Thionyl bromide

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Thionyl bromide
Structure of the thionyl bromide molecule Thionyl-bromide.png
Structure of the thionyl bromide molecule
3D model of a thionyl bromide molecule Thionyl-bromide-from-xtal-3D-vdW-B.png
3D model of a thionyl bromide molecule
Thionyl-bromide-xtal-3D-vdW.png
Names
IUPAC name
Thionyl bromide
Other names
Sulfur oxy dibromide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.332 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 208-064-3
PubChem CID
UNII
  • InChI=1S/Br2OS/c1-4(2)3 Yes check.svgY
    Key: HFRXJVQOXRXOPP-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Br2OS/c1-4(2)3
    Key: HFRXJVQOXRXOPP-UHFFFAOYAY
  • BrS(Br)=O
Properties
SOBr2
Molar mass 207.87 g/mol
Appearancecolorless liquid
Density 2.688 g/mL, liquid [1]
Melting point −52 °C (−62 °F; 221 K) ; may include supercooling [1]
Boiling point
  • 48 °C at 20 mmHg [1]
  • 136 °C at 1 atm but 13 decomposes [1]
decomposes
Solubility reacts in HBr, acetone, and alcohol
soluble in benzene, toluene, ether
Structure
trigonal pyramidal
1.47 D [1]
Hazards [2]
Occupational safety and health (OHS/OSH):
Main hazards
Readily decomposes in air to toxic gases
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg
Danger
H312, H314, H332
P280, P305+P351+P338, P310
Flash point Non-flammable
Safety data sheet (SDS) "External MSDS"
Related compounds
Related compounds
SOCl2, SeOCl2;

PBr3, Br2

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Thionyl bromide is the chemical compound SOBr2. It is less stable and less widely used than its chloride analogue, thionyl chloride, but engages in similar reactions. [3]

Contents

Chemistry

It is prepared by the action of hydrogen bromide on thionyl chloride, [4] although the corresponding reaction at higher pH (i.e. alkali bromides) proceeds only with difficulty: [1]

SOCl2 + 2 HBr → SOBr2 + 2 HCl

Phosphorus trichlorodibromide (but not phosphorus pentabromide!) converts sulfur dioxide to thionyl bromide. Thionyl chlorobromide appears to be a key intermediate in these syntheses, but has not been isolated. [1]

Thionyl bromide will convert alcohols to alkyl bromides and carboxylic acids to acyl bromides. Unlike with thionyl chloride, stoichiometric bases are problematic activating agents, because free bromide anions decompose thionyl bromide to tribromide, sulfur dioxide, and sulfur. [1]

It can be used for brominations of certain α,β-unsaturated carbonyl compounds. [5]

It may occasionally be used as a solvent. [6] [7]

Safety

SOBr2 hydrolyzes readily in air to release dangerous fumes of sulfur dioxide and hydrogen bromide.

SOBr2 + H2O → SO2 + 2 HBr

Decomposition to bromine and sulfur monoxide does not occur except at elevated temparatures. [1]

Related Research Articles

<span class="mw-page-title-main">Bromine</span> Chemical element with atomic number 35 (Br)

Bromine is a chemical element; it has symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from Ancient Greek βρῶμος (bromos) 'stench', referring to its sharp and pungent smell.

Hydrobromic acid is an aqueous solution of hydrogen bromide. It is a strong acid formed by dissolving the diatomic molecule hydrogen bromide (HBr) in water. "Constant boiling" hydrobromic acid is an aqueous solution that distills at 124.3 °C (255.7 °F) and contains 47.6% HBr by mass, which is 8.77 mol/L. Hydrobromic acid is one of the strongest mineral acids known.

In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

In organic chemistry, free-radical addition is an addition reaction which involves free radicals. These reactions can happen due to the free radicals having an unpaired electron in their valence shell, making them highly reactive. Radical additions are known for a variety of unsaturated substrates, both olefinic or aromatic and with or without heteroatoms.

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

Hydrogen bromide is the inorganic compound with the formula HBr. It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.6% HBr by mass form a constant-boiling azeotrope mixture that boils at 124.3 °C (255.7 °F). Boiling less concentrated solutions releases H2O until the constant-boiling mixture composition is reached.

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

Sulfur monoxide is an inorganic compound with formula SO. It is only found as a dilute gas phase. When concentrated or condensed, it converts to S2O2 (disulfur dioxide). It has been detected in space but is rarely encountered intact otherwise.

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

Oxalyl chloride is an organic chemical compound with the formula Cl−C(=O)−C(=O)−Cl. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

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

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides/oxychlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

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

Phosphorus tribromide is a colourless liquid with the formula PBr3. The liquid fumes in moist air due to hydrolysis and has a penetrating odour. It is used in the laboratory for the conversion of alcohols to alkyl bromides.

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

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

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

Thionyl fluoride is the inorganic compound with the formula SOF2. This colourless gas is mainly of theoretical interest, but it is a product of the degradation of sulfur hexafluoride, an insulator in electrical equipment. The molecule adopts a distorted pyramidal structure, with Cs symmetry. The S-O and S-F distances are 1.42 and 1.58 Å, respectively. The O-S-F and F-S-F angles are 106.2 and 92.2°, respectively.

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

Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.

<span class="mw-page-title-main">Molybdenum(V) chloride</span> Chemical compound

Molybdenum(V) chloride is the inorganic compound with the empirical formula MoCl5. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents.

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

Sulfur tetrafluoride is a chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous hydrogen fluoride gas upon exposure to water or moisture. Sulfur tetrafluoride is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

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

Arsenic trichloride is an inorganic compound with the formula AsCl3, also known as arsenous chloride or butter of arsenic. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of organoarsenic compounds.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

In inorganic chemistry, sulfonyl halide groups occur when a sulfonyl functional group is singly bonded to a halogen atom. They have the general formula RSO2X, where X is a halogen. The stability of sulfonyl halides decreases in the order fluorides > chlorides > bromides > iodides, all four types being well known. The sulfonyl chlorides and fluorides are of dominant importance in this series.

Organobromine chemistry is the study of the synthesis and properties of organobromine compounds, also called organobromides, which are organic compounds that contain carbon bonded to bromine. The most pervasive is the naturally produced bromomethane.

References

  1. 1 2 3 4 5 6 7 8 9 Magee, Philip S. (1971). "The SulfurBromine Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. pp. 271–276. ISBN   0-8247-1615-9. LCCN   70-154612.
  2. "Thionyl bromide". Sigma Aldrich.
  3. Mundy, B. P. (2004). "Thionyl Bromide". In Paquette, E. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York: J. Wiley & Sons. doi:10.1002/047084289X.rt098. ISBN   0471936235.
  4. Booth, Harold Simmons (1939). Inorganic syntheses. Volume 1. New York. p. 113. ISBN   978-0-470-13264-7. OCLC   86223179.{{cite book}}: CS1 maint: location missing publisher (link)
  5. Saraf, S. D. (1 August 1969). "Reaction of thionyl bromide with tropolone and phenol". Canadian Journal of Chemistry. 47 (15): 2803–2804. doi: 10.1139/v69-465 .
  6. Furlani, C.; Zinato, E. (May 1967). "Hexahalogenoniobates(V), Oxopentahalogenoniobates(V) and their electronic spectra". Zeitschrift für anorganische und allgemeine Chemie. 351 (3–4): 210–218. doi:10.1002/zaac.19673510311.
  7. The chemistry of the actinide and transactinide elements. Volumes 1-6 (4th ed.). Dordrecht: Springer. 2010. p. 526. ISBN   978-94-007-0211-0.