Locant

Last updated

In the nomenclature of organic chemistry, a locant is a term to indicate the position of a functional group or substituent within a molecule. [1]

Contents

Numeric locants

2-Pentanone.svg
Pentan-2-one or 2-pentanone
3-Pentanone.png
pentan-3-one or 3-pentanone

The International Union of Pure and Applied Chemistry (IUPAC) recommends the use of numeric prefixes to indicate the position of substituents, generally by identifying the parent hydrocarbon chain and assigning the carbon atoms based on their substituents in order of precedence. For example, there are at least two isomers of the linear form of pentanone, a ketone that contains a chain of exactly five carbon atoms. There is an oxygen atom bonded to one of the middle three carbons (if it were bonded to an end carbon, the molecule would be an aldehyde, not a ketone), but it is not clear where it is located.

In this example, the carbon atoms are numbered from one to five, which starts at one end and proceeds sequentially along the chain. Now the position of the oxygen atom can be defined as on carbon atom number two, three or four. However, atoms two and four are exactly equivalent - which can be shown by turning the molecule around by 180 degrees.

The locant is the number of the carbon atom to which the oxygen atom is bonded. If the oxygen is bonded to the middle carbon, the locant is 3. If the oxygen is bonded to an atom on either side (adjacent to an end carbon), the locant is 2 or 4; given the choice here, where the carbons are exactly equivalent, the lower number is always chosen. So the locant is either 2 or 3 in this molecule.

The locant is incorporated into the name of the molecule to remove ambiguity. Thus the molecule is named either pentan-2-one or pentan-3-one, depending on the position of the oxygen atom.

Any side chains can be present in the place of oxygen and it can be defined as simply the number on the carbon to which any thing other than a hydrogen is attached.

Greek letter locants

a- and b-carbons in the skeletal formula of benzylacetone. The carbonyl has two b-hydrogens and five a-hydrogens. Alpha and beta positions of benzylacetone-structure.svg
α- and β-carbons in the skeletal formula of benzylacetone. The carbonyl has two β-hydrogens and five α-hydrogens.
Skeletal formula of butyric acid with the a, b, and g-carbons marked Butyric acid carbons 2.svg
Skeletal formula of butyric acid with the α, β, and γ-carbons marked

Another common system uses Greek letter prefixes as locants, which is useful in identifying the relative location of carbon atoms as well as hydrogen atoms to other functional groups.

The α-carbon (alpha-carbon) refers to the first carbon atom that attaches to a functional group, such as a carbonyl. The second carbon atom is called the β-carbon (beta-carbon), the third is the γ-carbon (gamma-carbon), and the naming system continues in alphabetical order. [2]

The nomenclature can also be applied to the hydrogen atoms attached to the carbon atoms. A hydrogen atom attached to an α-carbon is called an α-hydrogen, a hydrogen atom on the β-carbon is a β-hydrogen, and so on.

Organic molecules with more than one functional group can be a source of confusion. Generally the functional group responsible for the name or type of the molecule is the 'reference' group for purposes of carbon-atom naming. For example, the molecules nitrostyrene and phenethylamine are quite similar; the former can even be reduced into the latter. However, nitrostyrene's α-carbon atom is adjacent to the phenyl group; in phenethylamine this same carbon atom is the β-carbon atom, as phenethylamine (being an amine rather than a styrene) counts its atoms from the opposite "end" of the molecule. [3]

Proteins and amino acids

In proteins and amino acids, the α-carbon is the backbone carbon before the carbonyl carbon atom in the molecule. Therefore, reading along the backbone of a typical protein would give a sequence of –[N—Cα—carbonyl C]n– etc. (when reading in the N to C direction). The α-carbon is where the different substituents attach to each different amino acid. That is, the groups hanging off the chain at the α-carbon are what give amino acids their diversity. These groups give the α-carbon its stereogenic properties for every amino acid except for glycine. Therefore, the α-carbon is a stereocenter for every amino acid except glycine. Glycine also does not have a β-carbon, while every other amino acid does.

The α-carbon of an amino acid is significant in protein folding. When describing a protein, which is a chain of amino acids, one often approximates the location of each amino acid as the location of its α-carbon. In general, α-carbons of adjacent amino acids in a protein are about 3.8 ångströms (380 picometers) apart.

