Die Reaktion von λ5-Diphospheten mit COS und CO2 Dihydro-λ5-Phosphete

Reactions of λ⁵-Diphosphetes with COS and CO₂. Dihydro-λ⁵-Phosphetes 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with COS to yield the (3-oxo-3,4-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 7 . Reaction of dimethyl substituted 1 , i.e. 1,1,3,3-tetrakis(dimethylamino)-2,4-dimethyl-1λ⁵,3λ⁵-diphosphete 4 , with COS and CO₂ results in (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 9 , and (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonic bis(dimethylamide) 10 , respectively. Reaction mechanisms are suggested. 7, 9 and 10 are characterized by their properties, and their nmr, mass-, and ir-spectra. The results of X-ray structural analyses of 9 and 10 are reported and discussed.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Bortrifluorid-katalysierte Umsetzung von 3-Amino-2H-azirinen mit Amiden: Bildung von 4,4-disubstituierten 4H-Imidazolen

Boron Trifluoride Catalyzed Reaction of 3-Amino-2H-azirines and Amides: Formation of 4,4-Disubstituted 4H-Imidazoles Reaction of trifluoroacetamide and 3-amino-2H-azirines 1 in refluxing MeCN affords 4-amino-2-(trifluoromethyl)-4H-imidazoles 5 in fair yields (Scheme 3). Less acidic amides do not react with 1 under similar conditions. Therefore, a procedure involving BF₃-catalysis has been elaborated: the aminoazirine 1 in CH₂Cl₂ at ?78° is treated with BF₃ · Et₂O and then with a solution of the sodium salt of an amide in THF, prepared by addition of sodium hexamethyldisilazane at ?78°. The 4H-imidazoles of type 5 are formed in ca. 50% yield (Scheme 4). Reaction mechanisms for this ring enlargement of 1 are proposed in Schemes 5 and 6.     

Cyclokondensationen mit primären Sulfinimidamiden: Herstellung sechsgliedriger Ringe mit λ4-Thiadiazin- und λ4-Thiatriazadiphosphorin-Konstitution

Cyclocondensations with Primary Sulfinimidamides: Synthesis of Six-membered Rings with λ⁴-Thiadiazine and λ⁴-Thiatriazadiphosphorine Constitution 1,1-Dimethyl-ethanesulfinimidamide ( 1 ,) reacts with tetracyanoethylene by elimination of hydrogen cyanide to give the 1,2,6-thiadiazine 2 . In the cyclocondensation reaction of 1 , with tetrachloromethane and phosphines Ph₂PR′ (R′ = Ph₂PNH or Ph) the 1,2,4,6,3,5-thiatriazaphosphorine 3 a , and the ring-open compound [t-BuS(NH)NHPPh₃]Cl ( 4 ,), respectively, are formed by P? N-bond formation. The compounds are characterized by IR, MS and NMR data, and for 3a , further by X-ray structure analysis (space group P1 , Z = 2).     

Umsetzung von 2-Dimethylamino-(1,3,2)-diox-, oxathi- und dithi-arsolanen mit Alkoholen und Thiolen

Reaction of 2-Dimethylamino-(1,3,2)-diox-, oxathi-, and dithi-arsolanes with Alcohols or Thiols The reactions of 2-dimethylamino-(l, 3,2)-diox-, oxathi- and dithi-arsolanes (CH₂)₂XYAs? N(CH₃)₂ (X = Y = O or S; X = S, Y = O) with alcohols and thiols yield by cleavage of the As? N bond in the formation of alkoxy and alkylmercaptoarsolanes (CH₂)₂XYAs? ZR (X = Y = Z = O or S; X = Y: O, Z = S; X = Y = S, Z = O; X = S, Y = O, Z = O or S), respectively. Some of these arsolanes are not stable but rearrange under formation of 1,2-Bis-(arsolanyl)ethane and arsinous acid esters.     

Reaktionen von 5H-1,2λ5-Azaphospholen mit Arylazocarbonitrilen sowie Acetylendicarbonsäure-estern

Reactions of 5H,2λ⁵-Azaphospholes with Arylazocarbonitriles and Dialkyl Acetylenedicarboxylates Azaphospholes 1a – c react with activated arylazocarbonitriles to 1,5,2λ⁵-diazaphosphorines 2a – c and 3a – c . The reaction of 1a – c with diethyl or dimethyl acetylenedicarboxyiates yields 7H-1,4λ⁵-azaphosphepines 4a – c . The structures of 2b , 3a , and 4a are established by an X-ray diffraction analysis.     

Neue 1λ5, 3λ5-[1,3]Diphosphinine mit Thio- und Selenophosphonsäureresten – Darstellung,Kristallstruktur, NMR-Daten und Komplexbildung mit PdII

Diphosphabenzenes. VI. New 1λ⁵, 3λ⁵-[1,3]Diphosphinines with Thio and Seleno Phosphonic Acid Groups – Preparation, Crystal Structure, NMR Data, and Coordination to Pd^II Preparation of N,N,N′,N′-tetraethyl-P-phenylethinyl phosphonothioacid diamide ( 2 ) and the corresponding phosphonoselenoacid diamide ( 3 ) are described. 2 and 3 react with 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete ( 1 ) to yield 1λ⁵,3λ⁵-[1,3]diphosphinine derivatives 4 and 5 . With (bzl)₂Cl₂Pd 5 forms the coordination compound 6 . All new compounds 2–6 are characterized by their nmr and ir spectra, the structures of 4–6 are further elucidated by X-ray structural analyses.