Alcohols and phenols

Alcohols are classified as primary, secondary or tertiary, depending on the number of organic groups bonded to the -OH carbon. 

Phenols are named according to rules discussed in Section 15.1. 

Alcohols have sp3 hybridization and a nearly tetrahedral bond angle. 

Alcohols and phenols have elevated boiling points, relative to hydrocarbons, due to hydrogen bonding. 

Alcohols and phenols are weakly acidic as well as weakly basic. 

5 Alcohols from Carbonyl Compounds Grignard Reaction 

A Deeper Look—Ethanol Chemical, Drug, Poison 

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Ethanol was one of the first organic chemicals to be prepared and purified. Its production by fermentation of grains and sugars has been carried out for perhaps 9000 years, and its piuification by distillation goes back at least as far as the 12th century. Today, approximately 55 million metric tons (18 billion gallons) of ethanol is produced worldwide each year, most of it by fermentation of com, barley, sorghum, and other plant sources. Essentially the entire amount is used for automobile fuel. 

Ethanol for industrial use as a solvent or chemical intermediate is largely obtained by acid-catalyzed hydration of ethylene at high temperature. 

Preparation of Alcohols via Reduction Preparation of Diols Preparation of Alcohols via Grignard Reagents 

Substitution and Elimination Reactions of Alcohols Oxidation Biological Redox Reactions Oxidation of Phenol Synthesis Strategies 

If necessary, review the suggested sections to prepare for this chapter. 

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Alcohols are compounds that possess a hydroxyl group (OH) and are characterized by 

Alcohols and phenols will show strong and broad hydrogen bonded O—H stretching bands centering between 3400 and 3300 cm F In solution, it will also be possible to observe a free O—H stretching band at about 3600 cm (sharp and weaker) to the left of the hydrogen bonded O—H peak. In addition, a C—O stretching band wUl appear in the spectrum at 1260-1000 cm.  

The free O—H stretch is a sharp peak at 3650-3600 cm This band appears in combination with the hydrogen-bonded O—H peak when the alcohol is dissolved in a solvent (see discussion). 

The hydrogen-bonded O—H band is a broad peak at 3400-3300 cm This band is usually e only one present in an alcohol that has not been dissolved in a solvent (neat liquid). When the alcohol is dissolved in a solvent, the free O—H and hydrogen-bonded O—H bands are present together, with the relatively weak free O—H on the left (see discussion). 

Bending appears as a broad and weak peak at 1440-1220 cm often obscured by the CH3 bendings. 

Stretching vibration usually occurs in the range 1260-1000 cm F This band can be used to assign a primary, secondary, or tertiary structure to an alcohol (see discussion). 

0-Hst 3650-3200 cm-i Position and shape depend on the degree of association. Often different bands for H-bonded and free OH 

Ahphatic weak, often missing in the case of primary and highly branched alcohols in this case, peaks at highest mass are often due to [M-18]+- or [M-15]+ 

CO and CHO elimination also from fragments. H2O elimination ( M-18]+ ) only with alkyl substituent in ortho position Elimination of H2O from M+ followed by alkene elimination elimination of H2O from produets of a-eleavage Vinylcarbinols spectra similar to those of ketones 

MS Aromatic Ortho effect with appropriate substituents  

Aliphatic Aromatic 200-210 nm (log e 3.8) 270 nm (log e 2.4) No absorption above 200 mn In alkaline solution, shift to longer wavelength and inerease in intraisity due to deprotonation  

Alcohols occur widely in nature and have many industrial and pharmaceutical applications. Methanol, for instance, is one of the most important of all industrial chemicals. Historically, methanol was prepared by heating wood in the absence of air and thus came to be called wooil alcohol. Today, approximately 

2 billion gallons of methanol is manufactured each vear in the United States bv 

Phenols occur widely throughout nature and also ser e as intermediates in the industrial synthesis of products as diverse as adhesives and antiseptics. Phenol itself is a general disinfectant found in coal tar methyl salicylate is a flavoring agent found in oil of wintergreen and the urushiols are the allergenic constituents of poison oak and poison i y. Note that the word phenol is the name both of the sj)ecific compound hydroxybenzene and of a class of compounds. 

