Reaktionen organoelementsubstituierter pentadiene: komplexierung mit übergangsmetallen sowie präparative anwendung der lithiierungsprodukte (1)

The pentadienyllithium compounds 3, 5, 9, 12, and 15 react with ketones exclusively in α-position of the organoelement group to give the alcohols 4, 6, and 10 or the triene 13 (R = Ph), respectively. By reaction of organoelement substituted pentadienes with Na₂PdCl₄, Fe₂ (CO)₉, Fe₃(CO)₁₂, and NiCl₂ five well defined transition metal complexes (16–20) and three palladium clusters of unexplored structure have been obtained. From 1-(phenylthio)-2,4-pentadiene 2-(methoxy)-1-(thiophenyl)-4-pentene (23) was synthesized via palladium complex 22.     

Synthese neuer N-Vinylpyrrole

Syntheses of New N-Vinylpyrroles The reactions of pyrrolyl potassium ( 1 ) with (ethoxymethylene)malonic acid derivatives 2a–e yielded the carbanions 3a–e , which could be hydrolyzed to 4a–e , but with the exception of 4b they were not isolated, because a transformation to the N-vinylpyrroles 5a , c–e by elimination of ethanol took place; 1 reacted with 2b at 80°C to give 4b and 6 . Hydrolysis of 4b with KOH yielded 4g , which eliminated 1 mol of ethanol to form 5f , decarboxylation of which led to N-vinylpyrrole 7 . By cyclization of 5e under various conditions the pyrrolizines 8a , b are obtained, the hydrolysis of which did not give ketone 9 but only amino alcohol 10 . Some other cyclizations of 11a–c and 13 yielded the 3H-pyrrolizine derivatives 12a–c and 14 , respectively.     

Synthese neuer Indolderivate

The synthesis of the ,-unsaturated ketones4, 5 und6 via the regiospecific aldol- andWittigreaction with some indolealdehydes is described.4 and5 are stable enough for NaBH₄-reduction to the corresponding alcohols.

     

Synthese neuer Nonafulvene

Synthesis of New Nonafulvenes Nonafulvenes 1c and 1m – s are prepared by the following methods: (a) Elimination of AcOH from acetoxyalkyl-cyclononatetraenes (Scheme 2; 1m ); (b) alkylation of nonafulvenolates (Scheme 3; 1c , 1n ); (c) elimination of alcohol from di- and trialkoxymethyl-cyclononatetraenes (Scheme 5; 1o , 1p , 1q ); (d) deprotonation of intermediary formed formamidiniumcyclononatetraenes (Scheme 6; 1r , 1s ). Scope and limitations of these preparative sequences are discussed and compared with the corresponding pentafulvene syntheses.     

Synthese makrocyclischer Ketone durch Ringerweiterung; ein neuer Weg zu(±)-Muscon

Synthesis of Macrocyclic Ketones by Ring-Enlargement Reactions; a New Path to (±)-Muscone A new synthetic route to macrocyclic ketones is described. Starting from 2-nitrocycloalkanones, the ring-enlarged compounds of the type 4 and 5 were prepared in three steps. Reduction of the NO₂ group with Bu³SnH and azobisisobutyronitrile led in moderate yields to simple β-keto-esters which were quantitatively hydrolyzed and decarboxylated to the ketones of the type 8 and 9 . The interesting fragrances Exaltone® ( 8a ) and (±)-muscone ( 9a ) were prepared in this way in overall yields of 22 and 18%, respectively.     

