Deuterio 1,3-Butadienes Derived by Reductive Dechlorination

Infrared study of the reaction of polyisoprene and polybutadiene with sulfur by use of deuterated polymers

“…The deuterated polyisoprenes and polybutadiene were prepared by Tucker13 to very high cis-1,4 concentrations by use of stereospecific polymerization techniques on the corresponding monomers prepared by Craig and co-workers, 14,15 all of these laboratories. The pcrprotio cis-polyisoprene and cis-polybutadiene were likewise stercoregular polymers.…”

Rotational analysis of bands in the high-resolution infrared spectra of the three species of butadiene-1,4-d2; refinement of the assignments of the vibrational fundamentals

“…The cis,cis species was prepared by the same reduction method applied to ttDClBDE-1,4-d 2 in water [9,10]. In the one-pot method, 33.6 mmol of powdered zinc metal (<10 l, Aldrich), 2.3 mmol of anhydrous cuprous chloride (Aldrich), and 0.43 mmol of potassium iodide were placed in a flask with 10.0 mL of deuterium oxide (99.9% Aldrich), after prerinsing the glassware with D 2 O, (or water) and refluxed for 1 h. Then, 3.4 mmol of the solid ttDClBDE (or the 1,4-d 2 species) dissolved in 5.0 mL of diglyme (Aldrich, anhydrous for making the trans,trans species) was dripped into the boiling solution from an addition funnel mounted at the top of the condenser, and the mixture was refluxed for 4 h. The gaseous butadiene product passed through the condenser into a cold trap held at about À125°C with a pentane slush bath.…”

“…The synthesis of the isotopomers of BDE-1,4-d 2 made use of a one-pot modification of Simmons-Smith reduction chemistry of 1,4-dichlorobutadiene [9,10]. Although this simple and efficacious modification of SimmonsSmith chemistry has been used by spectroscopists [11,12], it has been largely overlooked by organic chemists, who have used a more difficult two-pot version [13,14].…”

Deuterated organic compounds XXV synthesis of certain deuterated n‐undecanes and n‐dodecanes

“…Following the procedure of CRAIG and FOWLER [ 5 ] , hexachlorobutadiene (65 g; 0.25 mole) was added with constant stirring over a period of 4 hrs. to a boiling suspension of 120 g of zinc dust, 1.0 g sodium iodide and 7.6 g The above bromide was debrominated as described above for the cupric chloride dideuterate in 200 ml of deuterium oxide.…”

“…Actually, this peak was due, wholly or partly at least, to vinylacetylene present in our sample. Still more recently, CRAIG and FOWLER [5] estimated the acetylenic impurities in the crude butadienl: prepared by our method by measuring the percentage of product which reacted with maleic anhydride. These authors found that the yield of pure butadiene could be improved by carrying out the dechlorinstion in deuterium oxide which contained 0.5 % of dissolved sodium iodide and 3 % of cupric chloride.…”