Methanol is toxic to humans, causing blindness in low doses (15 mL) and death in larger amounts (100-250 mL). Industrially, it is used both as a solvent and as a starting material for production of formaldehyde (CHgO), acetic acid (CH3COOH), and the gasoline additive methyl ier -butyl ether IMTBE, CHj,OC(CH3)al. 

Despite the fact that the formation of these alkoxo and aryloxo vanadates is not favored relative to many other ligated species, they can still have important influences in enzymic systems. It has, for instance, been shown that vanadate in the presence of glucose and glucose-6-phosphate dehydrogenase readily produces gluconic acid, a normal product of glucose-6-phosphate metabolism [3], Similar reactivity has been observed with a number of enzymes that metabolize phosphate compounds [4], 

The electronic properties of both alkyl [5] and aryl alcohols [6] play a clearly definable role in ester formation, with formation constants decreasing with increase in electron withdrawing ability of the ligand. For both types of ligands, the electronic influences are quite small, but the resonance effects found with the aromatic ligands indicate there are 71-electron contributions to the empty d orbitals of vanadate [6], The influences of the electronic properties of ligands on coordination mode and geometry are discussed in detail in Chapter 9. 

Review Comprehensive Organic Synthesis, Eds. B. M. Trosi and I. Fleming, Pergamon, Oxford (1991), Vol 8, Part 4.2, p 811 

For reduction of allylic alcohols with double bond transposition, see page 229, Section 4. 

BH3-py, CF3CO2H BH BF3 OEt2 NaBH4, HOAc, CF3C02H NaBH4, CFjCOjH 

Acetates of fatty [1] and polyhydric [2] alcohols, phenols [3] and chlorophenols [4] have been studied. Fell and Lee [3] described a GC method for the determination of polyhydric phenols in urine, which, having been extracted, were acetylated with acetic anhydride in the presence of 4-dimethylaminopyridine. According to these authors this substance shows much stronger catalytic effects than does the usually used pyridine. The derivatives are formed rapidly and quantitatively even in very dilute solutions. In the absence of the catalyst, bifunctional phenols provide more than one GC peak. Slightly polar OV-210 is recommended for the separation of phenol acetates, but analysis on nonpolar OV-101 leads to tailing, probably as a consequence of insufficient deactivation of the column. 

Chau and Coburn [4] described the determination of pentachlorophenols (PCPs) in natural and industrial waters at 0.01 ppb levels. The PCPs are extracted into benzene and 

The purity of the acetic anhydride is important (repeated distillation in an all-glass apparatus is recommended) as it may contain impurities that interfere with the peaks of the PCP derivatives in the chromatogram. An identical procedure was also used by Krijgsman and Van de Kamp [5], but the GC analysis was carried out in a glass capillary column coated with SE-30. Using the ECD, the detection limit of PCP acetate was 1 pg. The recovery of the extraction—acetylation step was 80—100%. An example of the analysis is shown in Fig. 5.1. 

A tribenzoyl derivative was used by Decroix et al. [6] for the determination of glycerol. The preparation of the derivative was carried out directly in the sample as it does not require strictly anhydrous conditions. After performing the extraction with diisopropyl ether and after evaporating the solvent, the derivative dissolved in chloroform was injected. A detection limit of 1 pg of glycerol was reported. The low thermal stability of the derivative is a drawback. 

Makita et al. [7] chromatographed simple phenols as their O-isobutyloxycarbonyl derivatives. They were prepared by reaction with isobutyl chloroformate in aqueous 

In connection with the discussion of epoxide chemistry we have given examples for the directed stereoselective generation of alcohols already. 

At this stage, two procedures are added in which the result of a nucleophilic epoxide opening is complemented by a second type of reaction to selectively provide a set of diastereomers. 

In the investigation reported, y-lactone 363 was the desired stereoisomer from electrophilic attack, followed by acid hydrolysis. 

When this reaction was run with epoxide 360 as the electrophile, the undesired lactone 362 turned out to be the main reaction product in a 87 13 ratio. 

On replacement of 360 by the iodide 361, the selectivity was interestingly nearly completely reversed. This alkylation reaction provided a good yield of the desired lactone 363 in a 93 7 ratio [118]. 

