Ethylene derivatives phosphorus compound

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

Bochwic, B., and Michalski, J., Organic phosphorus compounds. Part 1. Addition of di-alkyl hydrogen phosphonates to ethylenic derivatives, Rocz. Chem., 25, 338, 1951 Chem. Abstr, 48, 12013a, 1954. 

A wide range of carbon, nitrogen, and oxygen nucleophiles react with allylic esters in the presence of iridium catalysts to form branched allylic substitution products. The bulk of the recent literature on iridium-catalyzed allylic substitution has focused on catalysts derived from [Ir(COD)Cl]2 and phosphoramidite ligands. These complexes catalyze the formation of enantiomerically enriched allylic amines, allylic ethers, and (3-branched y-8 unsaturated carbonyl compounds. The latest generation and most commonly used of these catalysts (Scheme 1) consists of a cyclometalated iridium-phosphoramidite core chelated by 1,5-cyclooctadiene. A fifth coordination site is occupied in catalyst precursors by an additional -phosphoramidite or ethylene. The phosphoramidite that is used to generate the metalacyclic core typically contains one BlNOLate and one bis-arylethylamino group on phosphorus. 

Melphalan and the racemic analog have been prepared by two general routes (Scheme I). In Approach (A) the amino acid function is protected, and the nitrogen mustard moiety is prepared by conventional methods from aromatic nitro-derivatives. Thus, the ethyl ester of N-phthaloyl-phenylalanine was nitrated and reduced catalytically to amine I. Compound I was reacted with ethylene oxide to form the corresponding bis(2-hydroxyethyl)amino derivative II, which was then treated with phosphorus oxychloride or thionyl chloride. The blocking groups were removed by acidic hydrolysis. Melphalan was precipitated by addition of sodium acetate and was recrystallized from methanol. No racemization was detected [10,28—30]. The hydrochloride was obtained in pure form from the final hydrolysis mixture by partial neutralization to pH 0.5 [31]. Variants of this approach, used for the preparation of the racemic compound, followed the same route via the a-acylamino-a-p-aminobenzyl malonic ester III [10,28—30,32,33] or the hydantoin IV [12]. 

Six-co-ordinated phosphorus(v) compounds are still relatively rare, but recently three such compounds containing three different bidentate oxygen ligands (derived from ethylene glycol, mandelic acid, benzil, or 2-hydroxy-2-methylpropionic acid) have been synthesized.475... 

If a slurry of ethylene oxide and phosphorus pentoxide is reacted with chloroform, the condensed derivative 2,2 -oxy(bis (1,3,2 dioxaphosphoIane-2,2 dioxide) is obtained. Removal of the solvent in vacuo results in the formation of bis ethylene pyrophosphate. The former compound reacts violently... 

As in recent years, the chemistry of hexacoordinated phosphorus polycyclic derivatives bearing transannular nitrogen-phosphorus has continued to attract some interest. A series of the hypervalent tetracyclic compounds was prepared by the phosphorylation of various substituted symmetrical salicylaldehyde diimines (91) with an equimolar amount of ethylene chlorophosphite (92), without a base, to furnish products (93) possessing... 

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