Allyl alcohol, decomposition

Figure 6. Comparison of acrolein desorption traces from allyl alcohol decomposition over (a) the Cu2O(100)-Cu surface and (b) the stoichiometric (111) surface.

Dianion formation from 2-methyl-2-propen-l-ol seems to be highly dependent on reaction conditions. Silylation of the dianion generated using a previously reported method was unsuccessful in our hands. The procedure described here for the metalation of the allylic alcohol is a modification of the one reported for formation of the dianion of 3-methyl-3-buten-l-ol The critical variant appears to be the polarity of the reaction medium. In solvents such as ether and hexane, substantial amounts (15-50%) of the vinyl-silane 3 are observed. Very poor yields of the desired product were obtained in dirnethoxyethane and hexamethylphosphoric triamide, presumably because of the decomposition of these solvents under these conditions. Empirically, the optimal solvent seems to be a mixture of ether and tetrahydrofuran in a ratio (v/v) varying from 1.4 to 2.2 in this case 3 becomes a very minor component. 

Therefore allylic alcohol is regarded as unstable. At 360-500°C, its enthalpy of decomposition is 0.67 kJ/g. This is rather low according to the CHETAH method (see para 2.3) but high according to T. Grewer, who regards a compound as unstable when IaH I > 0.5 kJ/g. 

Allylations of hydroquinone derivatives, 32 459-461 Allyl chloride oxidation, 41 305 thermal decomposition, 41 80 tl-Allyl complexes, 25 129-134 Allyl hydroperoxide, 27 187-189 Allylic alcohols, olefinic substitution of, 26 343-345... 

In contrast to benzyl p-tolyl sulfoxide 37, allyl p-tolyl sulfoxide 217 racemizes between 50 and 70°C. The values of the activation energy and the entropy (A/f = 23 kcal/mol AS = -4.9 e.u.) as well as the absence of decomposition products are indicative of a different racemization mechanism for this sulfoxide. In this connection, it is interesting to note that the condensation of p-toluenesulfenyl chloride with allyl alcohol labeled in the a-position with deuterium... 

Wierzbicki, T. and Wojcik, 0. Preliminary trials on the decomposition of acrolein, allyl alcohol, and glycerol by activated sludge, Zesz. Nauk. Polltech Slaska Inz. Sanit, 8 173-185 [Chemical Abstracts 68 1589z, 1968]. 

For substrates (often low molecular weight allylic alcohols) that are difficult to obtain, due to problems of decomposition and/or water solubility, an in situ transformation was reported by Sharpless and coworkers in 1987 , making possible the effective synthesis... 

It must be repeated that this argument depends upon the assumption that there is only one way in which the molecules of formic acid can be attached to the surface of the catalyst. There is, however, some evidence against this assumption. Constable finds that the two simultaneous reactions undergone by allyl alcohol when passed over heated copper are differently influenced by the physical state of the catalyst. This points to the conclusion that there are two independent centres of activity on the catalyst surface with two different modes of adsorption, or, at any rate, centres where the energy of adsorption is so different that different reactions are facilitated. Hoover and Rideal f find that the two alternative decompositions of ethyl alcohol by thoria show a different behaviour towards poisons, which points to the same conclusion. 

The methods for making allyl alcohol are many. It may be prepared by (a) the action of metals upon dichlorohydrin 1 (b) the reduction of acrolein 2 (c) the action of potassium hydroxide on trimethylene bromide 3 (d) the catalytic decomposition of glycerol with aluminum oxide 4 (e) the hydrolysis of allyl iodide 5 (/) the decomposition of glycerol triformate 6 (g) the action of formic acid upon glycerin 7 and (h) the action of... 

To probe hydroperoxide reactivity in these systems we studied the reaction of tert-butyl hydroperoxide in the presence of [C5H5V(CO)4]. In contrast to the rhodium(I) and molybdenum complexes, [C5H5V-(CO)4] catalyzed the rapid decomposition of tert-butyl hydroperoxide to oxygen and tert-butyl alcohol in both toluene and TME (Table II). When reaction was done by adding the hydroperoxide rapidly to the vanadium complex in TME, no epoxide (I) was produced. However, when the TME solution of [C5H5V(CO)4] was treated with a small amount (2-3 times the molar quantity of vanadium complex) of tert-butyl hydroperoxide at room temperature, a species was formed in situ which could catalyze the epoxidation of TME. Subsequent addition of tert-butyl hydroperoxide gave I in 13% yield (Table II). This vanadium complex also could catalyze the epoxidation of the allylic alcohol (II) to give tert-butyl alcohol and IV (Reaction 14). Reaction 14 was nearly quantitative, and the reaction rate was considerably faster than with TME. 

