(Chloromethylene)triphenylphosphorane

(Chloromethylene)triphenylphosphorane is the organophosphorus compound with he formula Ph3P=CHCl (Ph = phenyl). It is a white solid but is usually generated and used in situ as a reagent in organic synthesis. It is structurally and chemically related to methylenetriphenylphosphorane.

(Chloromethylene)triphenyl­phosphorane
Names
Preferred IUPAC name
(Chloromethylidene)tri(phenyl)-λ5-phosphane
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C19H16ClP/c20-16-21(17-10-4-1-5-11-17,18-12-6-2-7-13-18)19-14-8-3-9-15-19/h1-16H
    Key: KIZBYQRDCHVQID-UHFFFAOYSA-N
  • C1=CC=C(C=C1)P(=CCl)(C2=CC=CC=C2)C3=CC=CC=C3
Properties
C19H16ClP
Molar mass 310.76 g·mol−1
Appearance white solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

The reagent is prepared from the chloromethylphosphonium salt [Ph3PCH2Cl]Cl by treatment with strong base. The phosphonium compound is generated by treatment of triphenylphosphine with chloroiodomethane.[1]

(Chloromethylene)triphenylphosphorane converts aldehydes to vinyl chlorides:

RCHO + Ph3P=CHCl → RCH=CHCl + Ph3PO

These vinyl chlorides undergo dehydrochlorination to give alkynes:[2]

RCH=CHCl + NaN(SiMe3)2 → RC≡CH + NaCl + HN(SiMe3)2
  • (Iodomethylene)triphenylphosphorane[3]
  • (Dichloromethylene)triphenylphosphorane[4]

References
  1. Appel, Rolf; Morbach, Wolfgang (1977). "(Chloromethylene)triphenylphosphorane". Angewandte Chemie International Edition in English. 16 (3): 180–181. doi:10.1002/anie.197701801.
  2. Marth, Charles F. (2001). "Chloromethyltriphenylphosphonium Chloride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc134. ISBN 0471936235.
  3. Morin, Mathieu A.; Rohe, Samantha; Elgindy, Cecile; Sherburn, Michael S. (2020). "Preparation of a Z-Iodoalkene through Stork-Zhao-Wittig Olefination, Stereo-retentive Lithium–iodine Exchange and Z-Boronic acid Pinacol Ester Synthesis". Organic Syntheses. 97: 217–231. doi:10.15227/orgsyn.097.0217.
  4. Speziale, A. J.; Ratts, K. W.; Bissing, D. E. (1965). "Dichloromethylenetriphenylphosphoranne and β,β-Dichloro-p-dimethylaminostyrene". Organic Syntheses. 45: 33. doi:10.15227/orgsyn.045.0033.
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