Alcohol

This page was taken from the Wikipedia article, accessed January 21, 2007.

Functional group of an alcohol molecule. The carbon atom is attached to other carbon or hydrogen atoms.

In chemistry, an alcohol (Arabic: 'الكحول' transliterated as al kohol) is any organic compound in which a hydroxyl group (-OH) is bound to a carbon atom of an alkyl or substituted alkyl group. The general formula for a simple acyclic alcohol is C_nH_2n+1OH.

In general usage, the word alcohol, when used alone, usually refers to ethanol, also known as grain alcohol or (older) spirits of wine. Ethanol is a strongly-smelling, colorless, volatile liquid formed by the fermentation of sugars. It also often refers to any beverage that contains ethanol (see alcoholic beverage). This sense underlies the term alcoholism (addiction to alcohol).

Other forms of alcohol are usually described with a clarifying adjective, as in isopropyl alcohol (isopropanol) or wood alcohol ('methyl alcohol, or methanol). The suffix -ol appears in the official chemical name of all alcohols.

Structure

The functional group of an alcohol is a hydroxyl group bonded to an sp³ hybridized carbon. It can therefore be regarded as a derivative of water, with an alkyl group replacing one of the hydrogens. If an aryl group is present rather than an alkyl, the compound is generally called a phenol rather than an alcohol. Also, if the hydroxyl group is bonded to one of the sp² hybridized carbons of an alkenyl group, the compound is referred to as an enol. The oxygen in an alcohol has a bond angle of around 109° (c.f. 104.5° in water), and two nonbonded electron pairs. The O-H bond in methanol (CH₃OH) is around 96 picometres long.

Primary, secondary, and tertiary alcohols

There are three major subsets of alcohols- 'primary' (1°), 'secondary' (2°) and 'tertiary' (3°), based upon the number of carbons the C-OH carbon (shown in red) is bonded to. Methanol is the simplest 'primary' alcohol. The simplest secondary alcohol is isopropanol (propan-2-ol), and a simple tertiary alcohol is tert-butanol (2-methylpropan-2-ol).

Some common alcohols

The phenols with parent compound phenol have a hydroxyl group (attached to a benzene ring) just like alcohols but differ sufficiently in properties to warrant a separate treatment.

Methanol and ethanol

The simplest and most commonly used alcohols are methanol (common name methyl alcohol) and ethanol (ethyl alcohol), with the structures shown above in the chart. Methanol was formerly obtained by the distillation of wood and called "wood alcohol." It is now a cheap commodity, the chemical product of carbon monoxide reacting with hydrogen under high pressure. In common usage, "alcohol" often refers to ethanol or "grain alcohol." Methylated spirits ("Meths"), also called "surgical spirits," is a form of ethanol rendered undrinkable by the addition of methanol. Aside from its primary use in alcoholic beverages, ethanol is also used as a highly controlled industrial solvent and raw material.

Automotive

Alcohol is often used as an automotive fuel. Ethanol and methanol can be made to burn more cleanly than gasoline or diesel. Alcohol was once commonly used as an antifreeze in automobile radiators. To add to an internal combustion engine's performance, Methanol may be injected into turbocharged and supercharged engines. This cools the air intake charge, providing a denser air charge.

Scientific, medical, and industrial

Alcohols are in wide use in industry and science as reagents solvents. Because of its low toxicity and ability to dissolve non-polar substances, ethanol is often used as a solvent in medical drugs, perfumes, and vegetable essences such as vanilla. In organic synthesis, alcohols frequently serve as versatile intermediates.

Ethanol is often used as an antiseptic, to disinfect the skin before injections are given, often along with iodine. Ethanol-based soaps are now becoming commonplace within restaurants and are particularly convenient as they do not require drying due to the volatility of the molecule.

Cuisine

In the kitchen, alcoholic beverages are added to dishes not only for their inherent flavors, but also because the alcohol dissolves flavour compounds that water cannot.

Ethanol is commonly used in beverages to promote flavor, reduce social inhibitions, or induce a euphoric intoxication commonly known as drunkenness.

Effects of alcohol on the body

Ethanol is a drug, with potential for overdose or toxic poisoning if taken in excessive quantities. Alcoholism, the physiological or psychological dependency on ethanol, is one of the most common drug addictions. Upon cessation or decrease of use, the physiological dependency can lead to physical withdrawal symptoms, such as restlessness, trouble sleeping, "the shakes," or even death. Not everyone who abuses alcohol becomes physically dependent upon it, but can become psychologically addicted to it. Psychological addiction produces no physical withdrawal symptoms upon cessation of drinking alcohol, but the urge, or craving, to drink again can become quite intense and irresistible.

