Umsetzung von 2-Dimethylamino-(1,3,2)-diox-, oxathi- und dithi-arsolanen mit Alkoholen und Thiolen

Reaction of 2-Dimethylamino-(1,3,2)-diox-, oxathi-, and dithi-arsolanes with Alcohols or Thiols The reactions of 2-dimethylamino-(l, 3,2)-diox-, oxathi- and dithi-arsolanes (CH₂)₂XYAs? N(CH₃)₂ (X = Y = O or S; X = S, Y = O) with alcohols and thiols yield by cleavage of the As? N bond in the formation of alkoxy and alkylmercaptoarsolanes (CH₂)₂XYAs? ZR (X = Y = Z = O or S; X = Y: O, Z = S; X = Y = S, Z = O; X = S, Y = O, Z = O or S), respectively. Some of these arsolanes are not stable but rearrange under formation of 1,2-Bis-(arsolanyl)ethane and arsinous acid esters.     

Monomere Tetramethylarsen- und Antimon-Verbindungen mit fünffacher Koordination am Zentralatom

Monomeric Tetramethylarsenic and Antimony Compounds with Coordination Number Five at the Central Atom The pentaalkyl compounds (CH₃)₅As and (CH₃)₅Sb react with aequimolar amounts of alcohols, hydroxylamines, and oximes to produce methane and the compounds (CH₃)₄MX (with X = ? OR, ? ONH₂, ? ONR₂, ? ON?CR₂ and M?As, Sb). According to vibrational spectra and low temperature ¹H-n.m.r. spectra the monomeric compounds posses a trigonal bipyramidal structure.     

Massenspektrometrische Analyse von 2-Alkoxy-und 2-Alkylmerkapto-(1,3,2)Diox-, Oxathi-und Dithi-Arsolanen

The electron-impact and chemical ionisation mass spectra of the arsolanes (CH₂)₂XYAs? ZR (X, Y and Z = O or S) are compared and the main fragmentation routes given. Electron-impact and chemical ionisation spectra show a dimerisation of the arsolanes.     

α, ω-Alkan-bis-dimethylarsansulfide und -selenide,eine neue Klasse von Liganden

α ω-Alkane-bis-dimethylarsine Sulfides and Selenides, a Novel Class of Ligands The reaction of α,ω-alkane-bis-dimethylarsanes (CH₃)₂As? (CH₂)_n? As (CH₃)₂ with sulfur and selenium results in formation of the sulfides and selenides, respectively, (CH₃)₂As(X)? (CH₂)_n? As(CH₃)₂ or (CH₃)₂As(X)? (CH₂)_n? As(X)(CH₃)₂ (X = S, Se), which form chelat-complexes with the salts CoX₂ · 6 H₂O (X = Cl^?, Br^?, I^?, NO₃^?). The UV-spectra of the complexes are presented and discussed.     

Anilinolysis of nitro‐substituted diphenyl ethers in acetonitrile: The effect of some ortho‐substituents on the mechanism of SNAr reactions

Rate data are reported for the reactions of a series of X‐phenyl 2,4,6‐trinitrophenyl ethers 1a–e [X = H, 4‐NO₂, 2‐NO₂, 2,4‐(NO₂)₂, or 2,6‐(NO₂)₂] with substituted anilines 2a–e [Y = H, 2‐CH₃, 2,4‐(CH₃)₂, 2,6‐(CH₃)₂, or N‐CH₃] in acetonitrile as solvent. For individual amine, kinetic data show that there is little steric hindrance to attack at the 1‐position of the parent molecules, even in the presence of di‐ortho substitution. With each substrate, however, there is evidence for significant steric interactions; such effects leading to rate retardation were very severe for 2,6‐dimethylaniline 2d (2,6‐(CH₃)₂) and N‐methylaniline 2e (Y = N‐CH₃), the deactivating effect of N‐CH₃ in most cases is slightly higher than that of 2,6‐(CH₃)₂. However, the reactions with 2e are base catalyzed whereas those of 2d are not. The corresponding reactions with aniline 2a (Y = H) and mono‐ortho methyl‐substituted aniline 2b (Y = CH₃) are wholly base catalyzed. Only with the dinitro substrates, an uncatalyzed reaction is observed and when X = 2,6‐(NO₂)₂ this pathway takes all the reaction flux. A rationale is provided for the dichotomy of amine effects observed in this investigation. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 37–49, 2010     

Synthese von methyldihalogenarsinen CH3AsXY mit verschiedenen halogenen XY

The reactions of the methylhalogenodimethylaminoarsines CH₃As-[N(CH₃)₂]X (X  F, Cl, Br, I) with HY (Y = Cl, Br) yield the methyldihalogenoarsines CH₃AsXY. The compounds CH₃As[N(CH₃)₂]X are prepared by the reactions of CH₃AsCl₂ with HN(CH₃)₂, CH₃As[N(CH₃)₂]₂ with HX (X = Cl, Br) and by exchange reactions between CH₃As[N(CH₃)₂]₂ and CH₃AsX₂ (X = F, Cl, Br, I).     

