Mercaptobenzothiazole

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Mercaptobenzothiazole
Mercaptobenzthiazole.svg
Names
Preferred IUPAC name
1,3-Benzothiazole-2(3H)-thione
Other names
Mercapto-2-benzothiazole; 2-MBT
Identifiers
3D model (JSmol)
508810
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.005.216 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 205-736-8
KEGG
PubChem CID
UNII
  • InChI=1S/C7H5NS2/c9-7-8-5-3-1-2-4-6(5)10-7/h1-4H,(H,8,9)
    Key: YXIWHUQXZSMYRE-UHFFFAOYSA-N
  • InChI=1/C7H5NS2/c9-7-8-5-3-1-2-4-6(5)10-7/h1-4H,(H,8,9)
    Key: YXIWHUQXZSMYRE-UHFFFAOYAK
  • c1ccc2c(c1)[nH]c(=S)s2
Properties
C7H5NS2
Molar mass 167.24 g·mol−1
Appearancewhite solid
Melting point 177–181 °C (351–358 °F; 450–454 K)
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H317, H410
P261, P272, P273, P280, P302+P352, P321, P333+P313, P363, P391, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

2-Mercaptobenzothiazole is an organosulfur compound with the formula C6H4(NH)SC=S. A white solid, it is used in the sulfur vulcanization of rubber. [1]

Contents

Structure

Tautomers and deprotonated form of mercaptobenzothiazole Mercaptobenzothiazole equilibrium.svg
Tautomers and deprotonated form of mercaptobenzothiazole

The molecule is planar with a C=S double bond, so the name mercaptobenzothiazole is a misnomer, a more appropriate name could be benzothiazoline-2-thione. Solution measurements by NMR spectroscopy could not measure the presence of the thiol tautomer that the name implies, instead it exists as a thione/dithiocarbamate and the hydrogen appears on the nitrogen in the solid state, gas-phase, and in solution. [2] Theory indicates that the thione tautomer is about 39 kJ/mol lower in energy than the thiol, and a hydrogen-bonded dimer of the thione has even lower energy. [3] At alkaline pH greater than 7 the deprotonated thiolate form is most abundant. A protonated form could not be observed in the pH range 2-11. [4]

Synthesis

The compound has been produced by many methods. The industrial route entails the high temperature reaction of aniline and carbon disulfide in the presence of sulfur, which proceeds by this idealized equation: [3]

C6H5NH2 + CS2 + S → C6H4(NH)SC=S + H2S

The traditional route is the reaction of 2-aminothiophenol and carbon disulfide:

C6H4(NH2)SH + CS2 → C6H4(NH)SC=S + H2S

This method was developed by the discoverer of the compound, A. W. Hoffmann. Other routes developed by Hoffmann include the reactions of carbon disulfide with 2-aminophenol and of sodium hydrosulfide with chlorobenzothiazole. [5] Further synthetic advances were reported in the 1920s that included demonstration that phenyldithiocarbamates pyrolyze to benzothiazole derivative. [6]

Reactions

The compound is insoluble in water but dissolves upon the addition of base, reflecting deprotonation. [7] Treatment with Raney nickel results in monodesulfurization, giving benzothiazole: [3]

C6H4(NH)SC=S + Ni → C6H4(N)SCH + NiS

The benzo ring undergoes electrophilic aromatic substitution at the position para to nitrogen. [3]

Oxidation gives mercaptobenzothiazole disulfide. This disulfide reacts with amines to give sulfenamide derivatives such 2-morpholinodithiobenzothiazole. These compounds are used in sulphur vulcanization, where they act as accelerators.

Uses

Using 2-mercaptobenzothiazole, rubber vulcanizes with less sulfur and at milder temperatures, both factors give a stronger product. This effect was reported by workers at Pirelli and at Goodyear Tire & Rubber. [1] Lorin B. Sebrell won the 1942 Charles Goodyear Medal for his work on mercaptobenzothiazole.

