Synthesis of a transition metal-dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5)

The reaction of Na[η⁵-C₅H₅Fe(CO)₂] with large excess of SO₂ in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η⁵-C₅H₅)(CO)₂FeS(O)₂S(O)₂Fe(CO)₂(η⁵-C₅H₅).     

Photo-stabilising action of metal chelates in polypropylene—Part IV: Influence of metal stearates in an exchange mechanism

The effect of calcium and nickel stearates on the photo-stabilising action and photo-decomposition of one calcium and two nickel metal chelates in polypropylene has been examined using infra-red and ultraviolet derivative spectroscopy. Whereas the presence of calcium stearate antagonises the photo-stabilising action of one nickel chelate, Irgastab 2002, it strongly synergises with the other, Cyasorb UV 1084. The presence of nickel stearate synergises with the calcium chelate, Irganox 1425, in unprocessed polymer whereas, in processed polymer, it exhibits antagonism. Rates of photo-decomposition of the metal chelates are also affected by metal stearates. The data suggests that, with these nickel chelates, there might be some degree of metal exchange with certain metal stearates.     

Photo-stabilising action of metal chelates in polypropylene—Part I: Excited state quenching versus UV antioxidant action under polychromatic irradiation

The photo-stabilising action of three metal chelates—nickel (II) 2,2′ thiobis (4-tert-octylphenylato) n-butylamine and the nickel and calcium derivatives of bis (ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, in polypropylene—is examined using normal and second order derivative ultraviolet, infra-red and phosphorescence spectroscopic techniques and hydroperoxide analysis. Whilst all three stabilisers quenched the phosphorescence emission of a powerful photo-sensitiser, benzophenone, there was no protective action during photo-sensitised oxidation of the polymer. In the case of anthraquinone, there was no quenching and no protection. Processing history plays a dominant rôle in controlling the photo-stabilising performance of the chelates. Each stabiliser operates differently, being dependent on its relative stability during processing and photo-oxidation and on the formation and destruction of polymeric and antioxidant hydroperoxides during processing. Metal chelates operate by inhibiting polymer hydroperoxide formation during processing and acting as ultraviolet stable chain terminators or by giving products during the early stages of photo-oxidation which are themselves effective stabilisers.     

Azetidinyl ketone chemistry. C-Methylation reactions and stereostructure - spectra relationships

The C-methylation of the potassium salt of 1-t-butyl-2-phenyl-3-(p-phenylbenzoyl)azetidine ( 1a ) with methyl iodide was studied in three solvents, and the stereochemical outcome of the reaction was shown to be dependent upon the solvent used. These results are rationalized in terms of the probable relative rates of the reaction in the various solvents and/or the effect of solvent on the structure of the anionic intermediate. Similar treatment of the potassium salt of 1-t-butyl-2-phenyl-3-benzoylazetidine ( 3a ) in ethyl ether gave a comparable result. The configurations of the epimeric C-methyl products ( 2a and 2b , and 4a ) were assigned on the basis of their spectral properties. With the aid of spectral data for a model compound, l-t-butyl-3-benzoyl-azetidine ( 5 ), several stereostructure-spectra relationships for 3-azetidinyl ketones are presented.     

Photo-stabilising action of metal chelate stabilisers in polypropylene: Part VII—Additive interactions

The interactions of three metal chelates (nickel (II) 2,2′-thiobis (4-tertoctyl-phenolato), n-butylamine (Cyasorb UV 1084) and the nickel and calcium derivatives of bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (Irgastab 2002 and Irganox 1425)) with other commercial additives, in the stabilisation of polypropylene film, are examined using normal and second-order derivative ultraviolet and infra-red spectroscopic techniques. It is shown that the observed behaviour is dependent on the particular additive, the processing history of the polymer and the metal chelate concerned, and is therefore highly complex. All three chelates show antagonism with a hindered piperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770), in unprocessed polymer, whereas one of the chelates behaves synergistically with this additive in processed samples. The chelates also show antagonism with a primary antioxidant, tris((3-(3′,5′-di-tert-butyl-4-hydroxybenzyl)-2′'-aceto-ethyl)) isocyanurate (Goodrite 3125), whereas, with a secondary antioxidant, distearyl pent-aerithrityl diphosphite (Weston 618), their behaviour is synergistic in both unprocessed and processed polymer. Two of the chelates show synergism with 2-hydroxy-4-n-octoxybenzophenone (Cyasorb UV 531), the remaining chelate showing antagonism. Mixtures containing a three-additive system show a more complex behaviour. The results are explained in terms of hydroperoxide decomposition, inhibition, stabiliser dispersion, ultraviolet stability and additive compatibility.     

