Isobutyl alcohol, formation

Sulfuric acid is about one thousand times more reactive with isobutylene than with the 1- and 2-butenes, and is thereby very useful in separating isobutylene as tert-huty alcohol from the other butenes. The reaction is simply carried out by bubbling or stirring the butylenes into 45—60% H2SO4. This results in the formation of tert-huty hydrogen sulfate. Dilution with water followed by heat hydrolyzes the sulfate to form tert-huty alcohol and sulfuric acid. The Markovnikov addition implies that isobutyl alcohol is not formed. The hydration of butylenes is most important for isobutylene, either directiy or via the butyl hydrogen sulfate. 

Transient kinetic phenomena of another type were observed in the so-called purging experiments, whereby we switched from feeding the flow reactor with a helium-butyl alcohol mixture to one with pure helium and then back to the previous helium-butyl alcohol. A typical response of a catalyst to such purging is given in Fig. 6, referring to the dehydration of sec- and isobutyl alcohols over HZSM-5. For sec-butyl alcohol, the rate of butene formation initially increases by a factor of about 10 upon purging and then drops to zero. Return (8k) to the... 

The condensation of methanol with ethanol produces a mixture of 1-propanol and 2-methyl-l-propanol (isobutyl alcohol), as well as small amounts of other branched alcohols, including 2-methyl-l-butanol, and nonalcohol components, depending on the catalyst and reactant ratios (1-10). The reactions proceed through the formation of formaldehyde and... 

The Degussa process (now owned by Dupont) starts from acrolein, which is hydrated in the presence of an acidic ion exchanger into 3-hydroxypropanal (3HP, Fig. 8.8 a). The latter is subsequently extracted into isobutyl alcohol and hydrogenated over a Ni catalyst [53]. The overall yield does not exceed 85%, due to competing water addition at the 2-position and ether formation in the initial step. It has been announced that Degussa will supply up 10 kt a-1 to Dupont until the fermentative process of the latter company (see below) comes on stream [54]. 

The bicyclic product 59 proved not to be derived from diazo ketone 58. It may arise from the reaction of diazenyl ketene intermediate 53 with diazomethane via the postulated 2-[2-methyl-2-(phenyldiazenyl)propyl] cyclopropanone intermediate 60 and its subsequent isomerization to the bicyclic product 59 (Scheme 14). The formation of the diazenyl ketene intermediate 53 has been made plausible by carrying out the reaction in the presence of an excess of isobutyl alcohol to afford isobutyl 3-methyl-3-[(E)-phenyldiazenyl]butanoate (61) in a competing addition. 

In the oxidation of an alcohol RCH2OH to an aldehyde by chromic acid, the chief side-reaction is formation, not of the carboxylic acid, but of the ester RCOOCH2R. Experiment has shown that a mixture of isobutyl alcohol and isobutyraldehyde is oxidized much faster than either compound alone. Suggest a possible explanation f or these facts. Hint See Sec. 19.9.)... 

Go back to the temperature-mole fraction diagram for the isopropyl alcohol-isobutyl alcohol system (Fig. 175). The composition of the vapor is always different from that of the liquid, and we can separate the two compounds. If the composition of the vapor is the same as that of the liquid, that separation is hopeless. Since we ve used the notions of an ideal gas in deriving our equations for the liquid and vapor compositions (Clausius-Clapeyron, Dalton, and Raoult), this azeotropic behavior is said to result from deviation from ideality, specifically deviations from Raoult s law. Although you might invoke certain interactive forces in explaining nonideal behavior, you cannot predict azeotrope formation a priori. Very similar materials form azeotropes (ethanol-water). Very different materials form azeotropes (toluene-water). And they can be either minimum-boiling azeotropes or maximum-boiling azeotropes. 

Whatman No 3 MM paper in a system of isopropyl alcohol/isobutyl alcohol/ammonia/water (40 20 1 39), R+ 0.77-0.82. Store it in the dark as the ammonium salt at 0°. The -form crystallises in platelets from aqueous Me2CO, m 120°. It dissolves in dry MeCN. Alternatively purify it through a column of Dowex AG lx8(200-400mesh) equilibrated with 50mM NH4 formate, and elute with Me0H/H20/NH40H (95 5 05), then freeze-dry. [Dixit et al. J Org Chem 46 1967 1981. Beilstein 1IV 3580.]... 

The proper choice of catalysts for the vapor phase hydration of olefins under pressure to form alcohols is a very important factor. Apparently, catalysts active in promoting the hydration reaction are likewise active toward promotion of the undesirable polymerization reactions since this latter reaction often proceeds at a more rapid rate than that of alcohol formation as evidenced by the high yields of polymers and low yields of alcohols. The use of catalysts to lower the temperature for the reaction is necessitated by the fact that as the temperature is increased to obtain more favorable rates, the equilibrium conversion to alcohol becomes lower, and the tendency to polymerize is increased. Also, the catalyst must not promote dehydrogenation of the alcohol to form hydrogen and aldehyde since at the temperature of operation the equilibrium is very favorable for this reaction as has been pointed out in a previous chapter. Thus, the reaction, isobutanol = isobutyl aldehyde -f hydrogen has an equilibrium constant corresponding to about 72 per cent decomposition at 450° C even with 100 atmospheres of hydrogen pressure. 

