2- methylallyl alcohol

Caminati, W., A. C. Fantoni, B. Velino, K. Siam, L. Schafer, J. D. Ewbank, and C. Van Alsenoy. 1987a. Conformational Equilibrium and Internal Hydrogen Bonding in 2-Methylallyl Alcohol Detection of a Second Conformer by Microwave Spectroscopy on the Basis of Ab Initio Structure Calculations. J. Mol. Spectrosc. 124, 72-81. 

Attempts to use other hydroxymethyl monomers such as allyl alcohol, 2-methylallyl alcohol, and 2-chloroallyl alcohol for isomerizational copolymerizations with methyl acrylate gave mixed results due to the poor copolymerization rate constants of these olefins and the ability of acrylic radicals to abstract hydrogen atoms from allyl alcohols. 

The reaction of allyl alcohol, 2-methyl allyl alcohol and crotyl alcohol (trans cis= 4.45 1) were reacted with hydrogen peroxide at 30 °C using methanol assolvent, and the results are shown in Figures 1-3. It is apparent that the order of reactivity is cis-crotyl alcohol > trans-crotyl alcohol > allyl alcohol > 2 methylallyl alcohol. The latter alcohol was not particularly reactive and this indicates that substition at the 2-position inhibits the reaction significantly. 

Allylic alcohols, for example geraniol, 2-methylallyl alcohol, 3,3-dimethylallyl alcohol, 3-buten-2-ol, l-octen-3-ol, and l-hexen-3-ol, are epoxidized with tert-butyl hydroperoxide in the presence of a vanadyl salen oxo-transfer catalyst in supercritical CO2. The metal catalyst was prepared in a simple two-step, Schiff base-type reaction to form the salen ligand, followed by complexation to the vanadyl group. The use of non-toxic supercritical CO2 in the presence of the new epoxidation vanadium catalyst led to yields and diastereoselectivities that were comparable to those resulting from the use of environmentally hazardous solvents such as CH2CI2 [59]. 

Synonyms 3-Hydroxy-2-methylpropene Isobutenol Isopropenyl carbinol Methacryl alcohol p-Methallyl alcohol 2-Methylallyl alcohol P-Methylallyl alcohol 2-Methyl-2-propene-1-ol 2-Methyl-2-propen-1-ol Classification Alcohol Empirical C4H8O Formula H2C=C(CH3)CH20H Properties Clear liq. sol. in most org. soivs. si. 

Methyl aldehyde. See Formaldehyde 2-Methylallyl alcohol P-Methylallyl alcohol. See Methallyl alcohol 2-Methylallyl butyrate CAS 7149-29-3 FEMA 2678... 

Tetrafluoroethylene reacts with Fe(CO)3(butadiene) by a two-step oxidative addition process to give (43). The reaction of the rhodium(i) complex Rh(acac)(cod) with hexafluorobut-2-yne results both in trimer-ization of this alkyne, and either its insertion into a y-bonded acetyl-acetonate intermediate or a concerted addition to the acetylacetonate ring, to produce (44), RhCl3,3H20 reacts with 2-methylallyl alcohol, in the presence of 4-methylpyridine (pic), probably via two insertion reactions, to... 

The product of the oxidation of 2-butene with oxygen in the presence of bis (l-methyl-2-acetoxypropyl) selenide was 3-acetoxy-l-butene in acetic acid as solvent and 3-hydroxy-l-butene(a-methylallyl alcohol) in aqueous dioxane. The reaction rate depends on the selenide concentration. 

Other unsaturated substrates arylated by various diaryl iodonium salts included butenone, acrylic acid, methyl acrylate and acrylonitrile [46]. Allyl alcohols with diaryliodonium bromides and palladium catalysis were arylated with concomitant oxidation for example, from oc-methylallyl alcohol, aldehydes of the general formula ArCH2CH(Me)CHO were formed [47]. Copper acetylide [48] and phenyl-acetylene [49] were also arylated, with palladium catalysis. 

Aryl substituents which can release electrons to the allylic system increase the ease of isomerization of a-arylallyl alcohols. Aryl substituent effects support the hypothesis that the rate-limiting transition state has considerable car-bonium-ion character. The specific rate coefficients for acid catalyzed isomerization of a-aryl-y-methylallyl alcohols in aqueous 60% dioxane correlate poorly with Hammett s cr-substituent constants (see ref. 182, p. 184) whereas a plot of log versus Brown s cr -substituent constants is linear, with a slope of 2.7. 

Braude ei al. studied the dependence of rates of acid-catalyzed isomerization of of-ethynyl-y-methylallyl alcohoF and a-phenyl-y-methylallyl alcohol on the composition of mixed solvents such as aqueous ethanol and aqueous dioxane. If allowance is made for the effect of solvent on the concentration of the reactive conjugate acid of the alcohol, these data show that the rate of isomerization of the conjugate acid is nearly independent of solvent composi-tion as would be expected for a unimolecular rate-limiting dissociation of the conjugate acid to a solvated carbonium ion, Kwart and Herbig reached a... 

It is believed that this reaction undergoes dehydration in the presence of an acid to form an intermediate of vinyl ether that breaks down to the aldehyde. Some insight about the mechanism can be found in the rearrangement of methylallyl alcohol into isobutyraldehyde. ... 

Definition Ester of p-methylallyl alcohol and butyric acid... 

See Isopropenylacetylene. Methylvinylcarbinol l-Butenol-3, l-vinyl-ethyl alcohol, 3-hydroxy-l-hutylene, l-methylallyl alcohol)... 

The annulating agent 2-acetoxymethyl-3-alkyltrimethylsilane (40), which is prepared in 60% yield from a-methylallyl alcohol, reacts with olefins in the presence of a palladium(O) catalyst to give the methylenecyclopentane (41) in 50—85% yield. The reaction appears to work only with olefins containing electron-withdrawing groups simple olefins or electron-rich olefins such as enamines failed to react. The preferred catalyst is [Pd(Ph3P)4]-diphos, and the preferred solvent is THF. 

Between these two extremes of spontaneous rearrangement and total failure to rearrange, Braverman and Stabinsky36-38 have observed intermediate behavior. The reaction of crotyl alcohol with C13CSC1 afforded an equilibrium mixture of both crotyl trichlormethanesulfenate (13) and a-methylallyl trichloromethyl sulfoxide (14, equation 9). 

The addition of trimethyl (2-methylallyl)silane 28 to acetal 27 was chosen as the key step. The reaction proceeded smoothly and generated homoallylic ether 29 with high diastereoselectivity. The desired homoallylic alcohol 30 could subsequently be obtained, in high enantiomeric purity, by oxidative deprotection of the chiral template (Scheme 13.12). 

Terpenoid Synthesis from Isoprene.—Interest continues in new syntheses of iso-prene and its derivatives the dioxan (37) is obtained108 in good yield by the Prins reaction of methylallyl chloride with formaldehyde (cf. Vol. 5, p. 8) free-radical addition of isopropyl alcohol to vinyl acetate yields compound (38) which gives isoprene by acid-catalysed reaction over alumina.109 (Z)-2-Methylbut-2-en-l-ol and dimethylallyl alcohol are readily available from frans-crotyl alcohol.110... 

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