Bis(dialkylmetall)quadratate der elemente aluminium,gallium und indium

The reaction of squaric acid, H₂C₄O₄, with the trialkyl derivatives of aluminium, gallium and indium (R₃M with R = CH₃, C₂H₅) in a $\text{1}\text{2}$ molar ratio leads to bis(dialkylmetal) squarates. The Ga and In compounds dissociate in water forming R₂M⁺ and C₄O₄^2? ions. From these solutions the squarates crystallize as mono- and dihydrates, respectively. The vibrational spectra (IR and Raman) are discussed.     

Organotellurium derivatives: III. Synthesis of anionic complexes of 1-telluracyclopentane(IV) 11 diiodide

Complexes containing tetrahalotelluracyclopenzane anions of the type (R₄M₂)⁺[C₄H₈TeX₂X′₂]^2- (where R = CH₃, C₂H₅, C₃H₇, C₄H₉, C₆H₁₃, C₇H₁₅ or C₆H₅; M = N, P, As or Sb; X = Cl, Br, or I and X′ = I, Cl, Br, NCO, NCS, or N₃) have been synthesized, (i) by the interaction of 1-telluracyclopentane $\text{1}\text{1}$ diiodide with the corresponding tetraorganoammonium, -phosphonium, -arsonium, or -stibonium halides in nonaqueous solvents and (ii) via halogen exchange between complex anions and silver or alkali metal halides. The second method also yielded several pseudohalide and mixed halide-pseudohalide derivatives. The ionic nature of the new complex anions has been established by conductance and molecular weight measurements. NMR and IR spectra of some of the derivatives are discussed.     

N-halogeno-compounds. Part 9 [1]. Azoxy- and azo-arenes derived from 4-(dichloroamino)tetrafluoropyridine; crystal structure of trans-2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenyl-onn-azoxy)pyridine

The nitrosoarenes ArNO (Ar = C₆H₅, 2-MeC₆H₄, 2,4,6- Me₃C₆H₂ and C₆F₅) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds py_FN$\text{N}\text{+}$($\text{N}\text{-}$)Ar (py_F = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of py_FNNC₆H₂Me₃-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆F₅. X-Ray methods have been used to determine the molecular geometry of py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆H₂Me₃-2,4,6.     

Silicium-stickstoff-fluorverbidungen: V. Darstellung neuer silylaminofluorsilane

Compounds of the composition RR′SiFNR″Si(CH₃)₃ (R = H, F, CH₃, C₂H₅, C₃H₇, C₂H₃, C₆H₅, C(CH₃)₃; R = F, CH₃, C₆H₅; R″ = CH₃, C(CH₃)₃, Si(CH₃)₃) are obtained by the reaction of silicontetrafluoride or organo-substituted silicon-fluorides with the lithium salts of alkylsilylamines in a molar ratio of $\text{1}\text{1}$. The disubstituted compounds RSiF(NR′Si(CH₃)₃)₂ (R = H, F, CH₃, C₂H₃, C₆H₅; R′ = CH₃, C(CH₃)₃) result when the reactants are in a $\text{1}\text{2}$ molar-ratio. Likewise the unsymmetrical siliconfluorsilylamines of the formulae F₂Si(NRSi(CH₃)₃) (NR′Si(CH₃)₃) (R = CH₃, R′ = C(CH₃)₃), as well as the trisubstituted compounds FSi(NCH₃Si(CH₃)₃)₃ and FSi(NCH₃Si(CH₃)₃)₂(N(Si(CH₃)₃)₂) were made. By reacting phenyltrifluorsilane with dialkylamines ($\text{1}\text{2}$) C₆H₅SiF₂NR₂(R = CH₃, C₂H₅) was obtained. The IR-, mass-, ¹H and ¹⁹F NMR spectra of the above-mentioned compounds are reported.     

Aroyl anion trapping reactions. A preliminary study of direct nucleophilic aroylation by means of low temperature, insitu (CH3)nC6H5nLi/CO Systems.

Results of studies of the $\text{in}$$\text{situ}$ nucleophilic aroylation of PhCO₂Me, Me₃CCO₂Me and Ph₂CO by several low temperature ArLi/CO systems (Ar =C₆H₅, p-CH₃C₆H₄, $\text{o}$-CH₃C₆H₄, 2,6-(CH₃)₂C₆H₃ and 2,4,6-(CH₃)₃C₆H₂) are reported. The experiments with C₆H₅Li were unsuccessful and the best results were obtained with 2,6-(CH₃)₂-C₆H₃Li.     

