(Perhalogenmethylthio)heterocyclen. XVIII . Synthese und eigenschaften von halogenierten (perhalogenmethylthio)pyrrolen

(Trifluoromethyltho)pyrroles 1-5 and (chlorodifluoromethylthio)pyrroles 6 were chlorinated by sulfuryl chloride, sulfuryl chloride/silicon dioxide, sulfuryl chloride/disulfur dichloried/aluminium trichloried to give the corresponding chloropyrroles 1a-d , 2a,b , 3a,b , 4a , 5a , and 6a-c Bromination with bromine or iodination with iodine/potassium iodide of 2, 3, 4 , and 6 yielded the derivatives 2c,d, 3c,d, 4b, 6d , and 2e, 3e, f, 4c , 6e respectively. Mixed halogenated pyrroles 3g and h were obtained from 3a and bromne or 3a and iodine/potassium iodide. During some chlorination reactions 7, 8 , and 9 were fromed in low yield asbyproducts. The ¹H-nmr, ¹⁹F-nmr and ir spectroscopic data are presented.     

(Perhalogenmethylthio)heterocyclen. XVII. Darstellung und Eigenschaften von Tetrakis(trifluormethylthio)pyrrolyl-Verbindungen des Phosphors,Arsens und Antimons

Perhalogenomethylthio Heterocycles. XVII. Preparation and Properties of Tetrakis(trifluoromethylthio)-pyrrol Derivatives of Phosphorus, Arsenic, and Antimony 2,3,4,5-Tetrakis(trifluoromethylthio)pyrrolylsilver ( 2b ) reacts with phosphorus trihalides to the phosphaneces 3a–c . From the reaction of 3a with 2c at first compound 4 is obtained reacting further to tripyrrolylphosphane 5a by successive substitution. AsCl₃ und SbCl₃ react with 2c directly under complete elimination of KCl to 5b and 5c. 2b reacts with organo-chlorophosphanes always under entire exchange of chlorine to form 6a, b , and 7 . Reactions of 2b with chloro-phosphanes lead to 8a, b and 9a . The thio- and seleno-homologues of 9a can be prepared by oxidising 7 with elemental sulfur or selenium. An example for a pyrrolyl-fluoro exchange is shown in the reaction of 2c with PhPF₄ to give 10 . The substances 3 to 10 are extremely sensitive towards hydrolysis and react with traces of H₂O to 2a .     

(Perhalogenmethylthio)heterocyclen. X. Säurekatalysierte Substitutionen an (Perchlorfluormethylthio)pyrrolen und deren agrobiologische Wirkung

(Perhalomethylthio)heterocycles. X

1 IX. Mitt.: s. [1].

. Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C₄F₉SO₃H the (perhalomethylthio)pyrroles 1a–c react with Cl_3?nF_nCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF₃SCl (catalyst CF₃SO₃H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The ¹H- and ¹⁹F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.     

(Perhalogenmethylthio)heterocyclen. XII. Herstellung von Perfluoroalkylsulfonylharnstoff-Derivaten sowie CCl3−nFnX-substituierten Heterocyclen und deren biologische Wirkung

(Perhalomethylthio)heterocycles XII. Preparation of Perfluoroalkylsulfonylurea Derivatives as well as CCl_3?nF_nX-Substituted Heterocycles and Their Biological Activity

1 XI, Mitt., s.[1]

In the presence of CF₃SO₃H (chlorodifluoromethylthio)thiophene 1 reacts with CClF₂SCl to give the 2,5-disubstituted thiophene 2a which on oxidation with 30% H₂O₂-solution yields the corresponding sulfonyl compound 2b · R¹SO₂NCO adds amines to give R¹SO₂NHC(O)NHR 3a – g . Some biological properties of these compounds were investigated.     

(Perhalogenmethylthio)heterocyclen. XIX. Darstellung und eigenschaften von tetrakis(trifluoromethylthio)thiophen,tetrakis-(trifluoromethylthio), -1,2-dithiin, 2,3,4-tris(trifluoromethylthio)-5-trifluor-methylthiophen und 1-chlor-tetrakis(trifluormethylthio)pyrrol

Bis(trifluromethylthio)acetylene reacts with sulfur at 170° to yield tetrakis(trifluoromethylthio)thiophene, -1,2-dithiin and 2,3,4-tris)trifluoromethylthio)-5-trifluorothiophene. Sodium hyperchlorite forms with tetraksi(trifluoromethylthio)pyrrole in a slightly alkaline solution N0chliorotetrakis(trifluoromethylthio)pyrrole. Physical data of the newly synthesized products are provided.     

Über Reaktionen einiger halogenierter Heterocyclen und N-Oxide mit reaktiven Methylenverbindungen

Reactions between some halogenated heterocycles and heterocyclic N-oxides with compounds containing reactive methylene groups are described and the structures of the products were studied.     

