Alcohol commercial importance

CO. Alkynes will react with carbon monoxide in the presence of a metal carbonyl (e.g. Ni(CO)4) and water to give prop>enoic acids (R-CH = CH-C02H), with alcohols (R OH) to give propenoic esters, RCH CHC02R and with amines (R NH2) to give propenoic amides RCHrCHCONHR. Using alternative catalysts, e.g. Fe(CO)5, alkynes and carbon monoxide will produce cyclopentadienones or hydroquinols. A commercially important variation of this reaction is hydroformyiation (the 0x0 reaction ). 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

Most higher alcohols of commercial importance are primary alcohols secondary alcohols have more limited specialty uses. Detergent range alcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer range alcohols are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fats and oils are always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussed in Synthetic processes. 

All lnaphthalenesulfonic Acids. The aLkyLnaphthalenesulfonic acids can be made by sulfonation of aLkyLnaphthalenes, eg, with sulfuric acid at 160°C, or by alkylation of naphthalenesulfonic acids with alcohols or olefins. These products, as the acids or their sodium salts, are commercially important as textile auxiUaries, surfactants (qv), wetting agents, dispersants (qv), and emulsifying aids, eg, for dyes (qv), wettable powder pesticides, tars, clays (qv), and hydrotropes. 

The zwitterion (6) can react with protic solvents to produce a variety of products. Reaction with water yields a transient hydroperoxy alcohol (10) that can dehydrate to a carboxyUc acid or spHt out H2O2 to form a carbonyl compound (aldehyde or ketone, R2CO). In alcohoHc media, the product is an isolable hydroperoxy ether (11) that can be hydrolyzed or reduced (with (CH O) or (CH2)2S) to a carbonyl compound. Reductive amination of (11) over Raney nickel produces amides and amines (64). Reaction of the zwitterion with a carboxyUc acid to form a hydroperoxy ester (12) is commercially important because it can be oxidized to other acids, RCOOH and R COOH. Reaction of zwitterion with HCN produces a-hydroxy nitriles that can be hydrolyzed to a-hydroxy carboxyUc acids. Carboxylates are obtained with H2O2/OH (65). The zwitterion can be reduced during the course of the reaction by tetracyanoethylene to produce its epoxide (66). 

Sodium ethoxide was the first metal alkoxide described in 1837 (1). The alkoxides of many transition metals were developed after World War II (2—5). Today some alkoxides, including those of sodium, potassium, magnesium, aluminum, zirconium, and titanium, are commercially important. The name metal alkoxides is preferred, although metal alcoholates is also used. 

Alkylated phenol derivatives are used as raw materials for the production of resins, novolaks (alcohol-soluble resins of the phenol—formaldehyde type), herbicides, insecticides, antioxidants, and other chemicals. The synthesis of 2,6-xylenol [576-26-1] h.a.s become commercially important since PPO resin, poly(2,6-dimethyl phenylene oxide), an engineering thermoplastic, was developed (114,115). The demand for (9-cresol and 2,6-xylenol (2,6-dimethylphenol) increased further in the 1980s along with the growing use of epoxy cresol novolak (ECN) in the electronics industries and poly(phenylene ether) resin in the automobile industries. The ECN is derived from o-cresol, and poly(phenylene ether) resin is derived from 2,6-xylenol. 

All lation of Aromatic Amines and Pyridines. Commercially important aromatic amines are aniline [62-53-3] toluidine [26915-12-8], phenylenediamines [25265-76-3], and toluenediamines [25376-45-8] (see Amines, aromatic). The ortho alkylation of these aromatic amines with olefins, alcohols, and dienes to produce more valuable derivatives can be achieved with soHd acid catalysts. For instance, 5-/ f2 butyl-2,4-toluenediamine (C H gN2), which is used for performance polymer appHcations, is produced at 85% selectivity and 84% 2,4-toluenediamine [95-80-7] (2,4-4L)A)... 

