Organic Chemistry

Organic chemistry is the chemistry of carbon compounds. All organic compounds contain carbon; however, there are some compounds of carbon that are not classified as organic. For example, salts such as carbonates (e.g., Na₂CO₃, CaCO₃) and cyanides (e.g., NaCN, KCN) are usually designated as inorganic. Perhaps a more useful description might be: Organic compounds are compounds of carbon that usually contain hydrogen and that may also contain other elements such as oxygen, nitrogen, sulfur, phosphorus, or halogen (F, Cl, Br, or I). In any case, there are very few carbon compounds that are not organic, while there are millions that are.

History

Prehistoric civilizations obtained many useful chemicals from plants and animals. They were familiar with sugar, which they learned to ferment to make wine. Then they found that the wine could turn into vinegar. Ancient Egyptians used blue dye made from the indigo in madder root, and a royal purple dye extracted from a rare kind of mollusk. Soap was made by heating animal fat with base from wood ashes.

During the Middle Ages dry distillation of wood yielded mixtures of methyl alcohol, acetone, and acetic acid. Alchemists isolated cholesterol from gallstones, morphine from opium, and drugs such as quinine, strychnine, and brucine from various plants. Two hundred years ago chemists such as Antoine Lavoisier determined the elemental composition of many of these substances and noted that they all contained carbon and hydrogen, and that many also contained oxygen and nitrogen. It also appeared that there were two classes of materials: the mineral type (generally hard, high-melting, and noncombustible), and the organic type (often soft, liquid or low melting solids, and frequently easily combustible materials). Most organic chemicals could be burned to produce carbon dioxide; and any hydrogen present was converted to water (H₂O). Because organic compounds had for centuries been isolated only from plants and animals, it was commonly believed that some "vital force" in living things was necessary to produce them. This belief persisted until 1828, when Friedrich Wöhler was able to make urea, a chemical found in the urine of animals, from the inorganic salt ammonium cyanate.

Since that time organic chemistry has grown into a vast and ever expanding field that encompasses millions of chemical compounds.

Scope of Organic Chemistry

The field of organic chemistry includes more than twenty million compounds for which properties have been determined and recorded in the literature. Many hundreds of new compounds are added every day. Much more than half of the world's chemists are organic chemists. Some new organic compounds are simply isolated from plants or animals; some are made by modifying naturally occurring chemicals; but most new organic compounds are actually synthesized in the laboratory from other (usually smaller) organic molecules. Over the years organic chemists have developed a broad array of reactions that allow them to make all kinds of complex products from simpler starting materials.

Singular Attributes of Carbon

When one considers the millions of chemical compounds that are known and notes that more than 95 percent of them are compounds of carbon, one realizes that carbon is unique. Why are there so many carbon compounds? It turns out that atoms of carbon are quite remarkable in a number of ways.

Carbon atoms form very strong bonds with other carbon atoms. The bonds are so strong that carbon can form long chains, some containing thousands of carbon atoms. (Carbon is the only element that can do this.)

A carbon atom forms four bonds, therefore carbon not only can form long chains, but it also forms chains that have branches. It is a major reason why carbon compounds exhibit so much isomerism. The simple compound decane (C₁₀H₂₂), for example, has 75 different isomers .

Carbon atoms can be bonded by double or triple bonds as well as single bonds. This multiple bonding is much more prevalent with carbon than with any other element.

Carbon atoms can form rings of various sizes. The rings may be saturated or unsaturated. The unsaturated 6-membered ring known as the benzene ring is the basis for an entire subfield of "aromatic" organic chemistry.

Carbon atoms form strong bonds not only with other carbon atoms but also with atoms of other elements. In addition to hydrogen, many carbon compounds also contain oxygen. Nitrogen, sulfur, phosphorus, and the halogens also frequently occur in carbon compounds.

Various kinds of functional groups occur widely among carbon compounds, and many different kinds of isomers are possible.

Hydrocarbons

Compounds of carbon and hydrogen only are called hydrocarbons. These are the simplest compounds of organic chemistry. The most basic group of hydrocarbons are the alkanes, which contain only single bonds. The simplest member of the alkane series is methane, CH₄, the main component of natural gas. The names of some alkanes are listed in Table 1. Alkanes sometimes

have ring structures. Since a 4-carbon chain of the alkane series is called butane, a ring of 4 carbon atoms is called cyclobutane.

Simple hydrocarbons that contain one or more double bonds are called alkenes. They are named like alkanes, but their names end in " –ene." The simplest alkene has two carbon atoms and is called ethene. A 3-carbon chain that has a double bond is called propene.

