関: arylsulfonic acid

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/09/01 15:17:39」(JST)

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General structure of a sulfonic acid with the blue marked functional group

A sulfonic acid (or sulphonic acid) refers to a member of the class of organosulfur compounds with the general formula RS(=O)₂–OH, where R is an organic alkyl or aryl group and the S(=O)₂–OH group a sulfonyl hydroxide.^[1] A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound (with the organic substituent replaced by hydrogen) is the hypothetical compound sulfurous acid. Salts or esters of sulfonic acids are called sulfonates.

Preparation

Ball-and-stick model of methanesulfonic acid.

Sulfonic acid is produced by the process of sulfonation. Usually the sulfonating agent is sulfur trioxide. A particularly large scale application of this method is the production of alkylbenzenesulfonic acids:

RC₆H₅ + SO₃ → RC₆H₄SO₃H

In this reaction, sulfur trioxide is an electrophile and the arene undergoes electrophilic aromatic substitution.^[1]

Thiols can be oxidized to sulfonic acids:

RSH + 3/2 O₂ → RSO₃H

Certain sulfonic acids, such as perfluorooctanesulfonic acid are prepared by electrophilic fluorination of preformed sulfonic acids. The net conversion can be represented simplistically:

C₈H₁₇SO₃H + 17 F₂ → C₈F₁₇SO₃H + 17 HF

Properties

Sulfonic acids are much stronger acids than the corresponding carboxylic acids. p-Toluenesulfonic acid, with a pK_a of -2.8, is about a million times stronger acid than benzoic acid, with a pK_a of 4.2. Similarly, methanesulfonic acid, pK_a = -1.9, is also about one million times stronger acid than acetic acid. Because of their polarity, sulfonic acids tend to be crystalline solids. They are also usually colourless and nonoxidizing, which is convenient. Because of their high acidity, sulfonic acids are often soluble in water or exhibit detergent-like properties.

The structure of sulfonic acids is illustrated by the prototype, methanesulfonic acid. The sulfonic acid group, RSO₂OH features a tetrahedral sulfur centre, meaning that sulfur is at the center of four atoms: three oxygens and one carbon. The overall geometry of the sulfur centre is reminiscent of the shape of sulfuric acid.

Representative sulfonic acids and derivatives.
Taurine, a bile acid, and one of the few naturally occurring sulfonic acids (shown in uncommon tautomer).
PFOS, a surfactant and a controversial pollutant.
Toluenesulfonic acid, a widely used reagent in organic synthesis.
Nafion, a polymeric sulfonic acid useful in fuel cells.
Sodium dodecylbenzenesulfonate, an alkylbenzenesulfonate surfactant used in laundry detergents.

Applications

Although both alkyl and aryl sulfonic acids are known, most of the applications are associated with the aromatic derivatives.

Detergents and surfactants

Detergents and surfactants are molecules that combine highly nonpolar and highly polar groups. Traditionally, soaps are the popular surfactants, being derived from fatty acids. Since the mid-20th century, the usage of sulfonic acids has surpassed soap in advanced societies. For example, an estimated 2 billion kilograms of alkylbenzenesulfonates are produced annually for diverse purposes. Lignin sulfonates, produced by sulfonation of lignin are components of drilling fluids and additives in certain kinds of concrete.^[2]

Dyes

Many if not most of the anthroquinone dyes are produced or processed via sulfonation.^[3] Sulfonic acids tend to bind tightly to proteins and carbohydrates. Most "washable" dyes are sulfonic acids (or have the functional sulfonyl group in them) for this reason. p-Cresidinesulfonic acid is used to make food dyes.

