In organic chemistry, functional groups are specific groups of atoms within molecules that are responsible for the characteristic chemical reactions of those molecules. The same functional group will undergo the same or similar chemical reaction(s) regardless of the size of the molecule it is a part of.[1][2] However, its relative reactivity can be modified by nearby functional groups.
The word moiety ( /ˈmɔɪəti/) is often used synonymously to "functional group," but, according to the IUPAC definition,[3] a moiety is a part of a molecule that may include either whole functional groups or parts of functional groups as substructures. For example, an ester (RCOOR') has an ester functional group (COOR) and is composed of an alkoxy moiety (-OR') and an acyl moiety (RCO-), or, equivalently, it may be divided into carboxylate (RCOO-) and alkyl (-R') moieties. Each moiety may contain additional functional groups, for example, methyl para-hydroxybenzoate contains a phenol functional group within the acyl moiety.
Combining the names of functional groups with the names of the parent alkanes generates a powerful systematic nomenclature for naming organic compounds.
The atoms of functional groups are linked to each other and to the rest of the molecule by covalent bonds. When the group of covalently bound atoms bears a net charge, the group is referred to more properly as a polyatomic ion or a complex ion. Any subgroup of atoms of a compound also may be called a radical, and if a covalent bond is broken homolytically, the resulting fragment radicals are referred as free radicals.
The first carbon atom after the carbon that attaches to the functional group is called the alpha carbon; the second, beta carbon, the third, gamma carbon, etc. If there is another functional group at a carbon, it may be named with the Greek letter, e.g., the gamma-amine in gamma-aminobutanoic acid is on the third carbon of the carbon chain attached to the carboxylic acid group.
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Organic reactions are facilitated and controlled by the functional groups of the reactants. In general, alkyls are unreactive and difficult to get to react selectively at the desired positions, with few exceptions. In contrast, unsaturated carbon functional groups, and carbon-oxygen and carbon-nitrogen functional groups have a more diverse array of reactions that are also selective. It may be necessary to create a functional group in the molecule to make it react. For example, to synthesize iso-octane (the 8-carbon ideal gasoline) from the unfunctionalized alkane isobutane (a 4-carbon gas), isobutane is first dehydrogenated into isobutene. This contains the alkene functional group and can now dimerize with another isobutene to give iso-octene, which is then catalytically hydrogenated to iso-octane using pressured hydrogen gas.
The International Union of Crystallography in its Crystallographic Information File dictionary defines "moiety" to represent discrete non-bonded components. Thus, Na2SO4 would contain 3 moieties (2 Na+ and one SO42-). The dictionary defines "chemical formula moiety": "Formula with each discrete bonded residue or ion shown as a separate moiety".
Functionalization is the addition of functional groups onto the surface of a material by chemical synthesis methods. The functional group added can be subjected to ordinary synthesis methods to attach virtually any kind of organic compound onto the surface.
Functionalization is employed for surface modification of industrial materials in order to achieve desired surface properties such as water repellent coatings for automobile windshields and non-biofouling, hydrophilic coatings for contact lenses. In addition, functional groups are used to covalently link functional molecules to the surface of chemical and biochemical devices such as microarrays and microelectromechanical systems.
Catalysts can be attached to a material that has been functionalized. For example, silica is functionalized with an alkyl silicone, wherein the alkyl contains an amine functional group. A ligand such as an EDTA fragment is synthesized onto the amine, and a metal cation is complexed into the EDTA fragment. The EDTA is not adsorbed onto the surface, but connected by a permanent chemical bond.
Functional groups are also used to covalently link molecules such as fluorescent dyes, nanoparticles, proteins, DNA, and other compounds of interest for a variety of applications such as sensing and basic chemical research.
The following is a list of common functional groups. In the formulas, the symbols R and R' usually denote an attached hydrogen, or a hydrocarbon side chain of any length, but may sometimes refer to any group of atoms.
Functional groups, called hydrocarbyls, that contain only carbon and hydrogen, but vary in the number and order of π bonds. Each one differs in type (and scope) of reactivity.
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| Alkane | Alkyl | RH | alkyl- | -ane | Ethane |
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| Alkene | Alkenyl | R2C=CR2 | alkenyl- | -ene | Ethylene (Ethene) |
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| Alkyne | Alkynyl | RC≡CR' | alkynyl- | -yne | Acetylene (Ethyne) |
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| Benzene derivative | Phenyl | RC6H5 RPh |
phenyl- | -benzene | Cumene (2-phenylpropane) |
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| Toluene derivative | Benzyl | RCH2C6H5 RBn |
benzyl- | 1-(substituent)toluene | Benzyl bromide (α-Bromotoluene) |
There are also a large number of branched or ring alkanes that have specific names, e.g., tert-butyl, bornyl, cyclohexyl, etc.
Hydrocarbons may form charged structures: positively charged carbocations or negative carbanions. Carbocations are often named -um. Examples are tropylium and triphenylmethyl cations and the cyclopentadienyl anion.
