Alcohols yield

At temperatures of 220-240 C it functions as an efficient, neutral dehydrating agent, amides yielding nitriles and alcohols yielding alkenes. 

Zaitsev s rule as applied to the acid catalyzed dehydration of alcohols is now more often expressed in a different way elimination reactions of alcohols yield the most highly substituted alkene as the major product Because as was discussed in Section 5 6 the most highly substituted alkene is also normally the most stable one Zaitsev s rule is sometimes expressed as a preference for predominant formation of the most stable alkene that could arise by elimination... 

Addition of phenylmagnesium bromide to 4 tert butylcyclohexanone gives two isomeric ter tiary alcohols as products Both alcohols yield the same alkene when subjected to acid catalyzed dehydration Suggest reasonable structures for these two alcohols... 

Oxidation of an alcohol yields a carbonyl compound Whether the resulting carbonyl compound is an aldehyde a ketone or a carboxylic acid depends on the alcohol and on the oxidizing agent... 

The reaction of uiea with alcohols yields caibamic acid esters, commonly called urethanes (see Urethane polymers) ... 

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

The reaction of phosgene with alcohols yields chloroformates, and with a basic catalyst present, carbonates ate formed ... 

Transesterification reactions between the methyl propionate and various alcohols produce another family of stabili2ers. Stearyl alcohol yields octadecyl 3-(3,5-di-/ f2 -butyl-4-hydroxyphenyl)propionate (27) (16), pentaerythritol gives the tetrakis ester (28) (17), and trishy dr oxyethyl isocyanurate gives (29) (18). 

In the reaction of aEyl alcohol with an aqueous chlorine solution, addition of hypochlorous acid to the double bond of aEyl alcohol yields glycerol monochlorohydrin and as a by-product, glycerol dichlorohydrin. Thus, a poor yield of glycerol monochlorohydrin is obtained (8). To improve the yield of glycerol monochlorohydrin, addition of sodium carbonate in an amount equivalent to that of the hydrogen chloride in the aqueous chlorine solution, has been proposed (9). 

Process. A typical indirect hydration process is presented in Eigure 1. In the process, propylene reacts with sulfuric acid (>60 wt%) in agitated reactors or absorbers at moderate (0.7—2.8 MPa (100—400 psig)) pressure. The isopropyl sulfate esters form and are maintained in the Hquid state at 20—80°C. Low propylene concentrations, ie, 50 wt %, can be tolerated, but concentrations of 65 wt % or higher are preferred to achieve high alcohol yields. Because the reaction is exothermic, internal cooling coils or external heat exchangers are used to control the temperature. 

Thermochemical Data. Equilibrium considerations significantly limit alcohol yield at low pressures in the vapor-phase process (116). Consequently, conditions controlling equilibrium constants have been determined and give the following relation, where Tis in K (116,117) ... 

Isomerization and Hydrogenolysis. lsomeri2ation of propylene oxide to propionaldehyde and acetone occurs over a variety of catalysts, eg, pumice, siUca gel, sodium or potassium alum, and 2eohtes (80,81). Stronger acid catalysts favor acetone over propionaldehyde (81). AHyl alcohol yields of 90% are obtained from use of a supported lithium phosphate catalyst (82). 

An example of a sulfite ester made from thionyl chloride is the commercial iasecticide endosulfan [115-29-7]. A stepwise reaction of thionyl chloride with two different alcohols yields the commercial miticide, propaigite [2312-35-8] (189). Thionyl chloride also has appHcations as a co-reactant ia sulfonations and chlorosulfonations. A patent describes the use of thionyl chloride ia the preparation of a key iatermediate, bis(4-chlorophenyl) sulfone [80-07-9] which is used to make a commercial polysulfone engineering thermoplastic (see Polymers CONTAINING SULFUR, POLYSULFONe) (190). The sulfone group is derived from chlorosulfonic acid the thionyl chloride may be considered a co-reactant which removes water (see Sulfolanes and sulfones). 

Lanolin alcohols are obtained by saponification of purified wool grease, a mixture of high molecular esters that is recovered in wool (qv) scouring. Ethoxylation of purified lanolin alcohols yields a full series of lipophilic and hydrophilic nonionic emulsifiers whose largest use is in cosmetic preparations. Manufacturers include Amerchol, Croda, ICI, Henkel Corporation, Westbrook Lanolin, Witco, and Pulcra, SA. 