Enols and enolates

The α-carbon is important for enol- and enolate-based carbonyl chemistry as well. Chemical transformations affected by the conversion to either an enolate or an enol, in general, lead to the α-carbon acting as a nucleophile, becoming, for example, alkylated in the presence of primary haloalkane. An exception is in reaction with silyl chlorides, bromides, and iodides, where the oxygen acts as the nucleophile to produce silyl enol ether.

See also

Related Research Articles

<span class="mw-page-title-main">Beta sheet</span> Protein structural motif

The beta sheet is a common motif of the regular protein secondary structure. Beta sheets consist of beta strands (β-strands) connected laterally by at least two or three backbone hydrogen bonds, forming a generally twisted, pleated sheet. A β-strand is a stretch of polypeptide chain typically 3 to 10 amino acids long with backbone in an extended conformation. The supramolecular association of β-sheets has been implicated in the formation of the fibrils and protein aggregates observed in amyloidosis, Alzheimer's disease and other proteinopathies.

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is often written as R−COOH or R−CO2H, sometimes as R−C(O)OH with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

<span class="mw-page-title-main">Functional group</span> Group of atoms giving a molecule characteristic properties

In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the rest of the molecule's composition. This enables systematic prediction of chemical reactions and behavior of chemical compounds and the design of chemical synthesis. The reactivity of a functional group can be modified by other functional groups nearby. Functional group interconversion can be used in retrosynthetic analysis to plan organic synthesis.

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

Monosaccharides, also called simple sugars, are the simplest forms of sugar and the most basic units (monomers) from which all carbohydrates are built. Simply, this is the structural unit of carbohydrates.

In chemistry, a structural isomer of a compound is another compound whose molecule has the same number of atoms of each element, but with logically distinct bonds between them. The term metamer was formerly used for the same concept.

<span class="mw-page-title-main">Aldehyde</span> Organic compound containing the functional group R−CH=O

In organic chemistry, an aldehyde is an organic compound containing a functional group with the structure R−CH=O. The functional group itself can be referred to as an aldehyde but can also be classified as a formyl group. Aldehydes are a common motif in many chemicals important in technology and biology.

<span class="mw-page-title-main">Phenyl group</span> Cyclic chemical group (–C₆H₅)

In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6H5, and is often represented by the symbol Ph. The phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen, which may be replaced by some other element or compound to serve as a functional group. A phenyl group has six carbon atoms bonded together in a hexagonal planar ring, five of which are bonded to individual hydrogen atoms, with the remaining carbon bonded to a substituent. Phenyl groups are commonplace in organic chemistry. Although often depicted with alternating double and single bonds, the phenyl group is chemically aromatic and has equal bond lengths between carbon atoms in the ring.

<span class="mw-page-title-main">Acyl group</span> Chemical group (R–C=O)

In chemistry, an acyl group is a moiety derived by the removal of one or more hydroxyl groups from an oxoacid, including inorganic acids. It contains a double-bonded oxygen atom and an organyl group or hydrogen in the case of formyl group. In organic chemistry, the acyl group is usually derived from a carboxylic acid, in which case it has the formula R−C(=O)−, where R represents an organyl group or hydrogen. Although the term is almost always applied to organic compounds, acyl groups can in principle be derived from other types of acids such as sulfonic acids and phosphonic acids. In the most common arrangement, acyl groups are attached to a larger molecular fragment, in which case the carbon and oxygen atoms are linked by a double bond.

In chemical nomenclature, the IUPAC nomenclature of organic chemistry is a method of naming organic chemical compounds as recommended by the International Union of Pure and Applied Chemistry (IUPAC). It is published in the Nomenclature of Organic Chemistry. Ideally, every possible organic compound should have a name from which an unambiguous structural formula can be created. There is also an IUPAC nomenclature of inorganic chemistry.

<span class="mw-page-title-main">Skeletal formula</span> Representation method in chemistry

The skeletal formula, line-angle formula, or shorthand formula of an organic compound is a type of molecular structural formula that serves as a shorthand representation of a molecule's bonding and some details of its molecular geometry. A skeletal formula shows the skeletal structure or skeleton of a molecule, which is composed of the skeletal atoms that make up the molecule. It is represented in two dimensions, as on a piece of paper. It employs certain conventions to represent carbon and hydrogen atoms, which are the most common in organic chemistry.

