Methanethiol (also known as methyl

mercaptan In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...

) is an

organosulfur compound Organosulfur compounds 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 abounds with organosulfur compounds—sulfu ...

with the

chemical 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, ...

. It is a colorless gas with a distinctive putrid smell. It is a natural substance found in the

blood Blood is a body fluid in the circulatory system of humans and other vertebrates that delivers necessary substances such as nutrients and oxygen to the cells, and transports metabolic waste products away from those same cells. Blood in the c ...

brain A brain is an organ that serves as the center of the nervous system in all vertebrate and most invertebrate animals. It is located in the head, usually close to the sensory organs for senses such as vision. It is the most complex organ in a v ...

and

feces Feces ( or faeces), known colloquially and in slang as poo and poop, are the solid or semi-solid remains of food that was not digested in the small intestine, and has been broken down by bacteria in the large intestine. Feces contain a relati ...

of animals (including humans), as well as in plant tissues. It also occurs naturally in certain foods, such as some nuts and

cheese Cheese is a dairy product produced in wide ranges of flavors, textures, and forms by coagulation of the milk protein casein. It comprises proteins and fat from milk, usually the milk of cows, buffalo, goats, or sheep. During production, ...

. It is one of the chemical compounds responsible for

bad breath Bad breath, also known as halitosis, is a symptom in which a noticeably unpleasant breath odour is present. It can result in anxiety among those affected. It is also associated with depression and symptoms of obsessive compulsive disorder. Th ...

and the smell of

flatus Flatulence, in humans, is the expulsion of gas from the intestines via the anus, commonly referred to as farting. "Flatus" is the medical word for gas generated in the stomach or bowels. A proportion of intestinal gas may be swallowed environm ...

. Methanethiol is the simplest

thiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...

and is sometimes abbreviated as MeSH. It is very flammable.

Structure and reactions

The molecule is tetrahedral at the carbon atom, like

methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a ...

. It is a

weak acid Acid strength is the tendency of an acid, symbolised by the chemical formula HA, to dissociate into a hydron (chemistry), proton, H+, and an anion, A-. The Dissociation (chemistry), dissociation of a strong acid in solution is effectively comple ...

, with a p''K''_a of ~10.4, but is about a hundred thousand times more acidic than methanol. The colorless salt can be obtained in this way: :CH₃SH + CH₃ONa → CH₃SNa + CH₃OH The resulting thiolate anion is a strong

nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...

. It can be oxidized to

dimethyl disulfide Dimethyl disulfide (DMDS) is an organic chemical compound with the molecular formula which is the simplest disulfide. It is a flammable liquid with an unpleasant, garlic-like odor. Occurrence Dimethyl disulfide is a widespread natural odorifero ...

: :2CH₃SH + → CH₃SSCH₃ + H₂O Further oxidation takes the

disulfide In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . 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 ...

to two molecules of

methanesulfonic acid Methanesulfonic acid (MsOH) or methanesulphonic acid (in British English) is an organosulfuric, colorless liquid with the chemical formula and structure . It is the simplest of the alkylsulfonic acids (). Salts and esters of methanesulfonic aci ...

, which is odorless.

Bleach Bleach is the generic name for any chemical product that is used industrially or domestically to remove color (whitening) from a fabric or fiber or to clean or to remove stains in a process called bleaching. It often refers specifically, to ...

deodorizes methanethiol in this way.

Occurrence

Methanethiol (MeSH) is released as a by-product of

kraft pulping The kraft process (also known as kraft pulping or sulfate process) is a process for conversion of wood into wood pulp, which consists of almost pure cellulose fibres, the main component of paper. The kraft process involves treatment of wood chip ...

pulp mill A pulp mill is a manufacturing facility that converts wood chips or other plant fiber sources into a thick fiber board which can be shipped to a paper mill for further processing. Pulp can be manufactured using mechanical, semi-chemical, or ful ...

s. In kraft pulping,

lignin Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity ...

is depolymerized by nucleophilic attack with the strongly nucleophilic hydrosulfide ion (HS⁻) in a highly alkaline medium. However, in a side reaction, HS⁻ attacks methoxyl groups (OMe) in

, demethylating them to give free

phenolate Phenolates (also called phenoxides) are anions, salts, and esters of phenols. They may be formed by reaction of phenols with strong base. Properties Alkali metal phenolates, such as sodium phenolate hydrolyze in aqueous solution to form basic s ...

groups (PhO⁻) and releasing MeSH. Due to alkalinity, MeSH is readily deprotonated (

MeSNa Mesna, sold under the brand name Mesnex among others, is a medication used in those taking cyclophosphamide or ifosfamide to decrease the risk of bleeding from the bladder. It is used either by mouth or injection into a vein. Common side effec ...

), and the formed MeS⁻ ion is also a strong nucleophile, reacting further to

dimethyl sulfide Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a flammable liquid that boils at and has a characteristic disagreeable odor. It is a component of the smell produced from cook ...

. The compounds remain in the liquor and are burned in the

recovery boiler Recovery boiler is the part of kraft process of pulping where chemicals for white liquor are recovered and reformed from black liquor, which contains lignin from previously processed wood. The black liquor is burned, generating heat, which is usual ...

, where the sulfur is recovered as

sodium sulfide Sodium sulfide is a chemical compound with the formula Na2 S, or more commonly its hydrate Na2S·9 H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are gener ...

