Tolane chlorides

Benzal chloride also splits off hydrochloric acid, but no chlorine a mixture of a- and / -tolane dichlorides results ... 

Scheme 2. Condensation synthesis of pentaphenyl-Cp from diphenylacetylene (tolane) and benzal chloride. Yields are 24-51% (42).

Allylvanadium complexes (see Allyl Complexes) are synthesized by allylation with Grignard reagents as shown in Scheme 25. Another synthetic route lies in the allylation of a vanadium anionic species with allylic chloride. Codimerization of vanadium-coordinated diphenylacetylene (tolane) and 1,3-butadiene affords the allyl complex (49) (Scheme 26). ... 

Alkyne cyclotrimerization occurs at various homogeneous and heterogeneous transition metal and Ziegler-type catalysts [7], Substituted benzenes have been prepared in the presence of iron, cobalt, and nickel carbonyls [8] as well as trialkyl- and triarylchromium compounds [9]. Bis(acrylonitrile)nickel [10] and bis(benzonitrile)palladium chloride [11] catalyze the cyclotrimerization of tolane to hexaphenylbenzene. NiCl2 reduced by NaBH4 has been utilized for the trimer-ization of 3-hexyne to hexaethylbenzene [12]. Ta2Cl6(tetrahydrothiophene)3 and Nb2Cl6(tetrahydrothiophene)3 as well as 7 -Ind-, and 77 -Ru-rhodium... 

Tolane (9.5 g) was mixed under nitrogen with diisobutylhydridoaluminum (17 g) and warmed at 45-50° for 12 h. The red product was then cooled in ice, treated cautiously with methanol and dilute sulfuric acid, and extracted with ether. The extract was washed with water and sodium hydrogen carbonate solution, dried over calcium chloride, and evaporated, yielding a residue whence distillation in a vacuum afforded m-stilbene (7 g, 73 %) of b.p. 147-148°/15 mm. 

New reactions of isoquinoline derivatives include the following 3,4-di-hydroisoquinoline N-oxide with 2-acetylcycloalkane-l,3-diones, Reissert compounds with stilbene and tolan derivatives, isoquinoline with pyrrole derivatives and with 2-methylfuran " (both in the presence of benzyl chloride), and the chromium trioxide oxidation of the benzo[a]quinolizidine (49) to give (50). Compound (49) was prepared by the condensation of 3,4-dihydroiso-quinoline with the 5-lactone (51). Further examples of a classical benzo[a]-... 

A two-fold excess of benzal chloride added with efficient stirring under N2 to a mixture of tolane and dry powdered K-ferf-hutoxide in benzene, refluxed 3 hrs., cooled, water added to dissolve the inorganic salts, the layers separated, the aq. layer extracted with ether, and the dried soln. of the crude product in benzene-ether satd. with anhydrous HBr triphenylcyclopropenium bromide. Y >90%.—The intermediate tert-huiyl ether is hydrolyzed to bis (triphenyl-cyclopropenyl) ether during washing with water. F. e. s. R. Breslow and H. W. Ghang, Am. Soc. 83, 2367 (1961). 

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