The synthesis and chemistry of some bis-aziridinylketones and their spectral study

The synthesis and spectral characteristics of certain bis(1-alkyl-3-phenyl-2-aziridinyl)ketones are reported. The reactions of 1,2,4,5-tetrabromo-1,5-diphenyl-3-pentanone ( 2 ) with primary amines are assumed to have a mechanism similar to that of a simple dibromo-ketone. The so-called cis, cis- or trans, trans-configurations of the bis-aziridinylketones were determined by ¹H and ¹³C nmr spectra.     

The effect of electronegative atoms on the structures of hydrocarbons. ab initio calculations on molecules containing fluorine or (carbonyl) oxygen

A series of ab initio calculations have been carried out, using the 4-21G basis set. Ethane and propane were first studied to obtain reference points. The effect of adding an electronegative atom (fluorine, or carbonyl oxygen) onto the framework was then studied as a function of the torsional angle about the single bond. Some pronounced trends in structural changes were observed, and these can in part be correlated with hyperconjugative effects. For example, fluoroethane has bond lengths which are shorter than those in ethane itself, by 0.024 Åin the C C bond, and 0.003 Åin the α C H bonds. These changes are essentially torsionally independent. On the other hand, in propionaldehyde, the C C bond length of the methyl group and the C H bond lengths of the hydrogens attached to the alpha carbon vary as a function of the torsion angle. If the methyl C C bond in the carbonyl plane is taken as a reference, the bond stretches .016 Åwhen the torsion angle is increased to 90°, an α C H bond similarly stretches up to .007 Å. Many of these geometric changes are large, well beyond the experimental errors in modern measurements.     

Synthesis of 9-methyl-1H-[1,4]thiazino[3,2-g]quinoline-2,5,10(3H)-trione, the B,C,D ring core of the shermilamine alkaloids

Synthesis of 9-methyl-1H-[1,4]thiazino[3,2-g]quinoline-2,5,10(3H)-trione (4), from N-(4-bromo-2,5-dimethoxyphenyl)acetamide (23) is described. Oxidative cyclisation of 2,2'-disulfanediylbis[N-(2,5-dimethoxyphenyl)acetamide] (19) to 5,8-dimethoxy-2H-1,4-benzothiazin-3(4H)-one (7b) is also reported.     

Synthesis and NMR studies of (13)C-labeled vitamin D metabolites

Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state.     

Fundamental studies of mixed-gas inductively coupled plasmas

The effects of adding foreign gases to the central-gas flow or the intermediate-gas flow of an argon inductively coupled plasma are presented. In particular, the influence of up to 16.7% added helium, nitrogen or hydrogen on radially-resolved electron number density, electron temperature, gas-kinetic temperature and calcium ion emission profiles is examined. It is shown that these gases affect not only the fundamental parameters and bulk properties of the plasma, but also how energy is coupled and transported through the discharge and how that energy interacts with the sample. For example, added helium causes an increase in the gas-kinetic temperature, most likely due to the higher thermal conductivity of helium compared to argon but, in general, does not appear to affect significantly either the electron temperature or electron concentration. The shift in the calcium ion emission profile towards lower regions in the discharge with added helium may be attributable to higher droplet desolvation and particle vaporization rates. In contrast, the addition of nitrogen or hydrogen to an Inductively Coupled Argon Plasma (Ar ICP) results in dramatic changes in all three fundamental plasma parameters: electron number density, electron temperature, and gas-kinetic temperature. The net effect of these molecular gases (N₂ or H₂) on calcium ion emission and on the fundamental plasma parameters is shown to be dependent on the amount of gas added to the plasma and whether the gas is introduced as part of the central- or intermediate-gas flow. In general, nitrogen added to the central-gas flow causes a significant reduction in the number of electrons throughout most of the discharge (over an order of magnitude in certain regions), mainly in the central and upper zones of the ICP. A drop of 3000–5000 K in the central channel electron temperature and a smaller drop in the gas-kinetic temperature are also observed when N₂ is added to the central-gas flow. In contrast, the introduction of nitrogen in the intermediate flow causes about a 1 × 10¹⁵ electrons cm⁻³ increase in the electron concentration in the low, toroidal regions of the plasma and an increase in the gas-kinetic temperature of around 1000 K throughout most of the discharge. As seen with the addition of nitrogen to the central-gas flow, the electron temperature is found to increase in the toroidal zones of the plasma when N₂ is added to the intermediate flow. These combined effects cause a 20-fold depression in the calcium ion emission intensity only a 1.7-fold depression when N₂ is added to the central- or intermediate-gas flows, respectively. On the other hand, hydrogen causes a depression in the electron concentration in the upper areas of the plasma when this gas is added to the central flow but increases the number of electrons in the same region when added to the intermediate flow. Hydrogen also causes a dramatic effect on the electron and gas-kinetic temperatures, significantly increasing both of these parameters throughout the discharge. An increase in the calcium ion emission intensity, accompanied by a downward shift, elongation and broadening of the calcium ion emission profile is also observed with H₂ addition.