Esterification is frequendy carried out by direct reaction of the carboxyhc acid with an alcohol in the presence of a small amount of mineral acid, usually concentrated sulfuric or hydrochloric acid. The esters of commercial importance in both 0- and -hydroxyben2oic acid are the methyl esters. Direct esterification has the advantage of being a single-step synthesis, but being an equihbrium it is easily reversed. The reaction to the ester is driven by either of... 

Sulfonic acids are prone to reduction with iodine [7553-56-2] in the presence of triphenylphosphine [603-35-0] to produce the corresponding iodides. This type of reduction is also facile with alkyl sulfonates (16). Aromatic sulfonic acids may also be reduced electrochemicaHy to give the parent arene. However, sulfonic acids, when reduced with iodine and phosphoms [7723-14-0] produce thiols (qv). Amination of sulfonates has also been reported, in which the carbon—sulfur bond is cleaved (17). Ortho-Hthiation of sulfonic acid lithium salts has proven to be a useful technique for organic syntheses, but has Httie commercial importance. Optically active sulfonates have been used in asymmetric syntheses to selectively O-alkylate alcohols and phenols, typically on a laboratory scale. Aromatic sulfonates are cleaved, ie, desulfonated, by uv radiation to give the parent aromatic compound and a coupling product of the aromatic compound, as shown, where Ar represents an aryl group (18). 

Long-chain alcohols, such as are obtained by the hydrogenation of coconut oil, polymerization of ethylene, or the 0x0 process (qv), are sulfated on a large scale with sulfur thoxide or chlorosulfuhc acid to acid sulfates the alkaU salts are commercially important as surface-active agents (see Surfactants). Poly(vinyl alcohol) can be sulfated in pyhdine with chlorosulfuhc acid to the hydrogen sulfate (84). 

Important commercial sesquiterpenes mosdy come from essential oils, for example, cedrene and cedrol from cedarwood oil. Many sesquiterpene hydrocarbons and alcohols are important in perfumery as well as being raw materials for synthesis of new fragrance materials. There are probably over 3000 sesquiterpenes that have been isolated and identified in nature. 

Longifolene. There are at least four commercially important aroma chemicals made from (+)-1ongifo1ene and about thirteen products made from (-)-isolongifolene (90) (182). Acetoxymethyl longifolene or the formate are formed during the Prins reaction on (+)-1ongifo1ene. Saponification of the esters gives the useful perfumery alcohol (183) (Fig. 9). 

Methanethiol (eq. 6) and cyclohexanethiol (eq. 7) are the only commercially important thiols prepared using alcohol substitution. In most cases, when the alcohol is utilized, less control over the substitution patterns is obtained. Only one isomer is obtainable in the case of methanol and cyclohexanol. 

Analogously, poly(vinyl ketals) can be prepared from ketones, but since poly(vinyl ketals) are not commercially important, they are not discussed here. The acetalization reaction strongly favors formation of the 1,3-dioxane ring, which is a characteristic feature of this class of resins. The first of this family, poly(vinyl ben2al), was prepared in 1924 by the reaction of poly(vinyl alcohol) with ben2aldehyde in concentrated hydrochloric acid (2). Although many members of this class of resins have been made since then, only poly(vinyl formal) [9003-33-2] (PVF) and poly(vinyl butyral) [63148-65-2] (PVB) continue to be made in significant commercial quantities. 

Poly(vinyl alcohol) participates in chemical reactions in a manner similar to other secondary polyhydric alcohols (82—84). Of greatest commercial importance are reactions with aldehydes to form acetals, such as poly(vinyl butyral) and poly(vinyl formal). 

Salts and Derivatives. Generally the vitamers are high melting crystalline soHds that are very soluble in water and insoluble in most other solvents. Properties of the common forms are Hsted in Table 1. The only commercially important form of vitamin B is pytidoxine hydrochloride (7). This odorless crystalline soHd is composed of colorless platelets melting at 204—206°C (with decomposition). In bulk, it appears white and has a density of - 0.4 kg/L. It is very soluble in water (ca 0.22 kg/L at 20°C), soluble in propylene glycol, slightly soluble in acetone and alcohol (ca 0.014 kg/L), and insoluble in most lipophilic solvents. A 10% water solution shows a pH of 3.2. Both the hydrochloride and corresponding free base sublime without decomposition (16). 

