Die Synthese von 1,3-Bis(dichlorcarbo)-2,4-bis(dihalogen)cyclo-diborazanen

Zusammenfassung 1,3-Bis(dichlorcarbo)-2,4-bis(dihalogen)cyclodiborazane wurden durch Umsetzung von Rhodantrichlorid mit Trihalogenboranen dargestellt. Die Massenspektren und IR-Spektren bestätigen die Struktur der Verbindung, für welche die Punktgruppe D_2h angenommen wird.

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From the reaction of thiocyanogen trichloride with trihaloboranes 1,3-bis(dichlorcarbo)-2,4-bis(dihalogeno)cyclodiborazanes have been obtained. IR and mass spectra confirm the structure of these compounds, for which a D_2h symmetry is proposed.

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Mit 1 Abbildung     

Synthesis and properties of z-1,3-bis-(aryl)-4-bromo-2-buten-1-ones

Bromination of 1,3-bis(aryl)-2-buten-1-ones by N-bromosuccinimide in anhydrous carbon tetrachloride gives Z-1,3-bis(aryl)-4-bromo-2-buten-1-ones. The effect of the nature of substituent in the benzene ring on the course of a reaction with nucleophiles has been studied. Heating an alcohol solution of these ketones (Ar = 4-MeOC₆H₄, 4-ClC₆H₄) in the presence of acid or in the presence of base (Ar = Ph) gave 2,4-bis(aryl)furans. Treatment of 1,3-bis(aryl)-4-bromo-2-buten-1-ones with thioacetamide gave 2,4-bis(aryl)thiophenes. The oxidation of the halo-substituted dypnones with H₂O₂/NaOH gave (3-bromomethyl-3-aryl-2-oxiranyl)(aryl)methanones. The reaction of halo-substituted dypnones with aryl hydrazines gave 1,3,5-triaryl-1,6-dihydropyridazines or 1,3,5-triarylpyridazinium bromides depending on the structure of the reagents.     

Synthesis and characterization of poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] having high oxygen permselectivity

Cyclopolymerization of 4,4-bis(pivaloxymethyl)-1,6-heptadiyne containing a bulky ester group was examined by group 5,6-transition metal catalysts. Both of the MoCl₅-based and WCl₆-based catalysts were effective for the cyclopolymerization. The obtained polymer was characterized to have planar backbone and recurring cyclic ring structure by various spectroscopy. The poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] was soluble in common organic solvents to easily cast the free standing film. The polymer film had good mechanical property and high oxygen permselectivity to nitrogen. The oxygen permeability coefficient (PO₂) and permselectivity of oxygen to nitrogen (PO₂/PN₂) of poly[4,4-bis(pivaloxymethyl)-1,6-heptadiyne] were 19.7 barrer and 5.71, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4135–4139, 1999     

Unprecedented stereoselectivity in a reaction of a novel diboron compound — 1,6-bis(dialkylboryl)-2,4-hexadiene with carbonyl compounds

Arylboration of carbonyl compounds with a novel diboron reagent — 1,6-bis(dipropylboryl)-2,4-hexadiene — proceeds in a regio- and stereospecific way to give exclusivelyd,l-diastereomers of the corresponding 2,3-divinylsubstituted 1,4-diols. Their iodocyclization allowed preparation of 3,7-dioxabicyclo[3.3.0]octane derivatives withcis-junction of the tetrahydrofuran rings.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 160–164, January, 1993.     

Reaction of 3,4-dioxohexane-1,6-dioic acid esters with 2,4-dinitrophenylhydrazine

Reaction was studied of 3,4-dihydroxyhexa-2,4-diene-1,6-dioic acid esters with 2,4-dinitrophenylhydrazine that led to the formation of esters of (3E)-3-[2-(2,4-dinitrophenyl)-hydrazinylidene]-4-oxohexane-1,6-dioic and (3E,4E)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]-hexane-1,6-dioic acids. The structural features of compounds synthesized were established from the data of IR and NMR spectra and X-ray diffraction (XRD) analysis.     

Stereospecific synthesis of endo-endo-3,7-dioxabicyclo[3.3.0]octane lignans using 1,6-bis(dipropylboryl)-2,4-hexadiene

A general methodology for the stereoselective synthesis of compounds of the 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane series was developed. The strategy includes allylboration of aromatic aldehydes with 1,6-bis(dialkylboryl)-2,4-hexadiene, ozonolysis of the thus obtained 1,4-diaryl-2,3-divinyl-1,4-diols, and subsequent intramolecular cyclization. This methodology was used for obtaining the naturally occurring lignans of the furofuran series, viz., diaeudesmin, diayangambin, epiasarinin, epieudesmin, epiyangambin, and asarinin.     