Acid catalysts

Being strong acids, sulfonic acids are also used as catalysts. The simplest examples are methanesulfonic acid, CH₃SO₂OH and p-toluenesulfonic acid, which are regularly used in organic chemistry as acids that are lipophilic (soluble in organic solvents). Polymeric sulfonic acids are also useful. Dowex resin are sulfonic acid derivatives of polystyrene and is used as catalysts and for ion exchange (water softening).Nafion, a fluorinated polymeric sulfonic acid is a component of proton exchange membranes in fuel cells.^[4]

Drugs

Antibacterial drugs sulfa drugs are produced from sulfonic acids.

Flow Batteries

Methanesulfonic acid is used as the supporting electrolyte of the zinc-cerium and lead-acid (methanesulfonate) flow batteries.

Reactions

Esterification

Methyl triflate

Sulfonic acids can be converted to esters. This class of organic compounds has the general formula R-SO₂-OR. Sulfonic esters such as methyl triflate are considered good alkylating agents in organic synthesis. Such sulfonate esters are often prepared by alcoholysis of the sulfonyl chlorides:

RSO₂Cl + R'OH → RSO₂OR' + HCl

Halogenation

Sulfonyl halide groups occur when a sulfonyl functional group is singly bonded to a halogen atom. They have the general formula R-SO₂-X where X is a halide, almost invariably chloride. They are produced by chlorination of sulfonic acids using thionyl chloride and related reagents.

Displacement

Although the C-SO₃H bond is strong, the (aryl)C-SO₃ bond can be cleaved by certain nucleophiles. Of historic and continuing significance is the α-sulfonation of anthroquinone followed by displacement of the sulfonate group by other nucleophiles, which cannot be installed directly.^[3] An early method for producing phenol involved the base hydrolysis of sodium benzenesulfonate, which can be generated readily from benzene.^[5]

C₆H₅SO₃Na + 2 NaOH → C₆H₅OH + Na₂SO₃ + H₂O

References

^ ^a ^b March, Jerry (1992), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (4th ed.), New York: Wiley, ISBN 0-471-60180-2
^ Kosswig, K. “Surfactants” in Ullmann’s Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a25_747.
^ ^a ^b Hans-Samuel Bien, Josef Stawitz, Klaus Wunderlich “Anthraquinone Dyes and Intermediates” Ullmann's Encyclopedia of Industrial Chemistry 2002 Wiley-VCH, Weinhem. doi:10.1002/14356007.a02_355
^ Guido Busca "Acid Catalysts in Industrial Hydrocarbon Chemistry" Chem. Rev. 2007, 107, 5366-5410. doi:10.1021/cr068042e
^ Manfred Weber, Markus Weber, Michael Kleine-Boymann "Phenol" in Ullmann's Encyclopedia of Industrial Chemistry 2004, Wiley-VCH. doi:10.1002/14356007.a19_299.pub2.

English Journal

A Resin-linker-vector approach to radiopharmaceuticals containing 18F: application in the synthesis of O-(2-[18F]-fluoroethyl)-L-tyrosine.

Topley AC1, Isoni V, Logothetis TA, Wynn D, Wadsworth H, Gibson AM, Khan I, Wells NJ, Perrio C, Brown RC.
Chemistry (Weinheim an der Bergstrasse, Germany).Chemistry.2013 Jan 28;19(5):1720-5. doi: 10.1002/chem.201202474. Epub 2012 Dec 19.
A Resin-linker-vector (RLV) strategy is described for the radiosynthesis of tracer molecules containing the radionuclide (18)F, which releases the labelled vector into solution upon nucleophilic substitution of a polystyrene-bound arylsulfonate linker with [(18)F]-fluoride ion. Three model linker-ve
PMID 23255371

Removal of potentially genotoxic acetamide and arylsulfonate impurities from crude drugs by molecular imprinting.

