Limiting diffusion currents are estimated by an indirect method which consists in determining the chemical yield of substitution product in the electrosynthesis of a biaryl by an SRN type reaction. The limiting diffusion currents can then be deduced from the yields. Different industrial cathodic materials have been investigated both in liquid ammonia (−40° C) and dimethylformamide (20°C). The limiting diffusion currents are generally about 2.8 times larger in ammonia than in dimethyl-formamide.
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- R :
yield in biaryl with respect to the reacted aromatic halide
- k d :
diffusion rate constant
- k 2 :
rate constant of the key-reaction between Ar• and Nu−
- A :
- D :
diffusion coefficient of the mediator
- D 1 :
diffusion coefficient of mediator P 1
- D 2 :
diffusion coefficient of mediator P 2 (in the same medium as for D 1)
- D NH 3 :
diffusion coefficient of the mediator in NH3
- D DMF :
diffusion coefficient of the mediator in DMF
- D 2,NH 3 :
diffusion coefficient of mediator P1 in NH3
- D 2,NH 3 :
diffusion coefficient of mediator P2 in NH3
- D 2,DMF :
diffusion coefficient of mediator P2 in DMF
diffusion layer thickness
- δNH 3 :
diffusion layer thickness in NH3
- δDMF :
diffusion layer thickness in DMF
- i lim :
limiting diffusion current of the mediator
- I lim :
limiting diffusion current of the mediator per unit of concentration of the mediator
- I lim :
limiting diffusion current of the mediator per unit of concentration of the mediator and per unit of cathode area
- I lim,NH 3 :
limiting diffusion current of the mediator in NH3 (normalized with respect to the cathode area and the concentration)
- I lim,DMF :
limiting diffusion current of the mediator in DMF (normalized with respect to the cathode area and the concentration)
- ip :
reduction peak current of the mediator
- ip NH 3 :
reduction peak current of the mediator in NH3 (measured by cyclic voltammetry)
- ip DMF :
reduction peak current of the mediator in DMF (measured by cyclic voltammetry in the same conditions of concentration, cathode and scan speed as in NH3)
solvent association factor
- M s :
solvent molecular weight
solvent absolute viscosity
- V :
substrate molecular volume
- V 1 :
molecular volume of mediator P1
- V 2 :
molecular volume of mediator P2
rotation speed of the electrode
kinematic viscosity, ν = η/d
- d :
- ArH :
amount of reduction product, mol
- ArNu :
amount of coupling product, mol
J. F. Bunnett, Acc. Chem. Res. 11 (1978) 413.
R. A. Rossi and R. H. de Rossi, in ‘Aromatic Nucleophilic Substitution by the SRN 1 Mechanism’, ACS Monograph 178, American Chemical Society, Washington (1983).
J. M. Savéant, Acc. Chem. Res. 13 (1980) 323.
C. Amatore, J. Pinson, J. M. Saveant and A. Thiebault, J. Electroanal. Chem. 128 (1981) 231.
N. Alam, C. Amatore, C. Combellas, A. Thiebault and J. N. Verpeaux, J. Org. Chem. 55 (1990) 6347.
J. Chaussard,J. C. Folest, J. Y. Nedelec,J. Périchon, S. Sibille, M. Troupel, Synthesis (1990) 369.
C. Combellas, H. Marzouk, A. Thiebault, J. Appl. Electrochem. 21 (1991) 267.
A. Savall, Actualité Chimique 1 (1992) 35.
C. Amatore, J. Pinson, J. M. Saveant and A. Thiebault, J. Am. Chem. Soc 104 (1982) 1979.
N. Alam, C. Amatore, C. Combellas, J. Pinson, J. M. Saveant, A. Thiebault and J. N. Verpeaux, J. Org. Chem. 53 (1988) 1496.
M. Medebielle, J. Pinson and J. M. Saveant, J. Am. Chem. Soc. 56 (1991) 6872.
C. Degrand, Tetrahedron 46 (1990) 5237.
C. Thobie-Gautier, M. Genesty, C. Degrand, J. Org. Chem. 56 (1991) 3452.
C. Thobie-Gautier, C. Degrand, ibid. 56 (1991) 5703.
C. Combellas, Y. Lu, A. Thiebault, Euchem Conference on Electrochemistry, Wiesbaden (21–25 April 1992).
A. J. Bard, L. R. Faulkner, in ‘Electrochemical Methods’, Wiley, New York (1980).
M. Herlem, Bull. Soc. Chim. Fr. (1967) 1687.
C. P. Andrieux, J. M. Saveant and D. Zann, Nouv. J. Chim. 8 (1984) 107.
C. Amatore, M. A. Oturan, J. Pinson, J. M. Saveant, A. Thiebault, J. Am. Chem. Soc. 107 (1985) 3451.
C. R. Wilke, P. Chang, Am. Inst. Chem. Eng. J. 1 (1955) 264.
J. J. Lagowski, G. A. Moczygemba, in ‘The Chemistry of Non-aqueous Solvents’, Part II, Acidic and Basic Solvents, Academic Press, New York (1967).
Riddick, Bunger, in ‘Techniques of Chemistry’, 2: ‘Organic Solvents, Physical Properties and Methods of Purification’, 3rd edn., Wiley Interscience, New York (1972) p. 446.
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Combellas, C., Lu, Y. & Thiebault, A. Electroinduced SRN 1 preparative reactions part 1: Estimation of the limiting diffusion currents on various cathodic materials in liquid ammonia and dimethylformamide. J Appl Electrochem 23, 841–847 (1993). https://doi.org/10.1007/BF00249958
- Physical Chemistry
- Cathodic Material
- Indirect Method