4-Toluenesulfonyl chloride

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4-Toluenesulfonyl chloride
P-Toluenesulfonyl chloride structure.svg
Tosyl-chloride-3D-vdW.png
Names
Preferred IUPAC name
4-Methylbenzene-1-sulfonyl chloride
Other names
Tosyl chloride, p-toluenesulfonyl chloride, p-TsCl, TsCl
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.002.441 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C7H7ClO2S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3 Yes check.svgY
    Key: YYROPELSRYBVMQ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C7H7ClO2S/c1-6-2-4-7(5-3-6)11(8,9)10/h2-5H,1H3
    Key: YYROPELSRYBVMQ-UHFFFAOYAN
  • O=S(Cl)(=O)c1ccc(cc1)C
Properties
C7H7ClO2S
Molar mass 190.65 g/mol
AppearanceWhite solid
Melting point 65 to 69 °C (149 to 156 °F; 338 to 342 K)
Boiling point 134 °C (273 °F; 407 K) at 10 mmHg
Reacts with water
Hazards [1]
Occupational safety and health (OHS/OSH):
Main hazards
Releases HCl on contact with water
NFPA 704 (fire diamond)
3
1
0
Flash point 128 °C (262 °F; 401 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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4-Toluenesulfonyl chloride (p-toluenesulfonyl chloride, toluene-p-sulfonyl chloride) is an organic compound with the formula CH3C6H4SO2Cl. This white, malodorous solid is a reagent widely used in organic synthesis. [2] Abbreviated TsCl or TosCl, it is a derivative of toluene and contains a sulfonyl chloride (−SO2Cl) functional group.

Contents

Uses

In characteristic manner, TsCl converts alcohols (abbreviated ROH) into the corresponding toluenesulfonate esters, or tosyl derivatives ("tosylates"):

CH3C6H4SO2Cl + ROH → CH3C6H4SO2OR + HCl

Tosylates can be cleaved with lithium aluminium hydride:

4 CH3C6H4SO2OR + LiAlH4 → LiAl(O3SC6H4CH3)4 + 4 RH

Thus, tosylation followed by reduction allows for removal of a hydroxyl group.

Likewise, TsCl is used to prepare sulfonamides from amines: [3]

CH3C6H4SO2Cl + R2NH → CH3C6H4SO2NR2 + HCl

The resulting sulfonamides are non-basic and, when derived from primary amines, are even acidic.

TsCl reacts with hydrazine to give p-toluenesulfonyl hydrazide.

The preparation of tosyl esters and amides are conducted in the presence of a base, which absorbs hydrogen chloride. The selection of the base is often crucial to the efficiency of tosylation. Typical bases include pyridine and triethylamine. Unusual bases are also used; for example, catalytic amounts of trimethylammonium chloride in the presence of triethylamine is highly effective by virtue of the trimethylamine. [2]

Other reactions

Being a widely available reagent, TsCl has been heavily examined from the perspective of reactivity. It is used in dehydrations to make nitriles, isocyanides and diimides. [2] In an unusual reaction focusing on the sulfur center, zinc reduces TsCl to the sulfinate, CH3C6H4SO2Na. [4]

Manufacture

This reagent is inexpensively available for laboratory use. It is a by-product from the production of ortho-toluenesulfonyl chloride (a precursor for the synthesis of the common food additive and catalyst saccharin), via the chlorosulfonation of toluene: [5]

CH3C6H5 + SO2Cl2 → CH3C6H4SO2Cl + HCl

Hazards

Tosyl chloride is considered to be a toxic and corrosive substance. [6]

Related Research Articles

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<span class="mw-page-title-main">Tosyl group</span> Functional group consisting of a tolyl and sulfonyl group

In organic chemistry, a toluenesulfonyl group is a univalent functional group with the chemical formula H3CC6H4SO2–. It consists of a tolyl group, H3CC6H4–, joined to a sulfonyl group, –SO2–, with the open valence on sulfur. This group is usually derived from the compound tosyl chloride, H3CC6H4SO2Cl, which forms esters and amides of toluenesulfonic acid, H3CC6H4SO2OH. The para orientation illustrated (p-toluenesulfonyl) is most common, and by convention tosyl without a prefix refers to the p-toluenesulfonyl group.