Synthesis of polyphosphazenes bearing alkoxyethoxy and trifluoroethoxy groups

The synthesis of various phosphoranimines including (CH₃OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si(CH₃)₃, (CH₃OCH₂CH₂OCH₂CH₂O) (CF₃CH₂O)₂P?N? Si (CH₃)₃, (CH₃OCH₂CH₂O)₂(CF₃CH₂O) P?N? Si(CH₃)₃, and (CH₃OCH₂CH₂OCH₂CH₂O)(CF₃CH₂O) P?N? Si(CH₃)₃ via the Staudinger reaction of (CH₃)₃SiN₃ with the suitably substituted phosphite is reported. These monomers were polymerized using tetra-n-butylammonium fluoride and N-methylimidazole in various solvents at several temperatures. In situ ³¹P-NMR kinetic studies and M_n versus time studies were also performed for the monomers to understand the propagation mechanism. © 1994 John Wiley & Sons, Inc.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Umsetzung von Dimethylaminodimethylarsin mit 1,2-Diolen

Reaction of Dimethylamino Dimethylarsine with 1,2-Diols The reactions of (CH₃)₂As? N(CHs₃)₂ with 1,2-diols lead to the formation of the esters (CH₃)₂As? O? CR₂? CR₂? O? As(CH₃)₂ and (CH₃)₂As? O? CR₂? CR₂? OH. The same reaction with HS? CH₂CH₂? OH yields only (CH₃)₂As? S? CH₂CH₂OH, whereas the cleavage of the As? N bond with HS? CH₂CH₂? SH results in mixture of mono- and diesters. The mechanism and its influence on the products are discussed. IR and ¹H-NMR spectral data are presented.     

Synthesis und Reaktivität von Dimethylaminoalkylidenaminooxy-arsinen

Synthesis and Reactivity of Dimethylaminoalkylideneaminooxiarsines The reactions of As[N(CH₃)₂]₃ with oximes result in the formation of the oximates [(CH₃)₂N]₂AsONCRR′, (CH₃)₂N As(ONCRR′)₂ and As(ONCRR′)₃. The eleavage of the As-N-bond with alcohols, thiols and diols are described. The reactions of CH₃As[N(CH₃)₂]ONCRR′ with water, amine and alcohols are examined. IR-and ¹H-NMR-spectral data are presented.     

Reactions of N-heteroarylformamide oximes and N-heteroarylacetamide oximes with N,N-dimethylformamide dimethyl acetal. Synthesis of 2-methyl-s-triazolo[1,5-x]azines and N-methylcyanoaminoazines

N-Heteroarylformamide oximes 3 (R ? H) were converted with N,N-dimethylformamide dimethyl acetal (DMFDMA) into N-heteroaryl-N-methylcyanoamino compounds 5 , as the main products. In some instances N-heteroarylcyanoamino compounds 4 , cyanoimino compounds 7 , and some other products, such as 9 and 10 were also formed. On the other hand, N-heteroarylacetamide oximes 3 (R ? CH₃) were cyclized under the same reaction conditions into 2-methyl-s-triazolo[1,5-x]azines ( 6 ). N-Heteroarylacetamide O-methyl oximes 11 and 12 were prepared from the corresponding acetamidines 2 (R ? CH₃) and O-methylhydroxylamine.     