The characteristic bands observed in the spectra of alcohols and phenols result from O—H stretching and C—O stretching. These vibrations are sensitive to hydrogen bonding. The C—O stretching and O—H bending modes are not independent vibrational modes because they couple with the vibrations of adjacent groups. 

TABLE 2.3 C—H Out-of-Plane Bending Vibrations of a /3-Substitutcd Naphthalene 

Alcohols are conveniently named by replacing the final e in the name of the corresponding alkane with the suffix ol. Thus, the relationship between methane (CH4 or H3C-H) and methanol (H3C-OH or CH3OH) is clear. The names of the other alcohols follow the lUPAC system with the -OH being given the lowest number consistent with its position. Thus, the pentanol isomers 1-pentanol, 2-pentanol, and 3-pentanol differ only by the position of the hydroxyl group along the chain. 

In the event there is another substituent present, for example, a methyl group, the nomenclature follows the usual pattern save that the location of the hydroxyl (-OH) takes precedent. Thus, the series of methyl-1-pentanols is named as follows. 

Additionally, there is a second widespread nomenclature system in use. In this, common for simple alcohols, the alkyl group is named as a substituent and followed by the word alcohol. 

A third system depends on considering alcohols as derivatives of methanol. However, the word methanol is replaced by carbinol.  

Finally, the -OH group may be considered as a substituent and its position fixed with a number and the radical name hydroxy. The use of all four systems is illus- 

This group of ingredients has many useful properties. Alcohols and phenols are very common in household products. Alcohols are good solvents and are used in perfumes and flavorings to dissolve fats and oils. Heavier alcohols with long chains of hydrocarbons act as emulsifiers and surfactants, bringing oil and water together. 

When the word alcohol is used alone, it refers to ethanol, the alcohol found in wine, beer, and distilled spirits. Ethanol is used as a fast-drying solvent in many products, especially cosmetics and hairsprays. 

When used in products not licensed for drinking, ethanol usually occurs in the form of denatured alcohol, or specially denatured alcohol—alcohol that has been rendered unfit for drinking. You will often see SD alcohol mentioned on a label, sometimes followed by a number and letter, such as 40-B. This is the designation given by the U.S. Bureau of Alcohol, Tobacco, and Firearms to the denaturing method used. For example, SD-40 is ethanol denatured by adding tiny amounts of the most bitter-tasting substance known denatonium benzoate. 

There are a large number of alcohols besides ethanol. All of them have the hydroxyl group OH attached to a carbon atom. The simplest is methanol  

Methanol has one carbon, ethanol has two, and there are two forms of the alcohol that contain three carbons propanol 

The materials called synthetic rubber are not really synthetic rubber, since they are not identical with the natural product. They are, rather, substitutes for rubber—materials with properties and structure similar to but not identical with those of natural rubber. For example, the substance cliloroprene, C4H5CI, with the structure 

The aliphatic alcohols have a hydroxyl group, —OH, attached to a carbon atom in place of one of the hydrogen atoms of an aliphatic hydrocarbon. The two simplest alcohols, methyl alcohol (methanol) and ethyl alcohol (ethanol), have been discussed in Section 8-6. The melting points, boiling points, and densities of some alcohols are given in Table 13-1. 

Some of the heavier alcohols are made from the olefines that are obtained as by-products in the refining of petroleum. For example, propylene, CHa=CH—CH3, can be hydrated by addition of water vapor at high temperature and pressure in the presence of a catalyst  

The product is called isopropyl alcohol or 2-propanol (the number 2 means that the substituent is on the second carbon atom in the chain, and the suffix ol means that the substituent is the hydroxyl group). An alcohol 

The simplest example is /m-butyl alcohol (CH3)3COH. The propyl and butyl alcohols are used as solvents for lacquers and other materials. 

In this section, the formation and cleavage of eight protecting groups for alcohols and phenols are presented acetate acetonides for diols benzyl ether para-methoxybenzyl (PMB) ether methyl ether methoxymethylene (MOM) ether fe/f-butyldiphenylsilyl (TBDPS) silyl ether and tetrahydropyran (THP). 

Acetate is a convenient protecting group for alcohols—easy on and easy off. Selective protection of a primary alcohol in the presence of a secondary alcohol can be achieved at low temperature. The drawback of this protecting group is its incompatibility with hydrolysis and reductive conditions. 

