Allyl Ethyl Ether Research Articles

Photolysis of organopolysilanes. Reactions of trimethylsilylphenylsilylene with allylic halides and allyl ethyl ether

Summary The photolysis of tris(trimethylsilyl)phenylsilane (I) in the presence of allyl chloride, allyl bromide, 2-cyclohexenyl chloride, 2-cyclohexenyl bromide and 2-methylallyl chloride resulted in formation of the respective 1-(2-alkenyl)-1-halo-1-phenyltrimethyldisilanes in moderate yields. Irradiation of I in the presence of crotyl chloride, 1-methylallyl chloride, prenyl chloride and 1,1-dimethylallyl chloride afforded the corresponding α- and γ-substituted chlorodisilanes. Photolysis of I in the presence of allyl ethyl ether produced 1-phenyl-1-trimethylsilyl-2-ethoxymethyl-1-silacyclopropane, although this product was not isolated. The reaction of this silacyclopropane with hydrogen chloride, methanol and boron trifluoride etherate is described.

Organocobalt cluster complexes X. Evidence for the methylidynetricobalt nonacarbonyl radical

The azobisisobutyronitrile-initiated addition of HCCo 3(CO) 9 to the CC bonds of allyl acetate and allyl ethyl ether to give (OC) 9Co 3C(CH 2) 3O 2CCH 3 and (OC) 9Co 3C(CH 2) 3OC 2H 5, respectively, demonstrated the accessibility of the ·CCo 3(CO) 9 radical.

Thermochemical kinetics of nitrogen compounds. Part III. The unimolecular thermal decomposition of N-allylcyclohexylamine in the gas phase

The thermal, unimolecular gas-phase decomposition of N-allylcyclohexylamine to cyclohexylimine and propene has been studied in the temperature range 562–652 K. The rate constants for the homogeneous depletion of the starting material, using the internal standard technique fit the Arrhenius relationship log k/s–1= 11·44 ± 0·21 –(42·18 ± 0·57 kcal mol–1)/2·303RT and were independent of the initial pressure in the range 15–150 Torr. When toluene or ethylbenzene were added as diluent and potential radical traps, rate constants calculated on the basis of the products formed and the pressure changes observed were consistent with the internal standard results. The homogeneiety of the reaction was demonstrated by the concurring rate constants obtained in a packed reaction vessel with a 15-fold larger surface:volume ratio. The observed activation parameters are consistent with a concerted mechanism involving a cyclic six-centre-transition state and they are in good agreement with those reported for the analogous decompositions of allyl ethyl ether, but-3-en-1-ol, and but-3-enoic acid.

Reactions of the ethyl radical. Part 9.—Addition, dismutation and metathesis with allyl ethyl ether and diallyl ether

Detailed mechanisms have been proposed and confirmed for the interaction of the ethyl radical with allyl ethyl ether vapour (between 49 and 147°) and with diallyl ether vapour (between 63 and 153°). Arrhenius parameters have been measured for all the significant reactions of metathesis, addition and dismutation in these systems, and the results are discussed in relation to the structural characteristics of the ethers. Good yields of ethoxyl and allyl radicals may be obtained from the allyl ethyl ether and diallyl ether systems respectively, and the latter also yields allyloxyl radicals in significant quantity. The patterns of interaction of the ethyl radical with the ethoxyl radical and with the allyl radical have been studied over a range of temperature, and the results are consistent with the general equation governing the interaction of alkyl radicals.

Allyl polymerization. IV. Effective chain transfer in polymerization of allylic monomers

AbstractIn addition to degradative chain transfer, effective chain transfer is characteristic of the polymerization of allylic monomers. The order of increasing effective chain transfer in a series of allyl compounds is ethyl ether < ethyl carbonate < acetate < propionate < trimethylacetate < chloride < laurate < benzoate < chloroacetate, and varies from 3% in allyl ethyl ether to 85% in allyl chloroacetate. A constant value of dM/dC is obtained in all of these cases. The decreasing order of [dM/dC]cat←0 is chloroacetate > benzoate > laurate > chloride > propionate > acetate > ethyl carbonate > trimethylacetate > ethyl ether and ranges from 108 for the chloroacetate to 6.3 for the ether. The decreasing order of DP is ethyl carbonate > acetate > propionate > benzoate > chloride > chloroacetate > laurate > trimethylacetate > ethyl ether and ranges from 14 for the carbonate to 4 for the ether. A radical displacement reaction may be operative in the polymerization of the trimethylacetate and benzoate and possibly in the case of the ethyl carbonate and ethyl ether. Considerable effective chain transfer occurs in the polymerization of allyl chloride and allyl chloroacetate as the result of hydrogen abstraction to yield halogen‐containing radicals. Effective chain transfer is predominant in the polymerization of allyll laurate, possibly through the operation of an intramolecular hydrogen transfer.

The Anesthetic Properties of Certain Unsaturated Ethers.

From a general consideration of the chemo-pharmacological properties of di-ethyl ether and ethylene, especially in regard to their marked anesthetic power and relatively low toxicity, it seemed possible to predict that compounds combining the chemical characteristics of each would be interesting general anesthetic agents. This prediction might be made more specific by further reference to the theory of the relationship between chemical constitution and pharmacological action. In certain homologous series of absorbable aliphatic compounds (as the monohydric alcohols) toxicity increases (without a comparable increase in desired activity), in proportion to the number of carbon atoms in the straight carbon chain. Also related to chemical structure in such a series are certain anesthetically important physical properties, such as boiling points. So, one might venture to anticipate that the higher members of our proposed homologous series of unsaturated ethers would not be found as satisfactory inhalation anesthetic substances as the lower members of the series, because of too high boiling points and too great toxicity. Through the kindness of Professor Sigmund Fraenkel of Vienna, we obtained vinyl-ethyl ether, allyl-ethyl ether, and di-allyl ether, and through the courtesy of Professor Lauder Jones of Princeton, we secured from Doctor Randolph Major di-vinyl ether, vinyl-ethyl ether, and isopropenyl-ethyl ether. These agents are all volatile colorless liquids with odors varying from the rather pleasant aromatic vapor of di-vinyl ether to the pungent irritation of the allyl compounds. Unfortunately only small quantities of these substances could be supplied (none in excess of 12 cc), so that only tentative determinations could be made of their partition coefficients and of their action on inhalation in mice.