80-48-8

Basic information

• Product Name: Methyl p-toluenesulfonate
• Synonyms: 4-methyl-benzenesulfonicacimethylester;Benzenesulfonicacid,4-methyl-,methylester;Methyl 4-methylbenzenesulfonate;Methyl ester of 4-methylbenzenesulfonic acid;Methyl para-toluenesulfonate;Methyl p-methylbenzenesulfonate;Methyl toluene-4-sulfonate;methyl4-methylbenzenesulfonate
• CAS NO: 80-48-8
• Molecular Formula: C₈H₁₀O₃S
• Molecular Weight: 186.23
• EINECS: 201-283-5
• Product Categories: Organic Building Blocks;Sulfur Compounds;Tosylates;Building Blocks;Chemical Synthesis;Organic Building Blocks;Sulfur Compounds
• Mol File: 80-48-8.mol

Chemical Properties

• Melting Point: 25-28 °C(lit.)
• Boiling Point: 144-145 °C5 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: White to yellow/Liquid or Low Melting Solid
• Density: 1.234 g/mL at 25 °C(lit.)
• Vapor Density: 6.45 (vs air)
• Vapor Pressure: 1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.5172(lit.)
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Water Solubility: Insoluble
• Sensitive: Moisture Sensitive
• BRN: 609209
• CAS DataBase Reference: Methyl p-toluenesulfonate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl p-toluenesulfonate(80-48-8)
• EPA Substance Registry System: Methyl p-toluenesulfonate(80-48-8)

Safety Data

• Hazard Codes: C,Xn
• Statements: 22-34-43-40-36/37/38
• Safety Statements: 26-36/37/39-45-24
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 3
• RTECS: XT7000000
• F: 21
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 80-48-8(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
Methyl p-toluenesulfonate is used as a methylating agent in organic synthesis, facilitating the transfer of a methyl group to other molecules. This property makes it a useful intermediate in the production of various organic compounds.
Used in Catalyst Applications:
In the industry of alkyd resins, Methyl p-toluenesulfonate is utilized as a catalyst to accelerate the reaction process, enhancing the efficiency and quality of the final product.
Used in Pharmaceutical Industry:
Methyl p-toluenesulfonate is employed in selective 1-substitution reactions of tetrazole, a chemical structure found in certain pharmaceutical compounds. This selective substitution is crucial for the development of specific drug molecules.
Used in Dye Manufacturing:
Methyl p-toluenesulfonate is used in the preparation of dyes, contributing to the coloration and stability of various dye products. Its role in dye manufacturing is essential for producing a wide range of colored materials used in different industries.
Used as Raw Material for Methylation:
Methyl p-toluenesulfonate also serves as a raw material for methylation processes, where it provides the methyl group necessary for the synthesis of a variety of chemical products. This makes it a key component in the production of numerous compounds across different sectors.

Preparation

Methyl p-toluenesulfonate was synthesized by the reaction of p-toluenesulfonyl chloride with methanol. Mix p-toluenesulfonyl chloride and methanol, slowly add 25% sodium hydroxide solution, control the temperature below 25 °C, stop adding alkali when the pH is 9, continue stirring for 2 hours, and leave overnight. The lower layer of reactant was taken, the upper layer was extracted with benzene, the extract was recovered with benzene and then combined with the lower layer, washed with water and 5% potassium carbonate solution in turn, dried and distilled under reduced pressure to obtain the finished product of methyl p-toluenesulfonate.

Synthesis Reference(s)

Chemical and Pharmaceutical Bulletin, 29, p. 623, 1981 DOI: 10.1248/cpb.29.623Synthetic Communications, 15, p. 1057, 1985 DOI: 10.1080/00397918508076842

Hazard

Toxic by ingestion and inhalation, strongirritant to skin and eyes.

Safety Profile

Poison by ingestion and subcutaneous routes. An eye and severe skin irritant. A vesicant and skin sensitizer. Questionable carcinogen with experimental tumorigenic data. When heated to decomposition it emits toxic fumes of SOx.

