Synthesis and characterization of poly(1,8-diethynylnaphthalene)

Summary The cyclopolymerization of 1,8-diethynylnaphthalene(DEN) and its copolymerization with diethyl dipropargylmalonate(DEDPM) were carried out by various transition metal catalysts. MoCl₅-based catalyst was found to be very effective and gave almost a quantitative polymer yield. The resulting dark-brown homopolymer(PDEN) was partially soluble in chloroform, tetrahydrofuran, and dimethyl sulfoxide, whereas copolymer (1:1) with number avaerage molecular weight of 2.1x10⁴ by GPC showed good solubility in those solvents. The structure of the polymers was analysed by IR, NMR, and UV-VIS spectroscopies. From the spectral and solubility data, it is proposed that cyclized products with the conjugated system are formed. Room temperature conductivities of the I₂-doped homo and copolymer were found to be about 7.5x10^-3 and 5.1x10^-3 S/cm, respectively.     

Electrosynthesis in systems of two immiscible liquids and a phase transfer catalyst. V. The anodic chlorination of naphthalene

The anodic chlorination of naphthalene in a water/methylene chloride emulsion and using tetrabutylammonium ion as the phase transfer catalyst is demonstrated; in conditions where the aqueous phase is saturated NaCl, the organic yield of 1-chloronaphthalene is 56% and the current yield is 33% after the passage of 2.33 F mol^–1 of naphthalene. It is shown, however, that when the aqueous phase also contains zinc chloride so that the species transferred is [(C₄H₉)₄N⁺]₂ZnCl ₄ ^–– , the yields can be increased to 92% and 49% respectively. The mechanism of these chlorinations is discussed.     

Methyl Oct-cis-2-enoate. its synthesis,GLC behaviour and infrared spectra

Methyl oct-cis-2-enoate was synthesized by selective hydrogenation of methyl oct-2-ynoate at atmospheric pressure with quinoline poisoned palladium as catalyst. The resulting product contained only 7% of thetrans form, as determined by GLC. The structure was confirmed by infrared spectra. Analysis of the infrared spectra is given. The cis andtrans forms of methyl oct-2-enoate were separable by GLC in polar or non-polar columns. GLC runs in polar and non-polar phases showed that the α position of the double bond of methyl oct-2-enoate so affects its properties, that practically no interaction was observed between the double bond and the polar phase. Consequently volatility was the main factor determining the retention times of cis andtrans methyl oct-2-enoate in the polar and non-polar phases studied.