16548-51-9Relevant articles and documents
Terpolymers from Borane-Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission
Wang, De,Hadjichristidis, Nikos
, p. 6295 - 6299 (2019)
The first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers was achieved by one-pot borane-initiated random copolymerization of ω-methylallyl (C3 units, chain is growing by three carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain is growing by one carbon atom at a time) ylides, followed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well-defined, possess a predictable molecular weight and low polydispersity (Mn,NMR=1.83–9.68×103 g mol?1, ?=1.09–1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as confirmed by fluorescence and NMR spectroscopy. This phenomenon can be explained by the isomerization of the double bonds of allylic monomeric units along the chain of the terpolymers (isomerization-induced light emission).
Heteroorganic betaines 8. Synthesis and structures of silicon- and germanium-containing organoarsenic betaines R13As(1+)-CR2R3-EMe2-S(1-)- (E = Si, Ge)
Borisova, I. V.,Zemlyanskii, N. N.,Khrustalev, V. N.,Nechaev, M. S.,Kuznetsova, M. G.,Ustynyuk, Yu. A.
, p. 678 - 683 (2007/10/03)
The reactions of ylides R13As=CHR2 with hexamethyl-2,4,6-trisila- and hexamethyl-2,4,6-trigermatrithiacyclohexanes afforded betaines R13As(1+)-CHR2-SiMe2-S(1-) (2) (R1 = Et; R2 = Ph (a), Me3Si (b); R1 = R2 = Ph (c)) and Et3As(1+)-CH(SiMe3)-GeMe2-S(1-) (3), respectively. Betaines 2a,b and 3 were characterized by multinuclear NMR spectroscopy. According to the X-ray diffraction data, in the crystals the As(1+)-C-E-S(1-) main chain (E = Si or Ge) of molecules 2a,b and 3 adopts a twisted cis conformation due to strong intramolecular Coulomb interactions between the anionic and cationic centers. The equilibrium geometries of isolated molecules 2a and 3, which were calculated within the framework of the density functional theory (the PBE functional, the TZ2P basis set), are in qualitative agreement with the X-ray data. In solutions, betaines 2a (in the absence of Li salts) and 2c (in the presence of LiBr) selectively decomposed according to the Corey-Chaykovsky reaction, which was accompanied by elimination of R3As and, probably, the intermediate formation of silathiirane. The subsequent transformation of the latter afforded 2,2,4,4-tetramethyl-5-phenyl-2,4-disila-1,3-dithiolane.
Studies on Betaine Decomposition of Arsonium Ylides
Tewari, R. S.,Suri, S. K.,Gupta, K. C.
, p. 95 - 98 (2007/10/02)
A systematic study on the nature of decomposition of betaine formed by nucleophilic attack of semistabilized arsonium ylides on thiocarbonyl substrates has been carried out.A series of substituted benzylidenetriphenylarsenanes have been generated from their corresponding salts and condensed with few cyclic thioketones to yield exocyclic olefins as exclusive products.The non-availability of thioepoxides indicates that the mode of decomposition of such type of betaines is quite analogous to the betaine formed by phosphonium ylides.The structure of the products have been assigned by IR and NMR spectral studies. - Keywords: Betaine, Arsonium Ylides
