Benzotriazole

Last updated
Benzotriazole
Benzotriazole - numbered.png
Benzotriazole-3D-spacefill.png
Names
Preferred IUPAC name
1H-1,2,3-Benzotriazole
Other names
1H-Benzotriazole; 1,2,3-Benzotriazole; BTA; BtaH
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.002.177 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 202-394-1
PubChem CID
RTECS number
  • DM1225000
UNII
  • InChI=1S/C6H5N3/c1-2-4-6-5(3-1)7-9-8-6/h1-4H,(H,7,8,9) Yes check.svgY
    Key: QRUDEWIWKLJBPS-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H5N3/c1-2-4-6-5(3-1)7-9-8-6/h1-4H,(H,7,8,9)
    Key: QRUDEWIWKLJBPS-UHFFFAOYAH
  • n1c2ccccc2[nH]n1
Properties
C6H5N3
Molar mass 119.127 g·mol−1
AppearanceWhite solid
Density 1.36 g/mL [1]
Melting point 100 °C (212 °F; 373 K) [2]
Boiling point 350 °C (662 °F; 623 K) [2]
20 g/L [2]
Acidity (pKa)8.2 [3] [4]
Basicity (pKb)> 14 [4]
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H302, H319, H332, H411, H412
P261, P264, P270, P271, P273, P280, P301+P312, P304+P312, P304+P340, P305+P351+P338, P312, P330, P337+P313, P391, P501
Related compounds
Related compounds
Benzimidazole, Tolyltriazole
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Benzotriazole (BTA) is a heterocyclic compound with the chemical formula C6H5N3. Its five-membered ring contains three consecutive nitrogen atoms. This bicyclic compound may be viewed as fused rings of the aromatic compounds benzene and triazole. This white-to-light tan solid has a variety of uses, for instance, as a corrosion inhibitor for copper. [5]

Contents

Structure

Benzotriazole features two fused rings. Its five-membered ring can in principle exist as tautomers A and B: [6]

Benzotriazole tautomers and their derivatives (cropped).png

Various structural analyses with UV, IR and 1H-NMR spectra indicate that tautomer A is the dominant form at room temperature.

Synthesis and reactions

Synthesis of benzotriazole involves the reaction of o-phenylenediamine, sodium nitrite, and acetic acid. The conversion proceeds via diazotization of one of the amine groups: [7] [8]

Benzotriazole synthesis 01.svg

The synthesis can be improved when the reaction is carried out at low temperatures (5–10 °C) and briefly sonicated in an ultrasonic bath. [9] Typical batch purity is 98.5% or greater. [10]

Reactions

BTA is a weak acid with a pKa = 8.2 [3] [4]

It is a very weak Brønsted base with pKa < 0. [4]

Not only can it act either as an acid or base, it can also bind to other species, utilizing the lone pair electrons. Applying this property, the BTA can form a stable coordination compound on a copper surface and behave as a corrosion inhibitor. [6]

Benzotriazole (BtH) reacts with aromatic aldehydes (ArCHO) in the presence of ethanol to give benzotriazole-based N,O-acetals:

ArCHO + BtH + EtOH → ArCH(OEt)(Bt) + H2O

These acetals are susceptible to deprotonation, giving access to acylsilanes [11] and acylboranes.

N-amination of BtH with hydroxylamine-O-sulfonic acid gives 1-aminobenzotriazole. Oxidation of this amine with lead(IV) acetate affords benzyne, which rapidly dimerises to biphenylene. [12]

Dehydrobenzol aus Aminobenztriazol.svg

Applications

Benzotriazole has been known for its great versatility. It has already been used as a restrainer (or anti-fogging agent) in photographic emulsions or developing solutions, and as a reagent for the analytical determination of silver. More importantly, it has been extensively used as a corrosion inhibitor in the atmosphere and underwater. Also, its derivatives and their effectiveness as drug precursors have been drawing attention. Besides all the applications mentioned above, the BTA can be used as antifreezes, heating and cooling systems, hydraulic fluids, and vapor-phase inhibitors as well. [6]

Corrosion inhibition

Benzotriazole is an effective corrosion inhibitor for copper and its alloys by preventing undesirable surface reactions. It is known that a passive layer, consisting of a complex between copper and benzotriazole, is formed when copper is immersed in a solution containing benzotriazole. The passive layer is insoluble in aqueous and many organic solutions. There is a positive correlation between the thickness of the passive layer and the efficiency of preventing corrosion. [13] BTA is used in heritage conservation, notably for the treatment of bronze disease. The exact structure of the copper-BTA complex is controversial and many proposals have been suggested.[ citation needed ]

Chemical structure of the coordination polymer from benzotriazolate and copper(I), the active ingredient in the BT-derived corrosion inhibition PolyCubtri.svg
Chemical structure of the coordination polymer from benzotriazolate and copper(I), the active ingredient in the BT-derived corrosion inhibition