Cyclometallation reactions of N-(benzylidene)benzylamines with palladium compounds

The cyclometallation of p-RC₆H₄CHNCH₂C₆H₂, (R = H, Cl, NO₂) by PdX₂ (X = Cl, AcO) has been studied.In every case the cyclometallation occurs with formation of a five-membered ring containing the methine group. The structure of these compounds [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)]₂, derived from ¹H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt₃ gives the compounds [PdX(p-RC₆H₃CHNCH₂C₆H₅)(PEt₃)₂] but with an excess of PPh₃ only the complexes [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)(PPh₃)] are formed.     

Dynamic H NMR study of 4-methylphenoxyimidoyl azides: conformational or configurational isomerisation?

Dynamic ¹H NMR (500 MHz) investigation of 4-methylphenoxyimidoyl azides (4-CH₃-C₆H₄-O-CN-Y)-N₃, Y=4-CH₃-C₆H₄-SO₂-, 4-Br-C₆H₄-SO₂-, C₆H₅SO₂-, CH₃-SO₂-, -CN in acetone-d₆ at temperature range of 195-280 K is reported. The observed free energy barrier (almost 12 kcal mol⁻¹) is attributed to conformational isomerisation about the N-S bond for Y=4-CH₃-C₆H₄-SO₂-, 4-Br-C₆H₄-SO₂-, C₆H₅SO₂-, CH₃-SO₂- and (almost 14 kcal mol⁻¹) to configurational isomerisation (E/Z) about CN bond for Y=-CN.     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen XX. Darstellung,eigenschaften und kristallstruktur von λ4-thia-λ5-phospha-h2-metallabicyclo[2.2.1]heptadienen und ihre verwendung zur synthese von metallorganischen und organischen verbindungen

The novel λ⁴-thia-λ⁵-phospha-h²-manganabicyclo[2.2.1]heptadienes (OC)₃Mn[$\text{CR}{}^2\text{CR}{}^2\text{CR}{}^2\text{CR}{}^2\text{PR}{}^1{}_2\text{S}$] (R¹ = CH₃, C₆H₅; R² = CO₂CH₃, CO₂C₂H₅, CO₂C₆H₁₁) are formed by action of the activated alkynes R²C  CR² on the heterocycles [(OC)₄MnPR¹₂S]₂ via the isolable, five-membered heterometallacyclopentadienes (OC)₄$\text{MnSPR}{}^1{}_2\text{C(R}{}^2\text{)C}$(R²). The compound with R¹ = CH₃ and R² = CO₂CH₃ crystallizes in the triclinic space group P$\text{1}$ with Z = 2 and separates quantitatively the thiophene derivative $\text{CR}{}^2\text{CR}{}^2\text{CR}{}^2\text{CR}{}^2\text{S}$ under CO pressure or by reaction with (NH₄)₂Ce(NO₃)₆. The use of various acetylenes and of acetylenes with different alkyl groups yields the unsymmetric substituted manganabicycloheptadienes (OC)₃Mn[$\text{CR}{}^4\text{CR}{}^3\text{CR}{}^2\text{CR}{}^2\text{P(CH}{}_3\text{)}{}_2\text{S}$] (R² = CO₂CH₃, R³ = R⁴ = CO₂C₂H₅; R² = R⁴ = CO₂CH₃, R³ = H). With propionic acid methylester the alkyne insertion proceeds regiospecifically. With Raney nickel selective S elimination under ring contraction and formation of the λ⁴-phospha-h²-manganabicyclo[2.1.1]hexenes (OC)₃Mn[$\text{CR}{}^2\text{CR}{}^3\text{CR}{}^2\text{CR}{}^2\text{P}$R¹₂] (R¹ = CH₃: R² = R³ = CO₂CH₃, CO₂C₂H₅; R² = CO₂CH₃, R³ = H; R¹ = C₆H₅: R² = R³ = CO₂C₂H₅) occurs. (OC)₃Mn[$\text{CR}{}^2\text{CR}{}^3\text{CR}{}^2\text{CR}{}^2\text{P}$(CH₃)₂] (R² = R³ = CO₂CH₃) crystallizes in the monoclinic space group P2₁/m with Z = 2. The IR and NMR spectra of the heterocycles are discussed in detail.     

