Synthese von Mono- und Bis(silyl)hydroxylaminen

Synthesis of Mono- and Bis(silyl)hydroxylamines Silylamines reacts with hydroxylaminehydrochlorid to give the monosilylhydroxylamines: R₂FSiONH₂ (R = CMe₃ 1 ), R₂R′SiONH₂ (R = CMe₃, R′ = Me 2 ), R₂(NH₂)SiONH₂ (R = CMe₃ 3 ). The reaction of 1 in the present of HCl-acceptors or the reaction of lithiated 1 with Me₃SiCl or F₂Si(CMe₃)₂ leads to the formation of bis(silyl)hydroxylamines, (Me₃C)₂FSiONHSiMe₃ 4 , and (Me₃C)₂FSiONHSiF(CMe₃)₂ 5 . The lithium derivatives of Me₃SiONH₂ and 2 react with fluorosilanes to the bis(silyl)hydroxylamines: Me₃SiONHSiFRR′ (R = R′ = CMe₃, 6 , R = CMe₃, R′ = F 7 , R = R′ = NMeSiMe₃ 8 ), (Me₃C)₂MeSiNHOSiFRR′ (R = CMe₃, R′ = F 9 , R = (Me₃C)₃C₆H₂, R′ = F 10 , R = R′ = CMe₃ 11 , R = R′ = CHMe₂ 12 ). The bis(silyl)hydroxylamines 4 and 6 are structure isomers.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekeln. VI. Amidohalogenborane

Reaction of Metal and Metalloid Compounds with Polyfunctional Molecules. VI. Amidohalogenoboranes N-substituted halogenoacetamides react with halogenoboranes and (halogeno)-organoboranes resp. under formation of N-substituted imidohalides and (or) dimeric or (and) monomeric amidoboranes. In certain cases, carbiminoxidboranes and, as by-products, bis-(amido)boranes were isolated. By reaction of 2-trifluoracetylamino-benzonitrile with halogenoboranes and organohalogenoboranes resp. derivates of 1,3,2-diazaboranaphthaline were obtained, which decomposed on attempted sublimation at 0,001 Torr. ¹H, ¹¹B, and ¹⁹F n.m.r. spectra, mass spectra and characteristic i. r. group frequencies are reported.     

Synthesen und Eigenschaften von Bis(perfluoralkyl)zink‐Verbindungen

Syntheses and Properties of Bis(perfluoroalkyl)zinc Compounds The conditions for the syntheses of bis(perfluoroalkyl)zinc compounds Zn(R_f)₂ · 2 D (R_f = C₂F₅, n‐C₃F₇, i‐C₃F₇, n‐C₄F₉, n‐C₆F₁₃, n‐C₇F₁₅, and n‐C₈F₁₇; D = CH₃CN, tetrahydrofurane, dimethylsulfoxide) are described. Mass spectra, thermal decompositions, ¹⁹F‐ and ¹³C‐NMR spectra are discussed.     

Versuche zur Herstellung eines «Bis(triasterans)» und Synthese des heterocyclischen (Tricyclo[4.4.1.01,6]undeca-3,8-dien-11,11-dimethyl)sulfits

Tentative Synthesis of ‘Bis(triasterane)’ and Synthesis of the Heterocyclic (Tricyclo[4.4.1.0^1,6]undeca-3,8-diene-11,11-dimethyl)sulfite The synthesis of the bis(triasterane) ( 1 ) has been tried; the reaction of ‘isotetraline’ (1,4,5,8-Tetrahydronaphthalene; 2 ) with diazomalonate yielded the tricyclic systems 5 and 6 , and not 4 . Hydrolysis of 5 gave the monocarboxylic acid 7 , and not the dicarboxylic acid 9 . The latter could be obtained from the dibromoderivative 8 , but 9 couldn't be converted to the acyl chloride 10 . The reduction of 9 with LiAlH₄ yielded the crystalline diol 11 , which was cyclized with SOCl₂ to the heterocycle 12 . The spectral data of the new compounds 5, 6, 7, 11 and 12 are reported and discussed.     

