Patent GB-1027021-A (GB)
Title: Production of metallo-acetylenic compounds
IPC: C07F1/02
Filed: 1963-01-02
Abstract: The invention comprises compounds containing both (a) divalent units M and (b) -C­C-R1-C­C-units, the two valencies of the M unit are connected directly to said acetylenic units and the remaining valency of each of said acetylenic unit is connected to H, an M unit or an acetylenic unit, where M is S, Se, Te, RP, Hg, T1R, GeR2, SnR2, PbR2, AsR, SbR, BiR, Ni(M1R3)2, Pd(M1R3)2, Pt(M1R3)2; M1 is P, As or Sb; R is a hydrocarbon radical and R1 is a divalent hydrocarbon radical. These compounds may have the formula <FORM:1027021/C2/1> where n is an integer.  Specific types of compounds disclosed have:-  (i) M as Hg and R1 may be phenylene, ethylene -C3H6- or -C4H8.  (ii) M as C6H5As where R1 may be phenylene. These compounds may be made by treating the alkali metallo derivative of a diethynyl hydrocarbon with a dihalogen compound. In an example LiC6H5 is formed from Li and C6H5Br, the lithium compound is treated with p-diethynylbenzene to give the dilithio derivative and the derivative treated with HgCl2 to give a precipitate of a phenylene ethynyl mercury compound. Alternatively the mercury compounds may be prepared by direct reaction between a mercury halide and diethynyl hydrocarbon, in an embodiment HgCl2 is treated with eicosatebayne in alkaline KI solution to give the required compound.  Compounds corresponding to the formula above may be condensed to form polymers by treating them in solution with an amine-cuprous or basic cupric salt complex as an oxygen carrying intermediate, the amine nitrogen atom being free of directly bonded aryl substituents (see Division C3).ALSO:The invention comprises compounds containing both (a) SiR2 units and (b) -C­C-R1-­C-units, the two valencies of the SiR2 unit being connected directly to said acetylenic units and the remaining valency of each of said acetylenic units being connected to H, R being a hydrocarbon radical and R1 being a divalent hydrocarbon radical.  The preferred compounds have the formula <FORM:1027021/C3/1> where M=R2Si.  In specific examples the compounds disclosed have R as phenyl, ethyl or methyl and R1 as phenylene. These compounds are prepared by treating the alkali metalloderivative of a diethynyl hydrocarbon with a dihalogen silicon compound.  In specific examples the dilithioderivative of a diethynylbenzene is treated with a dichloro silane to give the desired product.  The invention further comprises polymers of formula <FORM:1027021/C3/2> wherein M is Hg, TlR, SiR2, GeR2, SnR2, PbR2, PR, AsR, SbR, BiR, S, Se, Te, Ni(M1R3)2, Pd(M1R3)2, Pt(M1R3)2; where M1 is P, As or Sb; R is a hydrocarbon radical and R1 is a divalent hydrocarbon radical, and n and m are integers. These polymers may be made by the self-condensation of a compound according to the first formula by treating a solution of them with an amine-cuprous or basic cupric salt complex as an oxygen carrying intermediate, the amine nitrogen atom being free of directly bonded aryl substituents. Numerous lists of suitable copper salts and amines are given together with passages explaining their oxygen carrying ability. In specific examples organomercury polymers having 6, 9 and 10 repeating units are illustrated.  A compound made from eicosatetrayne and mercuric chloride is further polymerized using a cuprous chloride/pyridine solution.  Organo-arsenic polymers are made from the reaction product of the dilithioderivative of a diethynyl benzene with phenyl di-iodoasine, by taking this product and treating it with copper salt/pyridine complex. Organo-silicon polymers are made by treating compounds having the first formula above with a solution of cuprous chloride or basic cupric chloride in pyridine.