Niederkoordinierte Phosphorverbindungen: LVII. Alkali(diphosphaallyl)ferrate,synthese und Reaktionen

Reaction of the diphosphapropene I with Na₂Fe(CO)₄, or treatment of its lithium salt with Fe(CO)₅, affords 1,3-diphosphaallylferrates(− 1). Their condensation with alkyl halides or chlorophosphanes yields either the η²,η¹- or η¹,η¹-1,3-diphosphapropene-iron complexes. Protolysis with hydrogen chloride in ether leads via the hydrido-iron species to a stable 1,3-diphosphapropene-iron compound.     

Über bismut-haltige heterocyclen: I. Methylierte und phenylierte bismocane,intra- und intermolekulare koordinationserhöhung an bismut(III)

Methyl and phenyl oxadithia and trithiabismocanes have been synthesized from methyl or phenyl diethoxybismutane and the respective dithiol. The light-sensitive compounds have been investigated by mass, vibrational and ¹³C NMR spectra: ν(BiMe) 470–460, ν(BiS₂) 300–240 cm^?1; δ(¹³Me) ?12 ppm. The crystal structure of 5-phenyl-1,4,6,5-oxadithiabismocane has been determined (R = 0.056). The eight-membered ring has the chair-chair conformation. Besides three direct bonds (BiPh 225(2), BiS 256.0(2) and 260.2(3) pm) there are one transannular (Bi?O 297(1) and two intermolecular contacts (Bi ?S 344.0(3) and 350.9(3) pm) to bismuth in resulting a ψ-monocapped octahedral sphere of coordination. These polyhedra are connected in sharing two different edges, and the crystal structure exhibits double chains of molecules.     

(Benzylthio)- und (Arylthio)-substituierte Nitril-ylide: Thermische Erzeugung und Reaktionen

Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile Ylides Thermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6 , at 110–155° in the presence of dipolarophiles with activated C≡C, C?C, C?O, C?S, and N?N bonds, led to 5-membered cyclo-adducts and CO² (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate ( 19 ) and ethyl pyridine-3-carboxylate( 22 ), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20 . The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8).     

Formamidinoylisothiocyanate—II : Isomerisierung,dimerisierung und kondensations-reaktionen von formamidinoylisothiocyanaten

Formamidinoylisothiocyanates isomerize easy and give 3 H-chinazolinthiones-(4). The dimerization of formamidinoylisothiocyanates yields derivatives of s-triazines by 1.4-1′.2′-cycloaddition. Further cycloadditions are possible with phenylisocyanate and hydrogen thiocyanate.Formamidinoylisothiocyanates undergo intermolecular elimination of hydrogen thiocyanate yielding derivatives of chinazolin, which are substituted with amidino-groups.     

Spezifische und selektive Reaktionen (Reagenzien)

Ohne Zusammenfassung     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: V. Synthese,reaktionen und struktur neuartiger manganacycloalkane

The colourless, six- and seven-membered manganacycloalkanes (OC)₄$\text{MnPR}{}_2\text{OCH}{}_2\text{XC}$H₂ are obtained by reaction of Na₂[(OC)₄MnPR₂O] with the bis(triflate)alkanes (YCH₂)₂X (R = C₆H₅; X = CH₂, C(CH₃)₂, CH₂CH₂; Y = CF₃SO₃). CO or SO₂ can be inserted into the reactive MnC-σ bonds under ring expansion. Some characteristic IR and ¹H NMR data are discussed. (OC)₄$\text{MnPR}{}_2\text{OCH}{}_2\text{CH}{}_2\text{C}$H₂ crystallizes monoclinic in the space group P2₁/c with Z = 4.     

Benzylnickel(II)-Komplexe und ihre Reaktionen

Benzyl Nickel(II) Complexes and their Reactions By the oxydative addition of p-substituted benzyl chlorides to (Ph₃P)₂Ni(C₂H₄) at ?20°C the violet nickel(II) complexes (Ph₃P)₂Ni(p-CH₂C₆H₄R)Cl (R ? CN, COOH, CH₃, Cl) are, formed. In water containing solutions the carbonic acid (Ph₃P)₂Ni(p-CH₂C₆H₄COOH)Cl is rearranged to the corresponding p-methylbenzoate. With carbon dioxide the complexes (Ph₃P)₂Ni(p? CH₂C₆H₄R)Cl react like Grignard compounds. Diphenyl ethine and butadien-1,3 are inserted in the Ni—C bond at room temperature. Substituted nickel-σ-vinyl or π-allyl complexes are obtained. The reactivity of the nickel-σ-benzyl compounds is compared with that of other nickel(II)-alkyl compounds.     

