36635-61-7

Basic information

• Product Name: TosMIC
• Synonyms: 1-[(isocyanomethyl)sulfonyl]-4-methyl-benzen;METHYLIDYNE[[(4-METHYLPHENYL)SULFONYL]METHYL]AMMONIUM;LABOTEST-BB LT00159629;BENZENE, 1-[(ISOCYANOMETHYL)SULFONYL]-4-METHYL-;1-[(ISOCYANOMETHYL)SULFONYL]-4-METHYLBENZENE;4-TOLUENSULFONYLMETHYL ISOCYANIDE;4-TOLUENESULPHONYLMETHYL ISOCYANIDE;4-TOLUENESULFONYLMETHYL ISOCYANIDE
• CAS NO: 36635-61-7
• Molecular Formula: C₉H₉NO₂S
• Molecular Weight: 195.24
• EINECS: 253-140-1
• Product Categories: Benzene derivatives;Boron, Nitrile, Thio,& TM-Cpds;Aliphatics;Sulfur Compounds (for Synthesis);Synthetic Organic Chemistry;Tosmic;Tesaglitazar Carbjdopa;Building Blocks;Chemical Synthesis;Isocyanides;Nitrogen Compounds;Organic Building Blocks;cyanide
• Mol File: 36635-61-7.mol

Chemical Properties

• Melting Point: 109-113 °C(lit.)
• Boiling Point: 400.9 °C at 760 mmHg
• Flash Point: 196.3 °C
• Appearance: Clear/Liquid
• Density: 1.2721 (rough estimate)
• Refractive Index: 1.5270 (estimate)
• Storage Temp.: -20°C
• Solubility: water: slightly soluble
• Water Solubility: insoluble
• Sensitive: Moisture Sensitive
• Merck: 14,9556
• BRN: 3592382
• CAS DataBase Reference: TosMIC(CAS DataBase Reference)
• NIST Chemistry Reference: TosMIC(36635-61-7)
• EPA Substance Registry System: TosMIC(36635-61-7)

Safety Data

• Hazard Codes: T,Xi
• Statements: 23/24/25
• Safety Statements: 36/37-45-38-36/37/39-28A
• RIDADR: UN 2811 6.1/PG 3
• WGK Germany: 3
• F: 21
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 36635-61-7(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
Tosylmethyl isocyanide is used as a synthetic reagent for the preparation of biologically active pyrroles and imidazoles, which are important in the development of new drugs and pharmaceutical compounds. Its ability to inhibit [Fe]-hydrogenase makes it a promising candidate for applications in drug discovery and design.
Used in Organic Chemistry Research:
As a versatile synthon in organic chemistry, Tosylmethyl isocyanide is employed in the synthesis of a variety of heterocyclic compounds. Its unique chemical properties allow for the creation of complex molecular structures that can be used in various research applications, including the development of new materials and the study of chemical reactions.
Used in Chemical Synthesis:
Tosylmethyl isocyanide is used as a reagent in the preparation of biologically active heterocycles, which are essential components in the synthesis of various chemical compounds. Its high affinity for [Fe]-hydrogenase inhibition makes it a valuable tool in the development of new chemical processes and the improvement of existing ones.

Preparation

N-(p-Tolylsulfonylmethyl)formamide 1609: A 3-L, three-necked, round-bottomed flask, equipped with a mechanical stirrer, a condenser, and a thermometer, was charged with sodium p-toluenesulfinate 1606 (267 g, 1.5 mol). After the addition of water (750 mL), a 34–37% solution of formaldehyde 1607 (350 mL, 378 g, ca. 4.4 mol), formamide 1608 (600 mL, 680 g, 15 mol), and formic acid (200 mL, 244 g, 5.3 mol), the stirred reaction mixture was heated at 90 C°. The sodium p-toluenesulfinate dissolved during the heating, and the clear solution was kept at 90–95 C° for 2 h. It was then cooled in an ice/salt bath with continued stirring and further cooled overnight in a freezer at 20 C°. The white solid produced was collected by suction filtration. It was washed thoroughly in a beaker by stirring with three 250 mL portions of iced water. The product was dried under reduced pressure over phosphorus pentoxide at 70 C° to provide 134–150 g (42–47%) of crude N-(p-tolylsulfonylmethyl)formamide 1609; mp 106–110 C°. This product was sufficiently pure to be used directly in the following reaction.