Synthesis,structural characterization,and in vitro antimicrobial properties of salicylate and pyrazoline complexes of bismuth(III)

Displacement reactions of dichlorobismuth(III)pyrazolinates with oxygen donors such as sodium salicylate and acetate in 1?:?1 and 1?:?2 molar ratio in refluxing anhydrous benzene yields (C₁₂H₁₅N₂OX)Bi(C₆H₄O₃), (CH₃COO)BiCl(C₁₅H₁₂N₂OX), and (CH₃COO)₂Bi(C₁₅H₁₂N₂OX) [C₁₂H₁₅N₂OX?=?3(2′-hydroxyphenyl)-5-(4-X-substituted phenyl) pyrazoline X?=?H in 1,5,9, CH₃ in 2,6,10, OCH₃ in 3,7,11, and Cl in 4,8,12, respectively, (C₆H₄O₃)?=?salicylate and (CH₃COO)?=?acetate]. Newly synthesized derivatives are brown solids, soluble in organic solvents like benzene, chloroform, and acetone. The compounds have been characterized by elemental analyses (C, H, N, Cl, and Bi), molecular weight measurements, and spectral (IR, ¹H NMR, ¹³C NMR) studies. The (C₁₂H₁₅N₂OX) and (C₆H₄O₃) are bidentate while (CH₃COO) is monodentate to bismuth(III), leading to a distorted trigonal bipyramidal structure. The complexes were screened against different bacteria and fungi showing potential antibacterial and antifungal activities.     

Synthesis and structural elucidation of some new heterocyclic β-diketone derivatives of boron

Some new β-diketone derivatives of boron having the general formula B₂O(OAc)_4?n[OC(R)$\text{C:CON(Ph)N:C}$ CH₃]_n (where n = 1 or 2; R = CH₃, C₂H₅, C₆H₅ and p-ClC₆H₄) have been synthesised by the reactions of oxy-bis(diacetatoborane) and substituted pyrazolones, such as 4-acyl-3-methyl-1-phenyl-2-pyrazolin-5-ones (acyl = acetyl, propionyl, benzoyl and p-chlorobenzoyl) in dry toluene solution in 1:1 and 1:2 molar ratios. These derivatives have been characterised by elemental analysis, molecular weight measurements. Structures have been proposed on the basis of chemical reactions, IR, ¹H and ¹¹B NMR spectral studies.In the derivatives B₂O(OAc)₃[OC(R)$\text{C:CON(Ph)N:C}$ CH₃] two of the three acetate groups are unidentate and the third is bridged between two boron atoms along with BOB linkage. Whereas the derivatives B₂O(OAc)₂[OC(R)$\text{C:CON(Ph)N:C}$ CH₃]₂ are the mixture of geometrical isomers.     

Cyclometallation reactions XII. On the effect of various leaving groups on internal metallation reactions with alkylmanganese complexes

The interaction of azobenzene and MnR(CO)₅ (R  Me, Et, CH₂Ph, CH₂-C₆Me₅, COCF₃, COCH₂C₆F₅, COCH₂OPh, Ph or C₆F₅) affords M$\text{n(C}{}_6\text{H}{}_4\text{NN}$Ph)-(CO)₄, together with a binuclear complex Mn₂(CO)₆(C₁₂H₁₀N₂) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH₂Ph)(CO)₅; with this reagent, the metallated complexes M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{P}$Me₂)-(CO)₃[PMe₂(CH₂Ph)] (two isomers) and M$\text{n(C}{}_6\text{H}{}_4\text{CH}{}_2\text{A}$sMe₂(CO)₄ have been obtained on treatment with EMe₂(CH₂Ph) (E  P and As, respectively).     

Oxidation of coordinated olefins: the reactions of Cl2 with trichloro(ehtylene)platinate(II)

The oxidation of [PtCl₃(C₂H₄)]- by Cl₂ in aqueous solution, to yield CH₂ClCH₂OH and [PtCl₄]^2-, has been shown to proceed through the following sequence of steps: [PtCl₃(C₂H₄)] Cl₂Cl [PtCl₅(CH₂CH₂Cl)]^2-$\text{H}{}_2\text{O}\text{(HCl)}$ [PtCl₅(CH₂CH₂OH)]^2- → [PtCl₄^2- + CH₂ClCH₂OHEach of the steps and intermediates in this mechanistic sequence has been identified and characterized.     