Protonenresonanzuntersuchungen an Aminoboranen—II: Einflüsse von para-Phenylsubstituenten auf die Rotationsbarriere um die N?B-Bindung

The electronic influence of substituents on the free enthalpy of rotation around the N? B bond in aminoboranes was investigated in two series of compounds: (a) (CH₃)₂N?BCl (phenyl-p-X), containing the para-phenyl substituent at the boron atom, and (b) (p-X-phenyl)CH₃N?B(CH₃)₂, containing the para-phenyl substituent at the nitrogen atom of the N? B linkage (X = ? NR₂, ? OCH₃, ? C(CH₃)₃, ? Si(CH₃)₃, ? H, ? F, ? Cl, ? Br, ? I, ? CF₃ and ? NO₂). By comparing the rotational barriers in corresponding compounds of both series, a reverse effect of the substituents could be observed. Electron-withdrawing substituents in the para position of the phenyl ring increase the ΔG_c^≠ if the phenyl group is attached to the boron atom; on the other hand, a lower ΔG_c^≠ is observed if the phenyl ring is bonded to the nitrogen atom of the N? B system. Substitution of the phenyl ring with electron-donating substituents in the paraposition exerts the opposite effect. Within each series of compounds, the differences of ΔG_c^≠ values [δ(ΔG_c^≠) = ΔG_c^≠ (X) ? ΔG_c^≠ (X = H)] between substituted and unsubstituted compounds can be explained in terms of inductive and mesomeric effects of the ring substituents and can be correlated with the Hammett σ constant of each substituent. A comparison of the slopes of the plotted lines shows that the influence of the ring substituents is more pronounced in compounds with N-phenyl-p-X than in those with B-phenyl-p-X.     

Synthese und Eigenschaften von Bis-[dialkylamino-methylarsino]-methanen

Synthesis and Properties of Bis-[dialkylamino-methyl-arsino]-methanes The reactions of methan-bis-[methyl-chlorarsine] H₂C[As(CH₃)Cl]₂ with secondary amines lead to the formation of bis-[dialkylamino-methylarsino]methanes H₂C[As(CH₃)NR₂]₂. The cleavage of the As? N bond with acid molecules HX (X?OH, OR, SR, NR₂, halogen) results in the formation of the compounds H₂C[As(CH₃)X]₂. The IR and ¹H-NMR spectra are discussed and presented.     

Spektroskopische Untersuchungen an Siliciumverbindungen. XXXI. Schwingungsverhalten von p-substituierten N,N-Bistrimethylsilylanilinen

The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C₆H₄? N[Si(CH₃)₃]₂ are prepared by silylation of free amines: X = H, CH₃, C₂H₅, CH₃O, CH₃CO, F, Cl, Br, J, CN, C₆H_S, (CH₃)₃SiO, and [(CH₃)₃Si]₂N, and the isotopic derivatives C₆H₅? ¹⁵N[Si(CH₃)₃]₂ and C₆D₅N[Si(CH₃)₃]₂. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH₃)₃Si]₂N? C₆H₄? N[Si(CH₃)₃]₂ is determined. The influence of the mass of the substituents X on the positions of the ν_sSiNSi vibrational frequencies is discussed.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. V. Darstellung,Eigenschaften und Reaktionen neuer Phosphonig- und Phosphinigsäureester

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. V. Preparation, Properties, and Reactions of New Phosphonous- and Phosphinous Acid Esters Phosphonous diesters R? P(OR′)₂ (R ? CH₃, Ph and R′ ? CH₂? CF₃) have been synthetized by reaction of phosphonous dichlorides with 2, 2, 2-trifluoroethanol in the presence of a base. These diesters react with trimethyl(trimethylsilylimino)phosphorane, (CH₃)₃P?N? Si(CH₃)₃ by desilylation and N? P-linking to phosphinous acid esters (CH₃)₃P?N? P(OR′)R. The phosphinous acid esters react with methyl iodide to the quaternary salts [(CH₃)₃P? N? P(OR′)(R)CH₃]⁺I^?. The compounds are characterized by elementary analysis and spectroscopical methods.     

1λ6,2,4-Thiadiazetidine und 1,2λ6,3-Oxathiazetidine

1λ⁶,2,4-Thiadiazetidines and 1,2λ⁶,3-Oxathiazetidines From the reaction of the sulfur triimides (RN?)₃S ( 2a R?(CH₃)₃C, 2b R?(CH₃)₃Si) with pentafluoroazapropene ( 11 ) the appropriate 1λ⁶,2,4 thiadiazetidines ( 13a, 13b ) are formed, while from ClSO₂N?CCl₂ ( 14 ) and 2a (CH₃)₃C? N?C?N? SO₂Cl ( 17 ) is isolated. 2b and hexafluoroacetone ( 18 ) give the rather unstable 1,2λ⁶,3-oxathiazetidine ( 20 ).     