Purification Methods

The ester is purified by distillation in vacuo and could be crystallised from pet ether or Et2O/pet ether at low temperature. It is a powerful methylating agent, is TOXIC andis a skin irritant, so it is better to purify it by repeated distillation. [IR: Schreiber Anal Chem 21 1168 1949, Buehler et al. J Org Chem 2 167 1937, Roos et al. Org Synth Coll Vol I 145 1948, Beilstein 11 IV 247.]

InChI:InChI=1/C8H10O3S/c1-7-3-5-8(6-4-7)12(9,10)11-2/h3-6H,1-2H3

Upstream product

• 493-02-7 trans-Decalin 
• 80-11-5 N-methyl-N-nitrosotoluene-p-sulfonamide 
• 98-95-3 nitrobenzene 
• 108-90-7 chlorobenzene 
• 67-56-1 methanol 
• 98-59-9 p-toluenesulfonyl chloride 
• 124-41-4 sodium methylate 
• 16836-95-6 silver(I) 4-methylbenzenesulfonate 
• 74-88-4 methyl iodide 
• 599-91-7 propyl tosylate 
• 756-79-6 dimethyl methane phosphonate 
• 80-40-0 ethyl ester of p-toluenesulfonic acid 
• 536-57-2 p-toluene sulfinic acid 
• 15210-25-0 bicyclo[10.3.0]pentadec-1⁽¹²⁾-en-13-one 

Downstream Products

• 123127-12-8 8,8-dimethyl-3endo-phenacyl-nortropanium; toluene-4-sulfonate 
• 109-02-4 4-methyl-morpholine 
• 109438-78-0 1-ethyl-1-methyl-piperidinium; toluene-4-sulfonate 
• 694-85-9 1-methyl-2-pyridone 
• 38542-71-1 N-methylpyridinium p-toluenesulfonate 
• 116998-58-4 1-methyl-pyrimidinium; toluene-4-sulfonate 
• 7327-42-6 1-Methyl-4-vinylpyridinium p-Toluenesulfonate 
• 53920-49-3 N-methoxypyridinium p-toluenesulfonate 
• 7403-46-5 2-chloro-1-methylpyridinium p-toluenesulfonate 
• 16183-05-4 2,3,4-trimethyl-thiazolium; toluene-4-sulfonate 
• 25985-99-3 N-methoxy-2-methylpyridinium tosylate 
• 1703-18-0 1-methoxy-4-pyridone 
• 4594-71-2 N-methylisocarbostyril 
• 53890-40-7 N-Methyl-isoquinoline tosylate 

Relevant articles and documents

Ring contraction of N-acetyl-2-aryl-1,2,3,4-tetrahydro-4-quinolones with [hydroxy(tosyloxy)iodo]benzene to trans methyl N-acetyl-2-aryl-2,3-dihydroindol- 3-carboxylates

The ring contraction of N-acetyl-2-aryl-1,2,3,4-tetrahydro-4-quinolones with [hydroxy(tosyloxy)iodo]benzene to trans methyl N-acetyl-2-aryl-2,3- dihydroindol-3-carboxylates in trimethylorthoformate in good yield is described.

Iron(III)-Mediated Oxysulfonylation of Enamides with Sodium and Lithium Sulfinates

An iron-mediated vicinal difunctionalization of enamides and enecarbamates with sulfinic acid salts and alcohols is described. This reaction proceeds under mild conditions and furnishes the oxysulfonylated products in moderate to excellent yields. Moreover, the direct incorporation of sulfur dioxide into the sulfonylated products via organolithium chemistry has been achieved. The formed N-O-acetals are competent acylimine precursors. Their utilization as building blocks for the synthesis of biologically relevant β-amidosulfones is described as well.

