Zur Darstellung von Cyclophosphaten,Cyclophosphatophosphonaten, Diphosphonaten und Diphosphiten in Harnstoffschmelzen

Preparation of Cyclophosphates, Cyclophosphatophosphonates, Diphosphonates, and Di-phosphites in Urea Melts Ammonium cyclotriphosphate (NH₄)P₃O₉, ammonium cyclotetraphosphate [P^IV? P^IV ? O? ]₂, ammonium cyclotriphosphatophosphonates Ammonium organyldiphosphonates And ammonium diphosphites are prepared in high yields on heating acidic phosphates, phosphonates, and phosphites in urea or urea/ammonium nitrate melts. The mechanism of the dehydration of phosphorus compounds containing POH groups in molten urea is discussed.     

Synthesis and psychotropic properties of furyl- and thienyl-germatranes

Trihalogermyl-furans and -thiophenes were prepared by inserting germanium dibromide (GeBr₂) generated from the dibromogermane(II) dioxanate complex into the carbon-halogen bond of halo-furans and -thiophenes. Their ethanolysis and transesterification by triethanolamine yielded the germatranes which were subjected to psychotropic activity assays. The psychotropic properties of germatranes were found to depend on the type of the heterocycle and on the position of the germatrane moiety.     

Mechanism of inhibiting action of quinones in oxidizing polymers and model compounds

Quinones (Q) do not affect the liquid-phase oxidation of hydrocarbons and retard the solid-phase oxidation of polymers terminating chains in reactions with alkyl macroradicals. This difference is the result of specific influence of a polymer matrix on the kinetics of free radical reactions. Quinones were found to terminate chains in oxidizing polypropylene containing hydroperoxide groups by the reaction with hydroperoxyl radicals. This is the result of peroxide group's decomposition with hydrogen peroxide production and chain termination in the following reactions: The equilibrium reaction between hydroquinone (QH₂) and quinonimine (QI) was evidenced to proceed as a chain reaction with chain propagation in reactions of •QH with QI and HQI• with QH₂. Analysis of the reactions of quinone with phenols (ArOH) proved that it can be important as an additional way of chain termination in oxidizing polymers and hydrocarbons at elevated temperatures.     

Polymerization of alkoxyallenes by transition-metal catalysts

The structure of polymers obtained by polymerization of methoxyallene and ethoxyallene with transition-metal catalysts depends on the catalyst employed. Rapid polymerization at 0°C through the unsubstituted double bond occurred with π-allylnickel halides, NiCl₂/AlEt₃ and CoCl₂/AlEt₃, yielding polymers with the structure Typical Ziegler–Natta catalysts (TiCl₄, VOCl₃ or FeCl₃ with AIEt₃) gave polymers mainly with the structure although some of the structural units were probably present as well. Polymers having conjugated double bonds were prepared with PdCl₂, [(π-allyl)PdCl]₂, and PdCl₂(C₆H₅CN)₂ as catalysts. Palladium iodide produced polymers with all three of the above structural units present. Polymerization occurred more slowly with these palladium catalysts. A preliminary examination of the effect of variation of solvent, ligand, co-catalyst, and temperature on the rate and structure of the polymers obtained with the palladium catalysts is reported.     

Massenspektrometrische Untersuchung organischer Stickstoffverbindungen. XXVII—Intramolekulare Redoxreaktionn bei ionisierten ortho-substituierten Nitroaromaten

Collisional activation demonstrates that the stable ions from o-nitrobenzaldehydedimethylacetale possess the structure of ionized o-nitroso benzoic acid methyl ester. Contrary to previous conclusions it is demonstrated that the structure of the stable ions (m/e 135) from different precursors [i.e. o-nitrobenzyl alcohol o-nitrobenzyl cyanide and o-nitrobenzaldoxime is best represented by 2,1-benzisoxazoline-3-one. Ionized o-nitrosobenzaldehtde rearranged to 2,1-benzisoxazoline-3-one prior to collision induced decomposition, whereas 2-benzoxazolinone and 3-hydroxy-1,2-benzisoxazole do not rearrange within 10^?5 s.     