Synthesis and reactions of fluorinated iminium salts

Different methods for the preparation of fluorinated iminium salts RR¹CNR²R³⁺MF₆^? (R=R¹=F ; R²=R³=CH₃, C₂H₅ M=As, Sb 4a ? c R=H, R¹=F; R²=R³=CH₃ M=As, Sb 5a, b R=R¹=CF₃; R²=H, R³=CH₃ M=Sb 12 R=R¹=CF₃; R²=R³=CH₃ M=As 14) are reported, the spectroscopic properties (IR, NMR) of the cations of these salts are briefly discussed. By F^?-addition to these salts, $\text{e.g.}$ to 16, perfluoroalkyl-bis(alkyl)-amines ($\text{e.g.}$ (CF₃)₂CFN(CH₃)₂ 15) can be prepared; from the methylation of CF₃NCF₂ bis(trifluoromethyl) methylamine (CF₃)₂NCH₃ (11) was obtained.     

Synthesis and Characterization of Diphenyltin(IV) Dicarboxylates Containing Germanium

Twelve new germanium substituted diphenyltin dipropionates with the general formula (R¹GeCHR²‐CHR³COO)₂SnPh₂ where R¹ = N(CH₂CH₂O)₃, (C₆H₅)₃ and (CH₃C₆H₄)₃, R² = H, CH₃, C₆H₅, p‐CH₃C₆H₄, p‐CH₃OC₆H₄, p‐ClC₆H₄, and R³ = H, CH₃ have been synthesized by the reaction of diphenyltin oxide with a germanium substituted propionic acid. All the compounds were characterized by elemental analysis, IR, multi‐nuclear (¹H, ¹³C, ¹¹⁹Sn) NMR and Mössbauer spectroscopies as well as mass spectrometry. The in vitro antibacterial activity of selected compounds is also reported.     

Organothallium compounds XII NMR spectra of some polyfluorophenylthallium (III) compounds

The PMR and ¹⁹F NMR spectra of the complexes R₂TlBr (R = C₆F₅, $\text{o}$-HC₆F₄, $\text{m}$-HC₆F₄, 3,5-H₂C₆F₃, or 3,6-H₂C₆F₃ and R₃Tl(diox) (R = C₆F₅, $\text{m}$-HC₆F₄, or 3,5-H₂C₆F₃; diox = 1,4-dioxan) have been recorded. Proton and fluorine chemical shifts, thallium-proton, thallium-fluorine, fluorine-fluorine, and fluorine-proton coupling constants, and thallium substituent chemical shifts are given and discussed     

The chemical oxidation and electronic spectra of the complexes trans-[M(CNR)2(Ph2PCH2CH2PPh2)2] (M = Mo or W)

Oxidation of the complexes $\text{trans}$-[M(CNR)₂(dppe)₂] (A) (M = Mo or W; R = Me, Bu^t or CH₃C₆H₄-$\text{4}$; dppe = Ph₂PCH₂CH₂PPh₂) with diiodine or silver (I) salts gives the paramagnetic cations $\text{trans}$-[M(CNR)₂(dppe)₂]⁺, (M = Mo, R = CH₃C₆H₄-$\text{4}$; M = W, R = Bu^t) and $\text{trans}$-[M(CNR)₂(dppe)₂]²⁺ (M = Mo, R = Me or CH₃C₆H₄-$\text{4}$; M = W, R = Me or Bu^t). Mixtures of products are generally produced when dichlorine or dibromine are the oxidising agents, however pure salts, the seven-coordinate complex cations [MX(CNC₆H₄CH₃-$\text{4}$)₂(dppe)₂]⁺ (B, X = Cl or Br) have been isolated. A simple molecular orbital scheme is proposed for complexes (A) and used to discuss their electronic spectra and their oxidation.     

Action of tert-butyl azidoformate on the conjugate bases of 1,2,3,4-tetrahydro-9H-carbazole and other indole derivatives

tert-Butyl azidoformate ($\text{2}$) reacts with the conjugate bases of $\text{3a}$, $\text{7a}$, $\text{9}$ (R¹ = R² = CH₃), and $\text{9}$ (R¹ = CH₃, R² = H) to give products [$\text{4}$, $\text{8}$, $\text{12}$, and $\text{14}$, respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives.     

Synthesis of triphenylphosphonopropionbetainetriorganotin(IV) salts [(C6H5)3P(CH2)2CO2SnR3]+X−, by nucleophilic displacement of anions from triorganotins

