Vinyl methyl carbinol

Butenes were subjected to photosensitized reaction with molecular oxygen in methanol. 1-Butene proved unreactive. A single hydroperoxide, l-butene-3-hydroperoxide, was produced from 2-butene and isolated by preparative gas chromatography, Thermal and catalyzed decomposition of pure hydroperoxide in benzene and other solvents did not result in formation of any acetaldehyde or propionaldehyde. The absence of these aldehydes suggests that they arise by an addition mechanism in the autoxidation of butenes where they are important products. l-Butene-3-hydroperoxide in the absence of catalyst is converted predominantly to methyl vinyl ketone and a smaller quantity of methyl vinyl carbinol —volatile products usually not detected in important quantities in the autoxidation of butene. 

A sample of the methanolic oxidation product was treated directly with powdered sodium borohydride. Water was added, the solvent allowed to evaporate, and the aqueous solution extracted with carbon tetrachloride. Methyl vinyl carbinol was shown to be the major product, but about 10% impurities were present. Reduction by stirring overnight with 1.0 Af sodium sulfite followed by extraction with carbon tetrachloride produced a solution which analyzed as methyl vinyl carbinol with about 1% impurities. 

Decomposition of a 0.07M solution of 2-butene-3-hydroperoxide in benzene at 100°C. had a half-life of 23 hours. The final products were 37% methyl vinyl ketone, 37% methyl vinyl carbinol, and 26% acetone. Attempts to substantiate the identity of the acetone were unsuccessful, but it was the only anticipated product with the correct gas chromatographic retention time on four different absorbents. 

The cleanest product composition may be effected by decomposition of the pure hydroperoxide or solutions in the injection block of the gas chromatograph. In carbon tetrachloride solution only methyl vinyl ketone and methyl vinyl carbinol were produced, the ratio of ketone to alcohol being 2.9. No definite traces of products from isomerized hydroperoxide were observed. 

Such a rearrangement was detected only in the presence of sulfuric acid, and furthermore at 100°C. it was supplanted by a homolytic breakdown. The products found in the purely thermal decomposition—methyl vinyl ketone and methyl vinyl carbinol—are in fact consistent with the behavior of alkyl hydroperoxides and are analogous to the products produced from the cyclic allylic hydroperoxide from cyclohexene (2). 

Of the many studies of the autoxidation of butenes, few (5,11) have emphasized methyl vinyl ketone and methyl vinyl carbinol as major products. In the cumene hydroperoxide-initiated oxidation of 1-butene at 105°C. with 60 atm. of air, Chernyak (5) reported an average hourly rate of production of these two products approximately equal to the combined rates of formation of hydroperoxide and epoxide. The reported rates for hydroperoxide plus vinyl ketone and alcohol indicate that 60% of the products occur by abstraction, in agreement with Van Sickle (17). 

Catalytic dehydrogenation of methyl vinyl carbinol at temperatures above 250 C in presence of a brass spelter catalyst is claimed to give a 33 per cent yield of methyl vinyl ketone, CHs-CO CH=CH2. Catalytic vapo>phase oxidation of the unsaturated alcohols to form unsaturated carbonyl compounds has been found to give considerably higher yields. Temperatures in the range of 360-550 C and use of a metallic silver catalyst are described. 

METHYL VINYL CARBINOL ACETATE + BUTYLENE GLYCOL... 

Minoura and Yamaguchi described the analogous reduction of poly methyl vinyl ketone to the optically active poly methyl vinyl carbinol [25] (Equation (6)). 

The first observation, of the reduction of a ketone by an organotin hydride appears to have been the result of an attempt to carry out the hydrostarma-tion of 2 moles of methyl vinyl ketone by 1 mole of diphenyltin dihydride (63, 64). Instead of the expected adduct the products were pol5rmeric diphenyltin, which precipitated during the reaction, and methyl vinyl carbinol, Eq. (32). This reaction is surprising because the alcohol is isolated... 