O-Isopropylidene acetal has been widely used in protecting 1,2- and 1,3-diols. They are resistant to very basic conditions, but are cleaved under acidic conditions. 

To a stirred solution of the diol starting material (0.8 g, 2.85 mmol) in CH2C12 (2 mL) at room temperature was added 2,2,-dimethoxypropane (0.52 mL, 4.2 mmol) and camphorsulfonic acid (CSA, 13 mg, 2 mol%). The reaction was stirred for 3 h and quenched with saturated aqueous sodium bicarbonate (10 mL) and the aqueous layer was extracted with ether (3 x 15 mL). The combined organic layers were washed with brine (10 mL), dried (Na2S04), hltered, and concentrated in vacuo. Purihcation of the residue by flash chromatography eluting with EtOAc/hexane (1 9) afforded the isopropylidene acetal (0.73 g, 80%) as a viscous oil. 

Protection of the 1,3-diol as an acetonide works similarly to the 1,2-diol. 

In some of the first studies connected with the discovery of the general phenomenon of cocatalysis, f-butanol was found to play such a role in the polymerisation of isobutene by boron fluoride There is an apparent contradiction between this observation and tire fact that polyisobutene chains bearing hydroxyl end groups , i.e. the same structure as f-butanol, do not exhibit a cocatalytic function (see all the evidence of limited yields due to water consumption by termination with counterion to give those end groups). The likely explanation of this dichotomy is that the OH groups on the polymer molecules are embedded in the macromolecular cofls and therefore much less reactive towards the Lewis acid-moncaner complex. 

Methanol is an effective cocatalyst in conjunction with boron fluoride. Okamura et al. aa ribed this initiation capability to the formation of a partly dissociated complex between Lewis acid and alccdud. This su esticm was recently verified in a specific study on this interaction involving vibrational spectroscopy Boron fluoride was found to give well-defined 1 1 and 1 2 adducts vnth methanol and the Raman spectrum of the latter complex indicated scmie dissociation according to tire reaction 

Eastham and collaborators carried out a thorough study of the isomerisation and polymerisation of butenes by the BF3-CH3OH pair They found that the initial rate of isomerisation of butene-2 was proportional to the concentration of both the catalyst-cocatalyst complex and the free catalyst. We think that these findings are 

Zlamal and Kazda investigated the effect of various alcohols and phenol on the polymerisation of isobutene catalysed by aluminium chloride in ethyl chloride at —78 C. They obtained evidence for the formation of complexes between this Lewis 

The implications of these findings have already been thorou y discussed by Plesch  

A carbon atom can be bonded to as many as four halogen atoms, so an enormous number of organic halides can exist. Completely fluorinated compounds are known 2 fluorocarbons or sometimes perfluorocarbons. The fluorocarbons are even less reactive than hydrocarbons. Saturated compounds in which all H atoms have been replaced by some combination of Cl and F atoms are called chlorofluorocarbom or sometimes freons. These compounds were widely used as refrigerants and as propellants in aerosol cans. However, the release of chlorofluorocarbons into the atmosphere has been shown to be quite damaging to the earth s ozone layer. Since January 1978, the use of chlorofluorocarbons in aerosol cans in the United States has been prohibited, and efforts to develop both controls for existing chlorofluorocarbons and suitable replacements continue. The production and sale of freons have been banned in many countries. 

Indeed, this is a better view. The structure of water was discussed in Section 8-9. The 

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CHAPTER 23 ORGANIC CHEMISTRY I FORMULAS, NAMES, AND PROPERTIES 

Solvents will always be a necessary part of indusfrial operations. While they can never be completely eliminated, researchers and regulators can work to accelerate the development and 

The intensity of the molecular ion peak in the mass spectrum of a primary or secondary alcohol is usually rather low, and the molecular ion peak is often entirely absent in the mass spectrum of a tertiary alcohol. Common fragmentations of alcohols are a-cleavage adjacent to the hydroxyl group and dehydration. 

