometry 2 (1969), S. 781-790 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: While heterolysis of oxonium ions generated upon electron-impact in the mass spectrometer is a well documented phenomenon in the fragmentation of aliphatic ethers, little analogy exists for structurally comparable immonium ions. Exceptions are ions of the latter class in which dissociation is facilitated by the presence of proper substituents in position allowing satabilization of daughter ions. Two main types of subtitution were explored providing(1) resonance stabilization of the product ions by aryl substituents in benzylic,heterolysis,and (2) aryl neighboring group participation in homobenzylic heterolysis, possibly yielding phenonium ions (or isometric ions via further rearrangement) as stable products in the gas phase. In the discussion emphasis will be placed on Case 2.
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  • 63
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    Biological Mass Spectrometry 2 (1969), S. 809-818 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a series of aliphatic acyclic α,β-unsturated aldehydes, ketones and ester have been examined. The spectra do not show evidence for McLafferty rearrangements, alkoxyl migration or for fragmentations which are dependent upon the s-trans or s-cis conformations of the compounds. There is some evidence for cis-trans isomerism about the double bond.
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  • 64
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    Biological Mass Spectrometry 2 (1969), S. 843-861 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 65
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    Biological Mass Spectrometry 2 (1969), S. 877-892 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of enol derivatives of β-diketones, such as enol ethers and enaminies are discussed. Their behaviour under electron-impact is in accordance with the fragmentation we suggested for an acyclic β-diketone in the enol form.Rearrangement of the enol functional group is observed in the spectra. This process is a general one, as it show not only migration of oxygen and nitrogen in the enol ethers and enamines, but also migeration of sulphur and chlorine in the thio-ether and in 4-chloro-3-pentene-2-one.Enol derivatives are suitable compounds for determining the branching of alkyl chains in β-diketones.
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    Biological Mass Spectrometry 2 (1969) 
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    Biological Mass Spectrometry 2 (1969), S. 223-239 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 2,6-di-unsaturated carbonyl compounds, two successive, site-specific hydrogen transfers are necessary to account for the loss of carbon atoms 1, 2, 3 and 4, together with one hydrogen from C-8. The deuterated methyl geranate required for this study was readily converted to pseudo-ionone, in which a similar fission was shown to occur. Previous predictions about the β-ionone mass spectrum2 have been shown to be substantially correct, and its similarity to the mass spectra of benzylidence acetones is pointed out.
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  • 68
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    Biological Mass Spectrometry 2 (1969), S. 213-221 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of two series of aliphatic polynitro compounds are reported and discussed. The fragmentation patterns of aliphatic nitro and polynitro compounds are similar in that no appreciable molecular ion current is observed; however, there are several other features in the fragmentation of aliphatic polynitro compounds which differ from that of nitroalkane spectra. Both series of compounds studied-C(NO2)x(CH3)4-x, where x = 4 to 0 and C2(NO2)x(CH3)6-x, where x = 6,4,2-show a decrease in the number and intensity of alkylions with an increase in the NO+ and NO2+ ion current as x increases. The main ions resulting from the more nitrated compounds are [NO]+, [NO2]+, [CO2]+. and [CH3CO]+, whose noncharged counterparts are the principal species produced in the detonation of these compounds. This similarity of the products of the two processes suggests the use of mass spectroscopy for the investigation of the initial explosive processes. The principal fragmentation pathways of the polynitroalkanes have been elucidated by exact mass measurements and the observation of metastable ion transitions.
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  • 69
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dependence of the cleavage of some cis/trans-isomers in the terpenoid and steroid series on the energy of the ionizing electrons have been studied.
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  • 70
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    Biological Mass Spectrometry 2 (1969), S. 375-386 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of doubly charged ions found in the mass spectra of various N, N′-alkyl substituted phenylenediamines is compared to that of their singly charged counterparts. Structural and electronic requirements for the resonance stabilization of doubly charged organic ions are suggested and it is shown that doubly charged ions could be used to differentiate between certain structural isomers which give practically identical singly charged ions. The doubly charged ions were distinguished from singly charged ions of the same integral m/e value by high resolution techniques.
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  • 71
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    Biological Mass Spectrometry 2 (1969), S. 481-519 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 72
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  • 73
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    Biological Mass Spectrometry 2 (1969), S. 1049-1060 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The composition of solid saturated hydrocarbons from slack-wax after reaction with urea has been investigated by electron-attachment (EA) mass spectrography with negative ions. From the spectra of the samples the content of paraffin hydrocarbons, monocyclic, dicyclic and other polycyclic naphthenes was calculated. The presence of n-paraffins up to C46, isoparaffins and cycloalkanes up to C52 has been confirmed. In the paraffin series the concentration of normal paraffin hydrocarbons containing one and two 13C atoms was determined. On the basis of the results obtained the constitution of the samples and the possible structures of the hydrocarbons were discussed. The results obtained have shown that the solid hydrocarbons which react with urea not only consist of one- or two-ring systems, but also of systems with up to five and six rings.
