Pigments of cottonseed. IV. Gossypurpurin,a purple pigment related to gossypol

Summary Gossypurpurin was prepared from gossypol via diaminogossypol, and its properties compared with gossypurpurin isolated from cottonseed pigment glands. A tentative molecular formula for synthetic gossypurpurin, C₃₀H₃₂O₇N, has been proposed on the basis of its elementary composition. The native pigment could not be obtained in the same degree of purity as the synthetic product and the analytical data could therefore not be brought into exact agreement for the two products. However solutions of both pigments in chloroform exhibit almost identical absorption spectra and identical antimony trichloride tests. Qualitative reactions seem to indicate that the functional groups of both native and synthetic gossypurpurin are identical, and the ready conversion of both products to gossypol upon contact with acid seems to indicate that their basic structures are similar. Presented before the 4th Southwest Regional Meeting of the American Chemical Society, Shreveport, La., December 9–10, 1948. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

New Aspects of Impact Reactivity of Polynitro Compounds. Part IV. Allocation of Polynitro Compounds on the Basis of their Impact Sensitivities

A linear relationship has been found between the drop energies of impact sensitivity detected by sound and the drop energies of “the first reaction” for 28 polynitro compounds. In the sense of this relationship, the compounds studied fall into three classes. The reason of the said diversification lies in the decomposition reaction rate at the temperature of the beginning of their thermolysis. It is stated that some relationship exists between vibrational excitation by impact, on the one hand, and thermal activation of the molecules of energetic materials, on the other one.     

The Anomalous Behaviour of 18O-Labelled Compounds. Part IV. Vibrational Spectra of Isotopic Vanadate Ions

The Raman spectra of crystalline hydrated normal and 80 atom% ¹⁸O-labelled sodium orthovanadates were investigated, the bands observed thus being assigned to their respective original modes of vibration. The Raman bands of the aqueous solutions of these vanadates, containing mainly the respective HVO^4?₂ or DVO^4?₂ ions, were also studied and in most cases observed to rise in frequency as a result of the ¹⁸O-labelling, as expected on the assumption that the hydrogen bonding between the solvating water molecules and the vanadate ions is weakened by ¹⁸O-labelling the latter.     

Hydrolytic Condensation of Tin(IV) Alkoxide Compounds to Form Particles with Well-Defined Morphology

The sol-gel-type condensation of tin(IV) ethoxide [Sn(OEt)₄] n (where OEt is ethoxide) under basic conditions produced spherical, submicrometer-sized tin(IV) oxide (cassiterite) particles. Transmission electron microscopy and powder X-ray diffraction data indicated that the grain size was approximately 20 to 30 Å (2 to 3 nm). The mixed-metal alkoxide compound [ZnSn(OEt)₆] was hydrolyzed under analogous conditions to give either spherical or octahedral submicrometer-sized crystalline particles of ZnSn(OH)₆ depending on the solvents used. These data demonstrated that the stoichiometry of the mixed-metal alkoxide precursor was retained during condensation. Thermal treatment of ZnSn(OH)₆ resulted in crystallization of ZnSnO₃ at approximately 676°C. At neutral pH, hydrolysis of [ZnSn(OEt)₆] resulted in formation of a high surface area (261 m²/g) amorphous powder.     

Arylmercury Compounds. Part VI. Asymmetric Diarylmercury Compounds

Asymmetric diarylmercury compounds were produced together with symmetric products via a symmetrization process. The asymmetric products could not be isolated from the reaction mixture and their existence was indicated through different analyses (mp, IR, PMR, mass spectra, elemental analysis and DTA). The asymmetric products were shown to be unstable and to disproportionate into two symmetric compounds at elevated temperatures, and in organic solvents even at room temperature.     

Theoretical Study for High-Energy-Density Compounds Derived from Cyclophosphazene. IV. DFT Studies on 1,1-Diamino-3,3,5,5,7,7-hexaazidocyclotetraphosphazene and Its Isomers

In the present study, a theoretical study of 1,1-diaminohexaazidocyclotetraphophazene (DAHA) and its isomers has been performed, using quantum computational density functional theory (B3LYP and B3PW91 methods) with 6-31G* and 6-31G** basis sets implemented in Gaussian 03 program suite. Molecular structure and bonding, vibrational frequencies, Milliken population analysis, and natural bond orbit (NBO) have been studied. The heats of formation from atomization energies have also been calculated based on the optimized geometry. The obtained heats of formation data are compared with their homologous cyclophosphazene in order to demonstrate the accuracy of the methods, which indicate that the studied compounds might be potentially used as high energetic materials. In addition, the relative stability of five isomers have been deduced based on the total energy and the gap of frontier orbital energies.     