A 5-carbon hydrocarbon chain with a double bond is called pentene, and if the double bond links the second and third carbons, it is 2-pentene. Like cycloalkanes, alkenes have the general formula C_nH_2n. Alkenes having ring structures are called cycloalkenes. A 5-carbon ring with a double bond is called cyclopentene.

Hydrocarbons that contain one or more triple bonds are called alkynes, and is the name ending is "–yne." A 2-carbon alkyne is therefore named ethyne. (However, the compound is often referred to by its common name, which is acetylene. )

Compounds that contain double or triple bonds are said to be "unsaturated"—because they are not "saturated" with hydrogen atoms. Unsaturated compounds are reactive materials that readily add hydrogen when heated over a catalyst such as nickel. The reverse reaction also occurs. Heating ethane with steam is an important commercial process for making ethene (or ethylene). This is an important commercial process called "steam cracking."

When a 6-carbon ring contains 2 double bonds, it is called cyclohexadiene, but when it has 3 double bonds, it is not called cyclohexatriene; this is because a 6-carbon ring with three double bonds takes on a special kind of stability. The double bonds become completely conjugated and no longer behave as double bonds. The ring, known as a "benzene ring," is said to be aromatic.

The removal of a hydrogen atom from a hydrocarbon molecule leaves an alkyl group that readily attaches to a functional group, or forms a branch on a hydrocarbon chain. The groups are named after the corresponding hydrocarbons. For example, CH₃– is named methyl; CH₃CH₂–, ethyl; CH₂= CH–, ethenyl; CH₃CH₂CH₂–, propyl; and so on. A benzene ring from which a hydrogen atom has been removed is often referred to as a phenyl. The branched molecules shown here would be given names as follows

Theoretically there is no limit to the length of hydrocarbon chains. Very large hydrocarbon molecules (polymers) have been made containing as many as 100,000 carbon atoms. However, such molecules are hard to make and very difficult to melt and to shape into useful products.

Hydrocarbons are obtained primarily from fossil fuels—especially petroleum and natural gas. Natural gas is a mixture that is largely methane mixed with varying amounts of ethane and other light hydrocarbons, while petroleum is a complex mixture of many different hydrocarbons. Coal, the other fossil fuel, is a much more complicated material from which many kinds of organic compounds, some of them hydrocarbons, can be obtained.

Functional Groups

Alkane molecules are rather unreactive (except for being very flammable), but alkenes react with many other substances. When a drop of bromine is added to an alkene, for example, the deep orange color of the bromine immediately disappears as the bromine adds across the double bond to form a dibromo derivative. The double bond is called a "functional group" because its presence in a molecule causes reactivity at that particular site. There are a dozen or so functional groups that appear frequently in organic compounds. Some of the most common ones are listed in Table 2. The same molecule may contain several functional groups. Aspirin, for example, is both a carboxylic acid and an ester , and cholesterol is an alkene as well as an alcohol.

Isomerism

Isomers are molecules with the same molecular formula but different structures. There is only one structure for methane, ethane, or propane; but butane, C₄H₁₀, can have either of two different structure:

The linear molecule (1) is called butane, or normal butane (n -butane), whereas the branched molecule (2) is methylpropane (rather than 2-methylpropane, as the methyl group has to be in a 2-position). If the methyl group of (2) were attached to a terminal carbon, the resultant molecule would be the same as (1). Methylpropane (2) is also called iso butane.

In a conjugated system, there are alternating double and single bonds, allowing electrons to flow back and forth. Molecules that contain such conjugated systems are said to be stabilized by "resonance." In the benzene ring every other bond is a double bond, all the way around the ring. This results in a special kind of stabilization called "aromaticity," in which the electrons are delocalized and free to travel all around the ring. Certain ring compounds, like benzene, that contain such a conjugated system of double and single bonds are described as "aromatic."

Pentane has 3 isomers: pentane (or n -pentane), methylbutane (or iso- pentane), and dimethyl propane (or neo pentane). Hexane has 5 isomers: hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane. Heptane has 9 different isomers, octane has 18, nonane has 35, and decane has 75. An increase in the number of carbon atoms greatly increases the possibilities for isomerism. There are more than 4,000 isomers of C₁₅H₃₂ and more than 366,000 isomers of C₂₀H₄₂. The formula C₃₀H₆₂ has more than 4 billion. Of course, most of them have never been isolated as pure compounds (but could be, if there were any point in doing it).

