Tert-Butylthiol

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tert-Butylthiol
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Names
Preferred IUPAC name
2-Methylpropane-2-thiol
Other names
t-BuSH
2-Methylpropane-2-thiol
2-Methyl-2-propanethiol
tert-Butyl mercaptan
Identifiers
3D model (JSmol)
AbbreviationsTBM
ChemSpider
ECHA InfoCard 100.000.810 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C4H10S/c1-4(2,3)5/h5H,1-3H3 Yes check.svgY
    Key: WMXCDAVJEZZYLT-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C4H10S/c1-4(2,3)5/h5H,1-3H3
    Key: WMXCDAVJEZZYLT-UHFFFAOYAT
  • SC(C)(C)C
Properties
C4H10S
Molar mass 90.18 g·mol−1
AppearanceColorless liquid
Density 0.8 g/mL
Melting point −0.50 °C (31.10 °F; 272.65 K)
Boiling point 62 to 65 °C (144 to 149 °F; 335 to 338 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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tert-Butylthiol, also known as tert-butyl mercaptan (TBM), and abbreciated t-BuSH, is an organosulfur compound with the formula (CH3)3CSH. This thiol is used as an odorant for natural gas,[ citation needed ] which is otherwise odorless. It may also have been used as a flavoring agent. [1]

Contents

Preparation

It was first prepared in 1890 by Leonard Dobbin [2] by the reaction of zinc sulfide and t-butyl chloride.

The compound was later prepared by the reaction of the Grignard reagent, t-BuMgCl, with sulfur to give the corresponding thiolate, followed by hydrolysis. [3] This preparation is shown below:

t-BuMgCl + S → t-BuSMgCl
t-BuSMgCl + H2O → t-BuSH + Mg(OH)Cl

It is made industrially by the reaction of isobutylene with hydrogen sulfide over a clay (silica alumina) catalyst. [4]

Reactions

tert-Butylthiol is deprotonated by lithium hydride in an aprotic solvent such as hexamethylphosphoramide (HMPA). The resulting lithium thiolate salt has been used as demethylating reagent. For example, treatment with 7-methylguanosine gives guanosine. Other N-methylated nucleosides in tRNA are not demethylated by this reagent. [5]

tert-Butylthiol reacts with thallium(I) ethoxide to give the thallium thiolate: [6]

(CH3)3CSH + TlOC2H5 → (CH3)3CSTl + HOC2H5

This thallium thiolate can be used to convert acyl chlorides to the thioester:

(CH3)3CSTl + RCOCl → RCOSC(CH3)3 + TlCl

tert-BuSLi reacts with MoCl4 with to give the tetrathiolate complex: [7]

MoCl4 + 4 t-BuSLi → Mo(t-BuS)4 + 4 LiCl

Commercial use and occurrence

tert-Butylthiol is the main ingredient in many gas odorant blends.[ citation needed ] It is always utilized as a blend of other compounds, typically dimethyl sulfide, methyl ethyl sulfide, tetrahydrothiophene or other mercaptans such as isopropyl mercaptan, sec-butyl mercaptan and/or n-butyl mercaptan, due to its rather high melting point of −0.5 °C (31.1 °F). These blends are used only with natural gas and not propane, as the boiling points of these blends and propane are quite different. Because propane is delivered as a liquid and vaporizes to gas when it is delivered to the appliance, the vapor liquid equilibrium would substantially reduce the amount of odorant blend in the vapor.

Food and flavor

tert-Butylthiol had been listed on the European Food Safety Authority (FL-no: 12.174) as a flavor additive. There is no indication of what flavor(s) it may have been used in. It has been removed from this list. [8]

tert-butylthiol as a very minor component of cooked potatoes. [9]

Safety

The Threshold limit value (TLV) is 0.5 ppm. tert-butylthiol has an odor threshold of <0.33 ppb. [10]

See also

Related Research Articles

<span class="mw-page-title-main">Thiol</span> Any organic compound having a sulfanyl group (–SH)

In organic chemistry, a thiol, or thiol derivative, is any organosulfur compound of the form R−SH, where R represents an alkyl or other organic substituent. The −SH functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols, and the word is a blend of "thio-" with "alcohol".

