1- phenyl-2-propyn-3-trimethylsilyl

The reaction of trichlorocyclopropenylium ion 5 with acetylenic compounds such as 1,2-bis(trimethylsilyl)acetylene and l-(trimethylsilyl)propyne gave the methylenecyclopropene 6 and cyclopropenone 7 containing ethynyl groups by substitution, whereas the reaction with phenylacetylene or l-phenyl-2-(trimethylsilyl)acetylene afforded the ring-opened products 8 via addition reactions. 

Alkylation and hydroxyalkylation of allenic sulfides, 46 -(22) 4-Phenyl-l-butyne, 48 - (23) l-Chloro-5-hexyne, 48 - 24) 3-Buty-noic acid, 49 - (2S) 2,3-Pentadienedioic acid, 50 - (2S) 2-riethyl-2,3--pentadienedioic acid, 51 - (37) 3-Trimethylsilyl-l-heptyne, 52 - 23) 3-Ethynyl-l-hexanol, 53 - (29) 3-Phenyl-3-trimethylsilyl-l-propyne,... 

A. Morisato, B.D. Freeman, I. Pinnau and C.G. Casillas, Pure Hydrocarbon Sorption Properties of Poly(l-trimethylsilyl-l-propyne) [PTMSP] and Poly(l-phenyl-l-propyne) [PPP] and PTMSP/PPP Blends, J. Polym. Sci., Polym. Phys. Ed. 34, 1925 (1996). 

The BF3-induced reactions of iodosylbenzene with l-trimethylsilyl-3-aryl-l-propynes in dioxane follow a divergent course and afford aryl silylethynyl ketones (equation 28)31. The ketone derived from l-trimethylsilyl-3-phenyl-l-propyne is also generated in dichloro-methane, but as a minor product. These oxidations are apparently facilitated by the presence of benzylic hydrogen atoms, since a similar alkynyl ketone is not obtained from 1-trimethylsilyl-l-decyne with PhIO/BF3 in dioxane31. 

The imine 188, derived from 3-(trimethylsilyl)-2-propynal and (S)-a-methyl-benzylamine, was treated at — 40 °C with the born enolate 187 prepared from S-phenyl butanethioate, 9-borabicyclo[3.3.1]nonyl triflate and DIPEA. After workup, a mixture of the anti p-amino acid 189 and the syn adducts 190 was formed in a 5.2 1 ratio. This mixture was then subjected to cyclization using tert-butylmagnesium chloride in diethylether to give the trans P-lactam 191 in... 

Many monomers with simple structures, including phenylacetylene, t-butyl-acetylene, 1-phenyl-1-propyne, 2-octyne, and 1-trimethylsilyl-l-propyne, are commercially available. These monomers are usually purified by distillation in the presence of suitable drying agents prior to use. On the other hand, monomers that are more complex, such as ort/zo-substituted phenylacetylenes, A-pro-pargylcarbamates, ring-substituted diphenylacetylenes, and 1-chloro-l-alkynes, must be synthesized. Derivatization of simple alkynes rather than formation of the acetylenic moiety, is frequently applied to synthesize such monomers. These are then purified by vacuum distillation or column chromatography. 

Methoxy-l-phenyl-l-propyne in anhydrous ether added at -75° under argon to 2 moles butyllithium in the same solvent, stirred 15 min., 1 mole ethyl bromide in ether added slowly, stirred 15 min., then trimethylsilyl chloride in ether added, allowed to warm to room temp, with stirring, the soln. of the intermediate allenyl ether (Y 82% if isolated) treated with 20%-HCl, and refluxed 5 hrs. product. Y 76%. F. e. s. Y. Leroux and R. Mantione, J. Organometal. Chem. 30, 295 (1971). 

The reaction of 1-21 with alkynes is regioselective. When unsymmetrical alkynes such as 1-phenyl-1-butyne was used, l-43a and l-44a both as single regioisomers were isolated upon hydrolysis of reaction mixture at 50 °C and 90 °C respectively. The Ph group was selectively located at a-position of CpaZr moiety. The substituents on alkynes also have an effect on the chemoselectivity of the reaction. When 1-trimethylsilyl-l-propyne was used, only zirconacyclopentadiene l-43b was isolated regioselectively, and the corresponding zirconacyclohexadiene complex was not isolated (Scheme 1.21) [47, 48]. 

Morisato A, Shen HC, Sankar SS, Freeman BD, Pinnau I, Casillas CG (1996) Polymer characterization and gas permeability of poly(l-trimethylsilyl-l-propyne) [PTMSP], poly (1-phenyl-1-propyne) [PPP], and PTMSP/PPP blends. J Polym Sci B Polym Phys 34 2209-2222... 

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