Alcohol and politics

Ethanol for consumption has been regulated by taxation. Those who manufacture it for other purposes often avoid this expense by "denaturing" it in a manner that renders it unfit for drinking. A common way to do this is by the addition of denatonium benzoate or methanol. "SD-40" and "SD Alcohol" sometimes followed by "40-B" are designations that were established by the United States' Bureau of Alcohol, Tobacco, Firearms and Explosives for this formulation.

Sources

Many alcohols can be created by fermentation of fruits or grains with yeast, but only ethanol is commercially produced this way — chiefly for fuel and drink. Other alcohols are generally produced by synthetic routes from natural gas, petroleum, or coal feed stocks; for example, via acid catalyzed hydration of alkenes. For more details see Preparation of alcohols.

Nomenclature

Systematic names

In the IUPAC system, the name of the alkane chain loses the terminal "e" and adds "ol", e.g. "methanol" and "ethanol". When necessary, the position of the hydroxyl group is indicated by a number between the alkane name and the "ol": propan-1-ol for CH₃CH₂CH₂OH, propan-2-ol for CH₃CH(OH)CH₃. Sometimes, the position number is written before the IUPAC name: 1-propanol and 2-propanol. If a higher priority group is present (such as an aldehyde, ketone or carboxylic acid), then it is necessary to use the prefix "hydroxy", for example: 1-hydroxy-2-propanone (CH₃COCH₂OH).

Some examples of simple alcohols and how to name them:

Examples of alcohols & their names

Common names for alcohols usually takes name of the corresponding alkyl group and add the word "alcohol", e.g. methyl alcohol, ethyl alcohol or tert-butyl alcohol. Propyl alcohol may be n-propyl alcohol or isopropyl alcohol depending on whether the hydroxyl group is bonded to the 1st or 2nd carbon on the propane chain. Isopropyl alcohol is also occasionally called sec-propyl alcohol.

As mentioned above alcohols are classified as primary (1°), secondary (2°) or tertiary (3°), and common names often indicate this in the alkyl group prefix. For example (CH₃)₃COH is a tertiary alcohol is commonly known as tert-butyl alcohol. This would be named 2-methylpropan-2-ol under IUPAC rules, indicating a propane chain with methyl and hydroxyl groups both attached to the middle (#2) carbon.

An alcohol with two hydroxyl groups is commonly called a "glycol", e.g. HO-CH₂-CH₂-OH is ethylene glycol. The IUPAC name is ethane-1,2-diol, "diol" indicating two hydroxyl groups, and 1,2 indicating their bonding positions. Geminal glycols (with the two hydroxyls on the same carbon atom), such as ethane-1,1-diol, are generally unstable. For three or four groups, "triol" and "tetraol" are used.

Etymology

The word "alcohol" almost certainly comes from the Arabic language (the "al-" prefix being the Arabic definite article); however, the precise origin is unclear. A Persian physician named Rhazes discovered this substance, but as he spoke Arabic under Arab rule, the word remains of Arabic origin. It was introduced into Europe, together with the art of distillation and the substance itself, around the 12th century by various European authors who translated and popularized the discoveries of Islamic alchemists [1].

A popular theory, found in many dictionaries, is that it comes from Template:Rtl-lang al-kuḥl, originally the name of very finely powdered antimony sulfide Sb₂S₃ used as an antiseptic and eyeliner. The powder is prepared by sublimation of the natural mineral stibnite in a closed vessel. According to this theory, the meaning of alkuhul would have been first extended to distilled substances in general, and then narrowed to ethanol. This conjectured etymology has been circulating in England since 1672 at least (OED).

However, this derivation is suspicious since the current Arabic name for alcohol, Template:Rtl-lang al-kuḥūl, does not derive from al-kuḥl. The Qur'an, in verse 37:47, uses the word Template:Rtl-lang al-ghawl — properly meaning "spirit" or "demon" — with the sense "the thing that gives the wine its headiness". The word al-ghawl is also the origin of the English word "ghoul", and the name of the star Algol. This derivation would, of course, be consistent with the use of "spirit" or "spirit of wine" as synonymous of "alcohol" in most Western languages. (Incidentally, the etymology "alcohol" = "the devil" was used in the 1930s by the U.S. Temperance movement for propaganda purposes.)

According to the second theory, the popular etymology and the spelling "alcohol" would not be due to generalization of the meaning of al-kuḥl, but rather to Western alchemists and authors confusing the two words al-kuḥl and al-ghawl, which have indeed been transliterated in many different and overlapping ways.

Physical and chemical properties

The hydroxyl group generally makes the alcohol molecule polar. Those groups can form hydrogen bonds to one another and to other compounds. Two opposing solubility trends in alcohols are: the tendency of the polar OH to promote solubility in water, and of the carbon chain to resist it. Thus, methanol, ethanol, and propanol are miscible in water because the hydroxyl group wins out over the short carbon chain. Butanol, with a four-carbon chain, is moderately soluble because of a balance between the two trends. Alcohols of five or more carbons (Pentanol and higher) are effectively insoluble because of the hydrocarbon chain's dominance.