Amino-phosphane. X. Einige Additionsreaktionen von N-Diphenylphosphinotetraphenyldiphosphin-imid

Diphenylphosphorous chloride and methyl iodide add readily to the N-bonded P(III)-atom of (C₆H₅)₂P? P(C₆H₅)₃?N? P(C₆H₅)₂ forming the salts [(C₆H₅)₂P? P(C₆H₅)₂ N P(C₆H₅)₂? P(C₆H₅)₂]Cl and [(C₆H₅)₂P? P(C₆H₅)₂ N P(C₆H₅)₂. CH₃]I, respectively. A similar behaviour is observed with sulfur: Under mild conditions (C₆H₅)₂P? P(C₆H₅)₂?N? P(C₆H₅)₂ = S is formed but forcing conditions are required to produce S = P(C₆H₅)₂? P(C₆H₅)₂?N? P(C₆H₅)₂?S. The monosulfide is also obtained by treating (C₆H₅)₂P(S)N[Si(CH₃)₃]₂ with diphenylphosphorous chloride, indicating the favoured formation of the phosphazene system as compared with the phosphazane system Confirmation of the structures comes from ³¹P nmr and IR data, and for the sulfides also from their degradation with bromine.     

Fluorsulfonylstickstoffverbindungen

The reactions of fluorosulfonylurea derivatives with phosphorus pentachloride in carbon tetrachloride leads to and . These compounds are easily fluroinated by arsenic trifluoride to the corresponding fluorosulfonyl derivatives. It was shown that PCl₅ is reliable for the fluorine-chlorine exchange. Isocyanate esterchlorides as well as carbonyl-fluoride derivatives react with compounds which have an active hydrogen atom. By this way were prepared: . By hydrolysis of , is probably formed as the first reaction product. The acid could be trapped with tetraphenylphosphoniumchloride as a well-cristalline salt. Fluorosulfonyl isocyanate reacts with aldehydes to the following compounds: FSO₂N ? CHCH₃, FSO₂N ? CHC₂H₅, FSO₂N ? CH? CH(CH₃)₂ and FSO₂N ? CHC₆H₅. The physical and chemical properties as well as IR and NMR spectra of the compounds are described and, in part, compared and discussed.     

Modification of poly(vinyl alcohol) through reaction with phosphorus-containing reactants

Crosslinked products of the form: and have been formed from the interfacial condensation of phosphorus diacid halides with poly(vinyl alcohol). Product yield and amounts of phosphorus reactant included in the product increases as the amount of base increases. Product stability in aqueous systems decreases in the order neutral > base > acid.     

Kinetics of recombination,dismutation, and disproportionation reactions involving neutral ketyl radicals and radical anions

The kinetics of fast elementary recombination of neutral ketyl radicals of benzophenone and its four derivatives (BPH?), the dismutation of benzophenone radical anions, the disproportionation between BPH? and stable nitroxyl radicals, ( ), and the electron transfer have been investigated in both individual solvents and binary mixtures of different viscosities. Reaction (1) for unsubstituted BPH in water, water glycerol, and n-hexane is controlled by diffusion with 2k₁ ? k_diff. In aliphatic alcohols and toluene, which form solvation complexes with BPH?, reaction (1) is diffusion-enhanced and activation-controlled, respectively, with 2k₁ < k_diff. In a viscous solvent such as 1-propanol–glycerol mixture (100 ? η ? 450 cP) reaction (1) is diffusion-controlled. Reaction (2) in alkaline 1-propanol and alkaline 1-propanol–glycerol mixture is activation controlled. The rates of reactions (3) and (4) for benzophenone radicals and nitroxyl radicals of the imidazoline series decrease as the viscosity of the water–glycerol and 1-propanol–glycerol mixtures is increased. The reactions are molecular mobility limited; nevertheless, the numerical values of k₃ (k₄) are 2–6 times as small as the corresponding k_diff values due to the low steric factor of the reactions (therefore called pseudodiffusion-controlled reactions). The theoretical estimates of k₃ (k₄) are in good agreement with the experimental results. The elimination of spin forbiddance in the process of radical recombination in viscous solvents is discussed.     