<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.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

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

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<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">Oxalyl chloride</span> Chemical compound

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<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">Triflic acid</span> Chemical compound

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p-Toluenesulfonyl hydrazide is the organic compound with the formula CH3C6H4SO2NHNH2. It is a white solid that is soluble in many organic solvents but not water or alkanes. It is a reagent in organic synthesis.

<i>p</i>-Toluenesulfonic acid Chemical compound

p-Toluenesulfonic acid (PTSA or pTsOH) or tosylic acid (TsOH) is an organic compound with the formula CH3C6H4SO3H. It is a white extremely hygroscopic solid that is soluble in water, alcohols, and other polar organic solvents. The CH3C6H4SO2 group is known as the tosyl group and is often abbreviated as Ts or Tos. Most often, TsOH refers to the monohydrate, TsOH.H2O.

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.

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

Triphenylphosphine oxide (often abbreviated TPPO) is the organophosphorus compound with the formula OP(C6H5)3, also written as Ph3PO or PPh3O (Ph = C6H5). This colourless crystalline compound is a common but potentially useful waste product in reactions involving triphenylphosphine. It is a popular reagent to induce the crystallizing of chemical compounds.

Methanesulfonyl chloride is an organosulfur compound with the formula CH3SO2Cl. Using the organic pseudoelement symbol Ms for the methanesulfonyl group CH3SO2–, it is frequently abbreviated MsCl in reaction schemes or equations. It is a colourless liquid that dissolves in polar organic solvents but is reactive toward water, alcohols, and many amines. The simplest organic sulfonyl chloride, it is used to make methanesulfonates and to generate the elusive molecule sulfene.

The Hinsberg reaction is a test for the detection of primary, secondary and tertiary amines. In this test, the amine is shaken well with Hinsberg reagent in the presence of aqueous alkali. A reagent containing an aqueous sodium hydroxide solution and benzenesulfonyl chloride is added to a substrate. A primary amine will form a soluble sulfonamide salt. Acidification of this salt then precipitates the sulfonamide of the primary amine. A secondary amine in the same reaction will directly form an insoluble sulfonamide. A tertiary amine will not react with the original reagent(benzene sulfonyl chloride) and will remain insoluble. After adding dilute acid this insoluble amine is converted to a soluble ammonium salt. Hinsberg Test Is Used to distinguish between 1,2,3 degree amine with help of sulphonly cloride In this way the reaction can distinguish between the three types of amines.

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<span class="mw-page-title-main">Sulfonamide</span> Organosulfur compounds with the –S(=O)2–N< structure

In organic chemistry, the sulfonamide functional group is an organosulfur group with the structure R−S(=O)2−NR2. It consists of a sulfonyl group connected to an amine group. Relatively speaking this group is unreactive. Because of the rigidity of the functional group, sulfonamides are typically crystalline; for this reason, the formation of a sulfonamide is a classic method to convert an amine into a crystalline derivative which can be identified by its melting point. Many important drugs contain the sulfonamide group.

References

  1. "P-TOLUENESULFONYL CHLORIDE (TOSYL CHLORIDE)".
  2. 1 2 3 Whitaker, D. T.; Whitaker, K. S.; Johnson, C. R.; Haas, J. (2006). "P-Toluenesulfonyl Chloride". p-Toluenesulfonyl Chloride. Encyclopedia of Reagents for Organic Synthesis. New York: John Wiley. doi:10.1002/047084289X.rt136.pub2. ISBN   978-0471936237. Archived from the original on 2016-03-05. Retrieved 2013-05-28.
  3. Ichikawa, J.; Nadano, R.; Mori, T.; Wada, Y. (2006). "5-endo-trig Cyclization of 1,1-Difluoro-1-alkenes: Synthesis of 3-Butyl-2-Fluoro-1-Tosylindole". Organic Syntheses . 83: 111.; Collective Volume, vol. 11, p. 834
  4. Whitmore, F. C.; Hamilton, F. H. (1922). "Sodium Toluenesulfinate". Organic Syntheses . 2: 89.; Collective Volume, vol. 1, p. 492
  5. Lindner, O.; Rodefeld, L. "Benzenesulfonic Acids and Their Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_507.
  6. 4-Toluenesulfonyl chloride: main hazards