Alcohol

From Wikipedia, the free encyclopedia

In chemistry, an alcohol is any organic compound in which a hydroxyl group (–OH) is bound to a carbon atom of an alkyl or substituted alkyl group. An important group of acohols is formed by the simple acyclic alcohols, the general formula for which is C_nH_2n+1OH. Of those, ethanol (C₂H₅OH) is the type of alcohol found in alcoholic beverages, and in common speech the word alcohol means, specifically, ethanol.

Other alcohols are usually described with a clarifying adjective, as in isopropyl alcohol (propan-2-ol) or wood alcohol (methyl alcohol, or methanol). The suffix -ol appears in the IUPAC chemical name of all alcohols.

There are three major subsets of alcohols: primary (1°), secondary (2°) and tertiary (3°), based upon the number of carbon atoms the C-OH group’s carbon (shown in red) is bonded to. Ethanol is a simple ‘primary’ alcohol. The simplest secondary alcohol is isopropyl alcohol (propan-2-ol), and a simple tertiary alcohol is tert-butyl alcohol (2-methylpropan-2-ol).

Contents [hide] 1 Simple alcohols 2 Nomenclature 2.1 Systematic names 2.2 Etymology 3 Physical and chemical properties 4 Applications 5 Production 5.1 Endogenous 6 Laboratory synthesis 7 Reactions 7.1 Deprotonation 7.2 Nucleophilic substitution 7.3 Dehydration 7.4 Esterification 7.5 Oxidation 8 Toxicity 9 Occurrence in nature 10 See also 11 References 12 Bibliography

Simple alcohols

The simplest and most commonly used alcohols are methanol and ethanol. Methanol was formerly obtained by the distillation of wood and called “wood alcohol.”

One sip of methanol (as little as 10ml) can cause permanent blindness by destruction of the optic nerve.^[1]

Apart from its familiar role in alcoholic beverages, ethanol is also used as a highly controlled industrial solvent and raw material. To avoid the high taxes on ethanol for consumption, additives are added to make it unpalatable (such as denatonium benzoate—”Bitrex”) or poisonous (such as methanol). Ethanol in this form is known generally as denatured alcohol; when methanol is used, it may be referred to as methylated spirits (“Meths”) or “surgical spirits”.

Two other alcohols whose uses are relatively widespread (though not so much as those of methanol and ethanol) are propanol and butanol. Like ethanol, they can be produced by fermentation processes. (However, the fermenting agent is a bacterium, Clostridium acetobutylicum, that feeds on cellulose, not sugars like the Saccharomyces yeast that produces ethanol.)

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”.^[2] 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”,^[2] for example: 1-hydroxy-2-propanone (CH₃COCH₂OH).

Some examples of simple alcohols and how to name them:

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.

Primary alcohol (1°)– Have general formulas RCH₂OH Secondary alcohol (2°)– Have general formulas RR’CHOH Tertiary alcohol (3°)– Have general formulas RR’RCOH Hydrogen bond strength order: 1°>2°>3° Boiling point order: 1°>2°>3° Acidity order: 1°>2°>3°

Etymology

Look up alcohol in Wiktionary, the free dictionary.

The word alcohol appears in English in the 16th century, loaned via French from medical Latin, ultimately from the Arabic الكحل (al-kuḥl, “the kohl, a powder used as an eyeliner”).

ال al is Arabic for the definitive article, the in English.

The current Arabic name for alcohol is الكحول al-kuḥūl, re-introduced from western usage.

kuḥl was the name given to the very fine powder, produced by the sublimation of the natural mineral stibnite to form antimony sulfide Sb₂S₃ (hence the essence or “spirit” of the substance), which was used as an antiseptic and eyeliner.

Bartholomew Traheron in his 1543 translation of John of Vigo introduces the word as a term used by “barbarous” (Moorish) authors for “fine powder”:

the barbarous auctours use alcohol, or (as I fynde it sometymes wryten) alcofoll, for moost fine poudre.