A second common mode of fragmentation involves dehydration. The importance of dehydration increases as the chain length of the alcohol increases. While the fragment ion peak resulting from dehydration (m/z = 70) is very intense in the mass spectrum of 1-pentanol, it is quite weak in the other pentanol isomers. Dehydration may occur by either thermal dehydration prior to ionization or by fragmentation of the molecular ion. Thermal dehydration is especially troublesome for alcohol samples analyzed by GC-MS. The injection port of the gas chromatograph is usually maintained at more than 200°C, and many alcohols, especially tertiary or allylic/benzylic, will dehydrate before the sample molecules even reach the GC column and certainly before the molecules reach the ion 

Alcohols containing four or more carbons may undergo the simultaneous loss of both water and ethylene. This type of fragmentation is not prominent for 1-butanol but is responsible for the base peak at miz = 42 in the mass spectrum of 1-pentanol (Fig. 8.45). 

Benzylic alcohols usually exhibit strong molecular ion peaks. The following sequence of reactions illustrates their principal modes of fragmentation. Loss of a hydrogen atom from the molecular ion leads to a hydroxytropylium ion (mIz = 107). The hydroxytropylium ion can lose carbon monoxide to form a resonance-delocalized cyclohexadienyl cation (m/z = 79). This ion can eliminate molecular hydrogen to create a phenyl cation, m/z = 77. Peaks arising from these 

The mass spectra of phenols usually show strong molecular ion peaks. In fact, the molecular ion at mh = 94 is the base peak in the EI-MS of phenol (Fig. 8.52). Favored modes of flagmentadon involve loss of a hydrogen atom to create an M - 1 peak (a small peak at miz = 93), loss of carbon monoxide (CO) to produce a peak at M - 28 (nilz = 66), and loss of a formyl radical (HCO-) to give a peak at M - 29. In the case of phenol itself, this creates the aromatic cyclopentadienyl cation at mIz = 65. In some cases, the loss of 29 mass units may be sequential initial loss of carbon monoxide followed by loss of a hydrogen atom. The mass spectrum of ort/to-cresol (2-methylphenol) exhibits a much larger peak at M - 1 (Fig. 8.53) than does unsubstituted phenol. Note also the peaks at miz = 80 and miz = 79 in the o-cresol spectrum from loss of CO and formyl radical, respectively. 

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Ethanol for nonbeverage use is obtained by acid-catalyzed hydration of ethylene. Approximately 110 million gallons of ethanol a year is produced in the United States for use as a solvent or as a chemical intermediate in other i nd us tr i a 1 reactions. 

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C2H4N2O3, NH2CONHCOOH. Unknown in the free state as it breaks down immediately to urea and COi- The NH4, Ba, Ca, K and Na salts are known and are prepared by treating ethyl allophanate with the appropriate hydroxide. The esters with alcohols and phenols are crystalline solids, sparingly soluble in water and alcohol. They are formed by passing cyanic acid into alcohols or a solution of an alcohol or phenol in benzene. The amide of allophanic acid is biuret. Alcohols are sometimes isolated and identified by means of their allophanates. 

Although these nitrations proceed smoothly, attempted nitration of an unidentified substance should always be carried out with extreme care, e.g., by working in a fume-cupboard and pointing the boiling-tube away from the operator. Many organic substances e.g., alcohols and phenols) react with great violence with a mixture of nitric and sulphuric acids. 

Tablel.10 Retained Trivial Names of Alcohols and Phenols with Structures 1.24...

This experiment describes a characterization analysis in which the degree of association, equilibrium constant, and hydrogen bond energy are measured for benzyl alcohol and phenol in CCI4. 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

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). 

Thiophosgene reacts with alcohols and phenols to form chlorothionoformates or thiocarbonates. The most studied reactions of thiophosgene are with primary amines to give isothiocyanates and with secondary amines to give thiocarbamyl chlorides ... 

The triaLkoxy(aryloxy)boranes are typically monomeric, soluble in most organic solvents, and dissolve in water with hydrolysis to form boric acid and the corresponding alcohol and phenol. Although the rate of hydrolysis is usually very fast, it is dependent on the bulk of the alkyl or aryl substituent groups bonded to the boron atom. Secondary and tertiary alkyl esters are generally more stable than the primary alkyl esters. The boron atom in these compounds is in a trigonal coplanar state with bond hybridization. A vacantp orbital exists along the threefold axis perpendicular to the BO plane. 