For molecules other than hydrocarbons, still other kinds of isomers are possible. The simple formula C₂H₆O can represent ethyl alcohol or dimethyl ether; and C₃H₆O could stand for an alcohol, an ether, an aldehyde , or a ketone (among other things). The larger a molecule is, and the greater the variety of atoms and functional groups it contains, the more numerous its isomers.

There is still another kind of isomerism that stems from the existence of "right-" and "left-handed" molecules. It is sometimes referred to as optical isomerism because the molecules that make up a pair of these isomers usually differ only in the way they rotate plane polarized light.

Nomenclature

There are so many millions of organic compounds that simply finding names for them all is a major challenge. It was not until the late nineteenth century that chemists developed a logical system for naming organic compounds. Compounds had often been named according to their sources. The 1-carbon carboxylic acid, for example, was first obtained from ants, and so it was called formic acid, from the Latin word for ants (formicae ). The 2-carbon acid was obtained from vinegar (acetum in Latin), and was called acetic acid.

To bring some order to the naming process an international meeting was held in 1892 at Geneva, Switzerland. The group later became known as the International Union of Pure and Applied Chemistry (IUPAC). Its objective was to establish a naming process that would provide each compound with a unique and systematic name. An initial set of rules was adopted at that first meeting in Geneva, and IUPAC has continued that work. Its systematic naming rules are used by organic chemists all over the world. The names of the alkanes form the basis for the system, with functional groups usually being indicated with appropriate suffixes. Some examples are given in Table 2.

Organic Reactions

Organic chemistry is concerned with the many compounds of carbon, their names, their isomers, and their properties, but it is mostly concerned with their reactions. Organic chemists have developed a huge array of chemical reactions that can convert one organic compound to another. Some reactions involve addition of one molecule to another; some involve decomposition of molecules; some involve substitution of one atom or group by another; and some even involve the rearrangement of molecules, with some atoms moving into new positions. Some reactions require energy in the form of heat or radiation; and some require a special kind of catalyst or some sort

of solvent. Of course, not all organic reactions are highly successful. One reaction might be a very simple one giving essentially 100 percent of the desired product; but another might be a complex multistep process yielding less than 5 percent overall of the wanted product.

Organic reactions can often give remarkable control as to what products should be formed. Adding water to propene for example, produces 2-propanol in the presence of acid, but it yields 1-propanol if treated first with B₂H₆ and then H₂O₂ in the presence of base.

Future Sources of Organic Chemicals

Fossil fuels have been our primary natural source for many organic chemicals for more than a century, but our fossil fuel resources are finite, and they are being rapidly depleted (especially oil and gas). What will be our sources of organic materials in the future? Since fossil fuels are nonrenewable resources, it is believed that the twenty-first century will see a shift toward greater dependence on renewable raw materials. The largest U.S. chemical company has a goal of becoming 25 percent based on renewable resources by 2010. It is already producing 1,3-propanediol from cornstarch using a gene-tailored E. coli bacterium. This diol is used in Du Pont's fiber Sorona, which is said to combine the best features of both polyester and nylon fibers. Succinic acid and polyhydroxybutyrate are also obtainable from renewable crops, and the list of such renewable raw materials is destined to grow. For example, ethylene (or ethene), CH₂=CH₂, which is a highly important commercial chemical used in making many industrial chemicals and polymers, is presently made by steam cracking of ethane obtained from oil or natural gas; but ethylene can also be made by dehydration of ethyl alcohol made by fermentation of sugar. Efforts are even being made to use biowaste materials, such as corn husks, nutshells, and wood chips as industrial raw materials.

Analytical Tools

Organic chemists often need to examine products for identification, purity analysis, or structure determination. There are some marvelous tools available to help them do these things. Chromatography , spectroscopy , and crystallography are especially widely used in organic chemistry.

Column chromatography, gas chromatography, and liquid chromatography are all important methods for separating mixtures of organic compounds. Spectroscopic tools include ultraviolet (UV), infrared (IR), nuclear magnetic resonance (NMR), and mass spectroscopy (MS), each capable of providing a different kind of information about an organic compound. Although it is limited to substances that can be prepared as pure crystals, x-ray crystallography is probably the ultimate tool for determining molecular structure.

Careers in Organic Chemistry

Some organic chemists are involved in basic research at government or academic institutions, but most have careers in industry. The industries vary from oil and chemical companies to industries producing food, pharmaceuticals, cosmetics, detergents, paints, plastics, pesticides, textiles, or other kinds of products. Many organic chemists work in laboratories, where they do various kinds of analysis or research, but many others do not. Some are teachers, or writers, or science librarians. Some study law and become patent attorneys; some study medicine and become medical researchers; and some study business and become administrators of companies, colleges, or other institutions. Organic chemistry is an enormous field full of many kinds of career possibilities.

see also Fossil Fuels; Lavoisier, Antoine; Organic Halogen Compounds; WÖhler, Friedrich.