Purification Methods

Use an efficient fume cupboard. Purify TOSMIC by dissolving (50g) in CH2Cl2 (150mL) and passing it through a column (40x3cm) containing neutral alumina (100g) in CH2Cl2 and eluting with CH2Cl2. A nearly colourless solution (700mL) is collected, evaporated in vacuo and the residue (42-47g) of TOSMIC (m 113-114o dec) is recrystallised once from MeOH (m 116-117o dec). [Hoogenboom et al. Org Synth 57 102 1977, Lensen Tetrahedron Lett 2367 1972.] It also crystallises from EtOH (charcoal) [Saito & Itano, J Chem Soc, Perkin Trans 1 1 1986].

InChI:InChI=1/C9H9NO2S/c1-8-3-5-9(6-4-8)13(11,12)7-10-2/h3-6H,7H2,1H3

Upstream product

• 593-75-9 methyl isocyanate 
• 455-16-3 p-toluenesulfonyl fluoride 
• 36635-56-0 N-(4-methylbenzenesulfonylmethyl)-formamide 
• 60-29-7 diethyl ether 
• 129747-73-5 3-thiophenecarboxaldehyde 
• 82072-22-8 3-hydroxymethylbenzyl bromide 
• 220244-10-0 (OC)4Mo(μ-CNCH2SO2-p-tolyl)(μ-dppa)Pt(PPh3) 
• 7446-09-5 sulfur dioxide 
• 1227697-28-0 phenyl 2-(chloro)ethane-2-[4({(4-methylphenyl)sulfonyl}-methylimino)-1,3-dithietan-2-ylidene]dithioate 
• 672-78-6 methyl p-toluene sulfinate 
• 106-45-6 para-thiocresol 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 98-59-9 p-toluenesulfonyl chloride 

Downstream Products

• 70380-73-3 2-(1,3-oxazol-5-yl)pyridine 
• 70380-75-5 4-(oxazol-5-yl)pyridine 
• 70380-74-4 3-(oxazol-5-yl)pyridine 
• 70380-67-5 5-(thiophen-2-yl)oxazole 
• 70380-70-0 5-(thiophen-2-yl)oxazole 
• 64269-61-0 5-butylsulfanyl-4-(toluene-4-sulfonyl)-thiazole 
• 65253-71-6 5-ethylsulfanyl-4-(toluene-4-sulfonyl)-thiazole 
• 64269-66-5 4-(toluene-4-sulfonyl)-4H-thiazole-5-thione; tetrabutylammonium salt 
• 38926-92-0 1-Formylamino-1-tosyl-2-(α-naphthyl)-propen 
• 37118-21-1 2-<4-(p-tolylsulfonyl)oxazol-5-yl>benzoic acid 
• 21101-85-9 2,3,3-trimethylbutanenitrile 
• 52329-81-4 4'ξ-ethoxy-4'H-(2endoO,5'rC¹)-spiro[bicyclo[2.2.1]heptane-2,5'-oxazole] 
• 35856-00-9 2-adamantanecarbonitrile 
• 38568-86-4 5-furan-2-yl-4-(toluene-4-sulfonyl)-thiazole 

Relevant articles and documents

Mechanochemical Syntheses of N-Containing Heterocycles with TosMIC

A mechanochemical van Leusen pyrrole synthesis with a base leads to 3,4-disubstitued pyrroles in moderate to excellent yields. The developed protocol is compatible with a range of electron-withdrawing groups and can also be applied to the synthesis of oxazoles. Attempts to mechanochemically convert the resulting pyrroles into porphyrins proved to be difficult.

Silver-Catalyzed Acyl Nitrene Transfer Reactions Involving Dioxazolones: Direct Assembly of N-Acylureas

Dioxazolones and isocyanides are useful synthetic building blocks, and have attracted significant attention from researchers. However, the silver-catalyzed nitrene transfer reaction of dioxazolones has not been investigated to date. Herein, a silver-catalyzed acyl nitrene transfer reaction involving dioxazolones, isocyanides, and water was realized in the presence of Ag2O to afford a series of N-acylureas in moderate to good yields.

Phenyl pyrrole compound and application thereof in bactericidal activity

The invention provides a novel phenyl pyrrole compound, and the phenyl pyrrole compound shows good bactericidal activity and can be used for preparing a broad-spectrum plant bactericide. In addition,the synthesis route is simple, the operation is convenient, the synthesis cost is reduced, and ecological environment pollution to soil, surface water, underground water and the like is avoided.