Haloalkanes are a class of molecule that is defined by a carbon-halogen bond. This bond can be relatively weak (in the case of an iodoalkane) or quite stable (as in the case of a fluoroalkane). In general, with the exception of fluorinated compounds, haloalkanes readily undergo nucleophilic substitution reactions or elimination reactions. The substitution on the carbon, the acidity of an adjacent proton, the solvent conditions, etc. all can influence the outcome of the reactivity.
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| haloalkane | halo | RX | halo- | alkyl halide | Chloroethane (Ethyl chloride) |
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| fluoroalkane | fluoro | RF | fluoro- | alkyl fluoride | Fluoromethane (Methyl fluoride) |
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| chloroalkane | chloro | RCl | chloro- | alkyl chloride | Chloromethane (Methyl chloride) |
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| bromoalkane | bromo | RBr | bromo- | alkyl bromide | Bromomethane (Methyl bromide) |
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| iodoalkane | iodo | RI | iodo- | alkyl iodide | Iodomethane (Methyl iodide) |
Compounds that contain C-O bonds each possess differing reactivity based upon the location and hybridization of the C-O bond, owing to the electron-withdrawing effect of sp hybridized oxygen (carbonyl groups) and the donating effects of sp2 hybridized oxygen (alcohol groups).
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| Alcohol | Hydroxyl | ROH | hydroxy- | -ol | Methanol |
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| Ketone | Carbonyl | RCOR' | -oyl- (-COR') or oxo- (=O) |
-one | Butanone (Methyl ethyl ketone) |
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| Aldehyde | Aldehyde | RCHO | formyl- (-COH) or oxo- (=O) |
-al | Ethanal (Acetaldehyde) |
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| Acyl halide | Haloformyl | RCOX | carbonofluoridoyl- carbonochloridoyl- carbonobromidoyl- carbonoiodidoyl- |
-oyl halide | Acetyl chloride (Ethanoyl chloride) |
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| Carbonate | Carbonate ester | ROCOOR | (alkoxycarbonyl)oxy- | alkyl carbonate | Triphosgene (Di(trichloromethyl) carbonate) |
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| Carboxylate | Carboxylate | RCOO− | carboxy- | -oate | Sodium acetate (Sodium ethanoate) |
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| Carboxylic acid | Carboxyl | RCOOH | carboxy- | -oic acid | Acetic acid (Ethanoic acid) |
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| Ester | Ester | RCOOR' | alkanoyloxy- or alkoxycarbonyl |
alkyl alkanoate | Ethyl butyrate (Ethyl butanoate) |
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| Hydroperoxide | Hydroperoxy | ROOH | hydroperoxy- | alkyl hydroperoxide | Methyl ethyl ketone peroxide |
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| Peroxide | Peroxy | ROOR | peroxy- | alkyl peroxide | Di-tert-butyl peroxide |
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| Ether | Ether | ROR' | alkoxy- | alkyl ether | Diethyl ether (Ethoxyethane) |
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| Hemiacetal | Hemiacetal | RCH(OR')(OH) | alkoxy -ol | -al alkyl hemiacetal | ||
| Hemiketal | Hemiketal | RC(ORʺ)(OH)R' | alkoxy -ol | -one alkyl hemiketal | ||
| Acetal | Acetal | RCH(OR')(OR") | dialkoxy- | -al dialkyl acetal | ||
| Ketal (or Acetal) | Ketal (or Acetal) | RC(ORʺ)(OR‴)R' | dialkoxy- | -one dialkyl ketal | ||
| Orthoester | Orthoester | RC(OR')(ORʺ)(OR‴) | trialkoxy- | |||
| Orthocarbonate ester | Orthocarbonate ester | C(OR)(OR')(ORʺ)(OR″) | tetralkoxy- | tetraalkyl orthocarbonate |
Compounds that contain nitrogen in this category may contain C-O bonds, such as in the case of amides.
