(chloromethylidene)dimethylazanium chloride

• ChemBase ID: 148986
• Molecular Formular: C3H7Cl2N
• Molecular Mass: 128.00038
• Monoisotopic Mass: 126.99555459
• SMILES: C[N+](=CCl)C.[Cl-]
• Canonical SMILES: ClC=[N+](C)C.[Cl-]
• InChI: InChI=1S/C3H7ClN.ClH/c1-5(2)3-4;/h3H,1-2H3;1H/q+1;/p-1
• InChIKey: QQVDYSUDFZZPSU-UHFFFAOYSA-M

NAMES AND DATABASE IDS

Names

• IUPAC name: (chloromethylidene)dimethylazanium chloride
• IUPAC Traditional name: (chloromethylidene)dimethylazanium chloride
• Synonyms: Arnold′s reagent; Dimethylchloroformiminium chloride; (Chlormethylene)dimethylammonium chloride; Vilsmeier reagent; (Chloromethylene)dimethyliminium chloride; Arnold's Reagent; N,N-Dimethylchloroformimidinium chloride; (Chloromethylene)dimethylammonium chloride; 氯甲叉二甲基氯化铵; 维尔斯梅尔试剂; (氯亚甲基)二甲基氯化铵

Database IDs

• CAS Number: 3724-43-4
• EC Number: 425-970-6
• MDL Number: MFCD00011868
• Beilstein Number: 3566322
• PubChem SID: 162243156; 24855124; 24856957
• PubChem CID: 77311

CALCULATED PROPERTIES

• H Acceptors: 0
• H Donor: 0
• LogD (pH = 5.5): -3.0188434
• LogD (pH = 7.4): -3.0188434
• Log P: -3.0188434
• Molar Refractivity: 35.0771 cm^3
• Polarizability: 9.141899 Å^3
• Polar Surface Area: 3.01 Å^2
• Rotatable Bonds: 0
• Lipinski's Rule of Five: true

PROPERTIES

Physical Property

• Melting Point: 130°C dec.; 132 °C (dec.)(lit.)

Safety Information

• Storage Warning: Moisture Sensitive
• European Hazard Symbols: Toxic (T)
• UN Number: 3261; UN3261
• German water hazard class: 3
• Hazard Class: 8
• Packing Group: 2; II
• Risk Statements: 61-14-22-35
• Safety Statements: 53-26-36/37/39-45; 53-45
• TSCA Listed: 是
• GHS Pictograms: GHS05; GHS06; GHS07; GHS08
• GHS Signal Word: Danger
• GHS Hazard statements: H301-H360-H314-H318; H302-H314-H360D
• GHS Precautionary statements: P201-P280-P305 + P351 + P338-P310; P260-P301+P310-P303+P361+P353-P305+P351+P338-P405-P501A
• Personal Protective Equipment: Eyeshields, Faceshields, full-face particle respirator type N100 (US), Gloves, respirator cartridge type N100 (US), type P1 (EN143) respirator filter, type P2 (EN 143) respirator cartridges, type P3 (EN 143) respirator cartridges; 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 3261 8/PG 2
• Supplemental Hazard Statements: Reacts violently with water.
• Storage Temperature: 2-8°C

Product Information

• Purity: ≥97.0% (AT); 95%; 96%
• Grade: purum
• Impurities: <5% DMF
• Linear Formula: ClCH=N(CH3)2Cl

DETAILS

Sigma Aldrich - 280909

Application
Reagent used to prepare β-lactams from β-amino acids via carboxyl activation and cyclodehydration.9 Also used to convert α-aminonitriles into 4-chloroimidazoles.10
Reagent or Reactant for the synthesis of:
• β-Lactams vis the Staudinger reaction1
• N-vinyl substituted indoles via cross coupling of NH-indoles with vinyl bromides2
• Multi ring-fused 2-pyridone-based fluorescent scaffold3
• ester prodrugs as anti-poxvirus agents4
• Trimethine cyanine dyes for sensing G-quadruplex formation5
• Phospha-isosteres via Hundsdiecker-Barton iododecacarboxylation6
• 2-Azetidinones via [2+2]-cycloaddition7Used for studying organic photosensitizers for application in dye-sensitized solar cells8
Packaging
5, 25 g in glass bottle

Sigma Aldrich - 25130

Other Notes
Reagent for preparing heterocycles9; For aromatic formylations10
Application
Reagent or Reactant for the synthesis of:
• β-Lactams vis the Staudinger reaction1
• N-vinyl substituted indoles via cross coupling of NH-indoles with vinyl bromides2
• Multi ring-fused 2-pyridone-based fluorescent scaffold3
• ester prodrugs as anti-poxvirus agents4
• Trimethine cyanine dyes for sensing G-quadruplex formation5
• Phospha-isosteres via Hundsdiecker-Barton iododecacarboxylation6
• 2-Azetidinones via [2+2]-cycloaddition7Used for studying organic photosensitizers for application in dye-sensitized solar cells8

REFERENCES

• Preformed, crystalline Vilsmeier reagent useful in, e.g. formylation, dehydration, and chlorination reactions, avoiding the use of POCl₃, COCl₂, (COCl)₂, etc. For further information on Vilsmeier reagents, see N,N-Dimethylformamide, A13547. Review: Adv. Org. Chem., 9, 225 (1976). Monograph: Synthesis Using Vilsmeier Reagents, C. M. Marson, P. R. Giles, CRC Press, Boca Raton, FL (1994).
• Reacts with alcohols to form iminium salts which undergo nucleophilic displacement under mild conditions with inversion of configuration. The advantages of this approach over the equivalent Mitsunobu reactions (see Triphenylphosphine, L02502) for the activation of alcohols towards nucleophiles are that it is more suitable for scale-up and that the by-products are easily separated and of low mass. For use in cyclodehydration of hydroxy phenols in the synthesis of ɑ ₂-adrenoreceptor antagonists, see: Tetrahedron Lett., 34, 7483 (1993):
  
• Similarly, iminium salts of secondary alcohols undergo nucleophilic displacement with K benzoate giving the ester of opposite configuration in high yield and ee: J. Chem. Soc., Chem. Commun., 1403 (1995).