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1995 (1)
1990 (1)
1Author    PeterG. Jones, Anke Meyer, Reinhard Schmutzler, FrauM. Prof, BeckeRequires cookie*
 Title    Uber die Darstellung neuer spirocyclischer N,N'-Dimethylsulfamid-substituierter Phosphorverbindungen und N,N'-DimethyIsulfamid-verbrückter Diphosphorverbindungen The Preparation of New Spirocyclic N,N'-Dimethylsulphamide-Substituted Phosphorus Compounds, and of Some N,N'-Dimethylsulphamide-Bridged Diphosphorus Compounds  
 Abstract    The reactions of 4-chloro-l,3,5,7-tetramethyl-2,2,6,6-tetraoxa-2,6-dithia-l,3,5,7-tetraaza-4x:'-phosphaspiro[3.3]heptane (1) with trimethylsilyl compounds and sodium azide led to a series of spirocyclic N,N'-dimethylsulphamide-substituted phosphoranes (2—5). The nature of the penta-aza-spirophosphorane (4) was confirmed by an X-ray crystal structure determination (C2/c, a = 991.8(4), b = 1185.6(6), c = 1224.9(5) pm ,ß= 108.64(3)°, Z = 4, R = 0.041 for 1065 unique observed reflections); a crystallographic twofold axis passes through phosphorus and the nitrogen atom of the NMe2 group. The geometry at phosphorus is to a good approximation trigonal bipyramidal. The azido-spirophosphorane (5) undergoes Staudinger-type reactions with phosphorus(III) com­ pounds (PPh3, dppm) to form the mixed-valence phosphorus compounds 6—8 . The reaction of N,N'-dimethylsulphamide or N,N'-dimethyl-N,N'-bis(trimethylsilyl)-sulphamide with dichloro-phosphines RPC12 (R = Me, Ph) in a molar ratio 1:2 leads to the formation of the acyclic N,N'-dimethylsulphamide-bridged diphosphorus compounds 9 and 10, respectively. The spectro­ scopic properties (and, for 4, the X-ray crystal structure) of the products are compared with those of analogous urea-bridged phosphorus compounds. 
  Reference    Z. Naturforsch. 45b, 175 (1990); eingegangen am 26. Juni/7. September 1989 
  Published    1990 
  Keywords    Spirophosphoranes, NN'-Dimethylsulphamide, X-Ray, Staudinger Reactions, Diphosphorus Compounds 
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 TEI-XML for    default:Reihe_B/45/ZNB-1990-45b-0175.pdf 
 Identifier    ZNB-1990-45b-0175 
 Volume    45 
2Author    Thomas Kaukorat, Ion Neda, Reinhard SchmutzlerRequires cookie*
 Title    Synthese und Eigenschaften von N-phosphorylierten Aminomethylen-dimethylphosphinoxiden und -sulfiden Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides  
 Abstract    In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed. These compounds were allowed to react with a series of P(III)C1 compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 -10) with phosphorus in the combination A4P(V)/A3P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea l:l-adduct (NH2)2C0 H20 2 or sulfur, the corresponding A4P-CH2-N(Me)-A4P-derivatives (11 -16) were formed. Different reaction behaviour was observed depending on the substituent at A4P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphe-nylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphos­ phorus compounds (17) and (18) with phosphorus in the combination A4P(V)/A5P(V) (17) and A4P(V)/A4P(V)+ (18). Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form. Re­ action of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation (>N-PPh2 —* >N-P(:0)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2 —► >NC(CF3)2-0 -P P h 2) occurred. In the reaction of 1 with methyldichlorophos-phine, both the mono-and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds. The reaction of 1 with bis(diethylamino)chlorophosphine was unusual. Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 -26 were formed, with the central phospho­ rus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed. 
  Reference    Z. Naturforsch. 50b, 1818—1832 (1995); eingegangen am 17. Mai 1995 
  Published    1995 
  Keywords    N-Methylaminomethyl Grouping, Diphosphorus Compounds, Oxidation NMR Spectra, Unusual Reaction Behaviour 
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 TEI-XML for    default:Reihe_B/50/ZNB-1995-50b-1818.pdf 
 Identifier    ZNB-1995-50b-1818 
 Volume    50