The mass spectra of some chlorinated aromatic pesticidal compounds

Mass spectral studies of some chlorinated aromatic pesticidal compounds are reported. The compounds studied include substituted diphenyl derivatives of methane, ethene and methanol. The diphenylmethanes are characterized by a relatively intense peak at m/e 165. Comparison of their low voltage spectra with 9-dichloromethylfluorene indicates that this ion has a fluorenyl ion structure. The structure of the base peak (m/e 246) of the diphenylethenes was investigated by comparing competitive metastable transitions with 9-dichloromethylenefluorene and utilizing defocusing metastables. Additional studies of model compounds suggest that the m/e 246 ion is very complex and is probably comprised of a number of structures. The mass spectra of the diphenylmethanols are significantly different from the other two groups. The hydroxyl group markedly affects the fragmentation process for these compounds; the characteristic peak is presumably the chlorobenzoyl ion and is probably precursor for other fragment ions. Mass spectral correlations of pesticidal compounds of similar structure are needed to obtain enough background to facilitate interpretation of the mass spectra of their metabolites. Furthermore, such studies make feasible the identification of characteristic product ions formed by rearrangement processes during ionization of organic molecules in the gas phase. This information can be a nucleus for correlating the other significant mass spectral data of an unknown compound. Intensive studies of carbamates,¹ organophosphorus² and bridged polycyclic chlorinated pesticidal³ compounds were invaluable in identifying metabolites of the aforementioned pesticides.^4,5,6 The compounds in this Work are chlorinated aromatic pesticidal compounds which consist of a diphenylemthane, a diphenylethylene, or a diphenylmethanol structure. The compounds p,?-DDE were briefly discussed by Jorg, Houriet and Spiteller.⁷ The compounds examined are listed in Table 1. Treatment of data. The mass spectra of the pesticides are presented as bar graphs in Figs 1 to 12 It a metastable peak is observed, the metastable transition is indicated by m^* on the figures and also by (m^*) when confirmed or identified using the defocusing technique.⁸ Since the relative abundances of the metastable peaks for these compounds are very small (<0.1%) on special effort was made to establish their presence unless they wre pertinent.     

The pyrolyses of tri- and tetramethylethylene in the presence of nitric oxide

The pyrolyses of trimethylethylene and tetramethylethylene have been investigated in the presence and absence of nitric oxide. It appears that apart from a unimolecular split, e.g., a disproportionation reaction such as may play an important role in initiation. Nitric oxide had no effect on H₂ production, which is probably a molecular process. There was similar behavior of both compounds in the presence of NO, indicating that the olefinic hydrogen atom does not play a decisive role. Other aspects of the mechanisms are discussed.     

Darstellung und Eigenschaften von Ti-substituierten N-Heterocyclen

Preparation and Properties of Ti-substituted N-Heterocycles The compounds (x = 2 to 6) have been prepared by transamination of Ti(NMe₂)₄ with the heterocyclic amines and have been characterised by elemental analyses and ¹H NMR and IR spectroscopy. The dependence on both x and n of the thermal decomposition has been studied for the series and . The results can be interpreted in terms of the steric strain of the R₂N and substituents. Apart from the piperidido groups none of the ligands exhibit protective group properties comparable to the R₂N groups.     

The potential energy surface for the [C2H2O]+˙ system: The ketene radical cation [CH2CO]+˙ and its isomers

Ab initio molecular orbital calculations with large, polarization basis sets and incorporating valence electron correlation have been employed to examine the [C₂H₂O]^+˙ potential energy surface. Four [C₂H₂O]^+˙ isomers have been identified as potentially stable, observable ions. These are the experimentally well-known ketene radical cation, [CH₂?C?O]^+˙ (a), and the presently unknown ethynol radical cation, [CH₂?C? OH]^+˙ (b), the oxirene radical cation (c) and an ion resembling a complex of CO with [CH₂]^+˙, (d). The calculated energies of b, c and d relative to a are 189, 257 and 259 kJ mol^?1, respectively. Dissociation of ions a and d is found to occur without reverse activation energy.     

