Reactions of dimethyl acetylenedicarboxylate—VI : Reaction with aldehyde and ketone phenylhydrazones

Benzaldehyde phenylhydrazone with dimethyl acetylenedicarboxylate gives dimethyl 1,3-diphenylpyrazoline-4,5-dicarboxylate, dimethyl 1,3-diphenylpyrazole-4,5-dicarboxylate and trimethyl 1-phenylpyrazole-3,4,5-tricarboxylate; p-chlorobenzaldehyde phenylhydrazone gives trimethyl 1-phenyl-3,4,5-tricarboxylate and 1,2-(bis-phenylazo)-1,2-di-p-chlorophenylethane. Under similar conditions, p-tolualdehyde phenylhydrazone gives only trimethyl 1-phenylpyrazole-3,4,5- tricarboxylate. Acetophenone phenylhydrazone with dimethyl acetylenedicarboxylate gives dimethyl 1,3-diphenylpyrazole-4,5-dicarboxylate. Benzophenone phenylhydrazone, on the other hand, gives a mixture of dimethyl 1,3-diphenylpyrazoline-4,5-dicarboxylate and dimethyl 1,3-diphenylpyrazole-4,5- dicarboxylate. Benzyl methyl ketone and dimethyl acetylenedicarboxylate gives an enamine maleate, which is the Michael addition product.     

Iron-57 Mössbauer effect study of the distribution of divalent and trivalent ions in potassium transition metal fluorides having the tetragonal bronze structure

Mössbauer studies are reported for compounds of the type KM^IIM^IIIF₆ (M = first-row transition metal ion, Zn, or Mg) which have the tetragonal bronze structure. The results of this investigation provide evidence that the trivalent ions are located on the 8(j) sites of the bronze structure and that the divalent ions are distributed over both the 8(j) and 2(c) sites.     

Symmetry allowed π4s+π2s additions silacyclopentadienes

π⁴s+π²s cycloaddition of hexaphenylsilacyclopentadiene with ethyl acrylate gives rise to a bicyclosilaheptene derivative. High resolution NMR studies have shown that the ester group in this adduct is in the endo position and that the ester methylene protons are magnetically inequivalent. Similar cycloadditions of hexaphenylsilacyclopentadiene, 1,1-dimethyl-2,3,4,5-tetraphenylsilacyclopentadiene, 1-methyl-1,2,3,4,5-pentaphenylsilacyclopentadiene, and 1-methyl-1-vinyl-2,3,4,5-tetra-phenylsilacyclopentadiene with dienophiles like acrylonitrile, maleic anhydride and dibenzoylacetylene have been carried out. The stereochemistry of these adducts has been deduced on the basis of NMR studies. Mass spectral fragmentation studies of some of the silabicycloheptenes have been carried out.     

Concerted cycloaddition of chlorosulfonyl isocyanate to α-pinene stepwise rearrangement of the β-lactam cycloadduct to a γ-lactam

Chlorosulfonyl isocyanate adds to α-pinene in concerted fashion to give the unrearranged N-chlorosulfonyl-β-lactam 2 (75%). Thermolysis of cycloadduct 2 affords the rearranged N-chlorosulfonyl-γ-lactam 6 (60%) via a sequence of transient carbonium ions (45). Reductive hydrolysis of 2 and 6 gave, respectively, the NH-β-lactam 3 (70%) and the NH-γ-lactam 7 (70%). Proof of structure of the rearranged γ-lactams 6 and 7 are provided, respectively, by X-ray crystallographic analysis and the application of the Eu(dpm)₃ NMR shift reagent.     

He I (584 Å) photoelectron spectra and photoionization cross sections of atomic chlorine and bromine

Well-resolved He I photoelectron spectra of atomic chlorine and bromine have been obtained without serious background electrons, giving rise to relative photoelectron intensities associated with differential photoionization cross sections at an angle of 90° with respect to the incident 584 Å radiation.     

Structural refinements of praseodymium and neodymium orthophosphate

The crystal structures of PrPO₄ and NdPO₄ have been determined by single crystal X-ray diffraction techniques. The structures are isostructural with CePO₄ and LaPO₄, and are monoclinic in space group $\text{P2}{}_1\text{n}$. The cell constants are a = 6.741(3), b = 6.961(4), c = 6.416(3) Å, and β = 103.63(3)° for PrPO₄ and a = 6.722(1), b = 6.933(1), c = 6.390(2) Å, and β = 103.72(2)° for NdPO₄. The least-squares structural refinements of PrPO₄ and NdPO₄ yielded R values of 0.034 and 0.038 based on 810 and 947 unique reflections, respectively. The lanthanide metal atoms are coordinated with nine oxygens and are linked together by very slightly distorted tetrahedral phosphate groups. The nine oxygen atoms ligating the lanthanide atoms form a polyhedron that is best described as a pentagonal interpenetrating tetrahedron.     

Low temperature spectroscopic observation of oxygen-protonated troponeiron tricarbonyl complexes

Troponeiron tricarbonyl and 7-methyltroponeiron tricarbonyl undergo kinetically controlled oxygen protonation at low temperatures to give the corresponding hydroxytropyliumiron tricarbonyl cations, observable by ¹C and ¹H NMR spectroscopy. At higher temperatures, the oxygen-protonated species isomerize to yield the thermodynamically more stable carbon-protonated pentadienyliron tricarbonyl cations.     

Spectrophotometric determination of phosphate by extraction of reduced molybdoantimonylphosphoric acid with acetophenone-chloroform

A 90% ($\text{v}\text{v}$) mixture of acetophenone-chloroform is an effective extractant for reduced molybdoantimonylphosphoric acid. The extraction is quantitative over the acidity range of 0.04 to 4.8 N sulfuric acid. The mixed solvent extractant is virtually immiscible with water and can be used at aqueous/organic volume ratios from 1:1 to 40:1 with no loss of solvent or decrease in % extraction. Phosphate is easily determined from 5 to 1000 ppb. No interference from silicate was experienced.     

A high pressure thermobalance

A high pressure thermobalance was assembled by placing a DuPont Model 950 balance into a stainless steel enclosure. The thermobalance is capable of operation to a maximum pressure (of N₂) to 500 atm and to a maximum temperature of 500°C. Operation of the instrument is illustrated by the thermogravimetric curves of BaBr₂·2H₂O, CuSO₄·5H₂0 and NaHCO₃ at various pres     

Non-linear relaxation methods: III. Current-controlled perturbations

A functional expression is derived valid for evaluating all orders of perturbation in potential when a current of known profile is super-imposed. Generalised expressions for the distortion and the rectification potential are given. The problems of “iR-drop” and “charging current” compensation are also discussed.