In polymerization, it finds use as a radical polymerization inhibitor, chain transfer agent, reforming agent, and additive for photoinitiators. [8]

The compound has also been used in the past in the gold-mining industry for the froth flotation of gold from ore residue as part of the extraction process. [9]

Sodium salt is used as a biocide and preservative in adhesives (especially based on latex, starch, casein, and animal glues), paper, textiles. Often found together with sodium dimethyldithiocarbamate as e.g. Vancide 51. Zinc salt is used as a secondary accelerator in latex foam vulcanization. [10]

It can be added to oil-based hydraulic fluids, heat-transfer fluids (oils, antifreezes), cutting fluids and other mixtures as a corrosion inhibitor, effective for copper and copper alloys. [11]

It is also used in veterinary dermatology. [12]

In electroplating it is used as a brightener for copper sulfate baths, at about 50-100 milligrams/liter. Also can be added to silver cyanide baths. [11]

Safety

Mercaptobenzothiazole has a low toxicity in mice, with LD50 of >960 mg/kg. [3]

Studies have identified it as a potential human carcinogen. [13] [14] In 2016, it was identified by the World Health Organization as probably carcinogenic to humans. [15]

It causes allergic contact dermatitis. [16] The derivative morpholinylmercaptobenzothiazole is a reported allergen in protective gloves, including latex, nitrile, and neoprene gloves. [17]

It becomes air-borne as a result of wear on car tires, and is able to be inhaled. [18]

Related Research Articles

<span class="mw-page-title-main">Vulcanization</span> Process of hardening rubber

Vulcanization is a range of processes for hardening rubbers. The term originally referred exclusively to the treatment of natural rubber with sulfur, which remains the most common practice. It has also grown to include the hardening of other (synthetic) rubbers via various means. Examples include silicone rubber via room temperature vulcanizing and chloroprene rubber (neoprene) using metal oxides.

In biochemistry, a disulfide refers to a functional group with the structure R−S−S−R′. The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In biology, disulfide bridges formed between thiol groups in two cysteine residues are an important component of the secondary and tertiary structure of proteins. Persulfide usually refers to R−S−S−H compounds.

<span class="mw-page-title-main">Carbon disulfide</span> Neurotoxic compound with formula S=C=S

Carbon disulfide is an inorganic compound with the chemical formula CS2 and structure S=C=S. It is a colorless, flammable, neurotoxic liquid that is used as a building block in organic synthesis. Pure carbon disulfide has a pleasant, ether- or chloroform-like odor, but commercial samples are usually yellowish and are typically contaminated with foul-smelling impurities.

Sulfur dyes are the most commonly used dyes manufactured for cotton in terms of volume. They are inexpensive, generally have good wash-fastness, and are easy to apply. Sulfur dyes are predominantly black, brown, and dark blue. Red sulfur dyes are unknown, although a pink or lighter scarlet color is available.

Thiourea is an organosulfur compound with the formula SC(NH2)2 and the structure H2N−C(=S)−NH2. It is structurally similar to urea, except that the oxygen atom is replaced by a sulfur atom ; however, the properties of urea and thiourea differ significantly. Thiourea is a reagent in organic synthesis. Thioureas are a broad class of compounds with the general structure R2N−C(=S)−NR2.

Accelerants are substances that can bond, mix, or disturb another substance to increase the rate of a natural or artificial chemical process. Accelerants play a major role in chemistry; most chemical reactions can be hastened with an accelerant. They may do so by altering a chemical bond, speeding up a chemical process, or bringing organisms back to homeostasis. Accelerants are not necessarily catalysts as they may be consumed by the process.

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.

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

Benzothiazole is an aromatic heterocyclic compound with the chemical formula C
7
H
5
NS
. It is colorless, slightly viscous liquid. Although the parent compound, benzothiazole is not widely used, many of its derivatives are found in commercial products or in nature. Firefly luciferin can be considered a derivative of benzothiazole.