Grob-type fragmentation of 5-oxabicyclo[2.1.1]hexane system: A strategy for synthesis of annulated and 2,2,5-trisubstituted tetrahydrofurans

Acid mediated, efficient Grob-type fragmentation reaction facilitated by vicinal ketal and ester moieties in variety of 5-oxabicyclo[2.1.1]hexanes leading to the corresponding annulated and 2,2,5-trisubstituted tetrahydrofurans is reported. Among the Br?nsted and Lewis acids tested, BF 3·OEt2 appears to give the best results, furnishing near quantitative yield (>99%) of tetrahydrofuran tricarboxylate derivatives under mild reaction condition. In case of unsymmetrical monosubstituted 5-oxabicyclo[2.1.1]hexanes two regioisomeric products are obtained. A strategy to transform one of the ester groups of the title compounds to protected hydroxymethyl moiety was evolved, which allows access to differentially protected 2-hydroxymethyl THF derivatives upon fragmentation. Employing TiCl4/R or S-BINOL as chiral Lewis acid, an enantioselective fragmentation (up to 66% ee) was described for the meso bis-furan derivative.

Method for the Preparation of Diamine Derivative

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A Scalable Metal-, Azide-, and Halogen-Free Method for the Preparation of Triazoles

A scalable metal-, azide-, and halogen-free method for the synthesis of substituted 1,2,3-triazoles has been developed. The reaction proceeds through a 3-component coupling of α-ketoacetals, tosyl hydrazide, and a primary amine. The reaction shows outstanding functional-group tolerance with respect to both the α-ketoacetal and amine coupling partners, providing access to 4-, 1,4-, 1,5-, and 1,4,5-substituted triazoles in excellent yield. This robust method results in densely functionalised 1,2,3-triazoles that remain challenging to prepare by azide–alkyne cycloaddition (AAC, CuAAC, RuAAC) methods and can be scaled in either batch or flow reactors. Methods for the chemoselective reaction of either aliphatic amines or anilines are also described, revealing some of the potential of this novel and highly versatile transformation.

6MNEP: A molecular cation with large hyperpolarizability and promise for nonlinear optical applications

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A simple method for the synthesis of sulfonic esters

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Design and Optimization of a Continuous Stirred Tank Reactor Cascade for Membrane-Based Diazomethane Production: Synthesis of α-Chloroketones

The development of a continuous diazomethane generator comprising a continuous stirred tank reactor (CSTR) cascade and membrane separation technology is reported. This reactor concept was applied for the telescoped three-step synthesis of a chiral α-chloroketone, a key building block for many HIV protease inhibitors, via a modified Arndt-Eistert reaction starting from N-protected l-phenylalanine. The initial mixed anhydride was generated in a coil reactor and directly introduced into the CSTR diazomethane cascade. The use of a semipermeable Teflon membrane (AF-2400) allowed the generation of anhydrous diazomethane, which diffuses through the membrane into the CSTR where it is immediately consumed by the anhydride to furnish the corresponding diazoketone. The subsequent halogenation with concentrated HCl was performed downstream in batch and allowed production of the α-chloroketone on a multigram scale, with a productivity of 1.54 g/h (5.2 mmol/h).

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

An alternative method for forming sulfonates through hypervalent iodine(III) reagent-mediated oxidation of sodium sulfinates has been developed. This transformation involves trapping reactive sulfonium species using alcohols. With additional optimization of the reaction conditions, the method appears extendable to other nucleophiles such as electron-rich aromatic systems or cyclic ethers through a ring opening pathway.

Methacetin preparation method

The invention discloses a methacetin preparation method. The preparation method comprises the steps of adding p-toluenesulfonyl chloride or p-toluenesulfonic acid, anhydrous methanol, a solvent and the like into a reactor, dropwise adding a reagent at a controlled temperature, monitoring the reaction, performing quenching, extracting, washing, drying, reduced-pressure filtering and concentrating to obtain an intermediate, then performing methylation to obtain a crude solid product of methacetin, and finally performing refining to obtain a white crystalline product of methacetin. Compared withconventional production technology and process, the synthesis and refining methods of the invention generate methacetin with less impurities and higher purity, and improve the product quality and theaccuracy of test results using the reagent methacetin.