Methylenverbindungen von Nichtmetallen. VI. Amide der Methan-bis(phosphonigsäure), -bis(phosphonsäure) und -bis(thiophosphonsäure)

Methylene Compounds of Non-Metals. VI. Amides of Methane-bis(phosphonous Acid), -bis(phosphonic Acid) and -bis(thiophosphonic Acid) Symmetrical- and asymmetrical-substituted amides of methane-bis(phosphonous acid), -bis(phosphonic acid) and -bis(thiophosphonic acid) have been obtained by stepwise aminolysis of the chlorides Cl₂(Z)PCH₂P(Z)Cl₂ ( 1 : Z = electron pair; 7 : Z = S; 13 : Z = O) and the fluoride F₂(S)PCH₂P(S)F₂ 19 with dimethylaminotrimethylsilane. Oxidation reactions of trivalent phosphonous amides with sulfur and dimethylsulfoxide have also been investigated.     

Trägerfixierte Organometallkomplexe. VI. Charakterisierung und Reaktivität Polysiloxan-gebundener (Ether-phosphan)ruthenium(II)-Komplexe

Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes The ligands PhP(R)CH₂D [R = (CH₃O)₃Si(CH₂)₃; D = CH₂OCH₃ ( 1b ); D = tetrahydrofuryl ( 1c ); D = 1,4-dioxanyl ( 1d )] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)₄ to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl₂Ru(CO)₂(P ～ O)₂ ( 3b ) and HRuCl(CO)(P ～ O)₃ ( 5b ) were treated with NaBH₄ to form cis,cis,trans-H₂Ru(CO)₂(P ～ O)₂ ( 4b ) and H₂Ru(CO)(P ～ O)₃ ( 6b ), respectively (P ～ O = η¹-P coordinated; = η²- coordinated). Addition of Si(OEt)₄ and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b ′, 6b ′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by ²⁹Si CP-MAS NMR spectroscopy. 4b ′ reacts with carbon monoxide to form Ru(CO)₃(P ～ O)₂ ( 7b ′). Chelated polysiloxane-bound complexes Cl₂Ru( )₂ ( 9c ′, d ′) and Cl₂Ru( )(P ～ O)₂ ( 10b ′, c ′) have been synthesized by the reaction of 1b–c with Cl₂Ru(PPh₃)₃ ( 8 ) followed by a copolymerization with Si(OEt)₄. The polysiloxane-bound complexes 9c ′, d ′ and 10b ′, c ′ react with one equivalent of CO to give Cl₂Ru(CO)( )(P ～ O) ( 12b ′– d ′). Excess CO leads to the all-trans-complexes Cl₂Ru(CO)₂(P ～ O)₂ ( 14b ′– d ′), which are thermally isomerized to cis,cis,trans- 3b ′– d ′. The chemical shift anisotropy of ³¹P in crystalline Cl₂Ru( )₂ ( 9a , R = Ph, D = CH₂OCH₃) has been compared with polysiloxane-bound 9d ′ indicating a non-rigid behavior of the complexes in the matrix.     

Acetylenbis(phosphonigsäurediamide), -bis(phosphonigsäurefluoridamide) und -bis(phosphonigsäuredifluorid)

Acetylene Bis(Phosphonous Diamides), Bis(Phosphonous Fluoride Amides), and Bis-(Phosphonous Difluoride) Synthesis and properties of the acetylene bis(phosphonous diamides) 2 – 5 , the acetylene bis(phosphonous fluoride amides) 6 and 7 and of acetylene bis(phosphonous difluoride), 8 , are described. The result of the X-ray structural analysis of 2 is reported.     

Synthetische Juvenilhormone 3. Mitteilung. p-Substituierte 4-Phenyl-buten(1)-carbonsäurederivate

The syntheses of p-substituted 2-methyl-4-phenylbuten(1)-carboxylic acid derivatives are described, using Blanc's chloromethylation reaction, the Friedel-Crafts alkylation of unsaturated ketones or the Meerwein arylation; the formed intermediates react in subsequent steps to the title compounds.     

Neue mehrkernige Organozinn(IV)–Stickstoff‐Verbindungen. Synthese und Kristallstrukturen von [(PhSn)4(NPh)5Cl2] und [(MeSn)4(NHPh)4(NPh)4]

New Polynuclear Organotin(IV)–Nitrogen Compounds. Synthesis and Crystal Structures of [(PhSn)₄(NPh)₅Cl₂] and [(MeSn)₄(NHPh)₄(NPh)₄] The reaction of the organotin halides PhSnCl₃ and MeSnCl₃ with LiNHPh leads to the formation of two new nitrogen bridged organotin compounds, [(PhSn)₄(NPh)₅Cl₂] ( 1 ) and [(MeSn)₄(NHPh)₄(NPh)₄] ( 2 ). The crystal structures of 1 and 2 have been determined by low temperature X‐ray diffraction. 1 contains a bicyclic Sn₄N₅ framework, which consists of two six‐membered Sn₃N₃‐rings. All tin atoms are coordinated nearly tetrahedrally. Two tin atoms are bonded to a phenyl group and three nitrogen atoms, the other two tin atoms are coordinated by a phenyl group, two nitrogen atoms and a terminal chlorine atom. In 2 the tin atoms define the corners of a distorted square. Each edge of the square is bridged by a μ²‐NHPh and a μ²‐NPh group. The bridging NHPh and NPh groups are arranged at opposite sides of the Sn₄ plane. The tin atoms are coordinated square pyramidally by 4 nitrogen atoms and a methyl group.     