Diorgano-tellur-bis-(dialkylcarbamate) und -(dithiocarbamate)

Diorganyltellurium Bis-(dialkylcarbamates) and -(dithiocarbamates) Compounds of the type R₂Te(X₂CNR′₂)₂, with R ? C₆H₅, CH₃; R′ ? CH₃, C₂H₅, i-C₃H₇, c-C₆H₁₁, C₆H₅, and X ? S, are obtained by reaction of dimethyltellurium with tetraorganyl-thiuram-disulfides. Dimethyltellurium diiodide or diphenyltellurium dichloride react with sodium dithiocarbamates or with in situ prepared ammonium dithiocarbamates. Some compounds can be synthesized by reaction of diphenyltellurium oxide with amine in solutions of carbon disulfide. The synthesis of diphenyltellurium- and dimethyltellurium bis-(dimethylcarbamates) results from the interaction of diorganyltellurium diethanolate with dimethylammonium dimethylcarbamate. Decomposition reactions of the compounds in solid and solution are studied ¹H-NMR, ¹³C-NMR, and mass spectroscopically. Diorganyltellurium diethylen-bis-(N,N′-dimethyldithiocarbamates) are obtained by reaction of dimethyltellurium diiodide or diphenyltellurium dichloride and sodium ethylen-bis-(N,N′-dimethyldithiocarbamate) as polymeric products.     

Synthesis,characterization, and structures of 1-(9-Fluorenyl)-germatrane and 1-(Phenylacetylenyl)germatrane

Syntheses of the title compounds, viz. N(CH₂CH₂O)₃GeY ( 2 Y?Fluorenyl; 4 Y?PhC?C) by the reaction of X₃GeY ( 1 Y?Fluorenyl, X?Br; 5 Y?PhC?C, X?Cl) with N(CH₂CH₂OSnR₃)₃ ( 3 R?Et; 6 R?Bu) are reported including the preparation of the new compound 1 . Identity and structures were established by elemental analyses, ¹H and ¹³C NMR spectroscopy. 2 and 4 were characterized by mass spectrometry. Single crystal structures of 1 , 2 and 4 were determined by X-ray diffraction methods.     

Alkoholyse von Tris(dimethylamino)-arsin

Alcoholysis of Tris (dimethylamino)arsine The reaction of tris(dimethylamino)arsine with alcoholes and thioles leads to the formation of esters of the general formula As(XR)₃ (X = O and S). The reaction is a suitable preparative method for the synthesis of the esters As(XR)₃ (X = O and S). By alcoholysis in steps results an equilibrium system containing the molecules AsX₃, AsX₂Y, AsXY₂, and AsY₃ (X = OR, Y = N(CH₃)₂).     

Bis(trimethylsilyl)-hypophosphit und Alkoxycarbonylphosphonigsäure-bis(trimethylsilyl)ester als Schlüsselsubstanzen für die Synthese von Organophosphorverbindungen

Bis(trimethylsilyl)hypophosphite und Alkoxycarbonylphosphonous Acid Bis(trimethylsilyl) esters as Building Blocks in Organophosphorus Chemistry The oxidation of pure bis(trimethylsilyl)hypophosphite ( BTH ) with chalcogenides forming (Me₃SiO)₂P(X)H (X = O, S, Se, Te) is described as well as its reactions with alkylhalides RX (X = Cl, Br, I) and Cl? C(O)OR (R = Me, Et, Bzl). By reaction with oxygen, sulfur, and selenium the alkoxycarbonylphosphonous acid bis(trimethylsilyl)esters form RO? C(O)? P(X)(OSiMe₃)₂ (X = O, S, Se) whereas with Cl? C(O)OR the bis(alkoxycarbonyl)-phosphinic acid trimethylsilylesters are obtained. After partial hydrolysis the resulting instable RO? C(O)? P(O)H(OSiMe₃) gives RO? C(O)? P(O)(OSiMe₃)? CH₂? NH? A? COOR′ (A = CH₂, CH₂CH₂, CHCH₃, CH₂CH₂SH, CHCH(CH₃)₂,…) when allowed to react with hexahydro-s-triazines of the aminoacid esters. Reactions of the alkoxycarbonyl-P-silylesters with NaOR or NaOH result in the corresponding mono-, di-, or trisodium salts. With mineral acids decarboxylation occurs, but H? P(O)(OH)? CH₂? NH? A? COOH can be obtained, too. The structure of the compounds described are discussed by their n.m.r. data.