Reaction of poly(vinyl alcohol) [9002-89-5] with //-butyraldehyde yields poly(vinyl butyral) [63148-65-2] (PVB), a commercially important resia. 

Physical and Chemical Properties. Although both the (E)- and (Z) [4510-34-3] isomers of cinnamyl alcohol are known in nature, (E)-cinnamyl alcohol [4407-36-7] is the only isomer with commercial importance. Its properties are summari2ed in Table 4. 

The catalytic hydrogenation of esters is of great commercial importance. It is one of the industrial methods used to produce long-chain fatty alcohols (eg, dodecyl and decyl alcohols) from fatty acid methyl esters (33). The method is also suitable for the conversion of dimethyl 1,4-cyclohexanedicarboxylate [94-60-0] into 1,4-cydohexanedimethanol [105-08-8] an important intermediate in the manufacturing of polyesters. 

The oxide—alcohol route is the only commercially important route to glycol ethers now ia use. Anhydrous alcohols must be used otherwise the water present forms contaminating glycols. 

Synthesis gas is also an important building block for aldehydes from olefins. The catalytic hydroformylation reaction (Oxo reaction) is used with many olefins to produce aldehydes and alcohols of commercial importance. 

Ethylene oxide is a precursor for many chemicals of great commercial importance, including ethylene glycols, ethanolamines, and alcohol ethoxylates. Ethylene glycol is one of the monomers for polyesters, the most widely-used synthetic fiber polymers. The current US production of EO is approximately 8.1 hillion pounds. 

In this chapter, we have examined the use of cells and enzymes to chemically transform lipids. We have had to be selective and have predominantly focused attention on the transformation of sterols and steroids. We first explained why these compounds were commercially important and why they only occur in low concentrations in natural systems. We pointed out that a very large number of reaction types are possible, but those which have found greatest use include stereospedfic hydroxylations, alcohol/ketone interconversion, hydrolysis, conjugation and isomerisation. 

The small molecules used as the basic building blocks for these large molecules are known as monomers. For example the commercially important material poly(vinyl chloride) is made from the monomer vinyl chloride. The repeat unit in the polymer usually corresponds to the monomer from which the polymer was made. There are exceptions to this, though. Poly(vinyl alcohol) is formally considered to be made up of vinyl alcohol (CH2CHOH) repeat units but there is, in fact, no such monomer as vinyl alcohol. The appropriate molecular unit exists in the alternative tautomeric form, ethanal CH3CHO. To make this polymer, it is necessary first to prepare poly(vinyl ethanoate) from the monomer vinyl ethanoate, and then to hydrolyse the product to yield the polymeric alcohol. 

Sulphosuccinates are of particular interest not only for their technical properties but also because structurally they combine the two hydrophile functions described earlier - the sulphonate and carboxylate moieties - in a single molecule (9.18). The sulphosuccinate diesters, however, are probably of greater commercial importance in textile processing than are the monoesters. The most important example is sodium dioctylsulphosuccinate (9.19), but the dinonyl, dimethylamyl and di-isobutyl analogues are also used commercially. As usual, a wide choice of hydrophobes is available and includes alcohols, lightly ethoxylated alcohols, alkanolamides and combinations of these. 

A simple synthesis of allethrolone, the alcohol component of the allethrine (commercially important insecticide), is shown in Scheme 4.11. The conjugated addition of 3-phenylthio-5-hexene-2-one to 1-nitro-l-propene followed by the Nef reaction and aldol condensation gives allethrolone in good yield.68... 

It is a commercially important reaction as a step in the synthesis of nonanol, an important plasticizer alcohol. Other long chain alcohols, derived from product aldehydes by hydrogenation are used as the basis of soaps and... 

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