Thus, depending on the metal complex used, cyclohexene oxidation can occur via one or more of at least three major pathways, as shown in Reaction 20 path A, radical initiated decomposition of cyclohexenyl hydroperoxide path B, metal catalyzed epoxidation of the olefin and path C, metal catalyzed epoxidation of an allylic alcohol. Ugo found that path B becomes more pronounced when molybdenum complexes are used to modify the oxidation of cyclohexene in the presence of group... 

Acrylic acid [79-10-7] - [AIR POLLUTION] (Vol 1) - [ALDEHYDES] (Vol 1) - [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) - [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) - [POLYESTERS, UNSATURATED] (Vol 19) - [FLOCCULATING AGENTS] (Vol 11) - [CARBOXYLICACIDS - SURVEY] (Vol 5) -from acetylene [ACETYLENE-DERIVED CHEMICALS] (Vol 1) -from acrolein [ACROLEIN AND DERIVATIVES] (Vol 1) -acrylic esters from [ACRYLIC ESTER P OLYMERS - SURVEY] (Vol 1) -from carbon monoxide [CARBON MONOXIDE] (Vol 5) -C-21 dicarboxylic acids from piCARBOXYLIC ACIDS] (Vol 8) -decomposition product [MAT. ETC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -economic data [CARBOXYLIC ACIDS - ECONOMIC ASPECTS] (Vol 5) -ethylene copolymers [IONOMERS] (Vol 14) -in floor polishes [POLISHES] (Vol 19) -in manufacture of ion-exchange resins [ION EXCHANGE] (V ol 14) -in methacrylate copolymers [METHACRYLIC POLYMERS] (Vol 16) -in papermaking [PAPERMAKING ADDITIVES] (Vol 18)... 

Aluminum compounds such as Al(OBu,)3 have also been shown to catalyze the selective transformation of allylic alcohols into syn-epoxides.249 Related to the mechanism of this reaction is the decomposition of the aluminum compound (83) to give ethylene oxide.250... 

Vinylation of allylic alcohols with only a tertiary amine as base is often a very slow reaction in which product (if any) decomposition may be a serious side reaction. Exceptions to this behavior occur when 3-... 

Activated alcohols are unstable, at least at high temperature, when the corresponding radicals are able to stabilize carbocations, for example in the case of allylic alcohols. The thermal decomposition of activated allylic alcohols leads to the formation of allylic chlorides. This decomposition can... 

Porphyrin complexes, however, are prone to oxidative decomposition and therefore synthetic applications are hampered by rapid catalyst deactivation. This problem can be overcome by attaching electron-withdrawing groups to the periphery of the porphyrin system. Another problem is the poor chemoselectivity. In many cases, addition to the C=C double bond and formation of the epoxide are much faster than the corresponding hydrogen abstraction, which leads to the allylic alcohols. This is... 

Polyethylene (PEI. In an unpublished study, pouches were made from paper/foil/PE laminates, and headspace gas was taken from the bag after incubation at 60° C for 20 minutes and analyzed by a gas chromatograph. Three major components were identified as acetaldehyde, allyl alcohol and acrolein. When odorous bags were compared with non-odorous bags, there showed a direct correlation between odor, acetaldehyde and allyl alcohol levels. Those compounds were considered to be thermal oxidative decomposition products of polyethylene (Baxter, J. A., W. Grayson and Assoc., Ltd., unpublished data). 

Acetone, likewise isomeric with allyl alcohol, gives the same products as propyl aldehyde. As the quantity of carbon monoxide does not decrease in the presence of phosphorus, Hemp-tinne concludes that the following decomposition process occurs ... 

The formation of both erythro and threo products from suitable allylic alcohols containing CD2OH groups implies that an j/ -aUyhc mechanism is involved in their decomposition (equation 3). 

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