Because of hydrogen bonding, alcohols tend to have higher boiling points than comparable hydrocarbons and ethers. The boiling point of the alcohol Ethanol is 78.29 °C, compared to 69 °C for the hydrocarbon Hexane (a common constituent of gasoline), and 34.6 °C for Diethyl ether. All simple alcohols are miscible in organic solvents. This hydrogen bonding means that alcohols can be used as protic solvents.

The lone pairs of electrons on the oxygen of the hydroxyl group also makes alcohols nucleophiles.

Alcohols, like water, can show either acidic or basic properties at the O-H group. With a pK_a of around 16-19 they are generally slightly weaker acids than water, but they are still able to react with strong bases such as sodium hydride or reactive metals such as sodium. The salts that result are called alkoxides, with the general formula RO^- M⁺.

Meanwhile the oxygen atom has lone pairs of nonbonded electrons that render it weakly basic in the presence of strong acids such as sulfuric acid. For example, with methanol:

Alcohols can also undergo oxidation to give aldehydes, ketones or carboxylic acids, or they can be dehydrated to alkenes. They can react to form ester compounds, and they can (if activated first) undergo nucleophilic substitution reactions. For more details see the reactions of alcohols section below.

Toxicity

Alcohols often have an odor described as 'biting' that 'hangs' in the nasal passages. Ethanol in the form of alcoholic beverages has been consumed by humans since pre-historic times, for a variety of hygienic, dietary, medicinal, religious, and recreational reasons. While infrequent consumption of ethanol in small quantities may be harmless or even beneficial, larger doses result in a state known as drunkenness or intoxication (which may lead to a hangover the next day) and, depending on the dose and regularity of use, can cause acute respiratory failure or death and with chronic use has medical repercussions. Alcohol has also been known to be a catalyst for reckless behaviors that may have undesirable results, such as accidents, fighting, and unprotected sex. The LD₅₀ of ethanol in rats 11,300 mg/kg.[2] This ratio would correspond to an 80kg (176.4lb) man drinking 65 shots of 80 proof alcohol, although the LD₅₀ does not necessarily translate directly to humans. A more accurate but less precise figure would estimate the LD₅₀ of the same 80kg (176.4lb) at about 15.5 shots of 80 proof alcohol.[3]

Other alcohols are substantially more poisonous than ethanol, partly because they take much longer to be metabolized, and often their metabolism produces even more toxic substances. Methanol, or wood alcohol, for instance, is oxidized by alcohol dehydrogenase enzymes in the liver to the poisonous formaldehyde, which can cause blindness or death.

An effective treatment to prevent formaldehyde toxicity after methanol ingestion is to administer ethanol. Alcohol dehydrogenase has a higher affinity for ethanol, thus preventing methanol from binding and acting as a substrate. Any remaining methanol will then have time to be excreted through the kidneys. Remaining formaldehyde will be converted to formic acid and excreted.

Preparation of alcohols

Laboratory

Several methods exist for the preparation of alcohols in the laboratory.

• Primary alkyl halides react with aqueous NaOH or KOH mainly to primary alcohols in nucleophilic aliphatic substitution. (Secondary and especially tertiary alkyl halides will give the elimination (alkene) product instead).
• Aldehydes or ketones are reduced with sodium borohydride or lithium aluminium hydride (after an acidic workup). Another reduction by aluminumisopropylates is the Meerwein-Ponndorf-Verley reduction.
• Alkenes engage in an acid catalysed hydration reaction using concentrated sulfuric acid as a catalyst which gives usually secondary or tertiary alcohols.
• The hydroboration-oxidation and oxymercuration-reduction of alkenes are more reliable in organic synthesis.
• Grignard reagents react with carbonyl groups to secondary and tertiary alcohols
• Noyori asymmetric hydrogenation is the asymmetric reduction of β-keto-esters

The formation of a secondary alcohol via reduction and hydration is shown:

Industrial

Industrially alcohols are produced in several ways:

• By fermentation using glucose produced from sugar from the hydrolysis of starch, in the presence of yeast and temperature of less than 37°C to produce ethanol. For instance the conversion of invertase to glucose and fructose or the conversion of glucose to zymase and ethanol.
• By direct hydration using ethene or other alkenes from cracking of fractions of distilled crude oil. Uses a catalyst of phosphoric acid under high temperature and pressure.
• Methanol is produced from water gas: It is manufactured from synthesis gas, where carbon monoxide and 2 equivalents of hydrogen gas are combined to produce methanol using a copper, zinc oxide and aluminium oxide catalyst at 250°C and a pressure of 50-100 atm.

