Reactions of Polyfluoro Olefins. II.<sup>1</sup> Reactions with Primary and Secondary Amines<sup>2</sup>

Pruett, Roy L.; Barr, John T.; Rapp, Karl E.; Bahner, Carl Tabb; Gibson, J. Donald; Lafferty, R.H.

doi:10.1021/ja01164a090

Cited by 107 publications

(27 citation statements)

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“…[5121 13% Primary amines and perfluoro-olefins give enamines or Schiff's bases, while secondary alpines give a,a-difluoroamines, which sometimes, especially in the fluorocyclobutene series, eliminate hydrogen fluoride and give also enamines [513]. (315) NH(C.H5).…”

Section: Additions Of Ammonia and Aminesmentioning

confidence: 99%

Organic Fluorine Chemistry

Hudlický

1971

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Section: Additions Of Ammonia and Aminesmentioning

confidence: 99%

Organic Fluorine Chemistry

Hudlický

1971

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“…A prominent (and archetypical) example for an electron donor is tetrakis(dimethylamino)ethylene (TDAE, 1 ), which was first synthesized in 1950 3. The related compound 1,1′,3,3′‐tetraphenyl‐2,2′‐biimidazolidinylidene ( 2 ) followed ten years later 4.…”

Section: Introductionmentioning

confidence: 99%

What Makes a Strong Organic Electron Donor (or Acceptor)?

Eberle

Hübner

Ziesak

et al. 2015

Chemistry A European J

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Organic electron donors are of importance for a number of applications. However, the factors that are essential for a directed design of compounds with desired reduction power are not clear. Here, we analyze these factors in detail. The intrinsic reduction power, which neglects the environment, has to be separated from extrinsic (e.g., solvent) effects. This power could be quantified by the gas-phase ionization energy. The experimentally obtained redox potentials in solution and the calculated ionization energies in a solvent (modeled with the conductor-like screening model (COSMO)) include both intrinsic and extrinsic factors. An increase in the conjugated π-system of organic electron donors leads to an increase in the intrinsic reduction power, but also decreases the solvent stabilization. Hence, intrinsic and extrinsic effects compete against each other; generally the extrinsic effects dominate. We suggest a simple relationship between the redox potential in solution and the gas-phase ionization energy and the volume of an organic electron donor. We finally arrive at formulas that allow for an estimate of the (gas-phase) ionization energy of an electron donor or the (gas-phase) electron affinity of an electron acceptor from the measured redox potentials in solution. The formulas could be used for neutral organic molecules with no or only small static dipole moment and relatively uniform charge distribution after oxidation/reduction.

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“…It was incidentally discovered by Pruett and co-workers at the DuPont Company in 1950 [27] from the condensation of chlorotrifluoroethylene (CTFE) and dimethylamine (both gas), under pressure, using an autoclave (Scheme 7). TDAE is a very electron-rich tetra-aminoethylene molecule and is a powerful organic reducing agent.…”

Section: Methods Using the Tetrakis(dimethylamino)ethylene (Tdae)mentioning

confidence: 99%