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Triazines are a class of nitrogen-containing
heterocycle
A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different chemical element, elements as members of its ring(s). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis ...
s. The parent molecules'
molecular formula
In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
is . They exist in three
isomer
In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers.
Iso ...
ic forms, 1,3,5-triazines being common.
Structure
The triazines have planar six-membered
benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
-like ring but with three carbons replaced by nitrogens. The three isomers of triazine are distinguished by the positions of their nitrogen
atoms
Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons.
Every solid, liquid, gas, an ...
, and are referred to as 1,2,3-triazine, 1,2,4-triazine, and
1,3,5-triazine.
Other
aromatic
In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
nitrogen
heterocycle
A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different chemical element, elements as members of its ring(s). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis ...
s are
pyridine
Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakly alkaline, water-miscible liquid with a d ...
s with one ring nitrogen atom,
diazine
In organic chemistry, diazines are a group of organic compounds having the molecular formula . Each contains a benzene ring in which two of the C-H fragments have been replaced by isolobal nitrogen. There are three structural isomers:
* pyridaz ...
s with 2 nitrogen atoms in the ring,
triazole
A triazole is a heterocyclic compound featuring a five-membered ring of two carbon atoms and three nitrogen atoms with molecular formula C2H3N3. Triazoles exhibit substantial isomerism, depending on the positioning of the nitrogen atoms within t ...
s with 3 nitrogens in a 5 membered ring, and
tetrazine
Tetrazine is a compound that consists of a six-membered aromatic ring containing four nitrogen atoms with the molecular formula C2 H2 N4. The name ''tetrazine'' is used in the nomenclature of derivatives of this compound. Three core-ring isomer ...
s with 4 ring nitrogen atoms.
Uses
Melamine
A well known triazine is
melamine
Melamine is an organic compound with the formula C3H6N6. This white solid is a trimer of cyanamide, with a 1,3,5-triazine skeleton. Like cyanamide, it contains 67% nitrogen by mass, and its derivatives have fire retardant properties due t ...
(2,4,6-triamino-1,3,5-triazine). With three
amino
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent s ...
substituent
A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as ''side ...
s, melamine is a precursor to commercial
resins
In polymer chemistry and materials science, resin is a solid or highly viscous substance of plant or synthetic origin that is typically convertible into polymers. Resins are usually mixtures of organic compounds. This article focuses on natu ...
.
Guanamine
In organic chemistry, a guanamine is an organic compound with the formula (H2NC)2N3CR. They are heterocycles of the triazine class. Guanamines are closely related to melamine ((H2NC)3N3), except with one amino substituent replaced by an organic ...
s are closely related to melamine, except with one amino substituent replaced by an organic group. This difference is exploited in the use of guanamines to modify the crosslinking density in
melamine resin
Melamine resin or melamine formaldehyde (also shortened to melamine) is a resin with melamine rings terminated with multiple hydroxyl groups derived from formaldehyde. This thermosetting plastic material is made from melamine and formaldehyde. ...
s. Some commercially important guanamines are
benzoguanamine
Benzoguanamine is an organic compound with the chemical formula (CNH2)2(CC6H5)N3. It is related to melamine but with one amino group replaced by phenyl. Benzoguanamine is used in the manufacturing of melamine resins. Unlike melamine ((CNH2)3N3 ...
and
acetoguanamine.
Cyanuric chloride
Another important triazine is
cyanuric chloride
Cyanuric chloride is an organic compound with the formula (NCCl)3. This white solid is the chlorinated derivative of 1,3,5-triazine. It is the trimer of cyanogen chloride. Cyanuric chloride is the main precursor to the popular but controver ...
(2,4,6-trichloro-1,3,5-triazine). Chlorine-substituted triazines are components of
reactive dye
In a reactive dye, a chromophore (an atom or group whose presence is responsible for the colour of a compound) contains a substituent that reacts with the substrate. Reactive dyes have good fastness properties owing to the covalent bonding that oc ...
s.