Synthese neuer Aminofluorsilane,sowie Alkoxylierung von Bis (trimethylsilyl)-amino-fluorsilanen

The reaction of aminofluorsilanes of the type (R=H,F) (Me ₃Si)₂N?SiF₂R with two moles of ammonia, or of a mono- or dialkylamine, yields the corresponding amino-compounds, e.g. (Me ₃Si)₂N?Si(F)R?NH₂, (Me ₃Si)₂N?Si(F)R?NHR′ and (Me ₃Si)₂N?Si(F)R?NR₂′ (R′=Me, Et). Analogous products are obtained by reaction of the aminofluorosilanes with lithium salts of amines with bulky organic substituents in a 1 : 1 molar ratio. Alkoxy- and aryloxyaminofluorosilanes are prepared by the reaction of sodium alcoholates and sodium phenolate with (Me ₃Si)₂N?Si(F₂)R (R=H, C₂H₃, C₂H₅, C₆H₅). The i.r.-, mass-,¹H- and¹⁹F-NMR spectra of the above compounds are reported.     

Synthese,spektroskopische Charakterisierung und bakterizide Wirksamkeit neuer Organylbis(thiophenolato)bismut(III)-Komplexe

New Organobis(thiophenolate)bismuth(III) derivatives C₆H₅Bi(SC₆H₄Cl-p)₂ (I), Ch₃Bi(SC₆H₄NH₂-p)₂ (II) and CH₃AS(SC₆H₄NH₂-p)₂ (III) can be prepared by the reaction of phenyldibromobismuth(III), methyldibromobismuth(III) and -arsenic(III), respectively, with stoichiometric amounts of lithium-p-chlorothiophenolate (for I), and lithium-p-aminothiophenolate. II reacts with an excess of iodomethane to form the bis(mercaptoanilinium) complex [CH₃Bi(SC₆H₄NH₂CH₃-p₂]²⁺ (I⁻)₂ (IV). Treating IV with adequate amounts of AgNO₃ or TINO₃ yields the analogous nitrate derivative [CH₃Bi(SC₆H₄NH₂CH₃-p)₂]²⁺ (NO₃⁻)₂ (V). The new compounds were characterized by elemental analysis, ¹H NMR, IR and mass spectroscopy and some of the compounds were also characterized by vapour pressure molecular weight osmometry too.The microbiological effect of the organometallic arsenic(III)- and bismuth(III)-bis(thiolates) I-IV was studied, the bismuth compounds generally inhibited bacterial growth more than the arsenic derivative. The aminothiophenolate complexes II and IV in particular were not inferior to the well-known organothiolatomercury(II) complexes with regard to their inhibition of bacterial growth. The hydrophilic mercaptoanilinium derivative IV has potential as a novel bactericide.     

Synthese und Struktur des tetrameren Tris(trimethylsilyl)silylindium(I) und neuer silylsubstituierter Indiumverbindungen

Synthesis and Structure of Tetrameric Tris(trimethylsilyl)indium(I) and of New Silyl substituted Indium Compounds The reaction of InCp* with [LiSi(SiMe₃)₃·3thf] yielded in the first silylsubstituted tetrahedrane of indium [In₄{Si(SiMe₃)₃}₄] ( 1 ). It crystallizes together with [In{Si(SiMe₃)₃}₃] ( 2 ) in dark green crystals. Colourless crystals of [Li(OH)(OSiMe₃)In{Si(SiMe₃)₃}₂]₂ ( 3 ) were isolated as a byproduct from this reaction. It's structural core are three connected four membered rings made up of In‐, Li‐ and O‐atoms. From the reaction of [InOSO₂CF₃] with [LiSi(SiMe₃)₃·3thf] colourless crystals of [In{Si(SiMe₃)₃}₂OSO₂CF₃·thf] ( 4 ) were isolated. InCp* reacted with [LiSiMe(SiMe₃)₂·3thf] to form the orange‐coloured monoindane [In{SiMe(SiMe₃)₂}₃] ( 5 ). 1 – 4 were characterized by X‐ray crystal structure analyses.     

