Alcohol

Alcohols are compound that have hydroxyl groups bonded to saturate sp 3 hybridized carbon
atoms, while phenols are compounds that have hydroxyl groups bonded to aromatic ring.
Both can be thought of as organic derivatives of water in which one of he water hydrogen I
replaced by an organic group: H-O-H versus R-O-H or Ar-O-OH.
Alcohol occur widely in nature and have many industrial and pharmaceutical applications.
Methanol and ethanol, for instance are two of the most important of all industrial chemicals.
Prior to the development of the modern chemical industry, methanol was prepared by heating
wood in the absence of air and thus came to be called wood alcohol. Today approximately 1.7
billion gallons of methanol manufactured each year in united states by catalytic reduction of
carbon monoxide with hydrogen gas.
McMurry, John. 1999. Organic Chemistry 5th edition. Pacific Grove : BROOKS/COLE. Page
654, 655
Every year in the United States about 25,000 people are killed and 500,000 more are injured
as a result of drunk driving. In spite of efforts to educate the public about the dangers of
driving
while intoxicated and stiffer penalties for drunk driving offenses, law enforcement agencies
still have to devote a great deal of work to removing drunk drivers from Americas roads. The
police often use a device called a breathalyzer to test drivers suspected of being drunk. The
chemical basis of this device is a redox reaction. A sample of the drivers breath is drawn into
the breathalyzer, where it is treated with an acidic solution of potassium dichromate. The
alcohol (ethanol) in the breath is
converted to acetic acid as shown in the following equation:
In this reaction, the ethanol is oxidized to acetic acid and the chromium(VI) in the orangeyellow dichromate ion is reduced to the green chromium(III) ion (see Figure 4.22 ). The
drivers
Breathalyzer blood alcohol level can be determined readily by measuring the degree of this
color change (read from a calibrated meter on the instrument). The current legal limit of
blood alcohol content in most states is 0.1 percent by mass. Anything higher constitutes
intoxication.
Chang, Raymond. 2010. Chemistry 10th edition. New York : McGraw-Hill. Page 146
The structure and properties of three simple alcoholsmethanol, 2-propanol, and ethylene
glycolare given in Figure 9.3. Ethanol (CH3CH2OH), formed by the fermentation of the
carbohydrates in grains, grapes, and potatoes, is the alcohol present in alcoholic beverages. It
is perhaps the fi rst organic compound synthesized by humans, because alcohol production

has been known for at least 4000 years. Ethanol depresses the central nervous system,
increases the production of stomach acid, and dilates blood vessels, producing a fl ushed
appearance. Ethanol is also a common laboratory solvent, which is sometimes made unfit to
ingest by adding small amounts of benzene or methanol (both of which are toxic). Ethanol is
a common gasoline additive, widely touted as an environmentally friendly fuel source. Two
common gasolineethanol fuels are gasohol, which contains 10% ethanol, and E-85, which
contains 85% ethanol. Ethanol is now routinely prepared from the carbohydrates in corn
(Figure 9.4). Starch, a complex carbohydrate polymer, can be hydrolyzed to the simple sugar
glucose, which forms ethanol by the process of fermentation. Combining ethanol with
gasoline forms a usable fuel, which combusts to form CO2, H2O, and a great deal of energy.
Since green plants use sunlight to convert CO2 and H2O to carbohydrates during
photosynthesis, next years corn crop removes CO2 from the atmosphere to make new
molecules of starch as the corn grows. While in this way ethanol is a renewable fuel source,
the need for large-scale farm equipment and the heavy reliance on fertilizers and herbicides
make ethanol expensive to produce. Moreover, many criticize the use of valuable farmland
for an energy-producing crop rather than for food production. As a result, discussion
continues on ethanol as an alternative to fossil fuels.
Methanol (CH3OH) is also called wood alcohol, because it can be obtained by heating wood
at high temperatures in the absence of air. Methanol is extremely toxic because of the
oxidation products formed when it is metabolized in the liver (Section 12.14). Ingestion of as
little as 15 mL
causes blindness, and 100 mL causes death.
2-Propanol [(CH3)2CHOH] is the major component of rubbing alcohol. When rubbed on the
skin it evaporates readily, producing a pleasant cooling sensation. Because it has weak
antibacterial properties, 2-propanol is used to clean skin before minor surgery and to sterilize
medical instruments.
Ethylene glycol (HOCH2CH2OH) is the major component of antifreeze. It is readily
prepared from ethylene oxide by reactions discussed in Section 9.15. It is sweet tasting but
toxic.
Smith, Janice Gorzynski. 2013. Organic Chemistry 3rd edition. New York : McGraw-Hill.
Page 313, 314,319
An alcohol has both a nonpolar alkyl group and a polar OH group. So is an alcohol molecule
nonpolar or polar? Is it soluble in a nonpolar solvent, or is it soluble in water? The answer