Monomere und dimere Oxovanadium(IV)-phenolate: Synthese,Struktur und Reaktionen mit reduzierenden und arylierenden Reagenzien

Monomeric and Dimeric Oxovanadium(IV)-phenolate Complexes: Synthesis, Structure, and Reaction with a Reducing and Arylation Agent Reaction of [OVCl₂(THF)₂] with LiOMes yields dimeric [Li(Et₂O)₂OVCl₂(μ-OMes)]₂ ( 1 ) which can be converted with excess LiOMes to the substitution product [Li(THF)₂OV(OMes)₃(THF)] ( 2 ). Treatment of ( 1 ) with LiMes results in the formation of complexes [Li(THF)₃OVMes₃] ( 3 ) and [Li(THF)₃OVMes₂(OMes)] ( 4 ). Complex [{Li(THF)₂OV(OMes)₂(μ-OH)}₂ · 2 THF] ( 6 ) has been isolated as a by-product of an unknown reaction of [OV(OMes)₃] and Li. The structures of 1 , 2 , 3 , and 6 have been determined by X-ray analysis. In 1 (monoclinic, P2₁/c, a = 9.522(1) Å, b = 19.777(2) Å, c = 12.311(1) Å, β = 104.45(1)°, Z = 2) the vanadium atoms which are bridged by the phenolate ligands show a square-pyramidal coordination sphere. The central atom in 2 (monoclinic, P2₁/c, a = 17.755(2) Å, b = 11.629(1) Å, c = 20.956(3) Å, β = 113.98(1)°, Z = 4) has a bipyramidal environment which is realized by coordination of a THF donor molecule. The (THF)₂Li fragment is bound via bridging phenolate ligands. The structure of 3 (orthorhombic, P2₁2₁2₁, a = 15.465(2) Å, b = 15.456(2) Å, c = 15.469(2) Å, Z = 4) is built up by two tetrahedrons linked by the oxo atom. Dimeric 6 (triclinic, P1, a = 10.780(4) Å, b = 11.428(2) Å, c = 13.734(3) Å, α = 77.24(2)°, β = 84.79(2)°, γ = 74.35(2)°, Z = 1) has a structure similar to 1 . The vanadium atoms are bridged by two OH groups while phenolate ligands link the lithium cations with the vanadium atoms.     

Bismalondialdehydverbindungen, 2. Mitt.: Darstellung und Reaktionen von Bipyrazolen und Biisoxazolen

Starting from 4-ethynyl-4H-pyrane-3,5-dicarbaldehyde (3 a) methane derivatives were obtained with substituents being five membered rings containing N-atoms—such as 4,4-dipyrazolylketone and 4,4-dipyrazolyl-4-triazolylmethane. Reactions of the new methane derivatives were studied.

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Mit 2 Abbildungen     

Cyanisocyanat: Darstellung,Reaktionen und Struktur

Zusammenfassung Bei der Reaktion von AgOCN mit CICN gebildetes polymeres Cyanisocyanat steht mit seinem Monomeren NCNCO in einem temperaturabhängigen Gleichgewicht. Das thermisch stabile, äußerst hydrolyseempfindliche Cyanisocyanat wird bei Temperaturen über 140° gebildet und polymerisiert sich bei Raumtemp. bereits bei niedrigen Drücken in kurzer Zeit; seine Reaktionen mit Äthanol und Wasser werden beschrieben. Das IR-Spektrum im gasförmigen und festen Zustand wird diskutiert und für das Gas C v^–, für die Festsubstanz C_s-Symmetrie vorgeschlagen.

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Cyanogen isocyanate: Synthesis, reactions and structure

Polymeric cyanogen isocyanate formed by reaction of AgOCN with CICN equilibrates with its monomer NCNCO. Monomeric cyanogen isocyanate is formed at temperatures above 140° and polymerizes rapidly at room temperature even at low pressures. It is thermally very stable, but extremely reactive towards moisture. Its reactions with ethanol and water are described. IR-spectra of gaseous and solid cyanogen isocyanate are discussed and interpreted in terms of C v^–symmetry for the gas and C_s-symmetry for the solid. *** DIRECT SUPPORT *** A3615139 00015

     

Nucleotide,XXI. Synthese und Eigenschaften Dihydrouridin-haltiger Oligonucleotide

Nucleotides, XXI. Synthesis and Properties of Dihydrouridine-Containing Oligonucleotides Substituted 5,6-dihydrouridine derivatives 1, 5 , and 8 have been used in condensation reactions to form a series of dinucleosidemono- and dinucleosidediphosphotriesters, 13 and 16–22 , respectively. Dihydrouridine-containing fully blocked oligomers have also been obtained by stepwise chain-elongation and block condensations including 5 trimers (25–29) and one pentamer (31) , hexamer (32) and octamer (34) each. The new compounds were characterized by UV and partly CD spectra as well as elementary analyses. NMR spectra prove the structures but are not reported in detail.