Functional group

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In organic chemistry, functional groups are lexicon-specific groups of atoms or bonds 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 (pron.: /mti/) is often used synonymously with "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.

Benzyl acetate has an ester functional group (in red), an acetyl moiety (circled with green) and a benzyloxy moiety (circled with orange). Other divisions can be made.

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.

Contents
1 Synthetic chemistry 2 Crystallography 3 Functionalization 4 Table of common functional groups 4.1 Hydrocarbons 4.2 Groups containing halogens 4.3 Groups containing oxygen 4.4 Groups containing nitrogen 4.5 Groups containing sulfur 4.6 Groups containing phosphorus 4.7 Groups containing boron 5 See also 6 References 7 External links

Synthetic chemistry
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.

Crystallography
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
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.

Table of common functional groups

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.

Hydrocarbons
Functional groups, called hydrocarbyls, that contain only carbon and hydrogen, but vary in the number and order of bonds. Each one differs in type (and scope) of reactivity. Chemical Group class Alkane Formula Structural Formula Prefix Suffix Example

Alkyl R(CH2)n H

alkyl-

-ane Ethane

Alkene

Alkenyl R2C=CR2

alkenyl-

-ene Ethylene (Ethene)

Alkyne

Alkynyl RCCR'

alkynyl-

-yne

Acetylene (Ethyne)

Benzene Phenyl derivative

RC6H5 RPh

phenyl-

-benzene Cumene (2phenylpropane)

RCH2C6H5 Toluene Benzyl derivative RBn

benzyl-

1(substituent )toluene Benzyl bromide (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.

Groups containing halogens

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)

fluoroalkane

fluoro

RF

fluoro-

alkyl fluoride

Fluoromethane (Methyl fluoride)

chloroalkane chloro

RCl

chloro-

alkyl chloride

Chloromethane (Methyl chloride)

bromoalkane bromo

RBr

bromo-

alkyl bromide

Bromomethane (Methyl bromide)

iodoalkane

iodo

RI

iodo-

alkyl iodide

Iodomethane (Methyl iodide)

Groups containing oxygen

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

Ketone

Carbonyl

RCOR'

-oyl- (-COR') or oxo- (=O)

-one

Butanone (Methyl ethyl ketone)

Aldehyde

Aldehyde

RCHO

formyl- (-COH) or oxo- (=O)

-al Acetaldehyde (Ethanal)

Acyl halide

Haloformyl

RCOX

carbonofluoridoylcarbonochloridoylcarbonobromidoylcarbonoiodidoyl-

-oyl halide Acetyl chloride (Ethanoyl chloride)

Carbonate

Carbonate

ester

ROCOOR

(alkoxycarbonyl)oxy- alkyl carbonate

Triphosgene (bis(trichloromethyl) carbonate)

Carboxylate

Carboxylate

RCOO

carboxy-

-oate

Sodium acetate (Sodium ethanoate)

Carboxylic acid

Carboxyl

RCOOH

carboxy-

-oic acid Acetic acid (Ethanoic acid)

Ester

Ester

RCOOR'

alkanoyloxyor alkoxycarbonyl methoxy-

alkyl alkanoate

Ethyl butyrate (Ethyl butanoate)

Methoxy

Methoxy

ROCH3

Hydroperoxide

Hydroperoxy

ROOH

hydroperoxy-

alkyl hydroperoxide

Methyl ethyl ketone peroxide

Peroxide

Peroxy

ROOR

peroxy-

alkyl peroxide Di-tert-butyl peroxide

Ether

Ether

ROR'

alkoxy-

alkyl ether

Diethyl ether (Ethoxyethane)

Hemiacetal

Hemiacetal

RCH(OR')(OH)

alkoxy -ol

-al alkyl hemiacetal -one alkyl hemiketal -al dialkyl acetal -one dialkyl ketal

Hemiketal

Hemiketal

RC(OR)(OH)R'

alkoxy -ol

Acetal

Acetal

RCH(OR')(OR")

dialkoxy-

Ketal (or Acetal) Orthoester

Ketal (or Acetal) Orthoester

RC(OR)(OR)R'

dialkoxy-

RC(OR')(OR)(OR)

trialkoxytetralkoxytetraalkyl orthocarbonate

Orthocarbonate Orthocarbonate C(OR)(OR')(OR)(OR) ester ester

Groups containing nitrogen

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 carboxamidoor carbamoylSuffix Example

Amide

Carboxamide RCONR2

-amide Acetamide (Ethanamide)

Primary amine

RNH2

amino-

-amine Methylamine (Methanamine)

Secondary amine Amines Tertiary amine

R2NH

amino-

-amine

Dimethylamine

R3N

amino-

-amine Trimethylamine

4 ammonium ion

R4N+

ammonio-

-ammonium Choline

Primary ketimine

RC(=NH)R'

imino-

-imine

Secondary ketimine Imine Primary aldimine

RC(=NR)R'

imino-

-imine

RC(=NH)H

imino-

-imine Ethanimine

Secondary RC(=NR')H aldimine

imino-

-imine

Imide

Imide

(RCO)2NR'

imido-

-imide Succinimide (Pyrrolidine-2,5-dione)

Azide

Azide

RN3

azido-

alkyl azide Phenyl azide (Azidobenzene)

Azo compound

Azo (Diimide)

RN2R'

azo-

-diazene

Methyl orange (p-dimethylaminoazobenzenesulfonic acid)