LiAlD4 is often applied to the preparation of deuterium-labeled compounds by reduction of C=0 bonds, for example, to the preparation of isobutyl alcohols labeled in the / -, or y-position29,30 and to the reduction of biacetyl to [2,3-D2]-2,3-butanediol.31 Monodeuterated secondary alcohols are also formed by its action on alicyclic ketones,27,32,33 on deuteration of camphor34 formation of the 2-deuterated product is accompanied by that of [3-Dx]-isoborneol, which indicates that enolization occurs under the reaction conditions. 

Isoamyl isovalerate Isoamyl octanoate Isoamyl phenethyl ether Isoamyl phenylacetate Isoamyl propionate Isoamyl salicylate Isoamyl tiqiate Isoamyl valerate Isobornyl acetate Isobornyl formate Isobornyl isovalerate Isobornyl methyl ether Isobornyl propionate Isobutyl alcohol Isobutyl angelate... 

Ethyl ether Ethyl formate Ethyl oleate Formamide Formic acid Glycerin Glyceryl caprylate/caprate Glyceryl formal Heptane 2-Hexanone Hexylene glycol Hybrid safflower (Carthamus tinctorius) oil Isoamyl alcohol Isobutyl acetate Isobutyl alcohol. 

Erlenmeyer found that the butyl alcohol present in fusel oil yields iso-butyric acid (see below) on oxidation, and is therefore isobutyl alcohol, and he also showed that from isobutyl iodide the same valeric acid is obtained as from the amyl alcohol of fusel oil, which is therefore isoamyl alcohol, derived from dimethylethylmethane. Secondary butyl alcohol was first obtained as hydrate de butylene from erythritol by de Luynes. A. Lieben obtained it from zinc ethyl and dichloroethyl ether, and since he found that on oxidation it gives a ketone he recognised it as secondary butyl alcohol. Lieben and A. Rossi obtained normal butyl alcohol from butyric acid, which was converted into butyraldehyde by distilling calcium butyrate and calcium formate, and a solution of this reduced with a large amount of sodium amalgam. They give structural formulae for the four butyl alcohols, with the boiling-points. 

The separation of two liquids which boil at temperatures even 20 or 30 apart, such as ethyl alcohol and water, or benzene and isobutyl alcohol, may be impossible owing to the formation of a mixture of minimum or, less frequently, of maximum boiling point. It is, indeed, only in the case of substances which are chemically clo ly related to each other that the statement can be definitely made that the difficulty of separating the components of a mixture diminishes as the difference between their boiling points increases. 

Formation of Binary Mixture of Minimum Boiling Point.—Suppose, for example, that we have a mixture of isobutyl alcohol and benzene containing 10 per cent, by weight of the alcohol. The components cannot be separated by fractional distillation because a mixture of minimum boil-... 

Isobutyl nitrite Butyl alcohol scc-Butyl alcohol t r -Butyl alcohol Ethyl ether Isobutyl alcohol Ethyl sulfide Pyridine Isovaleraldehyde 3-Methyl 2-butanone Isobutyl formate Isopropyl acetate Methyl isobutyrate Isoamyl nitrite tert-Amyl alcohol Isoamyl alcohol... 

Isopropyl alcohol Butyl alcohol aec-Butyl alcohol Isobutyl alcohol Cyclopentanol Butyl formate Methyl butyrate Propyl acetate Amyl alcohol (art-Amyl alcohol Isoamyl alcohol 2-Pentanol Allyl sulfide Ethyl butyrate Ethyl isobutyrate Isobutyl acetate Propyl sulfide Isopropyl sulfide Ethyl borate Toluene... 

Butyl alcohol sec-Butyl alcohol tert-B ity alcohol Isobutyl alcohol Isobutyl formate... 

Isobutyl alcohol Ethyl sulfide Cyclopentane 2-Methyl-2-butene 3>Pentanone Isobutyl formate Methyl isobutyrate Propyl acetate l-Bromo-3-methylbutane... 

Cyclopropane (0.5) -Propyl chloride (0.3) n-Propyl formate (0.3) Isopropyl chloride (0.3) Isopropyl alcohol (0.6) n-Butyl chloride (0.5) s-Butyl alcohol (0.6) Isobutyl bromide (—) Isobutyl alcohol (1) t-Butyl chloride (1). Butyl chloride (0.5).. t-Butyl alcohol (1.2) i-Butyl alcohol (0.3) t-Butyl alcohol (0.6) 3-Hexene (0.75) 3-Bromohexane (1) 3-Hexyl ether (0.18) Cyclohexene (1.5) Cyclohexyl bromide m.3)... 

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