Thio derivatives of β-diketones and their metal chelates. XXI. Mass spectra of 1,1,1-Trifluoro-4-mercapto-4-(2'-naphthyl)but-3-en-2-one and its metal chelates

1976 ◽  
Vol 29 (2) ◽  
pp. 283 ◽  
Author(s):  
SE Livingstone ◽  
DS Moore
Keyword(s):  
Mass Spectrum ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Fragmentation Pattern ◽  
Derivatives Of

The new monothio-β-diketone l,l,l-trifluoro-4-mercapto-4-(2'-naphthyl)but-3-en-2-one, βC10H7- C(SH)=CHCOCF3, and its chelates with iron(111), ruthenium(111), cobalt(111), rhodium(111, nickel(11), palladium(11), platinum(11) and zinc(11) have been prepared. The mass spectrum of the monothio-β-diketone displays considerably more peaks than that of its parent β-diketone. Both spectra give peaks for the ion CllH7+ (RC+ ; R = β-C10H7). The mass spectra of the metal chelates show some differences determined by the metal. All the metal chelates except that of zinc show peaks due to the ion M'-MetS and its daughter ions (M' = M for MetL2 and M - L for MetL3 ; L = β-C10H7C(S)=CHCOCF3). It is considered that the β-naphthyl group affects the fragmentation pattern, since the mass spectra differ considerably from those of metal chelates of other monothio-β-diketones.

Thio derivatives of β-diketones and their metal chelates. XIV. Mass spectra of palladium and platinum chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (4) ◽  
pp. 749 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Mass Spectra ◽  
Metal Chelates ◽  
Fragmentation Pattern ◽  
Derivatives Of ◽  
Zinc Nickel

The mass spectra of the palladium(11) and platinum(11) chelates of the fluorinated monothio-β- diketones, RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, p-BrC6H4, p-NO2C6H4, 2-thienyl), and of the palladium chelate of CH3C(SH)=CHCOCF3 have been obtained. The platinum chelates give rise to more metal-containing peaks than the palladium chelates. Mechanisms are proposed for the reactions involving the metal-containing fragments. A comparison of the mass spectra of the zinc, nickel, palladium and platinum chelates of these fluorinated monothio-β-diketones reveals that the fragmentation pattern is determined by the metal.

Thio derivatives of β-diketones and their metal chelates. XIX. Metal chelates of two new fluorinated Monothio-β-diketones and their mass spectra

1975 ◽  
Vol 28 (6) ◽  
pp. 1249 ◽  
Author(s):  
SE Livingstone ◽  
N Saha
Keyword(s):  
Mass Spectra ◽  
Metal Chelates ◽  
The Novel ◽  
Copper Chelates ◽  
Derivatives Of

The nickel(II), palladium(II), platinum(II), copper(II), zinc(II) and rhodium(III) chelates of the new fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Pri, Bui) and the iron(III), ruthenium(III) and cobalt(III) chelates of PriC(SH)=CHCOCF3 have been prepared. The mass spectra of all but the two copper chelates have been obtained. The novel features of the spectra are the occurrence of the ions M-(R-H), M-R, and M-LH and the loss of H2S from the ions M-LH and M-L.

Increased urinary excretion of analogs of Krebs cycle metabolites and arabinose in two brothers with autistic features

1995 ◽  
Vol 41 (8) ◽  
pp. 1094-1104 ◽  
Author(s):  
W Shaw ◽  
E Kassen ◽  
E Chaves
Keyword(s):  
Mass Spectrum ◽  
Citric Acid ◽  
Krebs Cycle ◽  
Response Factor ◽  
Fragmentation Pattern ◽  
Acid Analog ◽  
High Concentrations ◽  
Mass Shifts ◽  
Derivatives Of ◽  
Tms Derivatives

Abstract A marked increase in analogs of Krebs cycle metabolites was found in the urine of two brothers with autistic features. These metabolites included citramalic, tartaric (3-OH-malic), and 3-oxoglutaric acids and compounds tentatively identified as a citric acid analog and partially identified as a phenylcarboxylic acid by the fragmentation pattern of the trimethylsilyl (TMS) derivatives of the compounds and mass shifts of the same compounds derivatized with perdeuterated N,O-bis(trimethylsilyl)trifluoroacetamide. The molecular mass of the TMS derivative of the tentatively identified citric acid analog was 596 Da, based on a finding of a significant M - 15 ion at m/z 581. The citric acid analog was excreted in quantities as high as 137 mmol/mol creatinine, based on the response factor of citric acid as a surrogate calibrator. A carbohydrate with a retention time and mass spectrum identical to arabinose was also found in high concentrations in the urine of these brothers.