Conformational energy surfaces of triplet-state isomeric methyloxiranes

A conformational study was carried out on the three ring-opened structures of triplet methyloxirane with a minimal Gaussian basis set, within the unrestricted Hartree–Fock framework. For the two structures energy surfaces E(θ₁, θ₂) were generated, where θ₁ measures the methyl rotation and θ₂ is associated with the torsion about the other C? C bond. For the third structure an energy hypersurface E(θ₁, θ₂, θ₃) was generated, where energy was a function of methyl rotation θ₁ and two nonequivalent C? O rotations θ₂ and θ₃. Analysis of the surfaces revealed the locations and relative energies of the critical points (minima, saddle points, and maxima). The overall stereochemical finding was that these ring-opened triplet C₃H₆O species possessed rather flexible structures.     

Kinetics of the First Order Autocatalytic Decomposition Reaction of Nitrocellulose （13.86% N）

The kinetics of the first order autocatalytic decomposition reaction of nitrocellulose (NC, 13.86% N) was studied by using DSC. The results show that the DSC curve for the initial 50% of conversion degree of NC can be de scribed by the first order autocatalytic equation dy/dt =-10^16.3 exp (-181860/RT)y-10^16.7ex(-173050/RT)y(1-y) and that for the latter 50% conversion degree of NC described by the reaction equations dy/dt=-10^16.4exp(-154820/RT)y (n=1) and dy/dt=-10^16.9 exp(-155270/RT) y^2.80(n≠1).     

Synthesis and characterization of 4‐aryl‐5‐(1‐aryl‐2‐methyl‐2‐nitropropyl)‐1,2,3‐selenadiazoles

The synthesis of a new set of selenadiazoles, 4‐aryl‐5‐(1‐aryl‐2‐methyl‐2‐nitropropyl)‐1,2,3‐selenadiazoles ( 4 ) derived from 2‐[4‐methyl‐4‐nitro‐1,3‐diarylpentylidene]‐1‐hydrazinecarboxamide ( 3 ) has been reported. THF has been found to be the solvent of choice for this reaction. Structural features of 3 and 4 have been analyzed by NMR and X‐ray techniques.     

HNO,an Intermediate in (Light-induced) Rearrangement Reactions of Nitrosooxy Compounds and Nitrosamines

IR-spectroscopic investigations of light-induced rearrangement reactions of nitrosooxymethane (CH³ONO³), nitrosooxyethane (CH₃CH₂ONO) and N,N-dimethylnitrosamine ((CH₃)₂NNO) in low-temperature rare-gas matrices have established that these molecules are transformed in two photolysis steps to the previously unknown C-nitroso compounds nitrosomethanol (CH₂(OH)(NO)), 1-nitrosoethanol (CH₃CH(OH)(NO)), and methyl(nitrosomethyl)amine CH₂(NO)(NH)(CH₃). Evidence for a similar rearrangement reaction has been advanced for N-Nitrosopyrrolidine which is converted to C-nitrosopyrrolidine . The matrix-isolation technique in combination with wavelength-selective irradiation allowed to trap and characterize an intermediate of rearrangement which revealed to be nitroxyl (HNO) complex (CH₂…HNO, CH₃CHO…HNO, CH₃N = CH₂…HNO, and ). Since these findings have a close resemblance with rearrangement reactions of more complex nitrosooxy compounds, nitrosamines, or nitrosohydrazines used in organic synthesis, it is suggested that also in these reactions nitroxyl is present as an intermediate species.     

Flash Photolysis of 2,4,6-Trinitrotoluene Solutions

Flash photolysis of 2,4,6-trinitrotoluene solutions (TNT) indicates a photochemically induced isomerization leading to the aci-quinoid isomer with an absorption maximum at 460 nm in nonpolar solvents, or the conjugate base of the aci-quinoid isomer with absorption maxima at 500, 540, and 630 nm in polar solvents. Both species, the quinoid isomer and the conjugate base, have transient existence and their identification was based on detailed spectroscopic and kinetic studies presented here. The magnitude of the negative charge on the transient conjugate base was determined with salt effect experiments and found to be equal to unity.