M-Butylacetylene

Addition of n butyl bromide then gives M-butylacetylene (1-hexyne) ... 

The reaction has been carried out using HCI either neat or in acetic acid,84 or in the presence of HgCh,83 BiCla86 or Me4NCl.M In acetic acid, mixtures of syn and anti adducts are produced,84 but reactions catalyzed by HgCl2 proceed by stereospecific anti addition.83-87 The reaction of r-butylacetylene affords the expected vinylic chloride, plus a mixture of isomeric dichloride adducts.84-88 The hydrochlorination of phenylacetyiene produces mixtures of syn and anti adducts in which the ratio is significantly affected by the solvent and catalyst used.84-89-90... 

According to the procedure described in a patent [S. Nakagawa, A. Asai, S. Kuroyanagi, M. Ishihara, Y. Tanaka, US Patent 5 231 183 (1993), to Banyu Pharmaceutical Co.] the final step in the synthesis is carried out by reacting ii-N-(3-chloroprop-2-enyl)-N-methyl-l-naphthalenemethanamine with tert-butylacetylene at 20°C under the conditions shown in Equation 17. 

Hagele, G.. Goudetsidis. S., Wilke, E., Seega, J., Blum, H., and Murray, M., Synthesis and properties of compounds related to l-terf-butylacetylene-2-phosphonic acid and l-teri-butylethane-l,2,2-triph-osphonic acid. Sterically overcrowded phosphoms compounds. Part 1, Phosphorus, Sulfur Silicon Relat. Elem., 48, 131, 1990. 

M.p. 191-1-5 (sealed tube). Ale. - ierf.-butylacetylene. CaCOs H2O -> pinacolin. 

FIG U RE 21.6 The methyl signal in the C NMR spectra of poly(t r -butylacetylene)s obtained with various catalyst systems in toluene at 0 °C. (Reprinted with permission from Nakano, M. Masuda, T. Higashimura, T. Macromolecules 1994, 27, 1344. Copyright 1994 American Chemical Society.)... 

Nakano, M. Masuda, T. Higashimura, T. Stereospecific living polymerization of tert-butylacetylene by molybdenum-based ternary catalyst systems. Macromolecules 1994, 27,1344—1348. 

C15H5F1iMoOS, Cyclopentadienyl(hexafluorobut-2-yne)oxo(pentafluoro-phenylthio)molybdenum(IV), 42B, 661 C15H1 oFgORh2, M Carbonyl-bis(i7-cyclopentadienyl)-M i -(hexaf luoro-2-butyne)-dirhodium (Rh-Rh), 45B, 917 Cl 5H1 0O9RU3, Nonacarbonyl-/Li (t-butylacetylene)-triangulo-triruthen-ium, 39B, 588 43B, 968... 

KOH added to a soln. of pinacolone dichloride in mineral oil and abs. ethanol, heated until at 132 a vigorous reaction starts, distillate collected at a head temp, of 40-75°, heating resumed when the reaction subsides after 10-15 min. and take-off of distillate continued over a 1 hr. period to a pot temp, of 200° fcrf-butylacetylene (Y 73%) and 2-chloro-3,3-dimethyl-l-butene (Y 20%), which can be converted into fcrf-butylacetylene by the same procedure as above (Y 82%).—By the use of mineral oil, a fluid medium is obtained which greatly facilitates the reaction. W. H. Puterbaugh and M. S. Newman, Am. Soc. 81, 1611 (1959). 

Wd4 catalyzes the polymerization of tert-butylacetylene and PA to give high-MW polymers with M over 1 x 10 . In the presence of oxygen-containing compotmds such as methyl acetate, acetylacetone, acetophenone, and 1,4-dioxane, the catalyst activity increases significantly, and thus allows a moderate condition to give the polymer in higher yield. 

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