methyl 2-(triphenyl-$l^{5}-phosphanylidene)acetate

• ChemBase ID: 67362
• Molecular Formular: C21H19O2P
• Molecular Mass: 334.348121
• Monoisotopic Mass: 334.11226648
• SMILES: P(=CC(=O)OC)(c1ccccc1)(c1ccccc1)c1ccccc1
• Canonical SMILES: COC(=O)C=P(c1ccccc1)(c1ccccc1)c1ccccc1
• InChI: InChI=1S/C21H19O2P/c1-23-21(22)17-24(18-11-5-2-6-12-18,19-13-7-3-8-14-19)20-15-9-4-10-16-20/h2-17H,1H3
• InChIKey: NTNUDYROPUKXNA-UHFFFAOYSA-N

NAMES AND DATABASE IDS

Names

• IUPAC name: methyl 2-(triphenyl-$l^{5}-phosphanylidene)acetate; methyl 2-(triphenyl-λ^5-phosphanylidene)acetate
• IUPAC Traditional name: methyl 2-(triphenyl-$l^{5}-phosphanylidene)acetate; methyl 2-(triphenyl-λ^5-phosphanylidene)acetate
• Synonyms: Carbomethoxymethylene triphenylphosphorane; (Methoxycarbonylmethylene)triphenylphosphorane; Methyl (triphenylphosphoranylidene)acetate 98%; (Carbomethoxymethylene)triphenylphosphorane; Methyl (triphenylphosphoranylidene)acetate; Methyl (triphenylphosphoranylidene)acetate; (Methoxycarbonylmethylene)triphenylphosphorane; Methyl(triphenylphosphoranylidene)acetate; (三苯基膦烯)乙酸甲酯; 甲氧羰基亚甲基三苯基正磷; 甲氧甲酰基亚甲基三苯基膦; (甲氧基羰基亚甲基)三苯基膦烷

Database IDs

• CAS Number: 2605-67-6
• EC Number: 220-018-4
• MDL Number: MFCD00008455
• Beilstein Number: 618430
• PubChem SID: 24849709; 162033097
• PubChem CID: 17453

CALCULATED PROPERTIES

• H Acceptors: 1
• H Donor: 0
• LogD (pH = 5.5): 5.8956
• LogD (pH = 7.4): 5.8956
• Log P: 5.8956
• Molar Refractivity: 98.4491 cm^3
• Polarizability: 38.770615 Å^3
• Polar Surface Area: 26.3 Å^2
• Rotatable Bonds: 5
• Lipinski's Rule of Five: false

PROPERTIES

Physical Property

• Solubility: Chloroform
• Apperance: Off-White Solid
• Melting Point: 159-162°C; 165-169°C; 168-172 °C; 168-172 °C(lit.)

Safety Information

• Storage Condition: Refrigerator
• Storage Warning: Air Sensitive; IRRITANT; Irritant
• German water hazard class: 3
• TSCA Listed: false; 是
• Personal Protective Equipment: Eyeshields, Gloves, type N95 (US), type P1 (EN143) respirator filter

Product Information

• Purity: ≥97.0% (CH); 95+%; 98%
• Grade: purum
• Linear Formula: (C6H5)3P=CHCO2CH3

DETAILS

Sigma Aldrich - 157929

Application
Wittig reagent for the two-carbon homologation of aldehydes to α,β-unsaturated esters.1 Also used in an efficient synthesis of pyrazoles via reaction with methyl diazoacetate in the presence of triethylamine.2
Packaging
25, 100 g in poly bottle
5 g in glass bottle

REFERENCES

• For tandem Wittig reaction and Cope rearrangement, see: J. Chem. Soc., Chem. Commun., 381 (1995):
  
• Review of phosphacumulene ylides: Angew. Chem. Int. Ed.,16, 349 (1977).
• Stable ylide which undergoes the Wittig reaction with aldehydes to give substituted methyl acrylates. See also (Ethoxycarbonylmethylene)triphenylphosphorane, A12896 and Appendix 1. For a detailed study of the reaction with benzaldehyde, see J. Org. Chem., 59, 1126 (1994). For use of high pressure to increase the yield and trans-selectivity of reaction with aromatic aldehydes, see: Liebigs Ann. Chem., 2135 (1983).
• Strong base, for example Na bis(TMS)amide, brings about elimination of methanol, giving ketenylidenetriphenylphosphorane, which reacts with ɑ-hydroxy-ketones, e.g. in the steroid series, to give butenolides, by acylation and Wittig cyclization: Chem. Ber., 113, 2038 (1980):