1-isocyanomethanesulfonyl-4-methylbenzene

• ChemBase ID: 70085
• Molecular Formular: C9H9NO2S
• Molecular Mass: 195.23826
• Monoisotopic Mass: 195.03539953
• SMILES: C(S(=O)(=O)c1ccc(C)cc1)[N+]#[C-]
• Canonical SMILES: Cc1ccc(cc1)S(=O)(=O)C[N+]#[C-]
• InChI: InChI=1S/C9H9NO2S/c1-8-3-5-9(6-4-8)13(11,12)7-10-2/h3-6H,7H2,1H3
• InChIKey: CFOAUYCPAUGDFF-UHFFFAOYSA-N

NAMES AND DATABASE IDS

Names

• IUPAC name: 1-isocyanomethanesulfonyl-4-methylbenzene
• IUPAC Traditional name: TosMIC; 1-isocyanomethanesulfonyl-4-methylbenzene
• Synonyms: TosMIC; Tosylmethyl isocyanide; p-Toluenesulfonylmethyl isocyanide; 1-[(Isocyanomethyl)sulfonyl]-4-methylbenzene; (4-Methylphenylsulfonyl)methyl Isocyanide; 4-Toluenesulfonylmethyl Isocyanide; 4-Tolylsulfonylmethyl Isocyanide; Isocyanomethyl p-Tolyl Sulfone; NSC 631633; p-Toluenesulfonylmethylisonitrile; p-Tosylmethyl Isocyanide; p-Tosylmethyl Isonitrile; p-Tolylsulfonylmethyl isocyanide; Tosylmethyl isocyanide; 4-[(Isocyanomethyl)sulphonyl]toluene; (Toluene-4-sulphonyl)methyl isocyanide; Isocyanomethyl 4-methylphenyl sulphone; TosMIC; TosMIC, Toluene-4-sulfonylmethyl Isocyanide; p-Toluenesulfonylmethyl isocyanide; (p-Tolylsulfonyl)methyl isocyanide; N-对甲苯磺酰甘氨酸; 对甲基苯磺酰甲基异腈; 对甲苯磺酰甲基异腈

Database IDs

• CAS Number: 36635-61-7
• EC Number: 253-140-1
• MDL Number: MFCD00000005
• Beilstein Number: 3592382
• PubChem SID: 24889279; 162035810; 24851306
• PubChem CID: 161915
• Chemspider ID: 142204
• Wikipedia Title: TosMIC

CALCULATED PROPERTIES

• Acid pKa: 15.737245
• H Acceptors: 2
• H Donor: 0
• LogD (pH = 5.5): -0.69407797
• LogD (pH = 7.4): -0.69407797
• Log P: -0.69407797
• Molar Refractivity: 59.3927 cm^3
• Polarizability: 20.242544 Å^3
• Polar Surface Area: 38.5 Å^2
• Rotatable Bonds: 2
• Lipinski's Rule of Five: true

PROPERTIES

Physical Property

• Solubility: Chloroform; Methanol
• Apperance: Tan Solid
• Melting Point: 108-110°C (dec.); 109 - 113°C; 109-113 °C; 109-113 °C(lit.); 109-114°C; 113-114°C

Safety Information

• Storage Condition: 2-8°C; Refrigerator
• Storage Warning: IRRITANT; Moisture Sensitive; Toxic/Light Sensitive/Air Sensitive/Moisture Sensitive/Keep Cold/Store under Argon
• European Hazard Symbols: Toxic (T)
• UN Number: 2811; UN2811
• German water hazard class: 3
• Hazard Class: 6.1
• Packing Group: 3; II
• Risk Statements: 23/24/25; R23/24/25
• Safety Statements: 36/37-45; S36/37 S45
• TSCA Listed: false; 否
• GHS Pictograms: GHS06
• GHS Signal Word: Danger
• GHS Hazard statements: H300-H311-H331; H301-H311-H331
• GHS Precautionary statements: P261-P280-P301 + P310-P311; P280H-P309-P310
• Personal Protective Equipment: Eyeshields, Faceshields, Gloves, type P2 (EN 143) respirator cartridges
• RID/ADR: UN 2811 6.1/PG 3
• Storage Temperature: 2-8°C