In organic chemistry, a substituent is one or a group of atoms that replaces atoms, thereby becoming a moiety in the resultant (new) molecule.

<span class="mw-page-title-main">Michael addition reaction</span> Reaction in organic chemistry

In organic chemistry, the Michael reaction or Michael 1,4 addition is a reaction between a Michael donor and a Michael acceptor to produce a Michael adduct by creating a carbon-carbon bond at the acceptor's β-carbon. It belongs to the larger class of conjugate additions and is widely used for the mild formation of carbon-carbon bonds.

In organic chemistry, α-keto halogenation is a special type of halogenation. The reaction may be carried out under either acidic or basic conditions in an aqueous medium with the corresponding elemental halogen. In this way, chloride, bromide, and iodide functionality can be inserted selectively in the alpha position of a ketone.

Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature is abound with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.

In organic chemistry, umpolung or polarity inversion is the chemical modification of a functional group with the aim of the reversal of polarity of that group. This modification allows secondary reactions of this functional group that would otherwise not be possible. The concept was introduced by D. Seebach and E.J. Corey. Polarity analysis during retrosynthetic analysis tells a chemist when umpolung tactics are required to synthesize a target molecule.

<span class="mw-page-title-main">Flippin–Lodge angle</span>

The Flippin–Lodge angle is one of two angles used by organic and biological chemists studying the relationship between a molecule's chemical structure and ways that it reacts, for reactions involving "attack" of an electron-rich reacting species, the nucleophile, on an electron-poor reacting species, the electrophile. Specifically, the angles—the Bürgi–Dunitz, , and the Flippin–Lodge, —describe the "trajectory" or "angle of attack" of the nucleophile as it approaches the electrophile, in particular when the latter is planar in shape. This is called a nucleophilic addition reaction and it plays a central role in the biological chemistry taking place in many biosyntheses in nature, and is a central "tool" in the reaction toolkit of modern organic chemistry, e.g., to construct new molecules such as pharmaceuticals. Theory and use of these angles falls into the areas of synthetic and physical organic chemistry, which deals with chemical structure and reaction mechanism, and within a sub-specialty called structure correlation.

Monosaccharide nomenclature is the naming system of the building blocks of carbohydrates, the monosaccharides, which may be monomers or part of a larger polymer. Monosaccharides are subunits that cannot be further hydrolysed in to simpler units. Depending on the number of carbon atom they are further classified into trioses, tetroses, pentoses, hexoses etc., which is further classified in to aldoses and ketoses depending on the type of functional group present in them.

<span class="mw-page-title-main">Non-proteinogenic amino acids</span> Are not naturally encoded in the genome

In biochemistry, non-coded or non-proteinogenic amino acids are distinct from the 22 proteinogenic amino acids, which are naturally encoded in the genome of organisms for the assembly of proteins. However, over 140 non-proteinogenic amino acids occur naturally in proteins and thousands more may occur in nature or be synthesized in the laboratory. Chemically synthesized amino acids can be called unnatural amino acids. Unnatural amino acids can be synthetically prepared from their native analogs via modifications such as amine alkylation, side chain substitution, structural bond extension cyclization, and isosteric replacements within the amino acid backbone. Many non-proteinogenic amino acids are important:

In chemical nomenclature, a descriptor is a notational prefix placed before the systematic substance name, which describes the configuration or the stereochemistry of the molecule. Some listed descriptors are only of historical interest and should not be used in publications anymore as they do not correspond with the modern recommendations of the IUPAC. Stereodescriptors are often used in combination with locants to clearly identify a chemical structure unambiguously.

References

  1. Nomenclature of Organic Chemistry. IUPAC Recommendations and Preferred Names 2013 (PDF). London: International Union of Pure and Applied Chemistry. ISBN   978-0-85404-182-4 . Retrieved 14 December 2022.
  2. Hackh's Chemical Dictionary. 1969. p. 95.
  3. "Nomenclature". Ask Dr. Shulgin Online. Center for Cognitive Liberty & Ethics. Retrieved August 5, 2010.