William Johnson in his 1657 Lexicon Chymicum glosses the word as antimonium sive stibium. By extension, the word came to refer to any fluid obtained by distillation, including “alcohol of wine”, the distilled essence of wine. Libavius in Alchymia (1594) has vini alcohol vel vinum alcalisatum. Johnson (1657) glosses alcohol vini as quando omnis superfluitas vini a vino separatur, ita ut accensum ardeat donec totum consumatur, nihilque fæcum aut phlegmatis in fundo remaneat. The word’s meaning became restricted to “spirit of wine” (ethanol) in the 18th century, and was again extended to the family of substances so called in modern chemistry from 1850.

Physical and chemical properties

Alcohols have an odor that is often described as “biting” and as “hanging” in the nasal passages.

The hydroxyl group generally makes the alcohol molecule polar. Those groups can form hydrogen bonds to one another and to other compounds. This hydrogen bonding means that alcohols can be used as protic solvents. 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 in water because of the hydrocarbon chain’s dominance. All simple alcohols are miscible in organic solvents.

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.

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. The lone pairs of electrons on the oxygen of the hydroxyl group also makes alcohols nucleophiles. For more details see the reactions of alcohols section below.

Applications

Alcohols can be used as a beverage (ethanol only), as fuel and for many scientific, medical, and industrial utilities. Ethanol in the form of alcoholic beverages has been consumed by humans since pre-historic times. A 50% v/v solution of ethylene glycol in water is commonly used as an antifreeze.

Some alcohols, mainly ethanol and methanol, can be used as an alcohol fuel. Fuel performance can be increased in forced induction internal combustion engines by injecting alcohol into the air intake after the turbocharger or supercharger has pressurized the air. This cools the pressurized air, providing a denser air charge, which allows for more fuel, and therefore more power.

Alcohols have applications in industry and science as reagents or solvents. Because of its low toxicity and ability to dissolve non-polar substances, ethanol can be used as a solvent in medical drugs, perfumes, and vegetable essences such as vanilla. In organic synthesis, alcohols serve as versatile intermediates.

Ethanol can be used as an antiseptic to disinfect the skin before injections are given, often along with iodine. Ethanol-based soaps are becoming common in restaurants and are convenient because they do not require drying due to the volatility of the compound. Alcohol is also used as a preservative for specimens.

Alcohol gels have become common as hand sanitizers.

Production

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 ethylene (ethylene hydration^[4]) or other alkenes from cracking of fractions of distilled crude oil.

Endogenous

Several of the benign bacteria in the intestine use fermentation as a form of anaerobic respiration. This metabolic reaction produces ethanol as a waste product, just like aerobic respiration produces carbon dioxide and water. Thus, human bodies inevitably contain some quantity of alcohol endogenously produced by these bacteria.

Laboratory synthesis

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 aluminiumisopropylates 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. Alkenes react with NBS and water in halohydrin formation reaction
• Grignard reagents react with carbonyl groups to secondary and tertiary alcohols. Related reactions are the Barbier reaction and the Nozaki-Hiyama reaction.
• Noyori asymmetric hydrogenation is the asymmetric reduction of β-keto-esters
• Amines can be converted to diazonium salts which are then hydrolyzed.

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

Reactions

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⁺ + 2H₂↑

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 the 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 by unimolecular nucleophilic substitution. 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 (R-CH₂-OH) can be oxidized either to aldehydes (R-CHO) or to carboxylic acids (R-CO₂H), while the oxidation of secondary alcohols (R¹R²CH-OH) normally terminates at the ketone (R¹R²C=O) stage. Tertiary alcohols (R¹R²R³C-OH) are resistant to oxidation.

The direct oxidation of primary alcohols to carboxylic acids normally proceeds via the corresponding aldehyde, which is transformed via an aldehyde hydrate (R-CH(OH)₂) by reaction with water before it can be further oxidized to the carboxylic acid.