Product Information

• Purity: ≥98.0% (HPLC); 95+%; 97+%; 98%
• Grade: purum
• Linear Formula: CH3C6H4SO2CH2NC

DETAILS

MP Biomedicals - 02152153

Crystalline
Reagent used to convert a ketone to the next higher carboxylic acid or nitrile. Also used for synthesis of five-membered heterocycles.

Sigma Aldrich - 188204

Application
Reagent for use in the preparation of biologically active pyrroles and imidazoles.1,2
Used as the isonitrile component in a diastereoselective Passerini reaction employing sugar-derived aldehydes.
Packaging
5, 25 g in glass bottle

Sigma Aldrich - 89816

Other Notes
Versatile formyl anion equivalent1,2

Toronto Research Chemicals - T667500

Tosylmethyl Isocyanide is used as a synthetic reagent in the preparation of variety or biologically active heterocycles such as pyrroles and imidazoles. Tosylmethyl Isocyanide is reported to inhibit [Fe]-hydrogenase with very high affinity.

REFERENCES

• Shima, S. et al.: FEBS Lett., 585, 353 (2011)
• Yamada, N. et al.: Biosci. Biotechnol. Biochem., 56, 1943 (2011)
• Other applications in heterocyclic synthesis include the synthesis of:
• Imidazoles by reaction with imidoyl chlorides: Tetrahedron Lett., 2373 (1972). Thiazoles by reaction with CS₂ under phase-transfer conditions: Synthesis, 501 (1977). 1,2,4-Triazoles by reaction with diazonium salts, and pyrroles by reaction with Michael acceptors: Tetrahedron Lett., 5337 (1972). Pyrroles are also formed by reaction with aldehydes followed by either ethyl cyanoacetate to give 3-cyanopyrroles: J. Org. Chem., 57, 2245 (1992), or nitromethane to give 3-nitropyrroles: Tetrahedron, 47, 4639 (1991); Synthesis, 871 (1996). The same products are also obtained by reaction of TosMIC with nitroalkenes, from Henry reaction of the aldehydes with nitromethane:
  
• For a brief feature on uses of the reagent in synthesis, see: Synlett, 363 (2005).
• Successive alkylation with different alkyl groups, followed by acid hydrolysis, leads to unsymmetrical ketones: Tetrahedron Lett., 4229 (1977). Similarly, dialkylation with ɑω-dihalides gives cyclobutanones: Synthesis, 325 (1980), or larger-ring ketones: Tetrahedron Lett., 22, 4193 (1981). Reaction of monoalkylated TosMIC with ɑω-dihalides is a useful route to 1,5- or 1,6-diketones: Rec. Trav. Chim., 104, 50 (1985):
  
• In the presence of base (e.g. KO-t-Bu) in an aprotic solvent, e.g. DME, ketones are cyanated to give the homologous nitriles; see, e.g.: Org. Synth. Coll., 6, 41 (1988). Hindered ketones can be cyanated in DMSO: J. Org. Chem., 42, 3114 (1977). Aldehydes condense with TosMIC at -50^o, followed by hydrolysis in refluxing methanol: Synth. Commun., 10, 399 (1980).
• In contrast, aldehydes with K₂CO₃ in refluxing methanol lead to high yields of 5-substituted oxazoles: Tetrahedron Lett., 2369 (1972); with acid chlorides, the corresponding 4-tosyl oxazoles are obtained. For asymmetric induction in the oxazole synthesis by use of π-arylaldehyde-chromium tricarbonyl complexes, see: Tetrahedron: Asymmetry, 3, 287 (1992).