Formation of Ethers. Very high ether yields can be obtained from alcohols and phenols with dialkyl sulfates in CH2CI2 and concentrated NaOH—tetrabutylammonium chloride at room temperature or slightly elevated temperature within 1—5 h (18). Using excess aqueous caustic—N(C4H2)4HS04, unsymmetrical aUphatic ethers can be prepared with alkyl chlorides at 25—70°C in 3—4 h (19) (see Ethers). 

Addition of alcohols and phenols ia the presence of anhydrous hydrogen chloride gives 0-substituted pseudourea salts (17). The reaction is sluggish except with the lower alcohols, and long reaction time and temperatures up to 100°C are requited to obtain good yields. 

In an analogous manner, DCPD reacts with alcohols and phenols to form ether derivatives, and with halogen acids, thiocyanic acid, and various carboxyhc acids to form esters. These esters are used as perfume components (67). Dicyclopentadiene alcohol and a number of the ethers, esters, and glycol adducts have been claimed as coal and ore flotation aids (68). 

Substitution of chloropolymer is possible using a variety of nucleophiles. The most common are sodium salts of alcohols and phenols. Thermoplastics are obtained using a single substituent, whereas multiple substituents of sufficiently different size lead to elastomers (2). Liquid crystal behavior similar to polysHoxanes has been noted in most homopolymers. The homopolymer formed using trifluoroethanol as a substituent has received a fair amount of academic scmtiny (7). 

The reaction of alcohols and acid chlorides in the presence of magnesium has been described (68). With primary and secondary alcohols the reaction is very smooth, and affords high and sometimes quantitative yields. Difficulty esteritiable hydroxy compounds such as tertiary alcohols and phenols can be esteritied by this method. The reaction carried out in ether or benzene is usually very vigorous with evolution of hydrogen. 

Isopropenyloxytrimethylsilane. In the presence of an acid catalyst the reagent silylates alcohols and phenols. It also silylates carboxylic acids without added catalyst. 

The chemical resistance of the linear polymers is also very good. Resistant to most acids, aqueous bases, hydrocarbons, most halogenated hydrocarbons, alcohols and phenols, they are attacked by concentrated sulphuric acid, formic acid, some amines, benzaldehyde, nitromethane and a few other reagents. They will dissolve in 1-chloronaphthalene at elevated temperatures but in general have excellent solvent resistance. The polymer is cross-linked by air oxidation at elevated temperatures. 

Carboxylic acids react with trifluoroacetic anhydride to give mixed anhydrides that are especially useful for the acylation of hindered alcohols and phenols ... 

The mild nitrating agents thionyl chloride nitrate (equation 2a) and thionyl nitrate (equation 2b) rewith alcohols and phenols to form stable nitrates The trinitrate of 2,6-di(hydroxymethyl)-4-fluorophenol is prepared by either agent [2] (equation 2)... 

Bis(2,2,2-trifluoroethyl)]phosphite can be used to prepaie esters of phos phorous acid by a transestenfication reaction with alcohols and phenols [750] (equation 78)... 

Among the reactions appended to this preparation, the foi-mation of phenylcaibiniide from phenyl mustard oil is desciibetl. It should be noted that phenyl carbimide, like the thiocarbiniide, unites with ammonia, amines, and more especially with alcohols and phenols. The bases yield urea derivatives the alcohols and phenols foim urethanes. 

Bu3Sn)20, benzene, 80°, 2-24 h, 73-100% yield. Only relatively unhindered esters are cleaved with this reagent. Acetates of primary and secondary alcohols and phenols are also cleaved efficiently. ... 

Vinyl formates readily react with amines, alcohols, and phenols to give the formamide or ester. " ... 

II. Halides from Alcohols and Phenols by Triphenylphosphine Dihalide... 

With many organic compounds, aluminium shows high corrosion resistance either in the presence or absence of water. The lower alcohols and phenols are corrosive when they are completely anhydrous —rarely encountered in practice —since repair of breaks in the natural protective oxide film on aluminium cannot take place in the absence of water. Amines generally cause little attack unless very alkaline. 

Figure 17.1 Hydrogen-bonding in alcohols and phenols. A weak attraction between a positively polarized OH hydrogen and a negatively polarized oxygen holds molecules together. The electrostatic potential map of methanol shows the positively polarized O-H hydrogen (blue) and the negatively polarized oxygen (red).

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