Kenneth E. Kolb

Bibliography

Atkins, Robert C., and Carey, Francis A. (2002). Organic Chemistry: A Brief Course, 3rd edition. Boston: McGraw-Hill.

Bailey, Philip S., Jr., and Bailey, Christina A. (2000). Organic Chemistry: A Brief Survey of Concepts and Applications, 6th edition. Upper Saddle River, NJ: Prentice Hall.

Brown, William H., and Foote, Christopher S. (2002). Organic Chemistry, 3rd edition. San Diego: Saunders.

Fessenden, Ralph J.; Fessenden, Joan S.; and Logue, Marshall (1998). Organic Chemistry, 6th edition. Pacific Grove, CA: Brooks/Cole.

Solomons, T. W. Graham (1997). Fundamentals of Organic Chemistry, 5th edition. New York: Wiley.

Organic chemistry

Organic chemistry is the study of compounds of carbon. The name organic goes back to a much earlier time in history when chemists thought that chemical compounds in living organisms were fundamentally different from those that occur in nonliving things. The belief was that the chemicals that could be extracted from or that were produced by living organisms had a special "vitalism" or "breath of life" given to them by some supernatural being. As such, they presented fundamentally different kinds of problems than did the chemicals found in rocks, minerals, water, air, and other nonliving entities. The chemical compounds associated with living organisms were given the name organic to emphasize their connection with life.

In 1828, German chemist Friedrich Wöhler (1800–1882) proved that this theory of vitalism was untrue. He found a very simple way to convert chemical compounds from living organisms into comparable compounds from nonliving entities.

As a result of Wöhler's research, the definition of organic chemistry changed. The new definition was based on the observation that every compound discovered in living organisms had one property in common: they all contained the element carbon. As a result, the modern definition of organic chemistry—as the study of carbon compounds—was adopted.

Organic and inorganic chemistry

One important point that Wöhler's research showed was that the principles and techniques of chemistry apply equally well to compounds found in living organisms and in nonliving things. Nonetheless, some important differences between organic and inorganic (not organic) compounds exist. These include the following:

Major Organic Families and the Functional Groups They Contain

1. The number of organic compounds vastly exceeds the number of inorganic compounds. The ratio of carbon-based compounds to non-carbon-based compounds is at least ten to one, with close to 10 million organic compounds known today. The reason for this dramatic difference is a special property of the carbon atom: its ability to join with other carbon atoms in very long chains, in rings, and in other kinds of geometric arrangements. It is not at all unusual for dozens, hundreds, or thousands of carbon atoms to bond to each other within a single compound—a property that no other element exhibits.

2. In general, organic compounds tend to have much lower melting and boiling points than do inorganic compounds.

3. In general, organic compounds are less likely to dissolve in water than are inorganic compounds.

4. Organic compounds are likely to be more flammable but poorer conductors of heat and electricity than are inorganic compounds.

5. Organic reactions tend to take place more slowly and to produce a much more complex set of products than do inorganic reactions.

Functional groups and organic families

The huge number of organic compounds requires that some system be developed for organizing them. The criterion on which those compounds are organized is the presence of various functional groups. A functional group is an arrangement of atoms that is responsible for certain characteristic physical and chemical properties in a compound. For example, one such functional group is the hydroxyl group, consisting of an oxygen atom and hydrogen atom joined to each other. It is represented by the formula —OH.

All organic compounds with the same functional group are said to belong to the same organic family. Any organic compound that contains a hydroxyl group, for instance, is called an alcohol. All alcohols are similar to each other in that: (1) they contain one or more hydroxyl groups, and (2) because of those groups, they have similar physical and chemical properties. For example, alcohols tend to be more soluble in water than other organic compounds because the hydroxyl groups in the alcohol form bonds with water molecules.

The simplest organic compounds are the hydrocarbons, compounds that contain only two elements: carbon and hydrogen. The class of hydrocarbons can be divided into subgroups depending on the way in which carbon and hydrogen atoms are joined to each other. In some hydrocarbons, for example, carbon and hydrogen atoms are joined to each other only by single bonds. A single bond is a chemical bond that consists of a pair of electrons. Such hydrocarbons are known as saturated hydrocarbons.