[Horst Tappe, Walter Helmling, Peter Mischke, Karl Rebsamen, Uwe Reiher, Werner Russ, Ludwig Schläfer and Petra Vermehren "Reactive Dyes"in Ullmann's Encyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim. ] These compounds react through a chlorine group with hydroxyl groups present in
cellulose
Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell wall ...
fibres in
nucleophilic substitution
In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). The ...
, the other triazine positions contain chromophores. Triazine compounds are often used as the basis for various
herbicide
Herbicides (, ), also commonly known as weedkillers, are substances used to control undesired plants, also known as weeds.EPA. February 201Pesticides Industry. Sales and Usage 2006 and 2007: Market Estimates. Summary in press releasMain page fo ...
s.
Other
Triazines also have wide use in the oil and gas and petroleum processing industries as a non-regenerating sulfide removal agent; they are applied to fluid streams to remove hydrogen sulfide gas and mercaptan species, which can decrease the quality of the processed hydrocarbon and be harmful to pipeline and facility infrastructure if not removed.
Synthesis
The more common 1,3,5-isomers are prepared by trimerization of
nitrile
In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including met ...
and
cyanide
Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms.
In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of ...
compounds, although more specialized methods are known.
The 1,2,3- and 1,2,4-triazines are more specialized methods. The former family of triazines can be synthesized by thermal rearrangement of 2-azidocyclopropenes. Also mainly of specialized interest, the 1,2,4-isomer is prepared from condensation of 1,2-dicarbonyl compounds with
amidrazone
Amidrazones are a class of chemical compounds formally derived from carboxylic acids. Amidrazones can exists in two tautomeric forms: hydrazide imides (RC(=NH)NHNH2) and amide hydrazones (RC(NH2)=NNH2).
Uses
Some amidrazones have been employed ...
s. A classical synthesis is also the
Bamberger triazine synthesis The Bamberger triazine synthesis in organic chemistry is a classic organic synthesis of a triazine first reported by Eugen Bamberger in 1892.Hassner, A., Stumer, C., ''Organic Synthesis Based on Name Reactions'': 2nd. Ed. Tetrahedron Organic Chemi ...
.
Reactions
Although triazines are
aromatic
In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
compounds, their
resonance energy is much lower than in
benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
.
Electrophilic aromatic substitution
Electrophilic aromatic substitution is an organic reaction in which an atom that is attached to an aromatic system (usually hydrogen) is replaced by an electrophile. Some of the most important electrophilic aromatic substitutions are aromatic ni ...
is difficult but
nucleophilic aromatic substitution
A nucleophilic aromatic substitution is a substitution reaction in organic chemistry in which the nucleophile displaces a good leaving group, such as a halide, on an aromatic ring. Aromatic rings are usually nucleophilic, but some aromatic compou ...
easier than typical chlorinated benzenes. 2,4,6-Trichloro-1,3,5-triazine is easily hydrolyzed to
cyanuric acid
Cyanuric acid or 1,3,5-triazine-2,4,6-triol is a chemical compound with the formula (CNOH)3. Like many industrially useful chemicals, this triazine has many synonyms. This white, odorless solid finds use as a precursor or a component of bleaches ...
by heating with water. 2,4,6-Tris(phenoxy)-1,3,5-triazine results when the trichloride is treated with phenol. With amines, one or more chloride is displaced. The remaining chlorides are reactive, and this theme is the basis of the large field of
reactive dye
In a reactive dye, a chromophore (an atom or group whose presence is responsible for the colour of a compound) contains a substituent that reacts with the substrate. Reactive dyes have good fastness properties owing to the covalent bonding that oc ...
s.
Cyanuric chloride assists in the
amidation
In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it is p ...
of
carboxylic acid
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 or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...
s.
The 1,2,4-triazines can react with
electron
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family,
and are generally thought to be elementary particles because they have no kn ...