Synthetische Juvenilhormone 4. Mitteilung. p-Substituierte 5-Phenyl-penten(1)-carbonsäurederivate

The synthesis of p-substituted 2-methyl-5-phenyl-penten(1)-carboxylic acid derivatives is described: the formed Grignard compounds react with ethylene-oxide to the corresponding alcohols which are transformed by following reactions to the above mentioned compounds.     

Insertion von Rhodizonsäure in die Gallium‐Gallium‐ bzw. Indium‐Indium‐Bindungen von Digallan(4)‐ bzw. Diindan(4)‐Verbindungen

Insertion of Rhodizonic Acid into the Gallium‐Gallium and Indium‐Indium Bonds of Digallane(4) and Diindane(4) Compounds Rhodizonic acid (C₆O₆H₂, 5, 6‐dihydroxy‐5‐cyclohexene‐1, 2, 3, 4‐tetraone) did not react with tetrakis[bis(trimethylsilyl)methyl] digallane(4) ( 1 ) and the corresponding diindium compound ( 2 ) by the transfer of protons. Instead the acid was completely inserted into the element‐element bonds of the starting compounds and the gallium or indium atoms were oxidized from the oxidation state of +II to +III. In contrast to the free acid, the OH groups of the products are not attached to neighbouring carbon atoms, but occupy the 1, 4‐positions of the central six‐membered rings. Both dialkylgallium and dialkylindium groups of the products ( 3 (Ga) and 4 (In)) are coordinated by two oxygen atoms. They adopt opposite positions at the C₆O₆ molecular core.     

Electropolymerization of aminophthalic acids. II. Polymerization of 4-(4′-aminobenzamido)-, 4-(2′-aminobenzoyl)-, and 4-(3′-aminobenzoyl) phthalic acid

The electrochemical polymerization of the amino phthalic acid series has been extended to the following derivatives: 4-(4′-aminobenzamido), 4-(2′-aminobenzoyl), and 4-(3′-aminobenzoyl)phthalic acid. Reactions were performed in both dimethylacetamide and ethanol. Both systems produced a film deposit at the anode which was identified as the amide acid of the starting material. Conversion by heat to the imide produced a brittle coating. Inherent viscosity measurements indicate that only low molecular weight material was formed.     

Photochemie von Benzisoxazolen. (vorläufige Mitteilung)

The photochemical behaviour of benzisoxazoles 1 is remarkably solvent-dependent: Irradiation in H₂O or CH₃O or CH₃OH leads to benzoxazoles 2 in a virtually quantitative yield. However, at low concentrations of H₂O or CH₃OH in acetonitrile or hexane, photolysis of 3-alkyl-benzisoxazoles 1b–1e yields salicylamides 4 and salicylesters 5 , while under these conditions o-cyanophenol ( 3a ) is the only photoproduct of benzisoxazole ( 1a ). The course of these photochemical reactions is discussed from the standpoint of solvent-dependence, multiplicity and the behaviour at low temperatures.     

Mehrkernige Kobaltkomplexe. V. Präparative Herstellung von Tetrakis (äthylendiamin)-μ-peroxo-μ-amido- und μ-peroxo-μ-thiocyanatodikobalt (III)-Komplexen ausgehend von Tetrakis (äthylendiamin)bis-(ammin)-μ-peroxo-dikobalt (III)-tetraperchlorat

Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en)₂(NH₃)Co(O₂)(NH₃)(en)₂](ClO₄)₄. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en)₂Co(O₂, SCN)Co(en)₂](NO₃)₃ suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm^?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given.     

Stoffwechselprodukte von Mikroorganismen. 101. Mitteilung. Synthese der trans-5-Hydroxy-3-methylpenten-(2)-säure (trans-Δ2-Anhydromevalonsäure)

trans-Δ²-Anhydromevalonic acid (XVII) was prepared by a Wittig reaction, starting from (4-tetrahydro-2-pyranyloxy)-2-butanone. On the other hand, the corresponding 4-acetoxy-2-butanone gave, under similar conditions, the cyclohexene derivative V, explainable by a twofold Michael addition of the Wittig reagent to methyl vinyl ketone, followed by an intramolecular alcol condensation.     

