4-methylbenzene-1-sulfonohydrazide

• ChemBase ID: 70112
• Molecular Formular: C7H10N2O2S
• Molecular Mass: 186.2315
• Monoisotopic Mass: 186.04629857
• SMILES: c1(ccc(cc1)C)S(=O)(=O)NN
• Canonical SMILES: NNS(=O)(=O)c1ccc(cc1)C
• InChI: InChI=1S/C7H10N2O2S/c1-6-2-4-7(5-3-6)12(10,11)9-8/h2-5,9H,8H2,1H3
• InChIKey: ICGLPKIVTVWCFT-UHFFFAOYSA-N

NAMES AND DATABASE IDS

Names

• IUPAC name: 4-methylbenzene-1-sulfonohydrazide
• IUPAC Traditional name: 4-toluenesulfonyl hydrazide
• Synonyms: p-Toluenesulfonic acid hydrazide; p-Toluenesulfonyl hydrazide; Tosylhydrazide; p-Toluenesulfonhydrazide; p-TOLUENESULFONYLHYDRAZINE; 4-Methylbenzenesulfonyl hydrazide; p-Toluenesulfonohydrazide; 4-Methylbenzenesulfonhydrazide; p-Toluenesulfonhydrazide; p-Toluenesulfonyl hydrazide; 4-甲苯磺酰肼; 发泡剂 TSH; 甲苯磺酰肼; 对甲苯磺酰肼; 对甲苯磺酰肼; 4-甲苯磺酰肼

Database IDs

• CAS Number: 1576-35-8
• EC Number: 216-407-3
• MDL Number: MFCD00007588
• Beilstein Number: 610130
• PubChem SID: 24847540; 162035837
• PubChem CID: 15303

CALCULATED PROPERTIES

• Acid pKa: 10.2463665
• H Acceptors: 3
• H Donor: 2
• LogD (pH = 5.5): 0.79622304
• LogD (pH = 7.4): 0.8005806
• Log P: 0.79622227
• Molar Refractivity: 47.7412 cm^3
• Polarizability: 18.81267 Å^3
• Polar Surface Area: 72.19 Å^2
• Rotatable Bonds: 1
• Lipinski's Rule of Five: true

PROPERTIES

Physical Property

• Melting Point: 103-108 °C(lit.); 108-111°C
• Flash Point: 140 °F; 60 °C
• Density: 1.4

Safety Information

• Storage Warning: IRRITANT
• RTECS: MW0210000
• European Hazard Symbols: Flammable (F); X; Harmful (Xn)
• UN Number: 3226; UN3226
• German water hazard class: 3
• Hazard Class: 4.1
• Packing Group: II
• Risk Statements: 11-22; 11-22-44
• Safety Statements: 7-16-36
• TSCA Listed: false; 是
• GHS Pictograms: GHS02; GHS06
• GHS Signal Word: Danger
• GHS Hazard statements: H242-H228-H301; H242-H301-H319
• GHS Precautionary statements: P210-P280F-P309-P310; P301 + P310-P305 + P351 + P338
• Personal Protective Equipment: Eyeshields, Faceshields, full-face particle respirator type N100 (US), Gloves, respirator cartridge type N100 (US), type P1 (EN143) respirator filter, type P3 (EN 143) respirator cartridges
• RID/ADR: UN 3226 4.1

Product Information

• Purity: ~99%; ≥95% (HPLC); 95+%; 97%; 98%
• Grade: technical
• Linear Formula: CH3C6H4SO2NHNH2

DETAILS

MP Biomedicals - 05218793

MP Biomedicals Rare Chemical collection

Sigma Aldrich - 132004

Packaging
25, 100, 500 g in poly bottle
Application
Widely used reagent for the preparation of tosylhydrazones.1,2,3,4

REFERENCES

• Reaction of tosylhydrazones with base leads to alkenes (Bamford-Stevens reaction): J. Chem. Soc., 4735 (1952). Dianion formation from the tosylhydrazone with an alkyllithium or LDA results in a vinyllithium intermediate, which, on protonation, also gives the alkene (Shapiro-Heath reaction). With unsymmetrical tosylhydrazones, this is a useful synthesis of the less-substituted of the two possible alkenes: J. Am. Chem. Soc., 89, 5734 (1967); J. Org. Chem., 43, 1404 (1978):
  
• For a reviews of the Bamford-Stevens, Shapiro-Heath and related reactions, see: Org. React., 23, 405 (1976); 39, 1 (1990). For an example (bornene: 63-66% yield from camphor tosylhydrazone and MeLi), see: Org. Synth. Coll., 6, 172 (1988).
• Precursor of the versatile synthetic intermediates, tosylhydrazones. For a brief feature on tosylhydrazones, see: Synlett, 1844 (1999). Preparation using AcOH rather than mineral acid was found to reduce azine formation: Synthesis, 957 (1984).
• Several simple methods are known for cleavage of tosylhydrazones, including:
• Exchange with refluxing acetone: J. Org. Chem., 40, 3302 (1975); acetone/ BF₃ etherate: Synthesis, 456 (1976); Amberlyst. 15 in aqueous acetone: J. Chem. Soc., Perkin 1, 2563 (1988).
• Reduction of tosylhydrazones to alkanes by NaBH₄ is a mild alternative to the Clemmensen and Wolff-Kishner methods: Chem. Ind. (London), 153, 1689 (1964). NaBH₄ in AcOH is a more selective system: J. Org. Chem., 43, 2299 (1978). For reduction of a steroidal ketone by catecholborane, see: Org. Synth. Coll., 6, 293 (1988). Aliphatic tosylhydrazones are also reduced to methylenes by NaBH₃CN, effective even for hindered ketones. For a study of the mechanism of this reduction, see: J. Org. Chem., 54, 4175 (1989).