Bildung Siliciumorganischer Verbindungen. 103. Bildung und Struktur von cis- und trans-2,4-Dichloro-2,4-bis(trimethyl-silyl)-1,1,3,3-tetramethyl-1,3-disilacyclobutan

Formation of Organosilicon Compounds. 103. Formation and Structure of cis and trans 2,4-Dichloro-2,4-bis(trimethylsilyl)-1,1,3,3-tetramethyl-1,3-disilacyclobutane The reaction of Me₃Si? CCl₂? SiMe₂Cl with LiBu in THF yields 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl) 1,3-disilabicyclo[1.1.0]butane. The product of the first reaction stage is Me₃Si? CCl(Li)-SiMe₂Cl. The 1,3-Disilacyclobutane 2 and 3 were isolated, when Me₃Si? CCl₂? SiMe₂Cl was treated with LiBu in Et₂O. This way the proof is given that 2 and 3 are intermediates of the formation of product 1 . The further products are 4 and 5 (CCl in 2 and 3 substituted by CH) and Me₃Si? CH₂? C(SiMeCl)₂SiMe₃. 2 crystallizes orthorhombically in the space group Fdd 2 (no. 43) with a = 2149.1 pm, b = 2229.2 pm, c = 1763.6 pm and Z = 16 molecules per cell. The central ring of disilacyclobutane is slightly folded (17.9°). The configuration of the C-Atoms in this four membered ring gets closer to a sp² configuration built up by three Si? C bonds. The Cl-atoms approximately have orthogonal positions to these CSi₃ arrangements. The extension of the C? Cl bonds (184.6 pm) and the mutual approximations of the Cl-atoms in the cis-position indicate a high reactivity of the molecule.     

Synthesis and structure of 1,3-bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane

Trans-silylation reactions of (Me₃Si)₂NH with PhRSiCl₂ (R = Me, Ph) gave HN(SiMePhCl)₂ (1) or ClMePhSiNHSiPh₂Cl (2). The treatment of 1,3-dichlorodisilazane (1 or 2) with an equimolar amount of n-BuLi led to the formation of 1,3-bis(chloro-silyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane (ClSiMePh)₂(NSiMePh)₂ (3) or (ClSiPh₂)₂(NSiMePh)₂ (4), which was allowed to hydrolyze to form 1,3-bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane (HOSiMePh)₂(NSiMePh)₂ (5) or (HOSiPh₂)₂(NSiMePh)₂ (6), respectively. The cyclodisilazane monomers were characterized by elemental analysis, NMR and IR spectroscopy. Compound 3 was obtained as a 4:6 cis/trans mixture while 4 adopted trans-structure considering the hindrance of pendent groups. In addition, the molecular structures of trans-5 and trans-6 were determined by X-ray crystallographic analysis and discussed in detail.     

New method of synthesis of 1,1-bis(trialkylsilyl)- and bis(trialkylgermyl)germacyclopenta-2,4-dienes

The reactions of 1,1-dichloro-2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-diene (1), magnesium, and R₃ECl (E = Si, Ge) under mild conditions (20 °C, THF) gave 1,1-bis(trimethylsilyl)-2,3,4,5-tetraphenyl-1-germacyclopenta-2,-4-diene (2a) and 1,1-bis(triethylgermyl)-2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-diene (2b) respectively. The reaction is versatile and applies to the compounds R₃ECl (E = Si, Ge) that do not react with magnesium.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2234–2236, October, 2004.     

Studies on partially polymerized 2,4-hexadiyn-1,6-bis(p-toluenesulfonate)

An improved procedure for the synthesis of high-purity 2,4-hexadiyn-1,6-bis(p-toluenesulfonate) (PTS) is described. The melting point of partially polymerized PTS increases monotonically with increasing polymer conversion (<12%). The increase in melting point is due to formation of a solid solution of unreacted monomer and polymer chains. The relation between the melting point and polymer conversion can be used for determination of polymer conversion. The low-conversion (<12%) poly PTS is soluble in dimethylformamide. The solution is yellow (λ_max ? 450 nm) and does not undergo a color change when the temperature is lowered or a nonsolvent is added. Gel permeation chromatography (GPC) studies show that the molecular weight distribution of poly PTS is very broad and does not change with increasing polymer conversion up to <12%. The degree of polymerization for the low-conversion polyPTS is very low, about 20 repeat units. The G value for initiation centers (radicals) is about 2. The properties of the low-conversion partially polymerized PTS are compared with the corresponding properties of poly(diacetylene diurethanes).     