Nitrogen-substituted phenyl pyrrole compound and application thereof in plant sterilization

The invention provides a novel nitrogen-substituted phenyl pyrrole compound. The phenyl pyrrole compound shows good bactericidal activity and can be used for preparing bactericides with high-selectivity sterilization. Moreover, the synthesis route is simple, the operation is convenient, the synthesis cost is reduced, and ecological environment pollution to soil, surface water, underground water and the like is avoided.

Catalytic Enantio- and Diastereoselective Mannich Addition of TosMIC to Ketimines

Chiral amines bearing a stereocenter in the α position are ubiquitous compounds with many applications in the pharmaceutical and agrochemical sectors, as well as in catalysis. Catalytic asymmetric Mannich additions represent a valuable method to access such compounds in enantioenriched form. This work reports the first enantio- and diastereoselective addition of commercially available p-toluenesulfonylmethyl isocyanide (TosMIC) to ketimines, affording 2-imidazolines bearing two contiguous stereocenters, one of which is fully-substituted, with high yields and excellent stereocontrol. The reaction, catalyzed by silver oxide and a dihydroquinine-derived N,P-ligand, is broad in scope, operationally simple, and scalable. Derivatization of the products provides enantioenriched vicinal diamines, precursors to NHC ligands and sp3-rich heterocyclic scaffolds. Computations are used to understand catalysis and rationalize stereoselectivity.

Silver-catalyzed [3+2+1] annulation of aryl amidines with benzyl isocyanide

A silver-catalyzed [3+2+1] annulation of amidines with benzyl isocyanide toward 2,4-diaryl-1,3,5-triazines was developed. A variety of symmetrical and unsymmetrical products were obtained in moderate to good yields. This work also features an oxidant-free approach to 2,4-disubstituted triazines.

SUBSTITUTED IMIDAZO[1,5-A]PYRIMIDINES AND THEIR USE IN THE TREATMENT OF MEDICAL DISORDERS

The invention provides substituted imidazo[1,5-a]pyrimidines and related organic compounds, compositions containing such compounds, medical kits, and methods for using such compounds and compositions to treat medical disorders, e.g., Gaucher disease, Parkinson's disease, Lewy body disease, dementia, or multiple system atrophy, in a patient. Exemplary substituted imidazo[1,5-a]pyrimidine compounds described herein include substituted 2,4-dimethyl-N-phenylimidazo[1,5-a]pyrimidine-8-carboxamide compounds and variants thereof.

A 2-fluoro-4-methyl sulfonyl methyl isonitriles method for the synthesis of

The invention discloses a synthesis method of 2-fluoro-4-toluenesulfonylmethyl isocyanide. The method comprises the following steps: with sodium p-tolylsulfinate as a raw material, carrying out similar Mannich condensation and amide dehydration reaction to prepare tolylsulfonylmethyl isocyanide; adding a hydrofluoric acid aqueous solution and an Ni-CO catalyst to tolylsulfonylmethyl isocyanide; and fully reacting under nitrogen protection, and carrying out suction filtration, washing and drying to obtain faint yellow crystal 2-fluoro-4-toluenesulfonylmethyl isocyanide, wherein the yield reaches over 92%, and the purity is 99.8%. The synthesis method has the advantages of being available in reaction raw materials, mild in condition, high in yield, suitable for industrial production and the like.

4 - (2,2-difluoro -1,3-Benzodioxole-4-yl) pyrrole-3-nitrile synthetic method

The invention discloses a synthetic method of 4-(2,2-difluoro-1,3-benzodioxole-4-yl)pyrrole-3-nitrile. The method comprises the following steps of: preparing an intermediate 2,2-difluorobenz-1,3-dioxole through reacting catechol with dibromodifluoromethane, and preparing an intermediate 2-cyano-3-(2,2-difluorobenz-1,3-dioxole-4-yl)-2-acrylate. The fludioxonil prepared by the synthetic method provided by the invention has the purity of more than 99.0% and the total yield of more than 45.0%; the synthetic method has the advantages of cheap and easily available raw materials, simple process, high product yield in each step, good purity, low production cost, applicability to batch industrial production and the like.

Alkyl sulfinates: Formal nucleophiles for synthesizing TosMIC analogs

Alkyl sulfinates function as formal nucleophiles in Mannich-type reactions to give sulfonyl formamides, which are readily dehydrated to the corresponding sulfonylmethyl isonitriles. The efficient, two-step synthesis provides a general route to sulfonylmethyl isonitriles from readily available methyl sulfinates or thiols. Mechanistic analysis reveals that the unusual nucleophlicity of the alkyl sulfinates arises from the in situ release of sulfinic acids.