Bis(Cyclodisilazan-1-yl)dimethylsilane Synthese und Reaktionen

Bis(cyclodisilazane-1-yl) dimethylsilanes — Synthesis and Reactions The monolithium derivate of trisilazan-1-yl-cyclodisilazane 1 reacts with F₃SiN (SiMe₃)₂ with substitution. The silyl-bridged cyclodisilazanes 3–6 are formed in the reaction of the dilithium derivate of 1 with fluoro- and chlorosilanes. Using lithiumamide and lithiummethanolate a controlled exchange of one fluoro atom of 4 occurs ( 7,8 ). 9 and 10 are formed by hydrolysis of 4 . The aminofunctional compounds 11 und 12 are obtained in the reaction of 5 and 6 with NH₃. The dispirocyclus 13 is formed in the reaction of 8 with tert.-butyllithium. The reaction of dilithiated 1 with 4 gives the spirocyclus 14 . The crystal structure of 14 is discussed.     

Bis(fluorbenzoyloxy)methylphosphanoxide

Bis(fluorbenzoyloxy)methyl phosphane oxides CH₃P(O)[OC(O)R]₂ [R = C₆H₄2F (1), C₆H₄3F (2), C₆H₄4F (3), C₆H₃2,6F₂ (4), C₆H2,3,5,6F₄ (5)] were prepared by treating silver salts of carboxylic acids AgOC(O)R with CH₃P(O)C?₂ (IR-, ¹H-, ¹⁹?F-and ³¹P{¹H}-NMR-data). The mixed anhydrides 1–5 show unusual thermal stability at room temperature. Stability against hydrolysis decreases with increasing number of fluorine-atoms. The reaction of R′P(O)C?₂ [R′ = CH₃, C₆H₅, (CH₃)₃C] with M^IOC(O)R_F [R_F = CF₃, C₂F₅, C₆F₅; M^I = Ag^I, Na^I T?^I] was investigated.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 16. Mitt.

The reaction of trimethylsilylcarbonamides with halogeno-diorganyl-boranes resp. trihalogenoboranes or organodihalogenoboranes gives monomeric resp. dimeric amidoboranes (borylcarbonamides) and derivatives of 4,8-diaza-1,5-dibora-2,6,9-trioxabicyclo[3.3.1]nonadienes. By reaction of the free acylamides with halogenoboranes in most cases the imide halides could be isolated as the only products. By reaction of the hydrochloride of bis(dimethylamino)-hydroxyborane withn-butyl-lithium followed by addition of the imide halides, the corresponding imidoylamines were formed.¹H,¹¹B, and¹⁹F-nmr spectra, mass spectra and characteristic ir group frequencies are reported.

15. Mitt.:W. Maringgele undA. Meller, Z. anorg. allg. Chem., im Druck.     

Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von (PPh4)[1-(NO)B10H9]

Synthesis, ¹¹B NMR, Vibrational Spectra, and Crystal Structure of (PPh₄)[1-(NO)B₁₀H₉] By reaction of (n-Bu₄N)₂[B₁₀H₁₀] in aqueous acetonitrile with NO₂ a reaction mixture is formed from which [1-(NO)B₁₀H₉]^– has been isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The X-ray structure determination of (PPh₄)[1-(NO)B₁₀H₉] (triclinic, space group P1, a = 7.6553(11), b = 13.179(2), c = 14.122(3) Å, α = 69.853(13), β = 82.445(14), γ = 87.230(13)°, Z = 2) reveals the coordination of the NO group via N in an apical position of the B₁₀ cluster with B1–N = 1.457(5) and N–O = 1.101(4) Å. The ¹¹B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of a in 1 position substituted B₁₀ cluster with a strong downfield shift of the ipso-B atom at +6.5 ppm. The IR and Raman spectra show a strong NO stretching vibration at 2219 cm^–1.     