An ESCA-study of solid 2,4-hexadiyne-1,6-diol bis(toluenesulfonate) and its constituents before and after polymerization

ESCA spectra of 2,4 hexadiyne-1,6-diol, toluenesulfonic acid and 2,4-hexadiyne-1,6-diol bis(toluenesulfonate) in monomeric and polymeric form are reported. It is shown that in the energy range of predicted deeper valence states of the polymer carbon chain the spectrum is dominated by the phenyl ring- and SO₂O-orbitals. Upon in situ-polymerization a deep valence band, 42 eV below vacuum, is formed and the highest monomer-π-orbitals constitute a 5 eV wide valence band. The ionization energy is 7 ± 1 eV.     

Mass spectral rearrangements of N,N-bis(4′-arylthio-2′-butynyl)anilines and N,N-bis(4′-arylsulfonyl-2′-butynyl)anilines

The title compounds display unusual modes of fragmentation under electron impact. One of the dominant modes is the concerted elimination of the two arylthio and arylsulfonyl moieties followed by further extrusion of the C₆H₄ unit as a cumulene. No elimination of SO₂ is observed from any of the sulfones nor an expulsion of the C₄H₄ fragment. Such behavior contrasts strikingly with that of 1,4-diarylsulfonyl-2-butynes and of the 1,6-diarylsulfonyl-2,4-hexadiynes.     

Acyl- und Alkylidenphosphane. XXVIII. Synthese und Struktur von 1,3-Dibenzyl- und 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetan

Acyl- and Alkylidenephosphines. XXVIII. Synthesis and Structure of 1,3-Dibenzyl- and 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetane Catalyzed by small amounts of solid sodium hydroxide, the adducts 1a and 1b formed from benzyl- or ethylbis(trimethylsilyl)phosphine and phenylisocyanate, react at +20°C slowly to give hexamethldisiloxane and oligomeric [(phenylimino)methylidene]phosphines. In different solvents the benzyl compound was found to exist only as a mixture of [N,N′-(E)/(Z)]-isomeric 2,4-bis-(phenylimino)-1,3-diphosphetanes 2a with their alkyl groups at the phosphorus atoms in trans position, whereas in case of the ethyl derivative 2b a second pair of [N,N′-(E)/(Z)]-isomeric dimers with their substituents in cis position and two trimeric forms ( 3b and 4b ) could be detected in cyclopentane. [N,N′-(E)]-1r,3t-dibenzyl- ( 2a ) and [N,N′-(E)]-1r,3t-diethyl-2,4-bis(phenylimino)-1,3-diphosphetane 2b isolated from 1,2-dimethoxyethane or cyclopentane, crystallize in the monoclinic space group P2₁/c or P2₁/n, resp., with following dimensions of the unit cell determined at temperatures of measurement of +20 ± 3°C/?130 ± 3°C: a = 2145.4(1)/569.3(1); b = 568.1(2)/719.1(2); c = 1960.2(2)/2042.6(4) pm; β 99.43(1)°/95.03(2)°; Z = (2+2) and 2, resp. X-ray structure determinations (R_w = 0.034/0.041) show both molecules to be centrosymmetric. Characteristic rounded bond lengths (pm) and angles (°) are: endocyclic P? C 185/184; C? P? C 82/81; P? C? P 98/99; exocyclic P? C 186/184; C?N l27/127; C?N? C 121/11.     

Reaction of acylaminocyanoesters with 2,4-bis (4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide leading to substituted aminothiazoles. Crysta

2-Acylamino-2-cyanoacetic acid ethyl esters $\text{2a-c}$ react with 2,4-bis (4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane 2,4-disulfide $\text{1}$ in refluxing benzene with formation of 2-alkyl(aryl)-5-aminothiazole-4-carboxylic acid ethyl esters $\text{3a-c}$. Structure $\text{3}$ was established by spectroscopic means and an X ray crystallographic investigation of $\text{3a}$. X-Ray analysis revealed that the thiazole ring, exocyclic nitrogen and carbonyl group forming a hydrogen-bonded cycle are nearly coplanar. A resonance interaction is manifested by distinctly shortened /1.447 (3)/ C_(carbonyl)-C_(thiazole) distance.     

Synthesis of 1,3-Bis[3-X-2-(X-acetoxy)propyl]-6-methyl- 1,2,3,4-tetrahydropyrimidine-2,4-diones

A procedure was developed for synthesizing nitrogen-and-sulfur-containing pyrimidine derivatives by reactions of 1,3-bis(3-chloro-2-hydroxypropyl)-6-methyluracil with 1-butanethiol and chloroacetyl chloride, followed by treatment of the resulting 1,3-bis[3-chloro-2-(chloroacetoxy)propyl]-6-methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione with 1-butanethiol, morpholine, and piperidine. Oxidation of the sulfur-containing products with NaIO₄ gave the corresponding sulfoxides.     