AN ELECTRON IMPACT STUDY OF SOME C8HI0 ISOMERS

1965 ◽  
Vol 43 (1) ◽  
pp. 211-218 ◽  
Author(s):  
F. Meyer ◽  
P. Haynes ◽  
Stewart McLean ◽  
A. G. Harrison
Keyword(s):  
Mass Spectrum ◽  
Electron Impact ◽  
Mass Spectra ◽  
Major Part ◽  
The Other ◽  
Fragmentation Pattern ◽  
Impact Study ◽  
Deuterium Labelling ◽  
Appearance Potential ◽  
Alkyl Benzenes

The mass spectra of 1-, 2-, and 6-methylspiro[2.4]hepta-1,3-diene have been measured and found to be very similar to the spectra of 7-methylcycloheptatriene and the isomeric alkyl benzenes. It is concluded that in all cases the major part of the fragmentation occurs by identical paths involving identical intermediates. This conclusion is supported by deuterium labelling and appearance potential data. On the other hand the mass spectrum of 2,5-dimethyl-1,5-hexadien-3-yne, an acyclic C8H10 isomer, shows a number of significant differences in its fragmentation pattern. These differences are reflected in the energetics of ion formation and it is concluded that in this case the fragmentation proceeds through different intermediates.

Thio derivatives of β-Diketones and their metal chelates. XV. Mass spectra of cobalt(III) and rhodium(III) chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (6) ◽  
pp. 1177 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Thermal Degradation ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Cobalt Complexes ◽  
Metal Chelates ◽  
Complex Ions ◽  
Molecular Ion ◽  
Derivatives Of ◽  
Bivalent State ◽  
Cobalt Chelates

The mass spectra of the cobalt(111) and rhodium(111) chelates of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, p-BrC6H4, p-FC6H4, and 2-thienyl) and of the cobalt(111) chelate of CH3C(SH)=CHCOCF3 have been obtained. The cobalt chelates do not give a peak for the molecular ion because of thermal degradation to the cobalt(11) complex CO(RCS=CHCOCF3)2, which then undergoes reactions in the mass spectrometer. Fluorine migration occurs with cobalt but not with rhodium. The cobalt complexes give rise to more metal-containing fragments than their rhodium analogues. Mechanisms are proposed for the reactions involving the metal-containing fragments. Cobalt undergoes valency changes to give cobalt(11) and cobalt(1) complex ions, whereas rhodium undergoes a valency change to the bivalent state only.

The mass spectra of trifluoroacetyl-2,5-diketopiperazines. I. cyclo-(-Gly-X), cyclo-(-Ala-X) (X = Gly, Val, Leu, Ile), and cyclo-(-Ala-Ala)

1979 ◽  
Vol 57 (15) ◽  
pp. 2037-2051 ◽  
Author(s):  
George P. Slater ◽  
Lawrence R. Hogge
Keyword(s):  
Mass Spectrum ◽  
Mass Spectra ◽  
High Resolution Data ◽  
Fragmentation Pathways ◽  
Molecular Ion ◽  
Metastable Ions ◽  
Fragmentation Patterns ◽  
The Individual ◽  
Derivatives Of ◽  
Resolution Data

The trifluoroacetyl derivatives of the 2,5-diketopiperazines cyclo-(-Gly-X), cyclo-(-Ala-X) (X = Gly, Val, Leu, Ile), and cyclo-(-Ala-Ala) were examined by GC–MS. The molecular ion was readily detectable only for TFA-cyclo-(-Gly-Gly) (m/e 306, 9%). For those compounds containing a valyl or leucyl/isoleucyl residue the ion of highest mass in the spectrum was formed by elimination of C3H6 or C4H8, respectively, from the molecular ion. In the TFA-cyclo-(-Gly-X) series this ion corresponded to the molecular ion of TFA-cyclo-(Gly-Gly) (m/e 306), and in the TFA-cyclo-(-Ala-X) series, to the molecular ion of TFA-cyclo-(-Ala-Gly) (m/e 320). The fragmentation patterns proposed for these compounds are based on the further degradation of these parent ions so that each compound within a series has a similar mass spectrum. However, sufficient differences were detectable in the various spectra to permit identification of the individual DKP's.Many of the fragmentation pathways devised to explain the mass spectra were supported by high resolution data and appropriate metastable ions.

Thio derivatives of β-Diketones and their metal chelates. XVII. Mass spectra of iron(III) and ruthenium(III) chelates of some fluorinated Monothio-β-diketones

1974 ◽  
Vol 27 (10) ◽  
pp. 2115 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Thermal Degradation ◽  
Mass Spectrometer ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Iron Chelates ◽  
Molecular Ion ◽  
Derivatives Of

The mass spectra of the iron(111) and rhodium(111) chelates of the fluorinated monothio-β-diketones RC(SH)=CHCOCF3 (R = Ph,p-MeC6H4, 2-thienyl) have been obtained. Whereas the ruthenium(111) chelates give a peak for the molecular ion, the iron(111) chelates do not, due to thermal degradation to the iron(11) complex Fe(RCS=CHCOCF3)2 which then undergoes reactions in the mass spectrometer. Fluorine migration occurs with two of the iron chelates but not with the ruthenium chelates. Mechanisms are proposed for the reactions of the ruthenium chelates.