Poly(vinyl alcohol) is readily cross-linked with low molecular weight dialdehydes such as glutaraldehyde or glyoxal (163). Alkanol sulfonic acid and poly(vinyl alcohol) yield a sulfonic acid-modified product (164). 

Alcohol Yield. With com containing 60% starch, distillers traditionally obtain 19—19.7 L (5.0—5.2 proof gaHons)/0.03 (bushel). Theoretical yields as Hters of absolute alcohol/100 kg of starch are... 

Oxidative Garbonylation. Carbon monoxide is rapidly oxidized to carbon dioxide however, under proper conditions, carbon monoxide and oxygen react with organic molecules to form carboxyUc acids or esters. With olefins, unsaturated carboxyUc acids are produced, whereas alcohols yield esters of carbonic or oxalic acid. The formation of acryUc and methacrylic acid is carried out in the Hquid phase at 10 MPa (100 atm) and 110°C using palladium chloride or rhenium chloride catalysts (eq. 19) (64,65). 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

The conditions for surfactants to be useful to form Hquid crystals exist when the cross-sectional areas of the polar group and the hydrocarbon chain are similar. This means that double-chain surfactants are eminently suited, and lecithin (qv) is a natural choice. Combiaations of a monochain ionic surfactant with a long-chain carboxyHc acid or alcohol yield lamellar Hquid crystals at low concentrations, but suffer the disadvantage of the alcohol being too soluble ia the oil phase. A combination of long-chain carboxyHc acid plus an amine of equal chain length suffers less from this problem because of extensive ionisa tion of both amphiphiles. 

Eijuilibrium Constant. At the pressures used in commercial production of ethanol (6.1—7.1 MPa or 60—70 atm), alcohol yield per pass is significantly limited by equiHbrium considerations. This fact has focused attention on deterrnination of equiHbrium constants and equiHbrium yields (122—124). The results of these deterrninations are as follows ... 

On distillation of the residue in the distillation flask there is obtained a fraction boiling at i70-200°/i8 mm. Crystallization of this material from methyl alcohol yields 8-10 g. of thianthrene, melting at 155-156°. 

Arecoline is hydrolysed by acids or alkalis to the corresponding acid, arecaidine, and conversely the latter, on esterification with methyl alcohol, yields arecoline, and vvith ethyl alcohol Ijomoarecoline. Syntheses of arecaidine, and therefore of arecoline, arc described above. 

The oxidation of lupanine has been investigated by a number of w orkers. Beckel noted that d-lupaniiie formed a perbromide, which on treatment with alcohol yielded cthoxylupanine dihydrobromide, C12H23ON2. OC2H5,2HBr (colourless needles, m.p. 227-8°, [a]7° — 129-4°), from which a number of interesting substances were obtained in yields too small for characterisation. 

Phosphoryl chloride converts protopine into the quaternary salt isoprotopine chloride, C20H18O4NCI, m.p. 215° (dec.), which on treatment with potassium hydroxide in methyl alcohol yields anhydroprotopine, C2qH4,04N, m.p. 114-5°,1 just as crj ptopine is convertible into iso-cryptopine chloride and this into anliydrocryptopine. Similarly, protopine forms protopine methosulphate, CjoHigOjN. Me2S04, m.p. 252°, which is converted by potassium hydroxide in methyl alcohol, into two methyl-protopines, a-, m.p. 145°, and y-, m.p. 112°, corresponding with the two methyleryptopines, a-, m.p. 153°, and y-, m.p. 110°, respectively. 

This synthesis came shortly after one by Prelog, Kohlberg, Cerkovnikov, Rezek and Piantanida (1937) based on a series of reactions which, with modifications and extensions. Prelog and his colleagues have applied to the syntheses of bridged heterocyclic nuclei, of which this is an example. 4-Hydroxymethyltetrahydropyran (VI R =. OH) is converted via the bromo-compound (VI R = Br) and the nitrile (VI R = CN) into tetrahydropyran-4-acetic acid of which the ethyl ester (VII) is reduced to 4-()3-hydroxyethyl)-tetrahydropyTan (VIII). This is converted by fuming hydrobromic acid into 3-(2-bromoethyl)-l 5-dibromopentane (IX) which with ammonia in methyl alcohol yields quinuclidine (V). 

On oxidation with permanganate, methylharmaline is converted into a neutral substance, CiaHj O Na, m.p. 228°, which, on reduction with sodium and n-butyl alcohol yields A -methyltetrahydronorharmine (XVII),... 

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