Often it is possible to interrupt the oxidation of a primary alcohol at the aldehyde level by performing the reaction in absence of water, so that no aldehyde hydrate can be formed.

Reagents useful for the transformation of primary alcohols to aldehydes are normally also suitable for the oxidation of secondary alcohols to ketones. These include:

• Chromium-based reagents, such as Collins reagent (CrO₃·Py₂), PDC or PCC.
• Activated DMSO, resulting from reaction of DMSO with electrophiles, such as oxalyl chloride (Swern oxidation), a carbodiimide (Pfitzner-Moffatt oxidation) or the complex SO₃·Py (Parikh-Doering oxidation).
• Hypervalent iodine compounds, such as Dess-Martin periodinane or 2-Iodoxybenzoic acid.
• Catalytic TPAP in presence of excess of NMO (Ley oxidation).
• Catalytic TEMPO in presence of excess bleach (NaOCl) (Anelli’s oxidation).

Allylic and benzylic alcohols can be oxidized in presence of other alcohols using certain selective oxidants such as manganese dioxide (MnO₂).

Reagents useful for the oxidation of secondary alcohols to ketones, but normally inefficient for oxidation of primary alcohols to aldehydes, include chromium trioxide (CrO₃) in a mixture of sulfuric acid and acetone (Jones oxidation) and certain ketones, such as cyclohexanone, in the presence of aluminium isopropoxide (Oppenauer oxidation).

The direct oxidation of primary alcohols to carboxylic acids can be carried out using:

• Potassium permanganate (KMnO₄).
• Jones oxidation.
• PDC in DMF.
• Heyns oxidation.
• Ruthenium tetroxide (RuO₄).
• TEMPO.

Alcohols possessing two hydroxy groups located on adjacent carbons —that is, 1,2-diols— suffer oxidative breakage at a carbon-carbon bond with some oxidants such as sodium periodate (NaIO₄) or lead tetraacetate (Pb(OAc)₄), resulting in generation of two carbonyl groups.

Toxicity

Ethanol in alcoholic beverages has been consumed by humans since prehistoric times for a variety of hygienic, dietary, medicinal, religious, and recreational reasons. The consumption of large doses of ethanol causes drunkenness (intoxication), which may lead to a hangover as its effects wear off. Depending upon the dose and the regularity of its consumption, ethanol can cause acute respiratory failure or death. Because ethanol impairs judgment in humans, it can be a catalyst for reckless or irresponsible behavior.

The LD₅₀ of ethanol in rats is 10,300 mg/kg.^[5] Other alcohols are substantially more poisonous than ethanol, partly because they take much longer to be metabolized and partly because their metabolization produces substances that are even more toxic. Methanol (wood alcohol), for instance, is oxidized to the poisonous formaldehyde in the liver by alcohol dehydrogenase enzymes; this can cause blindness or death.^[1]

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.^[6][7]

Methanol itself, while poisonous, has a much weaker sedative effect than ethanol. Some longer-chain alcohols such as n-propanol, isopropanol, n-butanol, t-butanol and 2-methyl-2-butanol do however have stronger sedative effects, but also have higher toxicity than ethanol.^[8][9] These longer chain alcohols are found as contaminants in some alcoholic beverages and are known as fusel alcohols,^[10][11] and are reputed to cause severe hangovers although it is unclear if the fusel alcohols are actually responsible.^[12] Many longer chain alcohols are used in industry as solvents and are occasionally abused by alcoholics,^[13][14] leading to a range of adverse health effects.^[15]

Occurrence in nature

Alcohol has been found outside the Solar system. It can be found in low densities in star and planetary system forming regions of space.

See

• http://www.springerlink.com/content/u3p6612j611w2hqv/
• http://www.physics.uq.edu.au/people/ross/phys2080/ism/ism.htm (species found)
• Astrophysical maser (species found)

See also

Wikiquote has a collection of quotations related to: Alcohol

Look up alcohol in Wiktionary, the free dictionary.

