Carbyl sulfate

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Carbyl sulfate
Carbylsulfat Strukturformel.svg
Names
Preferred IUPAC name
1,3,2λ6,4λ6-Dioxadithiane-2,2,4,4-tetrone
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.244 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C2H4O6S2/c3-9(4)2-1-7-10(5,6)8-9/h1-2H2
    Key: VSANMHWDSONVEE-UHFFFAOYSA-N
  • InChI=1/C2H4O6S2/c3-9(4)2-1-7-10(5,6)8-9/h1-2H2
    Key: VSANMHWDSONVEE-UHFFFAOYAN
  • O=S1(=O)OS(=O)(=O)OCC1
Properties
C2H4O6S2
Molar mass 188.17 g·mol−1
AppearanceWhite solid
Melting point 107.5–109 °C (225.5–228.2 °F; 380.6–382.1 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Carbyl sulfate is an organosulfur compound. The white solid is the product of the reaction of sulfur trioxide and ethylene. It is used in preparation of some dyes and other organosulfur compounds. [1] Carbyl sulfate is a colorless, crystalline, hygroscopic substance although commercial product can appear as a liquid. Because of its unpleasant properties carbyl sulfate is difficult to handle and is usually not isolated but further processed to give secondary products.

Contents

Production

Regnault [2] and Heinrich Gustav Magnus [3] [4] reported first in the years 1838 to 1839 on the compound as reaction product of anhydrous ethanol and anhydrous sulfuric acid.

Carbyl sulfate is produced in the highly exothermic (about 800 kcal/kg) reaction of ethylene and sulfur trioxide in the vapor phase in nearly quantitative yield. [5] [6]

Carbylsulfat Synthese.svg

Disulfuric acid and chlorosulfuric acid can also be used as a sulfonating agent, replacing sulfur trioxide. Instead of ethylene, ethylene-forming agents can be used, e.g. ethanol or diethyl ether. [5]

The product of industrial processes is a water-clear liquid which has - in accordance with D.S. Breslow [5] (107.5 to 109 °C) - a melting range from 102 to 108 °C. Previously stated melting point of about 80 °C [4] results from adhering sulfur trioxide. [5]

Reactions and use

As a cyclic sulfate ester, it is an alkylating agent. Hydrolysis affords ethionic acid, which retains one sulfate ester group. Ethionic acid undergoes further hydrolysis to isethionic acid:

Isethionic acid 2-step.svg

Carbyl sulfate is used as precursor for vinylsulfonic acid and sodium vinyl sulfonate, which are important activated alkenes and are used e. g. as anionic comonomers. A number of functional compounds with a variety of applications are available by nucleophilic addition at the activated double bond of the vinyl sulfonic acid and its derivatives. [7]

Safety

The material is highly reactive. It can decompose explosively when heated above 170 °C. [ citation needed ]

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">Phthalic acid</span> Chemical compound

Phthalic acid is an aromatic dicarboxylic acid, with formula C6H4(CO2H)2. Although phthalic acid is of modest commercial importance, the closely related derivative phthalic anhydride is a commodity chemical produced on a large scale. Phthalic acid is one of three isomers of benzenedicarboxylic acid, the others being isophthalic acid and terephthalic acid.

<span class="mw-page-title-main">Sulfonate</span> Organosulfur compound of the form R–S(=O)2–O (charge –1)

In organosulfur chemistry, a sulfonate is a salt or ester of a sulfonic acid. It contains the functional group R−S(=O)2−O, where R is an organic group. Sulfonates are the conjugate bases of sulfonic acids. Sulfonates are generally stable in water, non-oxidizing, and colorless. Many useful compounds and even some biochemicals feature sulfonates.

<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">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<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.

The Kolbe–Schmitt reaction or Kolbe process is a carboxylation chemical reaction that proceeds by treating phenol with sodium hydroxide to form sodium phenoxide, then heating sodium phenoxide with carbon dioxide under pressure, then treating the product with sulfuric acid. The final product is an aromatic hydroxy acid which is also known as salicylic acid.

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

Aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution. Aryl sulfonic acids are used as detergents, dye, and drugs.

Chloral, also known as trichloroacetaldehyde or trichloroethanal, is the organic compound with the formula Cl3CCHO. This aldehyde is a colourless liquid that is soluble in a wide range of solvents. It reacts with water to form chloral hydrate, a once widely used sedative and hypnotic substance.

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

Ethyl sulfate, also known as sulfovinic acid, is an organic chemical compound used as an intermediate in the production of ethanol from ethylene. It is the ethyl ester of sulfuric acid.