depends on the size of the alkyl group. As the alkyl group increases in size, it becomes a more
significant fraction of the alcohol molecule and the compound becomes less and less soluble
in water. In other words, the molecule becomes more and more like an alkane. Four carbons
tend to be the dividing line at room temperature. Alcohols with fewer than four carbons are
soluble in water, but alcohols with more than four carbons are insoluble in water. In other
words, an OH group can drag about three or four carbons into solution in water.
The four-carbon dividing line is only an approximate guide because the solubility of an
alcohol also depends on the structure of the alkyl group. Alcohols with branched alkyl groups
are more soluble in water than alcohols with nonbranched alkyl groups with the same number
of carbons, because branching minimizes the contact surface of the nonpolar portion of the
Bruice, Paula Yurkanis. 2013. Organic Chemistry 7th edition. New Jersey : Prentice Hall. Page
87
Normal Fischer esterification of tertiary alcohols is unsatisfactory because the acid catalyst
required causes dehydration or rearrangement of the tertiary substrate. Moreover, reactions
with acid chlorides or anhydrides are also of limited value for similar reasons. However,
treatment of acetic anhydride with calcium carbide (or calcium hydride) followed by addition
of the dry tertiary alcohol gives the desired acetate in good yield.
Monson, Ricard S. 1971. Advanced Organic Synthesis : Methods and Techniques. London :
Academic press. Page 62
Alcohols were introduced in Chapter 4 and have appeared regularly since then. With this
chapter we extend our knowledge of alcohols, particularly with respect to their relationship to
carbonyl-containing compounds. In the course of studying alcohols, we shall also look at
some relatives. Diols are alcohols in which two hydroxyl groups (OH) are present; thiols are
compounds that contain an SH group. Phenols, compounds of the type ArOH, share many
properties in common with alcohols but are sufficiently different from them to warrant
separate.
Until the 1920s, the major source of methanol was as a byproduct in the production of
charcoal from woodhence, the name wood alcohol. Now, most of the more than 10 billion
lb of methanol used annually in the United States is synthetic, prepared by reduction of
carbon monoxide with hydrogen.

Almost half of this methanol is converted to formaldehyde as a starting material for various
resins and plastics. Methanol is also used as a solvent, as an antifreeze, and as a convenient
clean-burning liquid fuel. This last property makes it a candidate as a fuel for automobiles
methanol is already used to power Indianapolis-class race cars but extensive emissions
tests remain to be done before it can be approved as a gasoline substitute. Methanol is a
colorless liquid, boiling at 65C, and is miscible with water in all proportions. It is poisonous;
drinking as little as 30 mL has been fatal. Ingestion of sublethal amounts can lead to
blindness. When vegetable matter ferments, its carbohydrates are converted to ethanol and
carbon dioxide by enzymes present in yeast. Fermentation of barley produces beer; grapes
give wine. The maximum ethanol content is on the order of 15%, because higher
concentrations inactivate the enzymes, halting fermentation. Since ethanol boils at 78C
Carey, Francis A. 2000. Organic Chemistry 4 th edition. New York : McGraw-Hill. Page 579,
580
The controlled oxidation of primary and secondary alcohols yields compounds which have
less hydrogen on the carbon atom to which the hydroxyl group is attached. The oxidation
products of primary alcohols are represented by the general formula RCHO and are called
aldehydes; the products from secondary alcohols have the general formula R2CO and are
called ketones. Both compounds have the carbonyl (CO) group as a functional group.
Oxidation on a large scale may be accomplished by dehydrogenation. For oxidation in the
laboratory, an acid-dichromate mixture, or manganese dioxide and sulfuric acid are used. The
use of these reagents is limited to the preparation of aldehydes and ketones that boil below
100. If the products are not removed as they are formed, further oxidation to acids generally
occurs. Under these conditions some of the alcohol unites with the acid, producing esters.
Generally, the yield of aldehydes and ketones obtained by oxidation of alcohol in the aqueous
phase is poor. The amount of oxidizing agent is calculated in the usual way:

Thus it is easy to calculate that a third of a mole of dichromate is required for every mole of
alcohol. Atmospheric oxygen may be used as the oxidizing agent. When a mixture of alcohol
vapor and air is passed over hot copper, the following reactions occur:

In the laboratory (for tests), the process can be demonstrated by heating a copper spiral and
plunging it into a dilute aqueous solution of methyl alcohol. The film of copper oxide acts as
the oxidizing gent; the process is then repeated until all of the alcohol is oxidized.
Cheronia, Nicholas D. 1942. Semimicro and Macro Organic Chemistry. New York : Thomas
Y. Crowell Company. Page 183
How do the alcohols from LiA1H 4 or catalytic reduction of ketones differ from those derived
from aldehydes? Ketones yield 2" alcohols while aldehydes give 1" alcohols

Herbert, Meislich. 1999. Schaums outline of theory and problems of organic chemistry. New
York : McGraw-Hill. Page 261

- Caryophyllene Alcohol

Corey, E. J. and Xue-Min Chelg. 2000. The Logic of Chemical Synthesis. New York : John
Wiley and Sons. Page 156