Evidence and hypothesis for a "Taube bridge electron transfer" propagating to a remote site through .sigma. bonding. Formation of ethylene from monoethyl sulfate

Abstract

stirred at -70°under a nitrogen atmosphere and phenyllithium10 (16 ml, 1.5 N in ether, 4 equiv) was added over a 5-min period, forming a dark red solution. After quenching with an excess of cold aqueous ammonium chloride, a red-brown organic layer was formed to which 25 ml of benzene was added. The two layers were filtered to remove 0.347 g of an insoluble dark brown solid, and the organic layer was then separated and washed with cold distilled water. The dark brown oily residue left on evaporation was taken up in 100 ml of dry benzene and filtered to remove insoluble material. After drying over sodium sulfate and evaporating, the residual brown oil was dried overnight at 0.004 mm and 18.4 mg of biphenyl distilled over into the trap. Anhydrous ether (20 ml) was added to the oily residue. The red solution was filtered from some insoluble material and cooled in an ice-water bath before adding 100 ml of cold petroleum ether (bp 30-60°). The brown solid which precipitated was collected by filtration, washed with petroleum ether, and then freeze dried from benzene to yield 121.5 mg (14%) of 1 -phenylthiabenzene, softening point 68-73°.1-Phenylthiabenzene (VI) was also prepared2 by treating 1.0 g of VII11 suspended in 50 ml of ether under nitrogen in a separatory funnel capped with a rubber serum cap with 15 ml of 2 M phenyllithium in etherbenzene (Lithium Corp. of America, New York, N. Y.) added by a syringe slowly with shaking. After 15 min additional shaking, it was worked up as above to give 72 mg of a brown solid, softening point 68-72°.

Ethylene Production of Ethyl Propylphosphonate, Niagara 10637

“…Vol. 46, 1970 ETHYLENE PRODUCTION OF ETHYL PROPYLPHOSPHONATE oxygen as described earlier (11), and some of the known responses to ethylene are observed.…”

“…A model system for generating ethylene was reported earlier (11) while the Y-substituent may be -H, -OH, or -S-CH3. It is reasonable to expect that propylphosphonate could function similarly to phosphate as an X-substituent and generate ethylene from the ethyl group.…”

Propylene—A Competitor of Ethylene Action

“…As a preliminary step in the search for a possible site of attachment of ethylene, the chemical analogue propylene was tested for its ability to compete with ethylene for a possible site of attachment. Propylene was chosen as a possible inhibitor of ethylene action because earlier we (5) had noticed that treatment of etiolated pea seedlings with ethyl propylphosphonate, which had been found to release ethylene and propylene in a proposed model system (8), did not show a very clear cut triple response. (The term "triple response" was coined by Knight and Crocker [6].…”