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  • 74
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    Biological Mass Spectrometry 2 (1969), S. 1103-1115 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of the alkyl cyanides up to n-pentyl cyanide were studied. Using metastablel ion transitions, appearance potentials and deuterium labelling, the fragmentation patterns, spectral characteristics and trends for this series can be given. The investigation of labelled compounds demonstrates the specificity of rearrangement and normal decomposition processes. Alkyl ions in nitriles are produced by simple cleavage of the carbon-carbon bond, while ions of the type [M -alkyl]+, which at the first sight could originate in the same way, are presumably formed via cyclic intermediates and are in fact rearrangement ions.Apart from the known γ and δ-hydrogen rearrangements, there is novel evidence for a β-hydrogen rearrangement via a five-membered ring transition state.
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  • 75
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    Biological Mass Spectrometry 2 (1969), S. 1171-1173 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    Biological Mass Spectrometry 2 (1969), S. 1265-1275 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of cinnoline and various alkyl derivatives, and their 1- and 2-mono-oxides and 1,2-dioxides and a quaternary salt have been investigated. The spectra are interpreted in the light of experiments with deutero and 15N labelled derivatives whose syntheses are described. The major fragmentation path for cinnoline is loss of nitrogen molecule while that for its homologues is loss of nitrogen plus a hydrogen atom in some instances. Various initial fragmentations occur with the N-oxides, and deoxygenation appears to be the dominant process; in both 4-methylcinnoline 1-oxide and 1,2-dioxide an important path is formation of a 3-methyl-anthranil cation by loss of HCN and HCNO respectively.
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  • 77
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    Biological Mass Spectrometry 2 (1969), S. 1309-1314 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of a series of deuteriated polymethylbenzenes confirm and extend the model derived from labeled p-xylenes for the loss of a methyl radical under electron impact. A methyl group flanked by two methyls undergoes no exchange before being lost. But one adjacent to an unsubstituted position appears to exchange with the o-hydrogen atom via a methyl-methylene-methyl cycle. At least in p-xylene, reformation of the methyl group may well be concerted with its loss. A similarly concerted coupling of CH2 and H and loss of the resultant methyl group could account for an apparent inconsistency between the mass spectra of methyl alkyl and phenyl alkyl ketones.
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  • 78
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    Biological Mass Spectrometry 2 (1969), S. 81-103 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of exo-2-norbornyl chloride, 1- and 2-methyl exo-2-norbornyl, exo-camphenilyl, apoisobornyl, bornyl and isobornyl chloride, and camphene hydrochloride, α- and β-fenchyl chloride and fenchene hydrochloride, and exo-isofenchyl chloride and 2,5,5-trimethyl exo-2-norbornylchloride, and camphene and α-fenchene have been examined at 12 to 16 and 80° eV and at 30 to 49 and 80°, or higher temperatures. Wagner-Meerwein rearrangements occur very readily in the ion source and compounds related by these rearrangements give very similar fragmentation patterns. Thermal decompositions are important with the tertiary chlorides especially at higher source temperatures. The rates of methanolysis of some of these chlorides were measured.
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  • 79
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    Biological Mass Spectrometry 2 (1969), S. 63-79 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of several fluoroalkyl, fluoroalkenyl and fluoroacyl complexes of manganese, rhenium, iron and ruthenium carbonyls are described. After loss of carbonyl groups, fluoroalkyl compounds eliminate an olefin, with formation of metal halide species. A trifluorovinyl complex shows a novel elimination of a carbon atom to give an ion postulated to be a difluorocarbene-metal fluoride; the occurrence of difluorocarbene-metal ions in the spectra of some related complexes is also discussed. The spectra of the acyl complexes show little evidence of elimination of the acyl carbonyl group; the major process is fission of the CO—Rf bond with loss of a fluoroalkyl radical and formation of the cationic metal carbonyl, e.g. π-C5H5M(CO)3+ (M = Fe or Ru). The relevance of thermal or photochemical model reactions to processes occurring in the mass spectrometer is discussed.
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  • 80
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    Biological Mass Spectrometry 2 (1969), S. 195-207 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of several compounds obtained during the process of Stork's isoxazole synthesis9 as well as the related isoxazoles have been investigated. The fragmentations of simple alkyl isoxazoles are nicely formulated via azirine intermediates. A striking difference between the spectra of isoxazoles and those of methylfurans as to the relative abundance of [M  -  l] peaks is noteworthy. The very low abundance of these peaks in the former reflects the unique character of isoxazole nucleus due to the preferential cleavage of N—O linkage rather than a benzylic C—H bond rupture. If an alkyl substituent is present at 4-position in 3,5-dimethylisoxazoles, strong peaks at m/e 110, 68 and 43 are common in their spectra. The analyses of metastable transitions and high resolution measurements have demonstrated that the formation of these ions can be interpreted by a mechanism involving the cleavage of N—O linkage.