(S)P(SSiMe3)3 als Ausgangsverbindung für die Synthese neuer Palladium-Clusterkomplexe

(S)P(SSiMe₃)₃ as Starting Material for the Synthesis of New Palladium Cluster Complexes The silylated derivative of thiophosphoric acid (S)P(SSiMe₃)₃ is used as a convenient starting compound for the synthesis of multinuclear Pd cluster complexes. (S)P(SSiMe₃)₃ reacts with Pd(acac)₂/PPh₃ and [PdCl₂(PPh₃)₂] to give the following crystalline compounds: [Pd₂(PS₄)Cl(PEt₃)₃] ( 1 ), [Pd₂(PS₄)(PEt₃)₄]Cl ( 2 ), [Pd₃(PS₄)(PS₃)(PEt₃)₄] ( 3 ), [Pd₆(PS₄)₄(PPh₃)₆] ( 4 ) and [Pd₆(PS₂(OEt)₂)₂(μ₃-S)₄(μ₂-SH)₂(PPh₃)₄] ( 5 ). The above mentioned compounds have been characterised by X-ray structure determination.     

Synthese und spektroskopische Eigenschaften neuer komplexierter Triphosphane

Synthesis and Spectroscopy of new Triphosphine Complexes The reaction of PCl₃ with [HPPh₂W(CO)₅] in the presence of NEt₃ affords stepwise the diand triphosphine complexes [Cl₂PPPh₂W(CO)₅] and ClP[PPh₂W(CO)₅]. Triphosphine complexes of the type [{M′(CO)₅}(H)P{PPh₂M(CO)₅}] (M = M′ = Cr or Mo) are not formed from the reaction of HP[PPh₂M(CO)₅] with [M′(CO)₅thf]. However they were prepared by reaction of [M′(CO)₅PCl₃] with Li[PPh₂M(CO)₅]. The products were characterized by NMR, IR spectroscopy, and mass spectrometry.     

Synthese und Eigenschaften einiger neuer Mono(π-cyclopentadienyl)-Nickel-Komplexe

During studies on the mechanism of ligand displacement reactions of nickelocene non-ionic monocyclopentadienylnickel complexes of the type π? C₅H₅Ni[P(OP)₃]X with X = Cl and P(O) (OR)₂ have been obtained. The new compounds have been characterised by means of their IR., UV., NMR. and Mass spectroscopic data. The phosphonate ligands are bonded with the phosphorus atom to the transition metal.     

Synthese neuer 4-Hydroxybenzonitrilderivate und deren herbizide Eigenschaften

The synthesis of several new derivatives of 2-amino-4-hydroxybenzonitrile2 and their herbicidal screening data are described. Thus, halogenation and furtherSandmeyer-Reaction of2 leads to the 2,3,5-trihalogenated derivatives5 a–e. Reaction of ethyl chloroformate with the amino group of2 gives6 a, acylation7 a, b and8. The 3,5-dihalogenated compounds10 a–e are obtained from6 a and7 a, b by bromination or iodation. The hydroxyl group of6 a, 7 a, b and10 a, c, e reacts with N,N-disubstituted carbamyl chlorides to give6 c, d, 9 a, b, 11, 12 and13 a, b.

     

Synthese neuer mono- und dihalogenierter Salicylsäurederivate

Syntheses of 3- and 4-monohalogenated (2a, b; 3a–c; 4a–e) and 3,4-dihalogenated (4f–l) ethyl 5-cyano-salicylates are described. Nitration of the ethyl 5-cyano-4-halo-salicylates3a, b leads to the ethyl 5-cyano-4-halo-3-nitro-salicylates5a, b. Hydrolysis of the ester and cyano group as well as reactions of various chloroformates, N,N-dimethylcarbamyl chloride and acetic anhydride with the hydroxyl group have been studied.

     

Synthese von (±) Seychellen

A four step synthesis of Seychellene ( 1 ) is described. Intramolecular Diels-Alder reaction of dienon 2 furnished the tricyclic ketones 3 and 4 in good yield. Hydrogenation of 3 gave 5 and 6 . The higher reactivity of 6 with methyllithium compared to 5 allowed the selective preparation of 8 , which, on subsequent acid-catalyzed rearrangment afforded Seychellen in 57,5% yield. In an analogues manner epi-Seychellene was synthetized via the intermediates 5 and 7 .