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| Amide | Carboxamide | RCONR2 | carboxamido- or carbamoyl- |
-amide | Acetamide (Ethanamide) |
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| Amines | Primary amine | RNH2 | amino- | -amine | Methylamine (Methanamine) |
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| Secondary amine | R2NH | amino- | -amine | Dimethylamine |
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| Tertiary amine | R3N | amino- | -amine | Trimethylamine |
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| 4° ammonium ion | R4N+ | ammonio- | -ammonium | Choline |
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| Imine | Primary ketimine | RC(=NH)R' | imino- | -imine | ||
| Secondary ketimine | RC(=NR)R' | imino- | -imine | |||
| Primary aldimine | RC(=NH)H | imino- | -imine | |||
| Secondary aldimine | RC(=NR')H | imino- | -imine | |||
| Imide | Imide | (RCO)2NR' | imido- | -imide | ||
| Azide | Azide | RN3 | azido- | alkyl azide | Phenyl azide (Azidobenzene) |
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| Azo compound | Azo (Diimide) |
RN2R' | azo- | -diazene | Methyl orange (p-dimethylamino-azobenzenesulfonic acid) |
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| Cyanates | Cyanate | ROCN | cyanato- | alkyl cyanate | Methyl cyanate |
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| Isocyanate | RNCO | isocyanato- | alkyl isocyanate | Methyl isocyanate |
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| Nitrate | Nitrate | RONO2 | nitrooxy-, nitroxy- |
alkyl nitrate |
Amyl nitrate (1-nitrooxypentane) |
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| Nitrile | Nitrile | RCN | cyano- | alkanenitrile alkyl cyanide |
Benzonitrile (Phenyl cyanide) |
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| Isonitrile | RNC | isocyano- | alkaneisonitrile alkyl isocyanide |
Methyl isocyanide |
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| Nitrite | Nitrosooxy | RONO | nitrosooxy- |
alkyl nitrite |
Isoamyl nitrite (3-methyl-1-nitrosooxybutane) |
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| Nitro compound | Nitro | RNO2 | nitro- | Nitromethane |
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| Nitroso compound | Nitroso | RNO | nitroso- | Nitrosobenzene |
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| Pyridine derivative | Pyridyl | RC5H4N |
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4-pyridyl 3-pyridyl 2-pyridyl |
-pyridine | Nicotine |
Compounds that contain sulfur exhibit unique chemistry due to their ability to form more bonds than oxygen, their lighter analogue on the periodic table. Substitutive nomenclature (marked as prefix in table) is preferred over functional class nomenclature (marked as suffix in table) for sulfides, disulfides, sulfoxides and sulfones.
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| Thiol | Sulfhydryl | RSH | sulfanyl- (-SH) |
-thiol | Ethanethiol |
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| Sulfide (Thioether) |
Sulfide | RSR' | substituent sulfanyl- (-SR') |
di(substituent) sulfide | (Methylsulfanyl)methane (prefix) or Dimethyl sulfide (suffix) |
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| Disulfide | Disulfide | RSSR' | substituent disulfanyl- (-SSR') |
di(substituent) disulfide | (Methyldisulfanyl)methane (prefix) or Dimethyl disulfide (suffix) |
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| Sulfoxide | Sulfinyl | RSOR' | -sulfinyl- (-SOR') |
di(substituent) sulfoxide | (Methanesulfinyl)methane (prefix) or Dimethyl sulfoxide (suffix) |
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| Sulfone | Sulfonyl | RSO2R' | -sulfonyl- (-SO2R') |
di(substituent) sulfone | (Methanesulfonyl)methane (prefix) or Dimethyl sulfone (suffix) |
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| Sulfinic acid | Sulfino | RSO2H | sulfino- (-SO2H) |
-sulfinic acid | 2-Aminoethanesulfinic acid |
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| Sulfonic acid | Sulfo | RSO3H | sulfo- (-SO3H) |
-sulfonic acid | Benzenesulfonic acid |
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| Thiocyanate | Thiocyanate | RSCN | thiocyanato- (-SCN) |
substituent thiocyanate | Phenyl thiocyanate |
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| Isothiocyanate | RNCS | isothiocyanato- (-NCS) |
substituent isothiocyanate | Allyl isothiocyanate |
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| Thione | Carbonothioyl | RCSR' | -thioyl- (-CSR') or sulfanylidene- (=S) |
-thione | Diphenylmethanethione (Thiobenzophenone) |
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| Thial | Carbonothioyl | RCSH | methanethioyl- (-CSH) or sulfanylidene- (=S) |
-thial |
Compounds that contain phosphorus exhibit unique chemistry due to their ability to form more bonds than nitrogen, their lighter analogues on the periodic table.
| Chemical class | Group | Formula | Structural Formula | Prefix | Suffix | Example |
|---|---|---|---|---|---|---|
| Phosphine (Phosphane) |
Phosphino | R3P | phosphanyl- | -phosphane | Methylpropylphosphane |
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| Phosphonic acid | Phosphono | RP(=O)(OH)2 | phosphono- | substituent phosphonic acid | Benzylphosphonic acid |
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| Phosphate | Phosphate | ROP(=O)(OH)2 | phosphonooxy- or O-phosphono- (phospho-) |
substituent phosphate | Glyceraldehyde 3-phosphate (suffix) |
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O-Phosphonocholine (prefix) (Phosphocholine) |
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| Phosphodiester | Phosphate | HOPO(OR)2 | [(alkoxy)hydroxyphosphoryl]oxy- or O-[(alkoxy)hydroxyphosphoryl]- |
di(substituent) hydrogen phosphate or phosphoric acid di(substituent) ester |
DNA | |
| O‑[(2‑Guanidinoethoxy)hydroxyphosphoryl]‑l‑serine (prefix) (Lombricine) |
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