Phosphorus hydrides reactions with

SAFETY PROFILE Poison by ingestion and intraperitoneal routes. A trace mineral added to animal feeds. Potentially explosive reaction with charcoal + ozone, metals (e.g., powdered aluminum, copper), arsenic carbon, phosphoms, sulfur, alkali metal hydrides, alkaline earth metal hydrides, antimony sulfide, arsenic sulfide, copper sulfide, tin sulfide, metal cyanides, metal thiocyanates, manganese dioxide, phosphorus. Violent reaction with organic matter. When heated to decomposition it emits very toxic fumes of I and K2O. See also lODATES. 

A new approach to piperidines via cyclization of dienes, such as 158, employs a phosphorus hydride mediated radical addition/cyclization reaction <06JOC3656>. This reaction proceeds with complete regioselectivity to create the 6-exo-trig product 159, although as an inseparable mixture of two of the four possible diastereomers. 

Royen and Hill reported that phosphonium bromide and solid phosphorus hydride are the products from the reaction of excess phosphine with bromine at low temperatures. 

A second peculiarity of 77 expresses itself in the reaction with n-butyllithium inJ which the hydrogen atom at the phosphorus atom is displaced nucleophilically as hydride ion to give butyl-bis-2,2 -biphenylylenephosphorane (25b). Deprotonation to the phosphoranyl anion 79 occurs only to a minor extent here. For 79, an equilibrium with the ring-opened carbanionic structure 86 was proven 94,95,97). 

Protopine has been isolated from Bocconia frutescens,110 Fumaria judaica,111 F. schleicheri,112 and Papaver bracteatum,146 cryptopine from F. schleicheri,112 and allocryptopine from B. frutescens110 and Zanthoxylum nitidum.141 The protopine ring-system has been prepared from tetrahydrobenzindenoazepines (75) by photo-oxidation to the amides (76) followed by reduction with lithium aluminium hydride and re-oxidation with manganese dioxide.148-150 The tetrahydrobenzindenoazepines have been prepared from A-chloroacetyl-/ -phenylethylamines (73) by cyclization to the lactam (74) followed by reaction with a benzyl bromide and phosphorus oxychloride. -Protopine (77 R R2 — CH2)148 and fagarine II (77 R1 = R2 = Me)149 have been synthesized in this way. 

The structure XXII for rhynehophylline has been confirmed, and the relative stereochemistry at C-15 and C-20 has been elucidated, by a total synthesis (80) of (+) JV-methylrhynchophyllane (XXVI) (Marion s N-methylisorhynchophyllane), which had been prepared earlier by methyl-ation of (iso)rhynchophyllane with sodium methoxide and methyl iodide (28). The lactone (XXVII) of threo-3,4-diethyl-5-hydroxyvaleric acid was converted by reaction with phosphorus pentachloride into the corresponding S-chloroacid chloride (XXVIII), which on treatment with methylaniline gave the anilide XXIX. Reduction of XXIX with lithium aluminum hydride gave the aldehyde XXX, which slowly reacted with... 

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