64435-39-8Relevant articles and documents
Reactions of 1- and 2-Halo and 1,2-Dichloroadamantanes with Nucleophiles by the SRN1 Mechanism
Santiago, Ana N.,Stahl, Adriana E.,Rodriguez, Gladis L.,Rossi, Roberto A.
, p. 4406 - 4411 (2007/10/03)
2-Bromoadamantane (2-BrAd) reacted in liquid ammonia under irradiation with diphenylphosphide (Ph2P-) ions whereas 2-chloroadamantane (2-ClAd) did not under the same experimental conditions. However, 2-ClAd yielded 2-(trimethylstannyl)adamantane in its photostimulated reaction with trimethylstannyl (Me3Sn-) ions. The compound 1-ClAd yielded the substitution product in a photostimulated slow reaction when the nucleophile is Ph2P- ion; the reaction occurs faster with the nucleophile Me3Sn- ion. All these reactions can be explained by the SRN1 mechanism as they did not occur in the dark and were inhibited by p-dinitrobenzene when photostimulated. In competition experiments, 1-haloadamantane showed more reactivity than 2-haloadamantane. Either with Ph2P- or Me3Sn- ions, 1-BrAd is 1.4 times more reactive than 2-BrAd while 1-ClAd is 12 times more reactive than 2-ClAd with Me3Sn- ions. In the photostimulated reaction of 1,2-dichloroadamantane (7) with Ph2P- the monosubstitution products 1-adamantyldiphenylphosphine (64%) and 2-adamantyldiphenylphosphine (15%) were formed, isolated as the oxides. From these results, it appears that when 7 receives an electron, the 1-position fragments ca. four times faster than the 2-position. The disubstitution product was not formed with Ph2P- ions, but when 7 reacted with a nucleophile having less steric bulk such as a Me3Sn- ion, the 2-chloro-1-(trimethylstannyl)-adamantane and the disubstitution product 1,2-bis(trimethylstannyl)adamantane were formed. The formation of these products is explained in terms of the different rates of the electron transfer reactions of the radical anion intermediates.
Phosphides and Arsenides as Metal-Halogen Exchange Reagents. Part 1. Dehalogenation of Aliphatic Dihalides
Gillespie, Donal G.,Walker, Brian J.
, p. 1689 - 1695 (2007/10/02)
Lithium diphenylphosphide and arsenide have been investigated as reagents for metal-halogen exchange.Reactions involving two molar equivalents of the anions with 1,2-dibromoethylenes lead to moderate to good yields of acetylenes and smaller yields of phosphorus-containing by-products.Similar reactions with 2,3-dichlorobuta-1,3-diene and 2-chlorobuta-1,3-diene give SN2' rather than direct substitution products.Evidence is presented that adamantene is an initial product in the reaction of lithium diphenylphosphide with 1,2-di-iodo- and 1,2-dibromo-adamantane, but not with 1,2-dichloroadamantane, although 1- and 2-adamantyldiphenylphosphine oxides are formed in every case.Finally reactions of phosphide anion with geminal dihalides were briefly investigated; 1,1-dibromo-2,2-diphenylethylene gave diphenylacetylene as the major product.