Zinn in der Peripherie von Bis(aren)metall‐Komplexen des Vanadiums und Chroms

Metal π Complexes of Benzene Derivatives. 53 [1] Tin in the Periphery of Bis(arene)metal Complexes of Vanadium and Chromium By means of metal‐atom ligand‐vapor cocondensation as well as via wet chemical methods (lithiation and follow‐up reaction) the first organostannyl substituted bis(arene)metal complexes (R₃Sn‐η⁶‐C₆H₅)₂M have been prepared: 15 (R = Me, M = V), 16 (R = Ph, M = V), 13 (R = Me, M = V), 17 (R = Ph, M = Cr). Despite the bulkiness of the Ph₃Sn groups the geometry of the central sandwich unit in 17 deviates only marginally from that of the parent complex (C₆H₆)₂Cr ( 2 ). The triclinic unit cell of 17 (space group: P1; a = 9.414(4), b = 9.877(5), c = 11.012(13) Å; α = 83.51(7), β = 87.95(7), γ = 72.67(4)°) contains one independent molecule. Perturbation of the electronic structure of the bis(arene)metal unit by organostannyl groups appears to be minute because EPR spectra of the M(d⁵) species fail to reveal deviations from axial symmetry. The potentials for reversible oxidation of the Me₃Sn‐substituted complexes 13 and 15 differ insignificantly (anodic shifts ≤ 20 mV) from those of the parent species 1 and 2 ; reductions are irreversible in both cases. More sizeable anodic shifts are observed for the Ph₃Sn‐derivatives 16 and 17 ; here as well, only the redox pairs 0/+ are reversible. The resistance of the neutral complexes to protic media contrasts to ready hydrodestannylation of the complex cations. By way of metal exchange, employing n‐butyl lithium, 13 affords (Li‐η⁶‐C₆H₅)₂Cr strictly 1,1′‐disubstituted and devoid of auxiliary base.     

Diacyltelluride: Synthesen durch Reaktionen von Acylchloriden mit Bis(trialkylsilyl)telluriden; Strukturbestimmungen an Di(1-adamantoyl)tellurid und Adamantancarbonsäureanhydrid

Diacyltellurides: Synthesis by Reactions of Acyl Chlorides with Bis(trialkylsilyl)tellurides. Structure Determinations of Di(1-adamantoyl)telluride and Adamantanecarbonic Anhydride Bis(isopropyldimethylsilyl)telluride ( 1 ) is prepared from tellurium with lithiumtriethylhydridoborate and chloro(isopropyl)dimethylsilane. From reactions of acylchlorides RCOCl with 1 , diacyltellurides (RCO)₂Te (R = CH₃- 2 , i-C₃H₇- 3 , i-C₄H₉- 4 , (CH₃)₃CH₂-) 5 are isolated in pure state after removal of chloro(isopropyl)dimethylsilane. With succinic and glutaric dichlorides, 1 leads to impure cyclic diacyltellurides 6 (tellurosuccinic anhydride) and 7 (telluroglutaric anhydride). The reactions of bulky pivaloyl chloride and 1-adamantoyl chloride with 1 are too slow to be synthetically useful, but using bis(trimethylsilyl)telluride, dipivaloyltelluride 8 and di(1-adamantoyl)telluride 9 are straightforwardly available. 9 is accompanied by traces of 1-adamantanecarbonic anhydride 10 and by small amounts of di(1-adamantyl)ditelluride 11 . Constitutions of the new compounds 1 , 3–7 and 9 were confirmed by multinuclear NMR and mass spectroscopy. The structures of 9 and 10 were determined by X-ray crystallography.     