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

Ethanethiol, commonly known as ethyl mercaptan, is an organosulfur compound with the formula CH3CH2SH. is a colorless liquid with a distinct odor. Abbreviated EtSH, it consists of an ethyl group (Et), CH3CH2, attached to a thiol group, SH. Its structure parallels that of ethanol, but with sulfur in place of oxygen. The odor of EtSH is infamous. Ethanethiol is more volatile than ethanol due to a diminished ability to engage in hydrogen bonding. Ethanethiol is toxic in high concentrations. It occurs naturally as a minor component of petroleum, and may be added to otherwise odorless gaseous products such as liquefied petroleum gas (LPG) to help warn of gas leaks. At these concentrations, ethanethiol is not harmful.

<span class="mw-page-title-main">Aroma compound</span> Chemical compound that has a smell or odor

An aroma compound, also known as an odorant, aroma, fragrance or flavoring, is a chemical compound that has a smell or odor. For an individual chemical or class of chemical compounds to impart a smell or fragrance, it must be sufficiently volatile for transmission via the air to the olfactory system in the upper part of the nose. As examples, various fragrant fruits have diverse aroma compounds, particularly strawberries which are commercially cultivated to have appealing aromas, and contain several hundred aroma compounds.

<span class="mw-page-title-main">Trimethylsilyl group</span> Functional group

A trimethylsilyl group (abbreviated TMS) is a functional group in organic chemistry. This group consists of three methyl groups bonded to a silicon atom [−Si(CH3)3], which is in turn bonded to the rest of a molecule. This structural group is characterized by chemical inertness and a large molecular volume, which makes it useful in a number of applications.

<i>n</i>-Butyllithium Chemical compound

n-Butyllithium C4H9Li (abbreviated n-BuLi) is an organolithium reagent. It is widely used as a polymerization initiator in the production of elastomers such as polybutadiene or styrene-butadiene-styrene (SBS). Also, it is broadly employed as a strong base (superbase) in the synthesis of organic compounds as in the pharmaceutical industry.

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

Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as (CH3)2SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agent in organic synthesis.

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

Thiophenol is an organosulfur compound with the formula C6H5SH, sometimes abbreviated as PhSH. This foul-smelling colorless liquid is the simplest aromatic thiol. The chemical structures of thiophenol and its derivatives are analogous to phenols. An exception is the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring is replaced by a sulfur atom. The prefix thio- implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, in the case of 'thiol' that the alcohol oxygen atom is replaced by a sulfur atom.

Potassium <i>tert</i>-butoxide Chemical compound

Potassium tert-butoxide (or potassium t-butoxide) is a chemical compound with the formula [(CH3)3COK]n (abbr. KOtBu). This colourless solid is a strong base (pKa of conjugate acid around 17), which is useful in organic synthesis. The compound is often depicted as a salt, and it often behaves as such, but its ionization depends on the solvent.

<i>tert</i>-Butyllithium Chemical compound

tert-Butyllithium is a chemical compound with the formula (CH3)3CLi. As an organolithium compound, it has applications in organic synthesis since it is a strong base, capable of deprotonating many carbon molecules, including benzene. tert-Butyllithium is available commercially as hydrocarbon solutions; it is not usually prepared in the laboratory.

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

Trimethylsilyl cyanide is the chemical compound with the formula (CH3)3SiCN. This volatile liquid consists of a cyanide group, that is CN, attached to a trimethylsilyl group. The molecule is used in organic synthesis as the equivalent of hydrogen cyanide. It is prepared by the reaction of lithium cyanide and trimethylsilyl chloride:

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

Methyllithium is the simplest organolithium reagent, with the empirical formula CH3Li. This s-block organometallic compound adopts an oligomeric structure both in solution and in the solid state. This highly reactive compound, invariably used in solution with an ether as the solvent, is a reagent in organic synthesis as well as organometallic chemistry. Operations involving methyllithium require anhydrous conditions, because the compound is highly reactive toward water. Oxygen and carbon dioxide are also incompatible with MeLi. Methyllithium is usually not prepared, but purchased as a solution in various ethers.

Pivalic acid is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odiferous organic compound is solid at room temperature. Two abbreviation for pivalic acid are t-BuC(O)OH and PivOH. The pivalyl or pivaloyl group is abbreviated t-BuC(O).

<i>sec</i>-Butyllithium Chemical compound

sec-Butyllithium is an organometallic compound with the formula CH3CHLiCH2CH3, abbreviated sec-BuLi or s-BuLi. This chiral organolithium reagent is used as a source of sec-butyl carbanion in organic synthesis.