The largest industrial use of LiC2H is in the production of vitamin A, where it effects ethynyl-ation of methyl vinyl ketone to produce a key tertiary carbinol intermediate. The acetylides and dicarbides of the other alkali metals are prepared similarly. It is not always necessary to prepare this type of compound in liquid ammonia and, indeed, further substitution to give the bright red perlithiopropyne Li4C3 can be effected in hexane under reflux ... 

Rideout and Breslow first reported [2a] the kinetic data for the accelerating effect of water, for the Diels Alder reactions of cyclopentadiene with methyl vinyl ketone and acrylonitrile and the cycloaddition of anthracene-9-carbinol with N-ethylmaleimide, giving impetus to research in this area (Table 6.1). The reaction in water is 28 to 740 times faster than in the apolar hydrocarbon isooctane. By adding lithium chloride (salting-out agent) the reaction rate increases 2.5 times further, while the presence of guanidinium chloride decreases it. The authors suggested that this exceptional effect of water is the result of a combination of two factors the polarity of the medium and the... 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

The carbinol HCCC(OH)(CH3)CH=CH2, b.p. 30 012 mmHg, nD(20 ) 1.4452, is obtained in -60% yield by a similar procedure, with the difference that only 1.5 mol of (freshly distilled and water-free) methyl vinyl ketone is added to 3.0 mol of LiGsCH. There remains a considerable amount of viscous residue after the distillation. 

Compound Name Vinyl Methyl Ether, Inhibited Methyl Vinyl Ketone Dimethylzinc Maleic Hydrazide Methyl Amyl Alcohol Methyl Isobutyl Carbinol Methyl Isobutyl Ketone Methyl Amyl Alcohol Methyl Isobutyl Carbinol Carboli Oil... 

The D-seco-acid (326) has been prepared by Diels-Alder reaction between the trimethoxy-vinyl-carbinol (325) and methyl acrylate, followed by reduction with sodium in liquid ammonia. ... 

Vitamin A synthesis. The addition of acetylene to methyl vinyl ketone is a key step in Isler s technical synthesis of vitamin A. The resulting carbinol (2) under... 

B.34) (B.34) 3-Buten-2-ol, 2-methyl-,2-methylbut-3-en-2-ol, l,l-dimethyl-2-propenol, 1,1-dimethylallyl alcohol, dimethyl vinyl carbinol, 3-hydroxy-3-methyl-l-butene 115-18-4]... 

Acetone (0.12 mol, 7.0 g) is added to the suspension of lithiated methyl vinyl sulfide, cooled at —70 °C to —90 °C. Five min after this addition the reaction mixture (solution) is treated with 200 ml of water. The aqueous layer is extracted three times with Et20. The unwashed organic solutions are dried over MgS04 and subsequently concentrated in vacuo. Distillation of the remaining liquid through a 20-em Yigreux column gives the carbinol, b.p. 70 °C/12 mm, n 0 1.5012, in 84% yield. 

The tertiary carbinol 92 is formed from 91 in a one-pot synthesis by etherification of the hydroxy group, formation of the Cn-lithium acetylenide with BuLi, reaction with the C4-unit methyl vinyl ketone, and reduction of the triple bond with sodium [bis-(2-methoxy)-ethoxy]aluminium dihydride. 

This reaction was initially studied by Anschutz between 1879 and 1886. It is the synthesis of anthracene from vinyl bromide and benzene in the presence of aluminum chloride. In addition, methyl phenyl carbinol or 1,1-diphenyl ethane can also be converted into anthracene derivative in the presence of aluminum chloride. 

Casting resins, laminates 2-Vinyl-l,3-dioxane-5-methyl-5-carbinol, 2-vinyl-l,3-dioxane-5-ol, 2-vinyl-l,3-dioxolan-4-carbinol United States 3,433,773 1969 Asahi Chemical... 

Vinyl-l,3-dioxane-5-methyl-5-carbinol, used in polyesters, 491... 

Pyridyl lithium gives a small yield of the Michael addition product with benzalacetophenone , as does 4-picolyl sodium with methyl vinyl ketone i2 . In contrast, 2-picolyl sodium forms the carbinol, perhaps because of initial reaction at the nitrogen atom... 

---