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  • 81
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    Biological Mass Spectrometry 2 (1969), S. 249-252 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 82
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    Biological Mass Spectrometry 2 (1969), S. 253-256 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 83
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    Biological Mass Spectrometry 2 (1969), S. 273-281 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis of the mass spectra of ortho, meta and para isomers of monoalkylanisoles and monoalkylphenols, the alkyls being n-amyl, n-octyl and n-undecyl, has been performed. The regularities found allow determination of the structure of such compounds by inspection of the mass spectrum only. It was shown that Hammett's equation may be used for evaluating a ration of intensities of peaks originating formally from the simple β-cleavage and that accompanied by hydrogen migration of the resulting fragment ions.
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  • 84
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    Biological Mass Spectrometry 2 (1969), S. 309-315 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of the non-benzenoid aromatic heterocycles 2H- and 2-methyl-2H-cyclopenta[d]pyridazine and several deuterated analogs have been analyzed. The majority of the nitrogen lost from these heterocycles occurs as HCN OR H2CN. The deuterium labeling suggests a rearrangement of the molecular ion prior to fragmentation.
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  • 85
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    Biological Mass Spectrometry 2 (1969), S. 325-330 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of the styryl ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm PhCH = }\mathop {\rm C}\limits^{\rm + } {\rm H} $\end{document} in the mass spectra of some cinnamic compounds is shown to occur via the intermediate formation of the cinnamoyl ion \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Ph} - {\rm CH} = {\rm CH} - {\rm C} \equiv \mathop {\rm O}\limits^{\rm + } $\end{document} rather than by direct cleavage of the bond α to the double bond.
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  • 86
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of allphatic ketones are drastically altered following substitution of a trifluoromethyl entity adjacent to the carbonyl group (II and III) or attachment to the γ-carbon atom (V). Loss of the trifluoromethyl group by α-cleavage far exceeds the alternative elimination of an alkyl radical. Virtually complete repression of the McLafferty rearrangement process (I → a) occurs when a CF3 group is attached to the γ-carbon atom. A fluorine atom is not transferred in lieu of hydrogen in the McLafferty rearrangement as demonstrated by the mass spectrum of 1,1,1,7,7,7-hexafluoroheptan-4-one (IV). Rationalization for these results are presented as is a description of the syntheses of several hitherto unknown fluorinated ketones.
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  • 87
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The positive ion mass spectra of the transition metal organometallic halide derivatives C5H5M(CO)3Cl(M = Mo or W), C7H7W(CO)2I, C3H5Fe(CO)3I, [C3H5PdCl]2, and [C5H5Mo(NO)I2]2 have been investigated. Further examples of the elimination of CO and C2H2 fragments were noted. In addition the following effects of particular interest were observed:(i) Evidence in the mass spectra of the chlorides for reactions with adventitious iodine and even bromine present in the mass spectrometer; (ii) Evidence for conversion of the compounds C5H5Mo(CO)3X to the new halides [C5H5Mo(CO)X]2 upon pyrolysis; (iii) Evidence for facile losses of the π-allyl group, the iodine atom, and methyl iodide in the mass spectrum of the π-allyl derivative C3H5Fe(CO)3I; (iv) Evidence for loss of iodine upon introducing [C5H5Mo(NO)I2]2 into the mass spectrometer to give ions derived from [C5H5Mo(NO)I]2.
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  • 88
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    Biological Mass Spectrometry 2 (1969), S. 425-426 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 89
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structure elucidation of organic compounds is only one of the applications of mass spectrometry to chemistry. Important subjects are also mass spectrometric quantitative analysis of mixtures of inorganic and of organic compounds, determination of isotopes and related problems. In ‘Massenspektrometrie’, edited by H. Kienitz, all these applications are discussed together with an excellent introduction to the function of mass spectrometers and the techniques of measurement. This book contains a lot of information and stimulation for mass spectroscopists and chemists, and is especially recomended for use in analytical laboratories.
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  • 90
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The field ionization mass spectra of a series of nucleosides are reported, and compared with spectra obtained by conventional electron-impact ionization. The latter are complex, with structurally significant molecular ion and sugar cleavage peaks often of low intensity or completely absent. In contrast, the field ion spectra are extremely simple, with all except guanosine (highest mass peak [M  -  18]) showing intense molecular ion peaks, and the characteristic sugar (S) and base (B + H) cleavage products as the only other important fragments.