• Alcohol fuel
• Alcoholic beverage
• Blood alcohol content
• Breathalyzer
• Fatty alcohol
• Fetal alcohol syndrome
• History of alcohol
• List of countries by alcohol consumption
• Oxidation of primary alcohols to carboxylic acids
• Oxidation of secondary alcohols to ketones
• Phenols
• Rubbing alcohol
• Sugar alcohol
• Surrogate alcohol
• Transesterification
• Cooking with alcohol

References

1. ^ ^{a b} “Methanol and Blindness“. Ask A Scientist, Chemistry Archive. http://www.newton.dep.anl.gov/askasci/chem03/chem03561.htm. Retrieved 22 May 2007.  
2. ^ ^{a b} William Reusch. “Alcohols“. VirtualText of Organic Chemistry. http://www.cem.msu.edu/~reusch/VirtualText/alcohol1.htm#alcnom. Retrieved 2007-09-14.  
3. ^ Global Status Report on Alcohol 2004
4. ^ Lodgsdon, J.E. (1994). “Ethanol.” In J.I. Kroschwitz (Ed.) Encyclopedia of Chemical Technology, 4th ed. vol. 9, p. 820. New York: John Wiley & Sons.
5. ^ Robert S. Gable (2004). “Comparison of acute lethal toxicity of commonly abused psychoactive substances” (reprint). Addiction 99 (6): 686–696. doi:10.1111/j.1360-0443.2004.00744.x. http://web.cgu.edu/faculty/gabler/toxicity%20Addiction%20offprint.pdf. 
6. ^ Zimmerman HE, Burkhart KK, Donovan JW. Ethylene glycol and methanol poisoning: diagnosis and treatment. Journal of Emergency Nursing. 1999 Apr;25(2):116-20. PMID 10097201
7. ^ Lobert S. Ethanol, isopropanol, methanol, and ethylene glycol poisoning. Critical Care Nurse. 2000 December;20(6):41-7. PMID 11878258
8. ^ McKee M, Suzcs S, Sárváry A, Adany R, Kiryanov N, Saburova L, Tomkins S, Andreev E, Leon DA. The composition of surrogate alcohols consumed in Russia. Alcoholism, Clinical and Experimental Research. 2005 October;29(10):1884-8. PMID 16269919
9. ^ Bunc M, Pezdir T, Mozina H, Mozina M, Brvar M. Butanol ingestion in an airport hangar. Human and Experimental Toxicology. 2006 Apr;25(4):195-7. PMID 16696295
10. ^ Woo KL. Determination of low molecular weight alcohols including fusel oil in various samples by diethyl ether extraction and capillary gas chromatography. Journal of AOAC International. 2005 September-October;88(5):1419-27. PMID 16385992
11. ^ Lachenmeier DW, Haupt S, Schulz K. Defining maximum levels of higher alcohols in alcoholic beverages and surrogate alcohol products. Regulatory Toxicology and Pharmacology. 2008 Apr;50(3):313-21. PMID 18295386
12. ^ Hori H, Fujii W, Hatanaka Y, Suwa Y. Effects of fusel oil on animal hangover models. Alcohol Clinical and Experimental Research. 2003 Aug;27(8 Suppl):37S-41S. PMID 12960505
13. ^ Wiernikowski A, Piekoszewski W, Krzyzanowska-Kierepka E, Gomułka E. Acute oral poisoning with isopropyl alcohol in alcoholics. (Polish) Przeglad Lekarski. 1997;54(6):459-63. PMID 9333902
14. ^ Mańkowski W, Klimaszyk D, Krupiński B. How to differentiate acute isopropanol poisoning from ethanol intoxication? — a case report. (Polish) Przeglad Lekarski 2000;57(10):588-90. PMID 11199895
15. ^ Bogomolova IN, Bukeshov MK, Bogomolov DV. The forensic medical diagnosis of intoxication of alcohol surrogates by morphological findings. (Russian) Sudebno Meditsinskaia Ekspertiza. 2004 September-October;47(5):22-5. PMID 15523882

Bibliography