Synthese und Strukturen von Bis(amino)germa- und -stanna-Chalkogeniden

Synthesis and Structures of Bis(amino)germa and -stanna Chalcogenides The cyclic bis(amino)germylene 1 and the -stannylene 2 react with elemental S, Se and Te to yield oxydation products of the general formula Me₂Si(NtBu)₂MEl₂M(NtBu)₂SiMe₂ (M = Ge, El = S ( 4 ), El = Se ( 5 ), El = Te ( 6 ); M = Sn, El = Se ( 9 ), El = Te ( 10 )). As may be deduced from X-ray structures ( 4, 5, 6, 9, 10 ) all compounds show similar central skeletons: the three spirocyclicly connected four-membered rings SiN₂M (2x) and MEl₂M are oriented in an orthogonal way to oneanother. The germanium and the tin atoms thus are in a distorted tetrahedral coordination while the chalcogen atoms only have two neighbours in acute angles. If 1 is allowed to react with trimethylamine-N-oxide, the oxygen is transferred to germanium and [Me₂Si(NtBu)₂GeO]₃ ( 3 ) is formed. Contrarily to the other compounds 3 can be described as a trimer. There is a central almost planar Ge₃O₃ six-membered ring, the germanium atoms serving as spiro-cyclic centres to three GeN₂Si four-membered rings (X-ray structure of 3 ). In the central four-membered rings of 4, 5, 6, 9 and 10 no transanular bonding between the chalcogen atoms have to be considered although these atoms have small distances to oneanother. The mean M-El distances have been found to be: Ge? O 1.762(5), Ge? S 2.226(3), Ge? Se 2.363(3), Ge? Te 2.592(5), Sn? Se 2.536(3), Sn? Te 2.741(3) Å.     

Bis(perfluor-n-hexyl)- und Bis(perfluor-n-octyl)cadmium: Darstellung,Eigenschaften, NMR-spektroskopische und massenspektrometrische Untersuchungen

Bis(perfluoro-n-hexyl) and Bis(perfluoro-n-octyl) Cadmium: Preparations, Properties, NMR Spectroscopic and Mass Spectrometric Investigations The perfluoroalkyl cadmium compounds Cd(C₆F₁₃)₂ and Cd(C₈F₁₇)₂ are isolated in pure states as well as complexes with dmf, CH₃CN, glyme, and diglyme. The reaction rate of Cd(R_f)₂ with PhHgCl increases with increasing dissociation, which is established by conductivity measurements. The NMR and the mass spectra are discussed.     

Synthesen und Strukturen von Bis(4,4′‐t‐butyl‐2,2′‐bipyridin)‐Ruthenium(II)‐Komplexen mit funktionellen Derivaten des Tetramethyl‐bibenzimidazols

Syntheses and Structures of Bis(4,4′‐t‐butyl‐2,2′‐bipyridine) Ruthenium(II) Complexes with functional Derivatives of Tetramethyl‐bibenzimidazole [(tbbpy)₂RuCl₂] reacts with dinitro‐tetramethylbibenzimidazole ( A ) in DMF to form the complex [(tbbpy)₂Ru( A )](PF₆)₂ ( 1a ) (tbbpy: bis(4,4′‐t‐butyl)‐2,2′bipyridine). Exchange of the two PF₆^? anions by a mixture of tetrafluor‐terephthalat/tetrafluor‐terephthalic acid results in the formation of 1b in which an extended hydrogen‐bonded network is formed. According to the ¹H NMR spectra and X‐ray analyses of both 1a and 1b , the two nitro groups of the bibenzimidazole ligand are situated at the periphery of the complex in cis position to each other. Reduction of the nitro groups in 1a with SnCl₂/HCl results in the corresponding diamino complex 2 which is a useful starting product for further functionalization reactions. Substitution of the two amino groups in 2 by bromide or iodide via Sandmeyer reaction results in the crystalline complexes [(tbbpy)₂Ru( C )](PF₆)₂ and [(tbbpy)₂Ru( D )](PF₆)₂ ( C : dibromo‐tetrabibenzimidazole, D : diiodo‐tetrabibenzimidazole). Furthermore, 2 readily reacts with 4‐t‐butyl‐salicylaldehyde or pyridine‐2‐carbaldehyde under formation of the corresponding Schiff base Ru^II complexes 5 and 6 . ¹H NMR spectra show that the substituents (NH₂, Br, I, azomethines) in 2 ‐ 6 are also situated in peripheral positions, cis to each other. The solid state structure of both 2 , and 3 , determined by X‐ray analyses confirm this structure. In addition, the X‐ray diffraction analyses of single crystals of the complexes [(tri‐t‐butyl‐terpy)(Cl)Ru( A )] ( 7 ) and [( A )PtCl₂] ( 8 ) display also that the nitro groups in these complexes are in a cis‐arrangement.     

