Some Reactions of the Etherate of Aluminum Triethyl¹

Abstract

Reactions of the Etherate of Aluminum Triethyl 5193 tetroxide in 1,4-dioxane there is no tendency toward polymerization. In the range up to 0.1 molal, X is equal to unity ±10%. The very slight upward trend at the two higher concentrations reflects the fact that as the concentration of dinitrogen tetroxide increases an appreciable partial pressure of dinitrogen tetroxide above the solution develops. This fact in addition to the general limitations of cryoscopy for molecular weight determinations limited our measurements to dilute solutions.On the basis of the cryoscopic and viscosimetric data reported herein we may conclude that there is little basis for postulating a polymeric, chaintype structure for the compound N204• 1,4-0-(CH2CH2)20.

A New High-Temperature Free-Radical Source

“…The solution was thoroughly extracted with Na2C03 and HC1 solutions and dried over Na2S04, and the solvent was evaporated to give 21. 3 Thermal Decomposition of Azobisisobutanol Diacetate.-In a constant-temperature bath held at ±0.1°were placed sealed tubes containing 3.5-ml. aliquots of a solution of 3.2 g. of azobisisobutanol diacetate in 100 ml.…”

Rediscovering the Chemistry of Sulfur Dioxide: New Developments in Synthesis and Catalysis

“…The reaction of organometallic reagents with sulfur dioxide gas to form metal sulfinate salts is a well-precedented reaction (Scheme 4). 2,33 The organometallic species employed include Grignard reagents, 32,34,35 organolithiums, 32,36,37 organozincs 38 as well as more unusual species such as organotins, 39 organoaluminiums 40 and organolead reagents. 41 The sulfinate salts can react with electrophiles at either the S-or O-atom, dependent on the nature of the electrophile.…”

Nucleophilic substitution of optically active 1-alkoxypolyfluoroalkyl sulfonates

“…This observation suggests that Lewis acid AlEt 3 induced the formation of an oxocarbenium ion intermediate, which led to racemization to some extent. 3 After some trials, we were delighted to find that the use of LiAlEt 4 12 instead of AlEt 3 gave (R)-(+)-4a in 59% yield with 83% ee, starting from (S)-(+)-3a (83% ee). ¶ It is noteworthy that the stereochemical integrity of the substrate was completely maintained (Table 1, entry 2).…”