Mercury diethyl reaction

Arsenobenzene, reaction with mercury diethyl, 35. Ethyldichloroarsine, 35. 

Seyferth et al. (//O) have also synthesized N,N-diethyl-trichlorovinyl-amine (128, R CjHj) from the reaction of triethylamine and phenyl-(trichloromethyl)mercury (138). The best yield was 23 %, obtained when a benzene solution of the amine (45 mM) was added to a refluxing solution of phenyl(trichloromethyl)mercury (10 mM) in benzene. Although no mechanistic study was attempted because of the low yields and the intractable nature of the reaction mixture, the authors proposed the following mechanistic sequence ... 

The heat of reaction brought about refluxing during the addition of the 2-bromo-3-hexyne, and when the addition was complete the reaction mixture was heated to refluxing for a further period of 30 minutes. A sufficient amount of water was then added to the reaction mixture to dissolve the sodium bromide which had formed, and the only organic layer was separated, washed with water and dried over anhydrous magnesium sulfate. The dried organic layer was then fractionally distilled under reduced pressure, and the diethyl (1-methyl-2-pentynyl) malonate formed in the reaction was collected at about 117° to 120°C at the pressure of 2 mm of mercury. 

Where X is phenyl, the result of irradiation (sunlight, mercury lamp) is the formation of Ru(NO)X3(PPh3)(OPPh3) (X = Cl, Br) in the case of the diethyl-phenylphosphine complex, irradiation causes isomerization to the cis,mer-isomer. The frans,mer-isomer is the usual synthetic product, but in the case of dimethylphenylphosphine the/ac-isomer was obtained using short reaction times it isomerized to the usual mer,trans-isomer on heating [123],... 

The mechanism for the photolysis of diethyl mercury is identical to that for the pyrolysis88, 90. The reaction of C2H5 with diethyl mercury, which apparently was of no importance under the conditions used in the pyrolysis studies, is also insignificant over the temperature range 25-75 °C. The photolysis produces ethyl radicals which initially have about 31 kcal.mole-1 excess energy so that the C4/C2 ratio is dependent on the surface/volume ratio and on the total pressure in the system. At 25 °C with essentially thermalized radicals (200 torr Ne added) CJC2 20 while at 20 torr CJC2 3. 

A diethyl ether solution containing 20 mmoles of methyllithium is placed in a 50-mL reaction vessel equipped with a stopcock and standard taper joint. The vessel is attached to a vacuum line stopcock equipped with a mercury blow-out manometer,3 and the contents are frozen at -196° (liquid nitrogen) prior to evacuation of the vessel. 

Nine hundred and twenty-five milliliters of absolute ethanol (Note 1) is placed in a 2-1. three-necked round-bottomed flask, fitted with a mercury or glycerin-sealed stirrer (Note 2), dropping funnel, and reflux condenser. To this is added 46 g. (2 gram atoms) 2 of freshly cut sodium, a few pieces at a time and at such a rate that the reaction proceeds rapidly but the solvent does not reflux too vigorously. When most of the sodium has dissolved, a calcium chloride drying tube is fitted to the top of the condenser and 320 g. (2 moles) of redistilled diethyl malonate is added from the dropping funnel. Then 205 g. (2 moles) of 3-chlorocyclopentene (p. 42) (Note 3) is added at such a rate that a gentle reflux is maintained. Towards the end of the addition, it is desirable to test the reaction mixture with pH test paper, and the addition should be stopped if the solution becomes acidic. 

An oven-dried, 500-mL, two-necked, round-bottomed flask equipped with a magnetic stirring bar, rubber septum inlet, and an outlet connected to a mercury bu oler is flushed with nitrogen and charged with 100 mL of tetrahydrcruran (THF) (Note 1). To this are added sequentially at 0°C, diIsopropyl amine (Note 2) (10.6 g, 14.7 mL, 105 mmol) and butyllithium in hexane (Note 3) (2.22 M, 47.3 mL, 105 nmol). The reaction mixture is stirred for 30 min and cooled to -78°C. 6-Ionone (Note 4) (19.2 g, 20.3 mL, 100 mmol) is slowly added. After stirring the mixture for 1 hr at -78°C, diethyl chlorophosphate (Note 5) (18.1 g, 15.2 mL, 105 mmol) is added, and the reaction mixture is allowed to warm to room temperature over 2-3 hr (Reaction mixture A) (Note 6). 

In an attempt to explain apparent inconsistencies in the ratio of disproportionation to combination of two ethyl radicals obtained in different investigations, Bradley et al. (13) carried out in 1956 a comparative study of the behavior of ethyl radicals produced by direct photolysis of diethyl mercury and by addition of hydrogen atoms to ethylene. The latter process involved the reactions... 

---