Reaktionen von TaCl5, MoCl5 und WCl6 mit Bis(trimethylsilyl) carbodiimid

Reactions of TaCl₅, MoCl₅, and WCl₆ with Bis(trimethylsilyl)carbodiimide When TaCl₅ reacts with Me₃SiNCNSiMe₃ (Me = CH₃) in a 1:1 molar ratio, 1 mol Me₃SiCl and dimeric [Cl₄TaNCNSiMe₃]₂ is formed. The vibrational spectra (IR and Raman) show a planar structure of approximate C_2h symmetry. Polymeric [Cl₄WNCN]_n is formed by the reaction of WCl₆ and Me₃SiNCNSiMe₃, but 2 mol Me₃SiCl result in this 1:1 molar interaction. On the other hand MoCl₅ and Bis(trimethylsilyl)carbodiimide (molar ratio 2:1) forms polymeric [(Cl₄Mo)₂NCN]_n, a compound with Mo? N? Mo and Mo—(Cl₂)—Mo bridges. The IR spectra of these carbodiimide derivatives are used for structural suggestions.     

Über Chalkogenolate. 184. Bis(thiocarbamoyl)- und Bis(N-methylthiocarbamoyl)sulfane

On Chalcogenolates. 184. Bis(thiocarbamoyl)- and Bis (N-methylthiocarbamoyl)sulfanes The sulfanes (H₂N? CS? )₂S₂ and (CH₃? NH? CS? )₂S_x with x = 1 and 2 have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra. The decomposition of the N-methyl substituted compounds has been studied kinetically at 20°C in ethanolic solution.     

Strukturen von polaren Magnesiumorganylen: Synthese und Struktur von Basen‐Addukten des Bis(cyclopentadienyl)magnesiums

Structures of Polar Magnesium Organyls: Synthesis and Structure of Base Adducts of Bis(cyclopentadienyl)magnesium Eight donor‐acceptor complexes of bis(cyclopentadienyl)magnesium ( 1 ) with N‐ and O‐donor Lewis bases have been synthesized and characterized by X‐ray structure analysis. With acetonitrile, dimethoxyethane, diethyleneglycoldimethylether, dioxane, and tetramethylethylenediamine simple 1:1 adducts are formed ( 2 – 6 ). In some cases a change of the hapticity of one cyclopentadienylring from η⁵ to η² or η¹ is observed ( 4 – 6 ). In the adduct with pentamethyldiethylenetriamine ( 7 ) one C₅H₅‐ring is removed from the magnesium atom forming the cation [Mg(C₅H₅)(PMDTA)]⁺ and an uncoordinated five‐ring anion. With the crown ether 15‐crown‐5 the two ionic Mg compounds 8 and 9 are formed which have a [Mg(15‐crown‐5)L₂]²⁺‐cation [L = pyridine, THF] and two uncoordinated cyclopentadienyl anions. Cyclopentadienyl‐methyl‐magnesium reacts with 15‐crown‐5 to the salt [Mg(CH₃)(15‐crown‐5)]⁺ C₅H₅^? ( 10 ) which has also a free cyclopentadienyl anion.     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