Reactions of alcohols

Deprotonation

Alcohols can behave as weak acids, undergoing deprotonation. The deprotonation reaction to produce an alkoxide salt is either performed with a strong base such as sodium hydride or n-butyllithium, or with sodium or potassium metal.

2 R-OH + 2 NaH → 2 R-O^-Na⁺ + H₂↑

2 R-OH + 2Na → 2R-O⁻Na + H₂

E.g. 2 CH₃CH₂-OH + 2 Na → 2 CH₃-CH₂-O⁻Na + H₂

Water is similar in pK_a to many alcohols, so with sodium hydroxide there is an equilibrium set up which usually lies to the left:

R-OH + NaOH <=> R-O^-Na⁺ + H₂O (equilibrium to the left)

It should be noted, though, that the bases used to deprotonate alcohols are strong themselves. The bases used and the alkoxides created are both highly moisture sensitive chemical reagents.

The acidity of alcohols is also affected by the overall stability of the alkoxide ion. Electron-withdrawing groups attached to the carbon containing the hydroxyl group will serve to stabilize the alkoxide when formed, thus resulting in greater acidity. On the other hand, the presence of electron-donating group will result in a less stable alkoxide ion formed. This will result in a scenario whereby the unstable alkoxide ion formed will tend to accept a proton to reform the original alcohol.

With alkyl halides alkoxides give rise to ethers in the Williamson ether synthesis.

Nucleophilic substitution

The OH group is not a good leaving group in nucleophilic substitution reactions, so neutral alcohols do not react in such reactions. However if the oxygen is first protonated to give R−OH₂⁺, the leaving group (water) is much more stable, and nucleophilic substitution can take place. For instance, tertiary alcohols react with hydrochloric acid to produce tertiary alkyl halides, where the hydroxyl group is replaced by a chlorine atom. If primary or secondary alcohols are to be reacted with hydrochloric acid, an activator such as zinc chloride is needed. Alternatively the conversion may be performed directly using thionyl chloride.^[1]

Alcohols may likewise be converted to alkyl bromides using hydrobromic acid or phosphorus tribromide, for example:

3 R-OH + PBr₃ → 3 RBr + H₃PO₃

In the Barton-McCombie deoxygenation an alcohol is deoxygenated to an alkane with tributyltin hydride or a trimethylborane-water complex in a radical substitution reaction.

Dehydration

Alcohols are themselves nucleophilic, so R−OH₂⁺ can react with ROH to produce ethers and water in a dehydration reaction, although this reaction is rarely used except in the manufacture of diethyl ether.

More useful is the E1 elimination reaction of alcohols to produce alkenes. The reaction generally obeys Zaitsev's Rule, which states that the most stable (usually the most substituted) alkene is formed. Tertiary alcohols eliminate easily at just above room temperature, but primary alcohols require a higher temperature.

This is a diagram of acid catalysed dehydration of ethanol to produce ethene:

A more controlled elimination reaction is the Chugaev elimination with carbon disulfide and iodomethane.

Esterification

To form an ester from an alcohol and a carboxylic acid the reaction, known as Fischer esterification, is usually performed at reflux with a catalyst of concentrated sulfuric acid:

R-OH + R'-COOH → R'-COOR + H₂O

In order to drive the equilibrium to the right and produce a good yield of ester, water is usually removed, either by an excess of H₂SO₄ or by using a Dean-Stark apparatus. Esters may also be prepared by reaction of the alcohol with an acid chloride in the presence of a base such as pyridine.

Other types of ester are prepared similarly- for example tosyl (tosylate) esters are made by reaction of the alcohol with p-toluenesulfonyl chloride in pyridine.

Oxidation

Primary alcohols generally give aldehydes or carboxylic acid upon oxidation, while secondary alcohols give ketones. Traditionally strong oxidants such as the dichromate ion or potassium permanganate are used, under acidic conditions, for example:

3 CH₃-CH(-OH)-CH₃ + K₂Cr₂O₇ + 4 H₂SO₄ → 3 CH₃-C(=O)-CH₃ + Cr₂(SO₄)₃ + K₂SO₄ + 7 H₂O

Frequently in aldehyde preparations these reagents cause a problem of over-oxidation to the carboxylic acid. To avoid this, other reagents such as PCC, Dess-Martin periodinane, 2-Iodoxybenzoic acid, TPAP or methods such as Swern oxidation and Corey-Kim oxidation are now preferred. In the Guerbet reaction aliphatic alcohols dimerize with an initial oxidation step.

Alcohols with a methyl group attached to the alcohol carbon can also undergo a haloform reaction (such as the iodoform reaction) in the presence of the halogen and a base such as sodium hydroxide.

Tertiary alcohols resist oxidation, but can be oxidised by reagents such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

References

• Sci-toys website explanation of denatured alcohol designations

External links

• Science Aid: Alcohols Aimed at high school students
• What Is Alcohol, Anyway? Interesting information about alcohols.