In other hydrocarbons, carbon and hydrogen atoms are joined to each other by double or triple bonds. A double bond consists of two pairs of electrons, and a triple bond consists of three pairs of electrons. The symbols used for single, double, and triple bonds, respectively, are —, =, and ≡. Hydrocarbons containing double and triple bonds are said to be unsaturated.

Hydrocarbons can also be open-chain or ring compounds. In an open-chain hydrocarbon, the carbon atoms are all arranged in a straight line, like a strand of spaghetti. In a ring hydrocarbon, the carbons are arranged in a continuous loop, such as a square, a pentagon, or a triangle.

ORGANIC CHEMISTRY

"Your Servant the Molecule"

(Monsanto slogan, 1944). During the 1940s advances in organic chemistry, the study of carbon compounds, led to the development of synthetic chemicals and a tremendous growth in the American chemical industry. Advances in the understanding of the arrangement of atoms in molecules and the nature of chemical reactions paved the way for the development of synthetics, such as saccharin and plastic, that had a wide-ranging effect on consumer products, transforming everything from fabrics to food production to home appliances. Ten chemical corporations built on the new synthetic chemistry—including Celanese and Monsanto, as well as old-line, giant chemical companies such as DuPont, Allied Chemical, and Union Carbide—accounted for nearly 9 percent of the total assets of the top one hundred industrials in 1948, signifying the "chemicalization" of American industry.

New Synthetics

While chemistry remained a mystery to most Americans, its applications changed their lives. The new plastic polyethylene, introduced in 1944 by Du Pont, is a tough thermoplastic able to withstand a wide temperature range. Its diverse uses include collapsible tubes for food and cosmetics, as well as medical equipment, lighting fixtures, and furniture. Also introduced in 1944, polysiloxane polymer (silicone) was produced by the Corning Company. By the end of the decade Shell, Dow, and Ciba had introduced epoxide resins for electrical use, laminates, paints, and varnishes. Research at the Shell Corporation from 1939 to 1942 made it possible to increase the octane rating of gasoline. Synthetic rubber was made from the petroleum derivative butadiene. By 1945 the ESSO Company (Standard Oil of New Jersey) had produced five hundred thousand tons of butadiene, almost all of which went into the production of synthetic rubber.

JAMES B. CONANT: ACADEMIC AT WAR

James Bryant Conant (1893-1978) gave up research in chemistry when he became president of Harvard University in 1933, but he continued to influence the course of American science, especially during World War II. In 1940 Vannevar Bush, head of the National Defense Research Committee (NDRC), appointed Conant to this new group, which was intended to coordinate scientific efforts on wartime projects. The following year Conant established an NDRC office in London and began an information-exchange program between British and American scientists. One of the most significant results of this exchange was the improvement of American radar installations. In 1941—when Bush became head of the Office of Scientific Research and Development (OSRD), which included the NDR C—Conant became head of the NDR C and held the post for the remainder of the war. During that time he was responsible for important projects such as microwave radar and synthetic rubber. He also worked closely with Bush in obtaining the funds for the Manhattan Project to build the atomic bomb, and then he designed and organized the research program. In fall 1942, after the military draft had created a severe shortage of trained scientists, Conant urged the Roosevelt administration to send students to college at federal expense and argued that well-trained scientists should not be drafted.

Source:

James Hershberg, James B. Conant: Harvard to Hiroshima and the Making of the Nuclear Age (New York: Knopf, 1993).

Source:

Arnold Thrackray, Jeffrey Sturchio, P. Thomas Carroll, and Robert Bush, Chemistry in America, 1876-1976 (Dordrecht, The Netherlands: Reidel, 1985).

organic chemistry branch of chemistry dealing with the compounds of carbon. While it is only the fourteenth most common element on earth, carbon forms by far the greatest number of different compounds. Organic chemistry is of vital importance to the petrochemical, pharmaceutical, and textile industries, where a prime concern is the synthesis of new organic molecules and polymers . Compounds containing only hydrogen and carbon, of which there are many thousands, are called hydrocarbons ; the simplest is methane (CH ₄ ). In general, a particular type of organic compound, such as an alcohol , aldehyde , ether , or ketone , is identified by the presence of a characteristic functional group of atoms. The functional group is the part of the molecule most responsible for its particular chemical nature. Organic compounds containing nitrogen are of great importance in biochemistry . They generally contain the amine group (NH ₂ ). Molecules containing both the NH ₂ and COOH groups are called amino acids and are the building blocks of proteins.

or·gan·ic chem·is·try • n. the chemistry of carbon compounds (other than simple salts such as carbonates, oxides, and carbides).

organic chemistry See chemistry