1,3,4,6-Tetracarbonyl Compounds: V. Reaction of 1,6-Disubstituted 3,4-Dihydroxy-2,4-hexadiene-1,6-diones with 2,3-Diaminopyridine

1,6-Disubstituted 3,4-dihydroxy-2,4-hexadiene-1,6-diones having two contiguous -dicarbonyl fragments readily react with 2,3-diaminopyridine to give (2Z,3Z)-bis(acylmethylene)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazines.     

Synthesis of 3,3′-(1,6-hexanediyl)bis-pyrimidine derivatives and 3,4-dithia[6.6](1.3)pyrimidinophane

Several 3,3′-(1,6-hexanediyl)bis[6-methyl-2,4(1H,3H)-pyrimidinedione] derivatives ( 4a, 4b , and 4c ) were synthesized from 1,6-(hexanediyl)bis[6-methyl-2H-1,3-oxazine-2,4(3H)-dione] (3) . Compound 4c was converted to 6, which reacted with thiourea giving thiuronium salt 7 . 3,3′-(1,6-Hexanediyl)bis [1-(2-mercaptoethyl)-6-methyl-2,4(1H,3H)-pyrimidinedione] (9) was obtained by the hydrolysis of 7 , and then 9 was oxidized to 12,22-dimethyl-3,4-dithia[6.6] (1.3)-1,2,3,4-tetrahydro-2,4-dioxopyrimidinophane (10) .     

Thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-2λ5, 4λ5-diphosphetidine

It was found that the first step of thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2, 4-dimercapto-2,4-dithioxo-1,3-diaza-2⁵,4⁵-diphosphetidine (I) most probably involves breakdown to the acid form HS(S)P(NHSiMe₃)₂P(S)SH (II). The latter is very unstable and decomposes further, the end-product being a polymer (PNS)_x. In this work, the mechanism of this process is investigated.

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Zusammenfassung Man fand, daß der erste Schritt der thermischen Zersetzung des Pyridiniumsalzes von 1,3-Bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-25,45-diphosphetidin (I) sehr wahrscheinlich einen Abbau zur Säureform HS(S)P(NHSiMe₃)₂P(S)SH (II) beinhaltet. Letztere ist sehr unbeständig und zersetzt sich, wobei als Endprodukt ein (PNS)_x-Polymer entsteht. In vorliegendem Manuskript wird der Mechanismus dieses Prozesses näher untersucht.

     

Synthesis and structure of 6-azido-2,4-bis(2,2,2-trinitroethylamino)-1,3,5-triazine and its <Emphasis Type="Italic">N</Emphasis>-nitro derivatives

Methods were developed for the synthesis of 6-azido-2,4-bis(2,2,2-trinitroethylamino)- 1,3,5-triazine and its N-nitro derivatives (6-azido-2,4-bis(2,2,2-trinitroethyl)nitramino-1,3,5-triazine and 6-azido-2-(2,2,2-trinitroethylamino)-4-(2,2,2-trinitroethyl)nitramino-1,3,5-triazine) containing combinations of azido, trinitroethyl, and nitramine groups. These compounds are of interest as components of energetic composites. The molecular and crystal structures of 6-azido-2,4-bis(2,2,2-trinitroethylamino)-1,3,5-triazine and 6-azido-2,4-bis(2,2,2-trinitroethyl) nitramino-1,3,5-triazine were studied by X-ray diffraction and NMR spectroscopy.     

Conformational analysis and electronic structure calculations of S-1,2-bis(2-dibutenoyl)glycerol and S-1,2-bis(2,4-hexadienoyl)glycerol,two analogues of 1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphorylcholine

As a model for 1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphorylcholine, a doubly unsaturated membrane-forming lipid molecule, force-field (MMP2) calculations were performed on S-1,2-bis(2-dibutenoyl)glycerol, and CNDO/S-calculations 2

1 CNDO: Complete neglect of differential overlap, a semi-empirical quantum-mechanical method.

on the derived minimum-energy conformations of S-1,2-bis(2,4-hexadienoyl)glycerol. The energy hypersurface especially with respect to the dihedral angles along the C(1)-C(2) and the two C O ester bonds was explored and the rotational strength as a function of these angles was calculated. The two gauche-forms were found to be most stable, with a slight preference for the g⁻-form. The experimental circular dichroism data obtained for 1,2-bis(2,4-hexadienoyl)-sn-glycero-3-phosphorylcholine, the corresponding phosphorylcholine, indicate a dynamic equilibrium between two forms of opposite chirality possibly involving the g⁺-and the g⁻-forms.