Reactions of Oxiranes and Carbonyl Compounds Catalyzed by Ammonium Decatungstocerate(IV)

Various types of oxiranes react with acetone in the presence of catalytic amounts of ammonium decatungstocerate(IV) icosahydrate, (NH₄)₈[CeW₁₀O³⁶] ? 20H₂O, to give the corresponding 1,3-dioxolanes in excellent yields.     

Emission of Volatile Organic Compounds to the Atmosphere in the Solvent Sublation Process. II. Volatile Chlorinated Organic Compounds

Abstract

The mass of trichloroethylene, chlorobenzene, and 1,3-dichlorobenzene removed from an aqueous solution and emitted to the atmosphere during solvent sublation was determined experimentally. It was shown that the emission of these compounds in solvent sublation was reduced by 30 to 85% over air stripping under the same experimental conditions. The efficiency of removal of these compounds from water was also studied. The reduction of emissions over air stripping was more effective for the more hydrophobic and less volatile compounds. Emissions are reduced as the thickness of organic layer on the top of the column is increased. The use of decyl alcohol as the layer compound decreases emissions to a greater extent than does paraffin oil. Removal of these chlorinated volatile organic compounds from water by solvent sublation at an elevated temperature of 45°C is significantly faster than at room temperature. However, the emissions to the atmosphere are also increased.     

Methanesulfonic acid-catalyzed additions IV. Additions to methyl linoleate

Varied aromatic compounds including phenol,o-chlorophenol, 2-naphthol, resorcinol, methyl salicylate, anisole, phenetole,p-toluenethiol,p-chlorobenzenethiol and 2-napthalenethiol were added to methyl linoleate. Using methanesulfonic acid as a solvent-catalyst the additions took place as readily as to oleic acid in previous experiments. The recovery of mono-adducts, however, was complicated by the presence of di-adducts and presumably polymeric material. As observed in the earlier oleic acid studies, evidence for the formation of ether intermediates was obtained. The only identified products from arylthiol additions were thioethers. Presented at the AOCS Meeting in Minneapolis, 1963. A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, USDA.     

Paired electrooxidation IV. Decarboxylation of sodium gluconate to D-arabinose

A paired electrooxidative method has been developed to synthesize D-arabinose in a divided cell. D-arabinose is a material which has an important role in the production of vitamin B2 and DNA. Sodium gluconate was directly oxidized at the anode and indirectly oxidized in the catholyte by bubbling oxygen which was reduced to H₂O₂ and OH free radicals. In the catholyte, indirect oxidation of sodium gluconate was mediated by Fe³⁺ and OH free radicals. The optimal current efficiencies for D-arabinose production in the anolyte and catholyte were found to be 88.37% and 39.12%, respectively, and the total current efficiency of the paired electrooxidation was 127.49%. The paired electrosynthesis of D-arabinose is more economical in terms of power consumption than electrosynthesis that employ a single anode or cathode as the working electrode. The influence of cathodic/anodic CV and I/E curves, redox mediators and the amount of charge passed were also examined.     

Synthesis of Solid Phosphate Compounds of Ti(III) and Ti(IV)

Several new methods for the synthesis of TiPO₄ are described. Crystalline phosphate compounds containing boron and titanium in a single III or mixed (III, IV) oxidation states have been synthesized and identified by X-ray diffraction. An additional family of phosphate compounds containing only Ti(III, IV) has also been synthesized and identified. All the compounds exhibit attractive colors, e.g., bright green, blue, purple, and black, and are stable at room temperature in air and in boiling water.     

Modified bead-spring theory of polymer solutions. IV. Extension to polymer melts

A constitutive equation which has proven quite successful in describing the nonlinear viscoelastic behavior of dilute polymer solutions is extended to the case of molten polymers. The techniques utilized and similar to those discussed by Ferry in a similar adaptation of the Rouse–Zimm Theory. The resulting model is found to quantitatively portray the shear rate dependence of the non-Newtonian viscosity and primary normal stress functions and the frequency dependence of the storage and loss moduli. Extensional flow data reported by Spearot and Metzner for two polyethylenes are well described, using parameters calculated from steady shearing measurements. Of major significance is the ability of the model to account for influences of molecular weight, molecular weight distribution, and temperature.     

Pyrolysis of phenolic resins. IV.

Thermoset resins were made from benzene, naphthalene, phenanthrene, anthracene, or pyrene by condensation with p-xylylene dichloride in presence of stannic chloride. The extent of reaction, consequently the crosslink density, was controlled by measurement of the HCl evolved. The absence of oxidation was confirmed by infrared spectroscopy. On pyrolysis at 500, 1000, and 1200°C. in vacuo (after Madorsky) it was found that the yield of char was directly related to the number fraction of carbon atoms in the aromatic nucleus used. Benzene was anomalous, and all resins gave lower char yields than standard phenol formaldehyde resins.