<span class="mw-page-title-main">1-Butanethiol</span> Chemical compound

1-Butanethiol, also known as butyl mercaptan, is a volatile, clear to yellowish liquid with a fetid odor, commonly described as "skunk" odor. In fact, 1-butanethiol is structurally similar to several major constituents of a skunk's defensive spray but is not actually present in the spray. The scent of 1-butanethiol is so strong that the human nose can easily detect it in the air at concentrations as low as 10 parts per billion. The threshold level for 1-butanethiol is reported as 1.4 ppb

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

Trimethyltin chloride is an organotin compound with the formula (CH3)3SnCl. It is a white solid that is highly toxic and malodorous. It is susceptible to hydrolysis.

An odorizer is a device that adds an odorant to a gas. The most common type is one that adds a mercaptan liquid into natural gas distribution systems so that leaks can be readily detected. Other types have been used for carbon dioxide fire extinguishers.

Organotellurium chemistry describes the synthesis and properties of organotellurium compounds, chemical compounds containing a carbon-tellurium chemical bond. Organotellurium chemistry is a lightly studied area, in part because of it having few applications.

The molecular formula C4H10S may refer to:

<span class="mw-page-title-main">Transition metal thiolate complex</span>

Transition metal thiolate complexes are metal complexes containing thiolate ligands. Thiolates are ligands that can be classified as soft Lewis bases. Therefore, thiolate ligands coordinate most strongly to metals that behave as soft Lewis acids as opposed to those that behave as hard Lewis acids. Most complexes contain other ligands in addition to thiolate, but many homoleptic complexes are known with only thiolate ligands. The amino acid cysteine has a thiol functional group, consequently many cofactors in proteins and enzymes feature cysteinate-metal cofactors.

<i>tert</i>-Butyl hypochlorite Chemical compound

tert-Butyl hypochlorite is the organic compound with the formula (CH3)3COCl. A yellow liquid, it is a rare example of an organic hypochlorite, i.e. a compound with an O-Cl bond. It is a reactive material that is useful for chlorinations. It can be viewed as a lipophilic version of sodium hypochlorite (bleach).

References

  1. "tert-butyl mercaptan". thegoodscentscompany.com.
  2. Dobbin, Leonard (1890). "On tertiary Butyl Mercaptan". Journal of the Chemical Society, Transactions. 57: 639–643. doi:10.1039/ct8905700639.
  3. Rheinboldt, Heinrich; Mott, Friedrich; Motzkus, Erwin; A. D. McMaster; B. M. Mattson; S. T. Michel (1932). "Tertiäres Butylmercaptan". Journal für Praktische Chemie. 134 (9–12): 257–281. doi:10.1002/prac.19321340901.
  4. Schulze, W.A.; Lyon, J.P. & Short, G.H. (1948). "Synthesis of Tertiary Alkyl Mercaptans". Industrial and Engineering Chemistry. American Chemical Society. 40 (12): 2308–2313. doi:10.1021/ie50468a019.
  5. Ho, Tse-Lok; Fieser, Mary; Fieser, Louis (2006). "Lithium 2-methylpropane-2-thiolate". Fieser and Fieser's Reagents for Organic Synthesis. doi:10.1002/9780471264194.fos06530. ISBN   0471264199.
  6. Spessard, Gary O.; Chan, Wan Kit; Masamune, S. (1990). "Preparation of thiol esters: s-tert-butyl cyclohexanecarbothioate and s-tert-butyl 3α,7α,12α-trihydroxy-5β-cholane-24-thioate". Organic Syntheses. 7: 87. doi:10.1002/0471264180.os061.28. ISBN   0471264229.
  7. Otsuka, Sei; Kamata, Masato; Hirotsu, Ken; Higuchi, Taiichi (1981). "A Novel Molybdenum Thiolato Compound, Tetrakis(tert-butylthiolato)molybdenum(IV). Preparation and Crystal and Molecular Structure". Journal of the American Chemical Society. 103 (11): 3011–3014. doi:10.1021/ja00401a017.
  8. "Scientific Opinion on Flavouring Group Evaluation 8, Revision 3 (FGE.08Rev3): Aliphatic and alicyclic mono-, di-, tri-, and polysulphides with or without additional oxygenated functional groups from chemical groups 20 and 30". EFSA. 11 May 2011. Retrieved 15 April 2013.
  9. Gumbmann, M. R.; Burr, H. K. (1964). "Food Flavors and Odors, Volatile Sulfur Compounds in Potatoes". Journal of Agricultural and Food Chemistry. 12 (5): 404–408. doi:10.1021/jf60135a004.
  10. Devos, M; Patte, F.; Rouault, J.; Lafort, P.; Van Gemert, L. J. (1990). Standardized Human Olfactory Thresholds. Oxford: IRL Press at Oxford University Press. p. 118. ISBN   0199631468.