A new reaction of phosphorylated N-sulfonylimines with hydrophosphoryl agents involving C → N transfer of phosphoryl groups

Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates.     

Linear Relations, Differential Inclusions, and Degenerate Semigroups

A generalized linear differential equation in a Banach space is studied. The construction of a phase space and solutions with the help of the spectral theory of linear operators, ergodic theorems, and degenerate semigroups of linear operators is carried out.     

New method for the preparation of O-carbamoyl derivatives in the 4-hydroxyaminoimidazolidin-2-one series

The corresponding 4-(O-carbamoylhydroxyamino)imidazolidin-2-ones were obtained by cyclization of O,N-dicarbamoyl derivatives of N-(3-oximino-2-methyl-2-butyl)- and N-(1-oximino-2-cyclohexyl)methylamines in alkaline media. It was shown that the carbamoylation of 1-methyl-4,5-tetramethylene-3-(3,4-dichlorophenyl)-4-hydroxy-aminoimidazolidin-2-one gives, respectively, an O- or N-carbamoyl derivative, depending on whether it is carried out in alkaline or neutral solutions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 399–401, March, 1984.     

New example of the dimroth rearrangement. Intramolecular cyclization of acyl derivatives of anthranilic acid nitrile

A new example of the Dimroth rearrangement in which 4-amino-1H-quinazolin-2-one 3(N)-oxide undergoes isomerization to 4-oximino-1H, 3H-quinazolin-2-one was observed. It is shown that the thermal cyclization of N-(2-amidoximophenyl)ureas and carbamates leads to the production of 4-amino-1H-quinazolin-2-one 3(N)-oxides, while their O-carbamoyl derivatives give 4-oximino-1H, 3H-quinazolin-2-one and 5-oxo-²-1,2,4-oxadiazolino[c3,4]-1H,3H-quinazolin-2-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1264–1266, September, 1981.     

Synthesis of thiirane oximes from 3,4-dibromo-3-methyl-2-butanone oxime

2-(-Oximinoethyl)-2-methylthiirane was obtained by the reaction of 3,4-dibromo-3-methyl-2-butanone oxime with sodium sulfide. At the same time, the O-carbamoyl derivative of the ,-dibromo oxime was converted to the corresponding substituted ,-unsaturated oxime under the same conditions. Thiirane oxime, like its O-carbamoyl derivative, underwent the desulfuration that is characteristic for thirranes under the influence of tributylphosphine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 751–753, June, 1982.     

High resolution emission Fourier transform infrared spectra of the 4p-5s and 5p-6s bands of ArH

In the 2500-8500 cm(-1) region several strong emission bands of (40)ArH were observed by Fourier transform spectroscopy through a dc glow discharge in a mixture of argon and hydrogen. Rotational-electronic transitions of the two previously unstudied 4p-5s and 5p-6s,v = 0-0, bands of (40)ArH were measured and assigned in the 6060 and 3770 cm(-1) regions, respectively. A simultaneous fit of the emission transitions of the 4p-5s and 5p-6s bands and an extended set of transitions of the 6s-4p band observed by Dabrowski, Tokaryk, and Watson [J. Mol. Spectrosc. 189, 95 (1998)] and remeasured in the present work yielded consistent values of the spectroscopic parameters of the electronic states under investigation. In the branch of the 4p-5s band with transitions of type (Q)Q(f(3)e) we observed a narrowing in the linewidths with increasing rotational quantum number N. The rotational dependence of the linewidth is caused by predissociation of the 5s state by the repulsive ground 4s state through homogeneous coupling and changes in overlap integrals of the vibrational wave functions with the rotational level. Analysis was based on the Fermi's golden rule approximation model. In the 4p-5s band region a vibrational sequence ofv(')-v(")=1-1, 2-2, and 3-3 were recorded and a number of transitions belonging to the strongest (Q)Q(f(3)e) form branch of the 1-1 band were analyzed.     

Direct vinylation of glucose derivatives with acetylene

Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.     

Facile syntheses of unsolvated UI3 and tetramethylcyclopentadienyl uranium halides

In the course of comparing the reaction chemistry of (C5Me5)3U, 1, and its slightly less crowded analogue (C5Me4H)3U, 2, new syntheses of UI3, (C5Me4H)3U, (C5Me4H)3UCl, 3, and (C5Me5)3UCl, 4, have been developed. Additionally, (C5Me4H)3UI, 5, and (C5Me4H)2UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated UI3 is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both UI3 and UI3(THF)4 react with KC5Me4H in toluene to make unsolvated (C5Me4H)3U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)3UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)3U reacts with PhI or HgI2 to generate (C5Me4H)3UI. These studies also provided a basis to improve the synthesis of (C5Me5)3UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)3UCl, the (C5Me4H)3UCl complex reacts with HgCl2 to form (C5Me4H)2 and (C5Me4H)2UCl2, 6, but unlike (C5Me5)3UX (X = Cl or I), the less substituted (C5Me4H)3UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl x THF and UCl4 is also included.     

Herbicidal hydroxylamine derivatives

The synthesis of 2-alkyl(dialkyl)amino-4-chloro-sym-triazine derivatives of hydroxylamine, N-methylhydroxylamine, and N-phenylhydroxylamine has been effected and their properties have been studied. The thermal and catalytic polycondensation of the 2-alkyl(dialkyl)amino-4-chloro-6-N-phenyl(methyl)hydroxyamino-sym-triazines accompanied by the liberation of hydrogen chloride and the formation of linear polycondensates with 3–4 members has been observed.For part IX see [9].