. Methanethiol is released from decaying organic matter in

marsh A marsh is a wetland that is dominated by herbaceous rather than woody plant species.Keddy, P.A. 2010. Wetland Ecology: Principles and Conservation (2nd edition). Cambridge University Press, Cambridge, UK. 497 p Marshes can often be found at ...

es and is present in the

natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbo ...

of certain regions, in

coal tar Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat psoriasi ...

, and in some

crude oil Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crude ...

s. It occurs in various plants and vegetables, such as radishes. In surface seawater, methanethiol is the primary breakdown product of the algal metabolite

dimethylsulfoniopropionate Dimethylsulfoniopropionate (DMSP), is an organosulfur compound with the formula (CH3)2S+CH2CH2COO−. This zwitterionic metabolite can be found in marine phytoplankton, seaweeds, and some species of terrestrial and aquatic vascular plants ...

(DMSP).

Marine bacteria Marine prokaryotes are marine bacteria and marine archaea. They are defined by their habitat as prokaryotes that live in marine environments, that is, in the saltwater of seas or oceans or the brackish water of coastal estuaries. All cellular ...

appear to obtain most of the sulfur in their proteins by the breakdown of DMSP and incorporation of methanethiol, despite the fact that methanethiol is present in seawater at much lower concentrations than sulfate (~0.3 nM vs. 28 mM). Bacteria in environments both with and without oxygen can also convert methanethiol to

(DMS), although most DMS in surface seawater is produced by a separate pathway. Both DMS and methanethiol can be used by certain microbes as substrates for

methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group ...

in some anaerobic soils. Methanethiol is a byproduct of the metabolism of

asparagus Asparagus, or garden asparagus, folk name sparrow grass, scientific name ''Asparagus officinalis'', is a perennial flowering plant species in the genus ''Asparagus''. Its young shoots are used as a spring vegetable. It was once classified in ...

. The production of methanethiol in urine after eating asparagus was once thought to be a genetic trait. More recent research suggests that the peculiar odor is in fact produced by all humans after consuming asparagus, while the ability to detect it (methanethiol being one of many components in "asparagus pee") is in fact the genetic trait. The chemical components responsible for the change in the odor of urine show as soon as 15 minutes after eating asparagus.

Preparation

Methanethiol is prepared commercially by the reaction of

with

hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...

gas over an aluminum oxide catalyst: :CH₃OH + H₂S → CH₃SH + H₂O Although impractical, it can be prepared by the reaction of

methyl iodide Iodomethane, also called methyl iodide, and commonly abbreviated "MeI", is the chemical compound with the formula CH3I. It is a dense, colorless, volatile liquid. In terms of chemical structure, it is related to methane by replacement of one h ...

with

thiourea Thiourea () is an organosulfur compound with the formula and the structure . It is structurally similar to urea (), except that the oxygen atom is replaced by a sulfur atom (as implied by the ''thio-'' prefix); however, the properties of urea ...

Uses

Methanethiol is mainly used to produce the essential amino acid

methionine Methionine (symbol Met or M) () is an essential amino acid in humans. As the precursor of other amino acids such as cysteine and taurine, versatile compounds such as SAM-e, and the important antioxidant glutathione, methionine plays a critical ro ...

, which is used as a dietary component in poultry and animal feed. Methanethiol is also used in the

plastic industry The plastics industry manufactures polymer materials—commonly called plastics—and offers services in plastics important to a range of industries, including packaging, building and construction, electronics, aerospace, and transportation. It is ...

as a moderator for free-radical polymerizations and as a precursor in the manufacture of

pesticide Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and lampri ...

s. This chemical is also used in the

industry as an odorant, as it mixes well with

methane Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Eart ...

. The characteristic rotting vegetation smell of the mix is widely known by natural gas customers as an indicator of a possible

gas leak A gas leak refers to a leak of natural gas or another gaseous product from a pipeline or other containment into any area where the gas should not be present. Gas leaks can be hazardous to health as well as the environment. Even a small leak into ...

, even a very minor one.

Safety

The

safety data sheet A safety data sheet (SDS), material safety data sheet (MSDS), or product safety data sheet (PSDS) is a document that lists information relating to occupational safety and health for the use of various substances and products. SDSs are a widely ...

(SDS) lists methanethiol as a colorless, flammable gas with an extremely strong and repulsive smell. At very high concentrations it is highly toxic and affects the central nervous system. Its penetrating odor provides warning at dangerous concentrations. An odor threshold of 1 ppb has been reported. The United States

OSHA OSHA or Osha may refer to: Work * Occupational Safety and Health Administration, a federal agency of the United States that regulates workplace safety and health * Occupational Safety and Health Act (United States) of 1970, a federal law in the Un ...

Ceiling Limit is listed as 10 ppm.

Accidents

In 2001 an explosion of left 3 people dead and 9 injured. On the 15th of November 2014, at Dupont's La Porte facility, a deadly release of Methyl Mercaptan occurred in a confined space, killing 4 and injuring 1 other. On 14 July 2022, there was an accidental release of methanethiol in

Charlotte, North Carolina Charlotte ( ) is the most populous city in the U.S. state of North Carolina. Located in the Piedmont region, it is the county seat of Mecklenburg County. The population was 874,579 at the 2020 census, making Charlotte the 16th-most populo ...

. While there were no injuries, a rare weather event caused the odor to persist for several hours. Many believed they were experiencing a natural gas leak, which lead to a high volume of emergency calls and the closure of several local government offices.

References

External links

NLM Hazardous Substances Databank – Methyl mercaptan
{{Authority control Alkanethiols Flatulence Foul-smelling chemicals Organic compounds with 1 carbon atom