Drug precursor

Benzotriazole derivatives have chemical and biological properties that are versatile in the pharmaceutical industry. Benzotriazole derivatives act as agonists for many proteins. For instance, vorozole and alizapride have useful inhibitory properties against different proteins. Benzotriazole esters are used as mechanism-based inactivators to treat severe acute respiratory syndrome (SARS) by inhibiting the SARS 3CL protease of the SARS-CoV-1 virus. The methodology is not only limited to heterocyclization but was also successful for polynuclear hydrocarbons of small carbocyclic systems. [14]

Environmental relevance

Benzotriazole is fairly water-soluble, not readily degradable and has a limited sorption tendency. Hence, it is only partly removed in wastewater treatment plants and a substantial fraction reaches surface water such as rivers and lakes. [15] It is considered to be of low toxicity and a low health hazard to humans although exhibiting some antiestrogenic properties. [16]

Tolyltriazole is a mixture of isomers or congeners that differ from benzotriazole by the addition of one methyl group attached somewhere on the benzene ring. Tolyltriazole has similar uses, but has better solubility in some organic solvents.[ citation needed ]

Related Research Articles

<span class="mw-page-title-main">Aromatic compound</span> Compound containing rings with delocalized pi electrons

Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated." The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were understood. The current definition of aromatic compounds does not have any relation to their odor. Aromatic compounds are now defined as cyclic compounds satisfying Hückel's Rule. Aromatic compounds have the following general properties:

<span class="mw-page-title-main">Heterocyclic compound</span> Molecule with one or more rings composed of different elements

A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different elements as members of its ring(s). Heterocyclic organic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and applications of organic heterocycles.

<span class="mw-page-title-main">Pyridine</span> Heterocyclic aromatic organic compound

Pyridine is a basic heterocyclic organic compound with the chemical formula C5H5N. It is structurally related to benzene, with one methine group (=CH−) replaced by a nitrogen atom (=N−). It is a highly flammable, weakly alkaline, water-miscible liquid with a distinctive, unpleasant fish-like smell. Pyridine is colorless, but older or impure samples can appear yellow, due to the formation of extended, unsaturated polymeric chains, which show significant electrical conductivity. The pyridine ring occurs in many important compounds, including agrochemicals, pharmaceuticals, and vitamins. Historically, pyridine was produced from coal tar. As of 2016, it is synthesized on the scale of about 20,000 tons per year worldwide.

Pyrrole is a heterocyclic, aromatic, organic compound, a five-membered ring with the formula C4H4NH. It is a colorless volatile liquid that darkens readily upon exposure to air. Substituted derivatives are also called pyrroles, e.g., N-methylpyrrole, C4H4NCH3. Porphobilinogen, a trisubstituted pyrrole, is the biosynthetic precursor to many natural products such as heme.

<span class="mw-page-title-main">Quinoline</span> Chemical compound

Quinoline is a heterocyclic aromatic organic compound with the chemical formula C9H7N. It is a colorless hygroscopic liquid with a strong odor. Aged samples, especially if exposed to light, become yellow and later brown. Quinoline is only slightly soluble in cold water but dissolves readily in hot water and most organic solvents. Quinoline itself has few applications, but many of its derivatives are useful in diverse applications. A prominent example is quinine, an alkaloid found in plants. Over 200 biologically active quinoline and quinazoline alkaloids are identified. 4-Hydroxy-2-alkylquinolines (HAQs) are involved in antibiotic resistance.

<span class="mw-page-title-main">Isoquinoline</span> Chemical compound

Isoquinoline is an individual chemical specimen - a heterocyclic aromatic organic compound - as well as the name of a family of many thousands of natural plant alkaloids, any one of which might be referred to as "an isoquinoline". It is a structural isomer of quinoline. Isoquinoline and quinoline are benzopyridines, which are composed of a benzene ring fused to a pyridine ring. In a broader sense, the term isoquinoline is used to make reference to isoquinoline derivatives. 1-Benzylisoquinoline is the structural backbone in many naturally occurring alkaloids such as papaverine. The isoquinoline ring in these natural compound derives from the aromatic amino acid tyrosine.

A corrosion inhibitor or anti-corrosive is a chemical compound added to a liquid or gas to decrease the corrosion rate of a metal that comes into contact with the fluid. The effectiveness of a corrosion inhibitor depends on fluid composition and dynamics. Corrosion inhibitors are common in industry, and also found in over-the-counter products, typically in spray form in combination with a lubricant and sometimes a penetrating oil. They may be added to water to prevent leaching of lead or copper from pipes.