Székely G1, Fritz E, Bandarra J, Heggie W, Sellergren B.
Journal of chromatography. A.J Chromatogr A.2012 Jun 1;1240:52-8. doi: 10.1016/j.chroma.2012.03.092. Epub 2012 Apr 5.
The present study describes the synthesis and preliminary testing of molecularly imprinted polymers (MIPs) as scavenger resins for removal of the genotoxic impurities (GTI) acetamide and arylsulfonates from active pharmaceutical ingredients (API). The MIPs were synthesized as monoliths using acetami
PMID 22525873

Clarification of the stereochemical course of nucleophilic substitution of arylsulfonate-based nucleophile assisting leaving groups.

Braddock DC1, Pouwer RH, Burton JW, Broadwith P.
The Journal of organic chemistry.J Org Chem.2009 Aug 21;74(16):6042-9. doi: 10.1021/jo900991z.
Secondary alcohols modified as tosylates, PEG-sulfonates, or quisylates undergo inversion of configuration at the reacting center when treated with lithium halide in acetone at reflux, where the PEG-sulfonates and quisylates are substantially more reactive. In sterically hindered cases, elimination
PMID 19591474

Japanese Journal

The Synthesis, Characterization and Lithography of Photo-Acid Generators with Improved Thermal Stability.

, , , , ,
Journal of Photopolymer Science and Technology 6(4), 515-524, 1993
… A new series of α-substituted-2-nitrobenzyl arylsulfonate PAG's was synthesized. …
NAID 130003488789

抗ピル性アクリル繊維の糸条形成と製糸過程における構造変化

青谷寛,山崎勝己
繊維学会誌 33(6), T239-T245, 1977
… a method for improving pilling tendency of acrylic fiber by strengthening intermolecular force, it has been shown in the previous papers that polymer composition should have been changed to be composed of more monomer with-SO3 Na such as sodium arylsulfonate.Mutual diffusion of solvent and coagulant, and change of the fine structure of the antipilling acrylic fiber during coagulation, drawing and drying of DMSO-H2O wet spinning process are studied in this report compared with conventional acrylic fiber.1) Diffusion of H2Oin during coagulation is much …
NAID 130004203089

アクリル繊維の微細構造と抗ピル性の関係について

青谷寛
繊維学会誌 33(6), T233-T239, 1977
… region and strong restrictive force to intermolecular bond are necessary to give anti-pilling property.For this purpose it is effective to strengthen CN-CN dipole interaction by reducing methylacrylate component and to raise density of crosslinkage by increasing sodium arylsulfonate component.It is also found that the higher crystallinity and the higher degree of orientation (Fx) determined by X-ray diffraction give fiber the better anti-pilling tendency, and above all whole molecular orientation (Fs) of fiber measured by velocity of sound has much …
NAID 130004203088

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リンク元	「駆虫薬」「arylsulfonic acid」「アリールスルホン酸」

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英: anthelmintic, anthelmintics
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antiplatyhelmintic agents	Antitrematodals (schistosomicides)	binds tubulin	benzimidazole (Triclabendazole#)
		acetylcholinesterase inhibitor	phosphonic acid (metrifonate)
		Other/unknown	quinoline (praziquantel#, oxamniquine#) · phenol (bithionol) · thiazole ([[niridazole]) · arylsulfonate (stibophen)
	anticestodals (taeniacides)	binds tubulin	benzimidazole (albendazole#)
	anticestodals (taeniacides)	Other/unknown	salicylanilide (niclosamide)# · aminoacridine (quinacrine) · butyrophenone (desaspidin) · chlorophenol (dichlorophen)
antinematodal agents (macrofilaricides)		binds tubulin	benzimidazole (mebendazole#, thiabendazole, albendazole#, fenbendazole, ciclobendazole, flubendazole)
		chloride channel	macrolide (ivermectin#)
		NMDA	tetrahydropyrimidine (pyrantel#, pyrantel pamoate, oxantel)
		Other/unknown	piperazine (piperazine · diethylcarbamazine#) · thiazole (levamisole#) · quinolinium (pyrvinium) · benzylammonium (bephenium) · naphthalenesulfonate (suramin#) · tribendimidine