Ringerweiterungsreaktionen von N-(2-Aminoäthyl)-, N-(4-Aminobutyl)-, N-(6-Amino-4-aza-hexyl)- und N-(8-Amino-4-aza-octyl)-lactamen. 7. Mitteilung über Umamidierungsreaktionen

Ring Enlargement Reactions of N -(2-Aminoethyl)- , N -(4-Aminobutyl)- , N -(6-Amino-4-aza-hexyl)- and N -(8-Amino-4-aza-octyl)-lactames The N-aminoalkyl-lactams 1 , 3 , 4 , 10 (Scheme 2) and 13 (Scheme 3) have been synthesized. In the presence of KAPA (potassium 3-aminopropylamide in 1,3-propanediamine) 1 is stable, whereas 3 , 4 and 10 rearrange under ring enlargement to 5 , 8 and 11 , respectively. The 4-aminobutyl derivate 13 rearranges in a fast reaction to 14 ; after a longer reaction time the 22membered ring 16 and the ring opened product 18 are formed. Hence it may be concluded that the 7membered lactam ring is more stable than the 10membered one, and the 11membered lactam ring is more stable than the 8 membered one. Moreover, the 5- and 6 membered ring intermediates of these transamidation reactions are prefered to the 7membered ring intermediates (cf. [10]).     

Beiträge zur Chemie des Phosphors. 94. Tetraphenyl-cyclotetraphosphan, (PPh)4, und 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphan, (PPh)3(PBut)

Contributions to the Chemistry of Phosphorus. 94. Tetraphenyl-cyclotetraphosphane, (PPh)₄, and 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) The homocyclic four-membered phosphorus ring compounds tetraphenyl-cyclotetra-phosphane, (PPh)₄ ( 1 ), and l,2,3-triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) ( 2 ), are obtained as main products by [3+l]-cyclocondensation of K(Ph)P? P(Ph)? P(Ph)K or Me₃Si(Ph)P? P(Ph)? P(Ph)SiMe₃ with PhPCl₂ or Bu^tPCl₂ respectively under suitable reaction conditions. At room temperature in solution 1 rearranges mostly to the oligomeric (PPh)₅, whereas 2 is remarkably stable. The ³¹P-NMR parameters of the mixed substituted four-membered ring compound 2 are reported and discussed.     

Chinazolincarbonsäuren. VII. Mitteilung. Ein einfacher Zugang zu (4-Oxo-3,4-dihydrochinazolin-3-yl)-alkansäuren, (4-Oxo-3,4-dihydro-1,2,3-benzotriazin-3-yl)-alkansäuren und deren Estern

Quinazoline Carboxylic Acids. An Easy Route to (4-Oxo-3,4-dihydroquinazolin-3-yl)-alkanoic Acids, (4-Oxo-3,4-dihydro-1,2,3-benzotriazin-3-yl)-alkanoic Acids and their Esters A new route was found for the synthesis of (4-Oxo-3,4-dihydroquinazolin-3-yl)-alkanoic acids ( 8 ) and (4-Oxo-3,4-dihydro-1,2,3-benzotriazin-3-yl)-alkanoic acids ( 6 ) by cyclization of the N-(2-aminobenzoyl)amino acids 5 with HCOOH or HNO₂. 2H-3,1-Benzoxazine-2,4(1H)-diones ( 1 ) reacted with glycine esters to 2 , which were cyclized by HNO₂ to the esters 4 . Ester 4 was hydrolyzed to 6 (X = CH₂). Diones 1 reacted with the most common amino acids (as the ammonium salt of tertiary amine) to amino-alkanoic acids 5 , which were cyclized with orthoformate to 7 or 8 depending on the reaction conditions.     

Über Reaktionen oxygenierter Kobalt(II)-Chelate. VI. Präparative Darstellung von diastereoisomeren Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxodikobalt(III)-perchloraten

On Reactions of oxygenated Cobalt(II) Chelates. VI. Preparation of diastereoisomeric tetrakis(ethylenediamine)-μ-peroxo-μl-hydroxo-dicobalt(III) Perchlorates Oxygenation of Co(en)₂²⁺ leads to a mixture of two isomeric forms of [(en)₂Co(O₂, OH)-Co(en)₂] (ClO₄)₃ · H₂O from which the less soluble meso form can be readily crystallized. Further crystallization from the mother liquor yields the racemate ΔΔ/ΔΔ. The pure racemate may be obtained by either of the following methods: (a) By ligand exchange starting from mono bridged [(NH₃)₅CoO₂Co(NH₃)₅] (NO₃)₄ or from doubly bridged [(SCN) (NH₃)₃Co(O₂, OH)Co(NH₃)₃(SCN)] SCN · 2H₂O. (b) By reaction of cis-[Co(en)₂(OH₂)₂]³⁺ with H₂O₂. Reaction (b) proceeds via an intermediate cis-[Co(en)₂(OOH) (OH₂)] (ClO₄)₂ · H₂O which at higher pH reacts with [Co(en)₂(OH) (OH₂)]²⁺ to yield the desired doubly bridged ΔΔ/ΔΔ tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxodikobalt(III)-perchlorate.