Reference

Addition by redox catalysis of carbon tetrachloride to monomers with two nonconjugated double bonds

Addition by redox catalysis of carbon tetrachloride to monomers with two nonconjugated double bonds. Corallo, Marcel; Pietrasanta, Yves (Lab. Chim. Appl., Ec. Natl. Super. Chim. Montpellier, Montpellier, Fr.). C.Some commonly used reagents like 96-05-9 is used in this experiment. R. Hebd. Seances Acad. Sci., Ser. C, 283(5), 187-90 (French) 1976. CODEN: CHDCAQ. DOCUMENT TYPE: Journal CA Section: 23 (Aliphatic Compounds) Section cross-reference(s): 22, 67 Addn. of CCl4 to monomers with 2 nonconjugated double bonds in the presence of a redox catalyst (Cu salts) was in the ratio of 2:1 with a no. of compds., e.g., tetramethylene diacrylate, ethylene dimethacrylate, divinylbenzene, and diallyl succinate, to give products such as Cl3CCH2CHClCH2O2CCH2CH2CO2CH2CHClCH2CCl3, from addn. to diallyl succinate. 1,5-Hexadiene gave principally Cl3CCH2CHCl(CH2)2CHClCH2CCl3, but yielded also small amts. of the monoaddn. product, CH2:CH(CH2)2CHClCH2CCl3, and cyclic products I and II. The principal product with diallyl ether was the cyclic product III, but diallyl sulfide decompd. during the reaction to give .apprx.50% Cl3CH2CHClCH2CCl3. .

Carbanions

Carbanions. 26. Formation of hexadienyl anions by the reactions of various hexadienes with cesium solutions in the presence of 18-crown-6 or with n-butyllithium-cesium tert-butoxide. Goel, Subhash C.; Grovenstein, Erling, Jr. (Sch. Chem., Georgia Inst. Technol., Atlanta, GA 30332, USA). Organometallics, 11(4), 1565-75 (English) 1992. CODEN: ORGND7. ISSN: 0276-7333. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 23 The formation of hexadienyl anions has been studied with cesium as counterion. 1,4-, 2,4-, Or 1,5-hexadiene can be deprotonated with Cs×18-crown-6 solns. and/or with BuLi×Cs(OCMe3) in THF to provide hexadienyl anions, and their geometry was revealed by chem. derivatization using trimethylsilylation or carbonation reactions. Thus, trans-1,4-hexadiene (I) at -75° gave a mixt. of exo-W-shaped anion as the major and exo-S-shaped anion as the minor product. cis-1,4-Hexadiene under similar conditions produced endo-W-shaped anion as the major and endo-S-shaped anion as the minor product.Several substances with their cas registry numbers 7318-67-4 and 629-35-6 may be metioned in this study. cis,trans-2,4-Hexadiene with BuLi×Cs(OCMe3) at 75° likely gave a mixt. of endo-W-shaped and exo-S-shaped anions, while trans,trans-2,4-hexadiene (II) gave the exo-W-shaped anion. At room temp., in short duration reactions of I and II, exo-S and/or endo-U anion was the major product. Storage of these anions derived from any diene at room temp. for long durations produced an equilibrated mixt. of anions which on silylation gave hexadienyltrimethylsilanes, trans,cis- or cis,trans-MeCH:CHCH:CHCH2SiMe3 as major products. The equilibration of these anions was faster in presence of catalytic amt. of Bu2Hg or at higher temp. (e.g., 65°). Biallyl is metalated by the Cs×18-crown-6 soln. at -75° and formed a mixt. of endo-III, as major product, and exo-IV, as minor product, which isomerized to III in 10 h and finally isomerized to give the equilibrated conjugated hexadienyl anions as the major product. .