Sulfur compounds are chemical compounds formed the element sulfur (S). Common oxidation states of sulfur range from −2 to +6. Sulfur forms stable compounds with all elements except the noble gases.

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

Thiocarbanilide is an organic chemical compound with the formula (C6H5NH)2CS. This white solid is a derivative of thiourea. It is prepared by the reaction of aniline and carbon disulfide.

<span class="mw-page-title-main">Dithiocarbamate</span> Chemical group (>N–C(=S)–S–)

In organic chemistry, a dithiocarbamate is a functional group with the general formula R2N−C(=S)−S−R and structure >N−C(=S)−S−. It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms.

<span class="mw-page-title-main">Thiuram disulfide</span> Class of chemical compounds

Thiuram disulfides are a class of organosulfur compounds with the formula (R2NCSS)2. Many examples are known, but popular ones include R = Me and R = Et. They are disulfides obtained by oxidation of the dithiocarbamates. These compounds are used in sulfur vulcanization of rubber as well as in the manufacture of pesticides and drugs. They are typically white or pale yellow solids that are soluble in organic solvents.

<span class="mw-page-title-main">Carbon subsulfide</span> Organic compound with the structure S=C=C=C=S

Carbon subsulfide is an organic, sulfur-containing chemical compound with the formula C3S2 and structure S=C=C=C=S. This deep red liquid is immiscible with water but soluble in organic solvents. It readily polymerizes at room temperature to form a hard black solid.

<span class="mw-page-title-main">Sulfenamide</span>

Sulfenamides (also spelled sulphenamides) are a class of organosulfur compounds characterized by the general formula RSNR'2, where R and R' are H, alkyl, or aryl. Sulfenamides have been used extensively in the vulcanization of rubber using sulfur. They are related to the oxidized compounds sulfinamides (RS(O)NR'2) and sulfonamides (RS(O)2NR'2).

David Spence was one of the pioneering rubber chemists. He helped the war effort during the Second World War by devising new ways of extracting natural rubbers from plants, and worked to improve the processing of the rubber. Over the course of his career, he worked to improve the dyeing processes for rubber products and the vulcanization of rubber, and in developing new accelerants for strengthening lower-quality natural rubber. In 1941, he became the first recipient of the Charles Goodyear Medal, awarded by the American Chemical Society.

Lorin Beryl Sebrell was an American scientist at the Goodyear Tire and Rubber Co. noted for identifying mercaptobenzothiazole as a vulcanization accelerator. In 1942, Sebrell received the Charles Goodyear Medal.

<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.

<i>N</i>-Methyl-2-thiazolidinethione Chemical compound

N-Methyl-2-thiazolidinethione is the organosulfur compound with the formula C2H4S(NCH3)CS. It is classified as a heterocycle called a thiazolidine. It is a colorless or off-white solid. It has gained attention as a proposed low toxicity replacement for ethylenethioureas, which are used as accelerators for the vulcanization of chloroprene rubbers. The compound is prepared by reaction of N-methylethanolamine and carbon disulfide.

<span class="mw-page-title-main">Sodium 1,3-dithiole-2-thione-4,5-dithiolate</span> Chemical compound

Sodium 1,3-dithiole-2-thione-4,5-dithiolate is the organosulfur compound with the formula Na2C3S5, abbreviated Na2dmit. It is the sodium salt of the conjugate base of the 1,3-dithiole-2-thione-4,5-dithiol. The salt is a precursor to dithiolene complexes and tetrathiafulvalenes.

<span class="mw-page-title-main">Sulfur vulcanization</span> Process to transform the material properties of natural rubber

Sulfur vulcanization is a chemical process for converting natural rubber or related polymers into materials of varying hardness, elasticity, and mechanical durability by heating them with sulfur or sulfur-containing compounds. Sulfur forms cross-linking bridges between sections of polymer chains which affects the mechanical and electronic properties. Many products are made with vulcanized rubber, including tires, shoe soles, hoses, and conveyor belts. The term vulcanization is derived from Vulcan, the Roman god of fire.

References

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