The in situ reaction of dialkoxydichlorosilanes, such as dimethoxy-, diethoxy-, dipropoxy-, dibutoxy-, and diisobutoxydichlorosilane, with isoprene and magnesium in tetrahydrofuran (THF) was investigated. It was found that the double annelation product, i.e., 2,7-dimethyl-5-silaspiro[4.4]nona-2,7-diene (1), was obtained from diethoxy-, dipropoxy-, and dibutoxydichlorosilane in 87.0, 65.2, and 66.5% yields respectively. On the other hand, the reaction of dimethoxy- and diethoxydichlorosilane with butadiene and magnesium in THF gave 5-silaspiro[4.4]nona-2,7-diene (7) in 20.7 and 35.4% yields respectively. Several silaspirononane derivatives were synthesized from 1.
ALTHOUGH numerous catalysts for the acetylation of cellulose have been proposed in the patent literature, sulfuric acid is one of the most effective.Commercial acetylations are usually carried out with this catalyst.The disadvantage of using sulfuric acid as the catalyst is that it enters into combination with cellulose during the acetylation; the stability of the acetate so produced is decreased so that the cellulose ester requires a stabilizing treatment such as the removal of sulfate groups or salt formation with metallic ions.The combination of sulfuric acid during acetylation has been reported by Caille [3], Cross and Bevan [4], Ost [7], Malm, Tanghe, and Laird [6], and * Parts I and II. respectively, appeared in C ellulosechelll1'e 18, 109 (1940) and Cellulosechemie 19, 137 ( 1941 ) .others, but the behavior of sulfuric acid throughout the acetylation has not been interpreted adequately.In Part I of this series [1] ] the present author reported on the behavior of sulfuric acid throughout the course of acetylation, and indicated that a large amount of sulfuric acid is taken up chemically by cellulose at the beginning of acetylation and then gradually split off from cellulose, showing that the sulfuric acid group is gradually replaced by acetyl.Such behavior of sulfuric acid suggests that catalysis by sulfuric acid in the acetylation of cellulose is more complicated than expected according to the theory of normal catalysis due to proton activity supported by Krueger et al. [5].In the present work, the relationship between the amount of combined sulfuric acid and the acetylation at East Carolina University on June 29, 2015 trj.sagepub.com Downloaded from
The polymerization of 1,1,3-trimethyl-1-silacyclopentene-3 (I), 1-methyl-, 1-allyl-1,1-diallyl-1-silacyclopentenes and -pentanes with aluminum chloride was carried out. By means of an IR spectroscopic analysis of the resulting polymers, it was established that not only ring opening but also vinyl polymerization due to the C–C double bond occur in this polymerization. Attempts to polymerize I with other catalysts, such as BF3·OEt2, AIBN, KOH, and a Ziegler catalyst, were unsuccessful.
Dichlorodiethoxysilane was treated with isoprene in the presence of magnesium in THF. It was found that new silacyclopentene derivatives i.e., 1,1-diethoxy-3-methyl-1-silacyclopentene-3(1), and 2,7-dimethyl-5-silaspiro[4.4]nonadiene-2,7(2), were produced in good yields, while sodium was used instead of magnesium in the reaction 2 was obtained in a low yield.
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