Fragmentation of isomeric dideoxy derivatives of 1,6-anhydro-β-D-hexopyranoses under electron impact

1981 ◽  
Vol 46 (10) ◽  
pp. 2390-2403 ◽  
Author(s):  
František Tureček ◽  
Tomáš Trnka ◽  
Miloslav Černý
Keyword(s):  
Electron Impact ◽  
Mass Spectra ◽  
Hydroxyl Group ◽  
Fragmentation Pattern ◽  
Positional Isomers ◽  
Deuterium Labeling ◽  
Stereochemical Assignment ◽  
Electron Impact Mass ◽  
Derivatives Of ◽  
Impact Mass

Electron impact mass spectra of all possible dideoxy derivatives of 1,6-anhydro-β-D-hexopyranoses and their sixteen specifically deuterium-labeled derivatives are reported. The spectra of positional isomers differ considerably making possible the reliable location of the hydroxyl group by mass spectrometry. The configuration of the hydroxyl group at C(2) and C(4) has only a negligible effect on the fragmentation pattern of stereoisomers. However, mass spectra of the C(3)-configurational isomers differ sufficiently to permit a stereochemical assignment. The fragmentation paths were elucidated by means of deuterium labeling and metastable spectra.

Thio derivatives of b-diketones and their metal chelates. XIII. Mass spectra of zinc and nickel chelates of some fluorinated monothio-b-diketones

1974 ◽  
Vol 27 (1) ◽  
pp. 53 ◽  
Author(s):  
M Das ◽  
SE Livingstone
Keyword(s):  
Metal Ion ◽  
Mass Spectra ◽  
Metal Chelates ◽  
Cyclic Structure ◽  
Molecular Ion ◽  
Metal Free ◽  
Strong Peak ◽  
Nickel Chelates ◽  
Valence Change ◽  
Derivatives Of

The mass spectra of the zinc(11) and nickel(11) chelates of four fluorinated monothio-β-diketones, RC(SH)=CHCOCF3 (R = Ph, p-MeC6H4, 2-thienyl, Me), have been obtained. The mass spectra of the nickel chelates have considerably more peaks due to metal-containing species than the spectra of the zinc chelates, while the reverse is true for the metal-free fragments. All the zinc chelates give peaks for M (molecular ion), M ? CF3, M - L (LH = monothio-β-diketone), M - L ? CF2, LH, L, L - F, RCSCH and RCS. All the nickel chelates give peaks for M, M - F, M ? CF3, M - COCF3, M - L, M- 2L and L. In addition, some of the metal chelates give other peaks. Mechanisms are proposed for the reactions giving rise to some of these species. All the zinc and nickel chelates give a strong peak due to L+ arising from a valence change of the metal ion from the bivalent to the univalent state as follows: [Me11L2]+ → L+ + Me1L (Me = Zn, Ni). It is suggested that the ion L+ has a resonance-stabilized cyclic structure.

scholarly journals Zur Chemie der 1,3,5-Triaza-2-phosphinan-4,6-dione, Teil V Darstellung der Phosphoryl(III)(λ4P)- und Thiophosphoryl(III)(λ4P)-Derivate der 1,3,5-Triaza-2-phosphinan-4,6-dione. Umsetzungen mit Ketonen Chemistry of the 1,3,5-Triaza-2-phosphinane-4,6-diones, Part V / Synthesis of Phosphoryl(III)(λ4P) and Thiophosphoryl(III)(λ4P) Derivatives of 1,3,5-Triaza-2-phosphinane-4,6-diones. Reactions with Ketones

1993 ◽  
Vol 48 (7) ◽  
pp. 860-866 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Mass Spectrum ◽  
Hydrogen Sulphide ◽  
Structure Determination ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Structural Element ◽  
Nmr Spectrum ◽  
X Ray ◽  
Derivatives Of

The phosphoryl(III)(λ4P) and thiophosphoryl(III)(λ4P) derivatives, 1,3,5-trimethyl-2-hydro-1,3,5-triaza-2-oxo-2λ4-phosphinane-4,6-dione 2 and 1,3,5-trimethyl-2-hydro-1,3,5-triaza-2-thio-2λ4-phosphinane-4,6-dione 3 were obtained from 2-chloro-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphinane-4,6-dione 1, by reaction either with water or with hydrogen sulphide. The reactions of 2 and 3 with the fluorine-containing ketones, hexafluoroacetone and trifluoroacetophenone, led to the compounds 4-7 with the P(:O)–O or P(:S)–O structural element. The compounds 2-6 were characterized via their 1H, 13C and 31P NMR spectra, mass spectra and through the X-ray structure determination of 4. Compound 7 was characterized from its 1H and 31P NMR spectrum and mass spectrum, only.

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