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

Isethionic acid is an organosulfur compound containing an alkylsulfonic acid located beta to a hydroxy group. Its discovery is generally attributed to Heinrich Gustav Magnus, who prepared it by the action of solid sulfur trioxide on ethanol in 1833. It is a white water-soluble solid used in the manufacture of certain surfactants and in the industrial production of taurine. It is most commonly available in the form of its sodium salt.

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

Crotonic acid ((2E)-but-2-enoic acid) is a short-chain unsaturated carboxylic acid, described by the formula CH3CH=CHCO2H. It is called crotonic acid because it was erroneously thought to be a saponification product of croton oil. It crystallizes as colorless needles from hot water. With a cis-alkene, Isocrotonic acid is an isomer of crotonic acid. Crotonic acid is soluble in water and many organic solvents. Its odor is similar to that of butyric acid.

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

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

<span class="mw-page-title-main">Pinacol rearrangement</span> Rearrangement of compound by charge rearrangement.

The pinacol–pinacolone rearrangement is a method for converting a 1,2-diol to a carbonyl compound in organic chemistry. The 1,2-rearrangement takes place under acidic conditions. The name of the rearrangement reaction comes from the rearrangement of pinacol to pinacolone.

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

The Bunsen cell is a zinc-carbon primary cell composed of a zinc anode in dilute sulfuric acid separated by a porous pot from a carbon cathode in nitric or chromic acid.

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

Boron sulfide is the chemical compound with the formula B2S3. It is a white, moisture-sensitive solid. It has a polymeric structure. The material has been of interest as a component of "high-tech" glasses and as a reagent for preparing organosulfur compounds.

<span class="mw-page-title-main">Organosulfate</span> Organic compounds of the form R–O–SO₃ (charge –1)

In organosulfur chemistry, organosulfates are a class of organic compounds sharing a common functional group with the structure R−O−SO−3. The SO4 core is a sulfate group and the R group is any organic residue. All organosulfates are formally esters derived from alcohols and sulfuric acid although many are not prepared in this way. Many sulfate esters are used in detergents, and some are useful reagents. Alkyl sulfates consist of a hydrophobic hydrocarbon chain, a polar sulfate group and either a cation or amine to neutralize the sulfate group. Examples include: sodium lauryl sulfate and related potassium and ammonium salts.

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

Conhydrine is a poisonous alkaloid found in poison hemlock in small quantities.

Radical theory is an obsolete scientific theory in chemistry describing the structure of organic compounds. The theory was pioneered by Justus von Liebig, Friedrich Wöhler and Auguste Laurent around 1830 and is not related to the modern understanding of free radicals. In this theory, organic compounds were thought to exist as combinations of radicals that could be exchanged in chemical reactions just as chemical elements could be interchanged in inorganic compounds.

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

Vinylsulfonic acid is the organosulfur compound with the chemical formula CH2=CHSO3H. It is the simplest unsaturated sulfonic acid. The C=C double bond is a site of high reactivity. Polymerization gives polyvinylsulfonic acid, especially when used as a comonomer with functionalized vinyl and (meth)acrylic acid compounds. It is a colorless, water-soluble liquid, although commercial samples can appear yellow or even red.

References

  1. Kosswig, Kurt (2000). "Sulfonic Acids, Aliphatic". doi:10.1002/14356007.a25_503. ISBN   978-3-527-30673-2.{{cite book}}: |journal= ignored (help); Missing or empty |title= (help)
  2. Regnault, V. (1838). "Ueber die Einwirkung der wasserfreien Schwefelsäure auf Doppeltkohlenwasserstoff". Annalen der Pharmacie. 25: 32–47. doi:10.1002/jlac.18380250103.
  3. "Ueber das Carbylsulphat und die Aethionsäure". Annalen der Pharmacie. 32 (3): 249–258. 1839. doi:10.1002/jlac.18390320310.
  4. 1 2 "Zur Erinnerung an Gustav Magnus". Nach einem am 14. December 1870 in der General-Versammlung der Deutschen Chemischen Gesellschaft zu Berlin gehaltenen Vortrage August Wilhelm Hofmann s, Berlin, Ferd. Dümmler's Verlagsbuchhandlung, 1871 (S. 32)
  5. 1 2 3 4 Breslow, David S.; Hough, Robert R. (1957), "The Synthesis of Sodium Ethylenesulfonate from Ethylene", Journal of the American Chemical Society (in German), vol. 79, no. 18, pp. 5000–5002, doi:10.1021/ja01575a046
  6. DE 2509738 "Verfahren zur Herstellung von Carbylsulfat." Inventor: Rudolf Irnich, Rolf Schneider
  7. H. Distler (1965-04-07). "Zur Chemie der Vinylsulfonsäure". Angewandte Chemie. 77 (7): 291–302. doi:10.1002/ange.19650770704.

Further reading