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  • 91
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    Biological Mass Spectrometry 2 (1969), S. 549-550 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 92
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    Biological Mass Spectrometry 2 (1969), S. 553-565 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eleven isomeric octenes were converted to the corresponding dideuterio derivatives and the mass spectra recorded. The cracking patterns of the various dideuterioctanes are unique and the distribution of peaks representing the higher molecular weight ions can be predicted using a simple fragmentation model. The application of this technique to the determination of the position of the double bond in olefins of known carbon skeleton is discussed.
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  • 93
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    Biological Mass Spectrometry 2 (1969), S. 603-609 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectra of the four stereoisomeric 1-methyldecalins and the four 2-methyldecalins have been measured. For each set of stereoisomers, the order of relative intensity of the parent-less-CH3 ion, but not of the parent ion, parallels the order of relative stability of the molecules. The correlation suggests that loss of the methyl group from the members of each set of stereoisomers leads to a common product, with the differing conformational energies converting into differences in vibrational energy, which in turn lead to differing extents of further decomposition.
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  • 94
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of five aryl (I to V) and four alkylsulfonylthioureas (VI toIX) have been recorded and mechanistic rationalizations are suggested for their principal fragmentation processes. The aryl analogs exhibited peaks in their mass spectra corresponding to skeletal rearrangements with elimination of SO2 from their molecular ions but this fragmentation was absent in those alkylsulfonylthioureas (VI to IX) examined.
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  • 95
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    Biological Mass Spectrometry 2 (1969), S. 653-654 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mass spectra of the two compounds 1,1,1,2-Tetrafluoroethane and 1,1,2,2-Tetrafluoroethane are presented.
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  • 96
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of the following compounds have been investigated: (i) The organotin derivatives (CH3)3SnMo(CO)3C5H5 and (CH3)3SnNCW(CO)5; (ii) The mercury derivatives Hg[Mn(CO)5]2, Hg[Co(CO)4]2, Hg[Mo(CO)3C5H5]2 and ClHgMo(CO)3C5H5; (iii) The polynuclear cyclopentadienyl metal derivatives [C5H5Ru(CO)2]2, [C5H5Cr(CO)3]2, [C5H5Cr(NO)2]2 and [C5H5Fe-CO]4; (iv) The trinuclear cobalt carbonyl derivatives YCCo3(CO)9 (Y = Cl and CH3); (v) The binuclear triene-iron carbonyl derivatives C4H4Fe2(CO)6 and C8H10Fe2(CO)6. The mass spectra of the trimethyltin derivatives exhibited stepwise loss of methyl groups as well as of carbonyl groups. The mass spectra of the mercury derivatives exhibited the facile loss of mercury. The mass spectrum of [C5H5Cr(CO)3]2 indicated a very weak chromium-chromium bond since it exhibited no ion containing two chromium atoms. The mass spectrum of the nitrosyl derivative [C5H5Cr(NO)2]2 exhibited the stepwise loss of its four nitrosyl groups. The mass spectrum of [C5H5FeCO]4 was rather complex and exhibited a variety of unusual processes including eliminations of neutral Fe and C5H5Fe fragments. Unusual ions observed in the mass spectrum of CH3CCo3(CO)9 include the bare polymetallic ions [Con]+ (n = 3 and 2). Many examples of the elimination of neutral CO, C2H2 and H2 fragments were noted in this work.
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  • 97
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 98
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the principles of the quasi-equilibrium theory, substituent effects, deuterium labeling and comparison of compound behavior, we provide strong evidence for aryl participation in the expalsion of Br· from the molecular ion of β-phenylethyl bromide and eleven of its ringsubstitued derivatives. This reaction shows a kinetic behavior which is typical of rearrangements, its activation energy is lower than that of similar reactions where participation is partially or completely precluded and substitute effects are not only consistent with a particular process, but are also consistent with those predicted from solution chemistry.
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  • 99
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    Biological Mass Spectrometry 2 (1969), S. 801-807 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of four alkyl substituted 9,10-anthraquinones are presented and discussed together with evidence in favour of a new fragmentation pattern for these derivatives.
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  • 100
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    Biological Mass Spectrometry 2 (1969), S. 835-842 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of substituents on the fragmentation of N-aryl trifluoracetamides has been investigated. The base peak in all ring-monosubstituted derivatives is the molecular ion. Other important ions arise by loss of CF3 and COCF3 from the molecular ion, and the latter daughter ion fragments further, by loss of the aromatic substituent and by expulsion of small neutral molecules. The effects of substituents on the intensity of these ions is discussed. 1-Phenylethyl trifluoracetamide exhibits a base peak which is the molecular ion, wheras the corresponding 2-phenyl derivative has a molecular ion of very low intensity.
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