Chloromethyl ethynyl

The preparation of lithium acetylides from acetylenes and butyl lithium can be carried out in THF at 20°. The lithium acetylides react with tellurium to form lithium ethynetellurolates. These tellurolates were reacted with chloroiodomethane at — 40° to — 60 to give the corresponding chloromethyl ethynyl telluriums11. Yields and physical properties of these latter products were not reported. 

The synthesis of 2,3-dihydrodiisopropyl-l,3-thiaborol-3-yl-amine 26 and subsequently lithium diisopropyl-1,3-thiaborol-3-ylamine 27 required a four-step synthesis starting from chloromethyl trimethylsilylethynyl sulfide 59 (Scheme 9). Desilylation of compound 59 with tetrabutylammonium fluoride (TBAF) in methanol afforded the labile chloromethyl ethynyl sulfide 60, which was treated with a solution of dibutylstannane and LDA in a mixture of TFIF and hexane at —78°C to give 3,3-dibutyl-2,3-dihydro-l,3-thiastannole 61, in 39% yield. Reaction of compound 61 with 2 equiv of -butyllithium in THF at —78°C gave the dilithio reagent 62, which could be detected by NMR... 

The reaction of sodium 4-ethoxybenzenetellurolate with dichloromethane gave products of indefinite composition. However, the reactions of lithium 2-benzothiophenetellurolate with dichloromethane and lithium benzenetellurolate with diiodomethane yielded his[aryltelluro]methane, and those of lithium ethynetellurolates with equimolar amounts of chloroiodomethane gave chloromethyl ethynyl tellurium compounds. v/c-Dibromides and sodium 4-ethoxybenzenetellurolate reacted to produce ethenes and bis[4-ethoxyphenyl] ditellurium. ... 

Pyrazolecarbinols can be dehydrated to vinylpyrazoles, (438) — (446) (72JHC1373), or transformed into chloromethyl derivatives (81T987). Compound (440 R = CH2C1) thus prepared is the starting material for the synthesis of the macrocycles (226)-(228) (Section 4.04.2.1.2(vi)). Vinyl- and ethynyl-pyrazoles have been extensively studied (B-76MI40402) and many vinylpyrazoles are polymerized by free radical initiators. 

Aziridine, cis-7V-t-butyl-3-ethynyl-2-vinyl-rearrangement, 7, 540 Aziridine, 2-chlorocarbonyl-ring expansion, 7, 42 Aziridine, 2-chloromethyl-synthesis, 7, 42 Aziridine, Mcyanodiphenyl-irradiation, 7, 61 Aziridine, dihalo-reduction, 7, 74 thermolysis, 7, 73... 

The fact that allyltributyltin and styrene which are electroneutral were successfully added to PCTFE led us to the question "Can electron-rich or electron-poor trapping agents be used ". The electron-rich agents that we examined were ethyl ethynyl ether and ethyl vinyl ether. On the side of the electron-poor alkenes, eight were investigated ethyl acrylate, methyl methacrylate, methyl vinyl ketone, acrylonitrile, methacrylonitrile, vinyl bromide, chloromethyl styrene, and 4-vinylpyridine. The details of each reaction are summarized. 

The easily accessible ethynyl tellurolates were reacted with chloroiodomethane to give ethynyl chloromethyl tellurium, which, in turn, combined with an alkali metal telluride to form (ethynyltelluro)methanetellurolates. These compounds cyclized through intramolecular addition of the tellurolate to the C —C triple bond to 2/7-1,3-ditelluroles3,4... 

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