Quinazoline is an organic compound with the formula C8H6N2. It is an aromatic heterocycle with a bicyclic structure consisting of two fused six-membered aromatic rings, a benzene ring and a pyrimidine ring. It is a light yellow crystalline solid that is soluble in water. Also known as 1,3-diazanaphthalene, quinazoline received its name from being an aza derivative of quinoline. Though the parent quinazoline molecule is rarely mentioned by itself in technical literature, substituted derivatives have been synthesized for medicinal purposes such as antimalarial and anticancer agents. Quinazoline is a planar molecule. It is isomeric with the other diazanaphthalenes of the benzodiazine subgroup: cinnoline, quinoxaline, and phthalazine. Over 200 biologically active quinazoline and quinoline alkaloids are identified.

Tetrazoles are a class of synthetic organic heterocyclic compound, consisting of a 5-member ring of four nitrogen atoms and one carbon atom. The name tetrazole also refers to the parent compound with formula CH2N4, of which three isomers can be formulated.

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 the ring.

1,2,3-Triazole is one of a pair of isomeric chemical compounds with molecular formula C2H3N3, called triazoles, which have a five-membered ring of two carbon atoms and three nitrogen atoms. 1,2,3-Triazole is a basic aromatic heterocycle.

<i>o</i>-Phenylenediamine Chemical compound

o-Phenylenediamine (OPD) is an organic compound with the formula C6H4(NH2)2. This aromatic diamine is an important precursor to many heterocyclic compounds. OPD is a white compound although samples appear darker owing to oxidation by air. It is isomeric with m-phenylenediamine and p-phenylenediamine.

Pyrylium is a cation with formula C5H5O+, consisting of a six-membered ring of five carbon atoms, each with one hydrogen atom, and one positively charged oxygen atom. The bonds in the ring are conjugated as in benzene, giving it an aromatic character. In particular, because of the positive charge, the oxygen atom is trivalent. Pyrilium is a mono-cyclic and heterocyclic compound, one of the oxonium ions.

<span class="mw-page-title-main">Indoline</span> Chemical compound

Indoline is an aromatic heterocyclic organic compound with the chemical formulation C8H9N. It has a bicyclic structure, consisting of a six-membered benzene ring fused to a five-membered nitrogen-containing ring. The compound is based on the indole structure, but the 2-3 bond is saturated. By oxidation/dehydrogenation it can be converted to indole.

<span class="mw-page-title-main">Isoindole</span> Chemical compound

In organic chemistry and heterocyclic chemistry, isoindole consists of a benzene ring fused with pyrrole. The compound is an isomer of indole. Its reduced form is isoindoline. The parent isoindole is a rarely encountered in the technical literature, but substituted derivatives are useful commercially and occur naturally. Isoindoles units occur in phthalocyanines, an important family of dyes. Some alkaloids containing isoindole have been isolated and characterized.

<span class="mw-page-title-main">Triacetic acid lactone</span> Chemical compound

Triacetic acid lactone is an organic compound derived enzymatically from glucose. It is a light yellow solid that is soluble in organic solvents.

<span class="mw-page-title-main">Pyrithione</span> Chemical compound

Pyrithione is the common name of an organosulfur compound with molecular formula C
5
H
5
NOS
, chosen as an abbreviation of pyridinethione, and found in the Persian shallot. It exists as a pair of tautomers, the major form being the thione 1-hydroxy-2(1H)-pyridinethione and the minor form being the thiol 2-mercaptopyridine N-oxide; it crystallises in the thione form. It is usually prepared from either 2-bromopyridine, 2-chloropyridine, or 2-chloropyridine N-oxide, and is commercially available as both the neutral compound and its sodium salt. It is used to prepare zinc pyrithione, which is used primarily to treat dandruff and seborrhoeic dermatitis in medicated shampoos, though is also an anti-fouling agent in paints.

<span class="mw-page-title-main">2-Carboxybenzaldehyde</span> Chemical compound

2-Carboxybenzaldehyde is a chemical compound. It consists of a benzene ring, with an aldehyde and a carboxylic acid as substituents that are ortho to each other. The compound exhibits ring–chain tautomerism: the two substituents can react with each other to form 3-hydroxyphthalide, a cyclic lactol. This lactol reacts readily with Grignard reagents, forming alkyl- and aryl-substituted phthalides. Other benzo-fused heterocyclic compounds can be derived from 2-carboxybenzaldehyde, including isoindolinones and phthalazinones, with a variety of pharmacological properties, such as the antihistamine azelastine.

<span class="mw-page-title-main">1,2,3-Benzothiadiazole</span> Organic heterocyclic aromatic chemical

1,2,3-Benzothiadiazole is a bicyclic aromatic chemical composed of a benzene ring that is fused to a 1,2,3-thiadiazole. A colorless solid, the compound is soluble in organic solvents.

Corrosion inhibitors are substances used in the oil industry to protect equipment and pipes against corrosion. Corrosion is a common problem in the oil industry due to the presence of water, gases, and other corrosive contaminants in the production environment.

References

Commons-logo.svg Media related to Benzotriazole at Wikimedia Commons

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  2. 1 2 3 1H-Benzotriazole Archived September 27, 2007, at the Wayback Machine , SRC PhysProp Database
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