11‐Vertex arachno‐Clusters with an NB10, SNB9, and SeNB9 Skeleton

One of the two bridging protons of the aza‐nido‐decaboranes RNB₉H₁₀X can be removed by certain bases to give nido‐anions [RNB₉H₉X]^– [R/X = H/H ( 1 a ), Ph/H ( 1 b ), p‐MeC₆H₄/H ( 1 c ), Bzl/H ( 1 d ), H/N₃ ( 1 ′ a )]; the stericly demanding base 1,8‐bis(dimethylamino)naphthalene (“proton sponge”, ps) is ideal. In the case of tBu anion, the deprotonation (→ C₄H₁₀) may be accompanied by a hydridation (→ C₄H₈), yielding the arachno‐anions [RNB₉H₁₁X]^– ( 2 a , b , d , 2 ′ a ); these are the main products, when stericly non‐demanding bases like H^– are applied. The Lewis acid BH₃ is added to 1 a and 1 ′ a to give the aza‐arachno‐undecaborates HNB₁₀H₁₂X [X = H ( 3 a ), N₃ (in position 2) ( 3 ′ a )]. Thia‐ and selenaaza‐arachno‐undecaborates, [S(RN)B₉H₁₀]^– ( 4 b , c ) and [Se(RN)B₉H₁₀]^– ( 4 ′ b , c ), are obtained from 1 b , c by the addition of sulfur or selenium, respectively. The methylation of the anions 4 c and 4 ′ c gives the thia‐ and selenaazaarachno‐undecaboranes (MeS)(RN)B₉H₁₀ ( 5 c ) and (MeSe)(RN)B₉H₁₀ ( 5 ′ c ), respectively. The action of HBF₄ on the arachno‐borates [HNB₁₀H₁₂X]^– ( 3 a , 3 ′ a ) leads to a mixture of nido‐HNB₉H₁₀X and nido‐HNB₁₀H₁₁X by the elimination of BH₃ or H₂, respectively; the aza‐nido‐decaborane predominates in the case of 3 ′ a and the aza‐nido‐undecaborane in the case of 3 a . The action of HBF₄ on the anion 4 c yields the hypho‐undecaborate [S(RN)B₉H₁₀F₂]^– ( 6 c ). The structures of the products are elucidated on the basis of ¹H and ¹¹B NMR spectra, supported by 2D COSY and HMQC techniques. Two types of 11‐vertex‐arachno structures and an 11‐vertex‐hypho structure are found for the products. The crystal structures of 5 c and [Hps] 6 c · CH₂Cl₂ are reported.     

Oxydative Kupplung von Indolinen und 1,2,3,4-Tetrahydrochinolinen mit Kaliumpermanganat. 153. Mitteilung über Alkaloide

It is shown that treatment of indolines like 4a-methyl-1,2,3,4,4a,9a-hexahydrocarbazole ( 1 ) and even indoline-alkaloids like 5 or 6 (cf. scheme 1) with KMnO₄ in boiling acetone solution leads to the indolenines 10, 29 and 33 , respectively, and, in relatively high yields, to N,N′- or C,N-coupling products (cf. schemes 2 and 5). The results of the oxidation of 6- or 8-methoxy-indolines are shown in schemes 3 and 4, respectively. Analogous ‘dimeric’ dehydrogenation products are observed when tetrahydroquinolines ( 8 and 9 , resp.) are treated with KMnO₄ (cf. schemes 7 and 8, resp.). The formation of the bis-compounds is almost certainly due to the coupling of two intermediate indolenyl or tetrahydroquinolyl radicals. The cleavage of the hydrazine derivatives 11 or 17 (scheme 9) also leads to ‘dimeric’ C,N-coupling products. By heating the hydrazine derivative 17 with aqueous HCl, a complete cleavage into indoline 2 and the indolenines 16 and 20 is observed. The reaction is rationalized in scheme 10. So far no naturally occurring alkaloids related to the above mentioned C,N-coupling products have been found.     

Darstellung,Eigenschaften und Konstitution von Bis(dimethylaminopropyl)cadmium und -quecksilber

Synthesis, Properties, and Constitution of Bis(dimethylaminopropyl) Cadmium and Mercury It is reported about synthesis and properties of the bis[3-(N,N-dimethylamino)propyl] compounds of cadmium and mercury. The ¹³C-NMR spectrum of the cadmium compound indicates a spiranoid chelate structure. The concentration dependence of the coupling constants ¹³C? ¹⁹⁹Hg in case of (Me₂NCH₂CH₂CH₂)₂Hg and Me₂NCH₂CH₂CH₂Hg? i-C₄H₉indicates a partial Hg? N interaction.