-rich dienophiles in an inverse electron demand
Diels-Alder reaction. This forms a bicyclic intermediate which normally then extrudes a molecule of nitrogen gas to form an aromatic ring again. In this way the 1,2,4-triazines can be reacted with
alkyne
\ce
\ce
Acetylene
\ce
\ce
\ce
Propyne
\ce
\ce
\ce
\ce
1-Butyne
In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and n ...
s to form pyridine rings. An alternative to using an alkyne is to use
norbornadiene
Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distin ...
which can be thought of as a masked alkyne.
In 2007, a method for synthesizing highly porous triazine-based polymers was discovered, and found to be useful (in conjunction with
palladium
Palladium is a chemical element with the symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1803 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas, which was itself na ...
) for the selective reduction of phenols.
Ligands
A series of 1,2,4-triazine derivatives known as
bis-triazinyl bipyridines
The ''bis''-triazinyl bipyridines (BTBPs) are a class of chemical compounds which are tetradentate ligands similar in shape to quaterpyridine. The BTBPs are made by the reaction of hydrazine and a 1,2-diketone (such as hexane-3,4-dione) with ...
(BTPs) have been considered as possible
extractant
Extraction in chemistry is a separation process consisting of the separation of a substance from a matrix. Common examples include '' liquid-liquid extraction'', and ''solid phase extraction''. The distribution of a solute between two phases ...
s for use in the advanced
nuclear reprocessing
Nuclear reprocessing is the chemical separation of fission products and actinides from spent nuclear fuel. Originally, reprocessing was used solely to extract plutonium for producing nuclear weapons. With commercialization of nuclear power, the ...
. BTPs are molecules containing a
pyridine
Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakly alkaline, water-miscible liquid with a d ...
ring bonded to two 1,2,4-triazin-3-yl groups.
Triazine-based
ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electr ...
s have been used to bind three dinuclear
arene
Aromatic compounds, also known as "mono- and polycyclic aromatic hydrocarbons", are organic compounds containing one or more aromatic rings. The parent member of aromatic compounds is benzene. The word "aromatic" originates from the past grouping ...
ruthenium
Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
(or
osmium
Osmium (from Greek grc, ὀσμή, osme, smell, label=none) is a chemical element with the symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a trace element in alloys, mos ...
) compounds to form
metallaprism Coordination cages are three-dimensional ordered structures in solution that act as hosts in host–guest chemistry. They are self-assembled in solution from organometallic precursors, and often rely solely on noncovalent interactions rather than co ...
s.
References
* ''Heterocyclic Chemistry'' T.L. Gilchrist 1985 (1997, )
See also
*
Hexahydro-1,3,5-triazine
In chemistry, hexahydro-1,3,5-triazine is a class of heterocyclic compounds with the formula (CH2NR)3. They are reduced derivatives of 1,3,5-triazine, which have the formula (CHN)3, a family of aromatic heterocycles. They are often called triaza ...
* 6-membered rings with one nitrogen atom:
pyridine
Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakly alkaline, water-miscible liquid with a d ...
* 6-membered rings with two nitrogen atoms:
diazine
In organic chemistry, diazines are a group of organic compounds having the molecular formula . Each contains a benzene ring in which two of the C-H fragments have been replaced by isolobal nitrogen. There are three structural isomers:
* pyridaz ...
s
* 6-membered rings with four nitrogen atoms:
tetrazine
Tetrazine is a compound that consists of a six-membered aromatic ring containing four nitrogen atoms with the molecular formula C2 H2 N4. The name ''tetrazine'' is used in the nomenclature of derivatives of this compound. Three core-ring isomer ...
s
* 6-membered rings with five nitrogen atoms:
pentazine
Pentazine is a hypothetical compound that consists of a six-membered aromatic ring containing five nitrogen atoms with the molecular formula C H N5. The name ''pentazine'' is used in the nomenclature of derivatives of this compound.
Pentazine ...
* 6-membered rings with six nitrogen atoms:
hexazine
Hexazine (also known as hexaazabenzene) is a hypothetical allotrope of nitrogen composed of 6 nitrogen atoms arranged in a ring-like structure analogous to that of benzene. It would be the final member of the azabenzene (azine) series, in which al ...
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Simple aromatic rings