Damage caused to the skin of mango fruit by contact with sap exuded from the cut or broken pedicel reduces consumer acceptance and storage life of the fruit. Mangoes of the Kensington cultivar are particularly susceptible to sapburn injury. On centrifugation, the fruit sap separated into two phases. Skin damage was caused predominantly by the upper non-aqueous phase. A major component of this phase was terpinolene which gave symptoms indistinguishable from sapburn injury when applied to the fruit surface. The same type of damage could be induced by the application of synthetic terpinolene when applied undiluted, diluted in hexane or as an aqueous emulsion. Non-volatile sap components separated by distillation were not damaging to mango skin. Sap exuded from the mango leaf petioles also contained terpinolene, but its concentration was less than 1% of the concentration in pedicel sap and this sap was not damaging to the fruit skin.The Florida cultivar Irwin is less susceptible to sapburn injury and the predominant terpene in its sap was identified as car-3-ene. When applied to Kensington skin, car-3-ene caused significantly less damage than terpinolene. We conclude that the primary cause of mango sapburn is entry of volatile components of the sap such as terpinolene through the lenticels, resulting in tissue damage and subsequent enzymic browning.

Ethane- and ethene-1,2-bisphosphonium salts are cleaved by alkali into a phosphine and a phosphine oxide with loss of the two-carbon bridge. When the phosphorus atom carries benzyl substituents, loss of the benzyl groups is competitive with loss of the bridge. ��� Based on a kinetic study, a synchronous mechanism, analogous to the alkaline hydrolysis of acyclic monophosphonium salts, is proposed to account for the fragmentation. ��� With 6-membered 1,4-diphosphonio heterocyclic salts the nature of the products is dependent on whether alkali or phosphonium salt is present in excess. With an excess of alkali a synchronous mechanism again appears to operate, while with an excess of salt the reaction proceeds stepwise and without loss of the bridge. A partial explanation of these facts is advanced in terms of non-bonded interactions in the intermediate phosphoranes. ��� The synchronous reaction appears to be favoured by coplanarity of the P-C-C-P system.

Ethane-1,2-bis-phosphonium salts are cleaved by sodium hydride to phos- phines in 55-80% yields with loss of the two-carbon bridge. The reaction is independent of the substituents at the phosphorus atoms. The same reaction is observed with an ethene-1,2-bis-salt and with but- 2-ene-1,4-bis(triphenylphosphonium) dibromide. It is suggested that a phosphorane is formed which subsequently fragments in a manner analogous to alkaline hydrolysis. ��� Lithium aluminium .hydride behaves similarly but loss of the bridge is competitive with loss of benzyl groups, and yields are generally better (> 70%).

Cyclic and acyclic bis-phosphonium salts with a two-carbon bridge are smoothly cleaved to phosphines in high yield by potassium cyanide in dimethyl sulphoxide. Evidence is presented that the reaction proceeds by an elimination-addition sequence. An elimination reaction also occurs when sodium methoxide, sodium azide, sodium acetate, and triethylamine react with ethane-1,2-bis(tri-phenylphosphonium) dibromide. ��� In a novel reaction, triphenylphosphine is converted into its oxide by a mixture of sodium azide and dimethyl sulphoxide.

The principal characteristics of the p.m.r, spectra of 21 previously unreported diphosphorus compounds and related substances are described, discussed, and compared with results already in the literature. A simple synthesis of unsymmetrical ethane-1,2-diphosphorus compounds is reported.