Cyanate Cyanates Isocyanate

ROCN

cyanato-

alkyl cyanate Methyl cyanate

RNCO

isocyanato-

alkyl isocyanate

Methyl isocyanate

Nitrate

Nitrate

RONO2

nitrooxy-, nitroxy-

alkyl nitrate Amyl nitrate (1-nitrooxypentane) alkanenitrile

Nitrile

Nitrile

RCN

cyano-

alkyl cyanide

Benzonitrile (Phenyl cyanide) Isonitrile RNC isocyanoalkaneisonitrile alkyl isocyanide

Methyl isocyanide

Nitrite

Nitrosooxy

RONO

nitrosooxy-

alkyl nitrite

Isoamyl nitrite (3-methyl-1nitrosooxybutane)

Nitro compound

Nitro

RNO2

nitroNitromethane

Nitroso compound

Nitroso

RNO

nitroso(Nitrosyl-) 4-pyridyl (pyridin-4-yl)

Nitrosobenzene

Pyridine derivative

Pyridyl

RC5H4N

3-pyridyl (pyridin-3-yl) 2-pyridyl (pyridin-2-yl)

-pyridine Nicotine

Groups containing sulfur

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 Thiol

Group

Formula

Structural Formula

Prefix sulfanyl(-SH)

Suffix

Example

Sulfhydryl

RSH

- thiol

Ethanethiol

Sulfide (Thioether)

Sulfide

RSR'

substituent sulfanyl(-SR')

di(substituent ) sulfide (Methylsulfanyl)methane (prefix) or Dimethyl sulfide (suffix)

Disulfide

Disulfide

RSSR'

substituent disulfanyl(-SSR')

di(substituent ) disulfide (Methyldisulfanyl)methane (prefix) or Dimethyl disulfide (suffix)

Sulfoxide

Sulfinyl

RSOR'

-sulfinyl(-SOR')

di(substituent ) sulfoxide (Methanesulfinyl)methane (prefix) or Dimethyl sulfoxide (suffix)

Sulfone

Sulfonyl

RSO2R'

-sulfonyl(-SO2R')

di(substituent ) sulfone (Methanesulfonyl)methane (prefix) or Dimethyl sulfone (suffix) - sulfinic acid

Sulfinic acid

Sulfino

RSO2H

sulfino(-SO2H)

2-Aminoethanesulfinic acid

Sulfonic acid

Sulfo

RSO3H

sulfo(-SO3H)

- sulfonic acid

Benzenesulfonic acid

Thiocyanate Thiocyanate

RSCN

thiocyanato(-SCN) isothiocyanato(-NCS) -thioyl(-CSR') or sulfanylidene(=S) methanethioyl(-CSH) or sulfanylidene(=S)

substituent thiocyanate Phenyl thiocyanate substituent isothiocyanate Allyl isothiocyanate

Isothiocyanate RNCS

Thione

Carbonothioyl RCSR'

- thione

Diphenylmethanethione (Thiobenzophenone)

Thial

Carbonothioyl RCSH

- thial

Groups containing phosphorus

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 Phosphine (Phosphane) Phosphonic acid

Group Phosphino

Formula R3P RP(=O) (OH)2

Structural Formula

Prefix phosphanyl-

Suffix -phosphane

Example

Methylpropylphosphane phosphonosubstituent phosphonic acid

Phosphono

Benzylphosphonic acid

Phosphate

Phosphate

ROP(=O) (OH)2

phosphonooxyor O-phosphono- (phospho-)

substituent phosphate

Glyceraldehyde 3-phosphate (suffix)

O-Phosphonocholine (prefix) (Phosphocholine)

[(alkoxy)hydroxyphosphoryl]oxy-

Phosphodiester Phosphate HOPO(OR)2

di(substituent ) DNA hydrogen phosphate or or O[(2Guanidinoethoxy)hydroxyphosphoryl]Lserine (prefix) O-[(alkoxy)hydroxyphosphoryl]phosphoric acid (Lombricine) di(substituent ) ester

Groups containing boron

Compounds containing boron exhibit unique chemistry due to their having partially filled octets and therefore acting as Lewis acids. Chemical class Group Formula Structural Formula Prefix Suffix Example

Boronic acid

Borono

RB(OH)2

Borono-

substituent boronic acid Bortezomib

([(1R)-3-methyl-1-({(2S)-3-phenyl-2-[(pyrazin-2ylcarbonyl)amino]propanoyl}amino)butyl]boronic acid)

Boronic ester Borinic acid Borinic ester

Boronate RB(OR)2

Osubstituent boronic acid [bis(alkoxy)alkylboronyl]- di(substituent ) ester

Borino

R2BOH

Hydroxyborino-

di(substituent ) borinic acid

Borinate R2BOR

O[alkoxydialkylboronyl]-

di(substituent ) borinic acid substituent ester

See also
For a list of all functional groups: Category:Functional groups Moiety conservation

References
1. ^ Compendium of Chemical Terminology (IUPAC "Gold Book") http://goldbook.iupac.org/F02555.html 2. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley, ISBN 0-471-85472-7 3. ^ IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8 doi:10.1351/goldbook.M03968 (http://dx.doi.org/10.1351%2Fgoldbook.M03968) http://goldbook.iupac.org/M03968.html

External links
IUPAC Blue Book (organic nomenclature) (http://www.acdlabs.com/iupac/nomenclature/) IUPAC ligand abbreviations (http://www.iupac.org/reports/provisional/abstract04/RB-prs310804/TableVII-3.04.pdf) (pdf) _chemical_formula_moiety in CIF dictionary (http://www.iucr.org/__data/iucr/cifdic_html/1/cif_core.dic/Ichemical_formula_moiety.html) Functional group synthesis (http://www.organic-reaction.com/organic-synthesis/functional-group-synthesis/) from organic-reaction.com Retrieved from "http://en.wikipedia.org/w/index.php?title=Functional_group&oldid=542040384" Categories: Functional groups Organic chemistry

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