Trimethyl- and triphenyl-tin(IV) hydroxide act on triphenyl(2-carboxyethyl)-phosphonium hydrochloride, which is made from 3-chloropropionic acid and triphenylphosphine, to release water in the presence of dimethylformamide (DMF) as a catalyst. The water is azeotropically distilled to drive the reaction forward and produce triphenylphosphonopropionbetainetrimethyl- and triphenyl-tin(IV) chlorides in high yield. The latter product also results from the displacement of chloride from triphenyltin(IV) chloride by the phosphobetaine, (C₆H₅)₃P(CH₂)₂CO₂, which is made by treating the phosphonium hydrochloride with bicarbonate, and the compounds [(C₆H₅)₃P(CH₂)₂CO₂Sn(C₆H₅)₃]⁺X^? where X = Cl, Br, I, N₃, NCS, NO₃, B(C₆H₅)₄ and Co(CO)₄ are made in the same way. The acetate salt results from metathesis from the chloride and lead(II) acetate. A double salt, [(C₆H₅)₃P(CH₂)₂CO₂SnR₃]⁺ [R₃SnX₂]^?, is formed for X = Cl, Br and N₃ by adding additional (C₆H₅)₃SnX to the already-formed simple salts. Double salts are also obtained from the $\text{1}\text{1}$ reactions between the phosphobetaine and triphenyltin(IV) isocyanate and methyldiphenyltin(IV) chloride. The phosphonium chloride double salt could be converted to the thiophosphonium derivative by heating with elemental sulfur in ethanol. The products of these novel nucleophilic displacement reactions are high melting solids. Tin-119m Mössbauer data are consistent with five-coordinated, triorganotin(IV) formulations with the exception of the diphenyl(8-hydroxyquinolinato)tin(IV) chloride salt in which the tin atom is six-coordinated, and the diphenyltin system cis-oriented. The parameters otherwise do not change with the nature of the X group, which is the tetracarbonylcobaltate derivative is tetrahedral by infrared, establishing the ionicity of the products. The chloride exhibits a molar conductivity indicative of a $\text{1}\text{1}$ electrolyte in DMF. A bridging acetate structure in the solid is consistent with the lowered ν(CO₂) frequencies. The Mössbauer spectra of the double salts give simple doublets of lowered isomer shift (IS) and raised quadrupole splitting (QS) which may arise from a cross-linking ion pairing of the polymer chains in the solid, and the NMR spectra of the two methyltin derivatives shows only a single resonance line and tin satellites which is rationalized by a dynamic exchange process. The products are formulated as associated in carboxylate polymers with dangling triphenylphosphonium cations.     

Organomercury compounds XX Reactions of lithium polyfluorobenzenesulphinates with mercuric salts

The lithium polyfluorobenzenesulphinates, Li O₂SR (R = C₆F₅, $\text{p}$-HC₆F₄, $\text{m}$-HC₆F₄, or $\text{o}$-HC₆F₄), and the dilithium tetrafluorobenzenedisulphinates, $\text{p}$- and $\text{o}$-(LiO₂S)₂C₆F₄, have been prepared by reaction of the appropriate polyfluoroaryllithium compounds with sulphur dioxide. All compounds were isolated as hydrates and gave the corresponding $\text{S}$-benzylthiouronium salts on treatment with $\text{S}$-benzylthiouronium chloride. From reactions of the lithium sulphinates with suitable mercuric salts in water, generally at room temperature, the derivatives RHgX (R = C₆F₅, X = Cl, Br, CH₃CO₂, or PhSO₂; R = $\text{p}$-HC₆F₄, X = Cl, Br, or CH₃CO₂; R = $\text{m}$-HC₆F₄, X = Cl or Br; R = $\text{o}$-HC₆F₄, X = Cl), $\text{p}$-(XHg)₂C₆F₄ (X = Cl, Br, or CH₃CO₂), and $\text{o}$-(XHg)₂C₆X₄ (X = Cl or Br) have been prepared. Similarly, the bispolyfluorophenylmercurials R₂Hg (R = C₆F₅, $\text{p}$-HC₆F₄, or $\text{m}$-HC₆F₄) have been prepared from the corresponding lithium sulphinates and either mercuric salts or polyfluorophenylmercuric halides in aqueous $\text{t}$-butanol. A possible mechanism for the sulphur dioxide elimination reactions is discussed.     

Darstellung und eigenschaften von diorganogermaniumdisulfinsäureestern

Diorganogermaniumdisulfinic esters of the type R₂Ge(O₂SR′)₂ (R = CH₃, R′ = CH₃, C₆H₅, p-CH₃C₆H₄; R = C₆H₅, R′ = CH₃, p-CH₃C₆H₄) which are sensitive to hydrolysis are obtained by reaction of the corresponding diorganogermanium dichlorides with anhydrous silver sulfinates. The newly prepared compounds are thoroughly investigated on the basis of their ¹H NMR, mass, IR and Raman spectra. The methyl ester (CH₃)₂Ge(O₂SCH₃)₂ is compared with the already known sulfinato complex of tin with the same formal composition.