Reactions of Halides of Tervalent Phosphorus with Imines and -Diimines

Abstract

Isobutylidenebutylamine reacts with phosphorus trichloride in the presence of organic bases to give N-butyl-N-isobutenylamidodichloro-or bis(N-butyl-N-isobutenylamido)chlorophosphites depending on the ratio of reagents. Reasons are given in Eavour of the reaction beginning with the nucleophilic attack of the nitrogen atom of the imine on the electrondeficient phosphorus atom of the chloride. Reactions of ethyldichloro- and diethylchlorophosphites with benzylidenmethylamine produce 2-chloro- and 2-ethyl-2-oxo-1,4,2-diazaphospholanes respectively. Interaction of diethylchlorophosphite with benzylidenmethylamine in the presence of triethyphosphite results in the formation of diethyl. (N-methyl-N-α-diethylphosphonobenzylamido)phosphite. As a result of interaction of bis(diethylamino)chlorophosphine with NIN-dibutyl-2,3-butandiimine in the presence of triethylamine new compounds (2-diethylamino-1,3-dibutyl-4,5-dimethyl-1,3,2-diazaphospholane and 4,8-dibutyl-3,7-bis(diethylamino)-[3.3.01-bicyclooctadiene-l15) are obtained. The structure of the latter is proved by means of ¹H, ³¹ p NMR-spectroscopy, and a complete X-ray analysis. Alkyldichlorophosphines form phosphonium salts of 1,3,2-diazaphospholene structure with a-diimines and 2-chloro-1,3-dicyclohexyl-4-chloro-1,3,2-diazaphospholene resulting from the reaction of N,N-dicyclohexylethylenediimine with PCl₃. In this product the P-C1 bond is unusually long, which is confirmed by X-ray analysis. In the course of the interaction of tervalent phosphorus halides with α,β-unsaturated imines a new reaction has been discovered with the formation of 1,2-dihydro-1,2-azaphosphorines.     

Reactions of N,N'-Dialkylcyclohexane-1,2-diimines with Trivalent Phosphorus Acid Chlorides

N,N'-Dialkylcyclohexane-1,2-diimines react with trivalent phosphorus acid chlorides to give, depending on the structure of the organophosphorus reagent and reaction conditions, either 1,3,2-diazaphospholanes (three-coordinate phosphorus) containing the cyclohexadiene fragment in positions 4 and 5, or 1,3,2-diazaphospholines (four-coordinate phosphorus).     

The Cycloaddition Reactions Catalyzed by Some Rare Earth Chlorides

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Phosphorylated Allenes in the Cycloaddition Reactions

Abstract

The reactions of phosphorus-containing allenes with the derivatives of phosphorus of low coordination are investigated. The interaction of the l -vinyl-l-phosphoryloxy-3,3-di-methylallene with (dimethylaminomethylidene)phenylphosphine was shown to occur over 1,3-diene system according to Diels-Alder reaction. The formation of the six-membered heterocycle was accompanied by changing the coordination of the phosphorus atom from P^II to P^III. The reaction of the phosphorus containing 1,3-dipole (diethylaminobenzylidene)-aminodimethoxyphosphine with 1-vinyl-1-phosphoryloxy-3,3-dimethylallene was found to give the seven-membered aza-phosphepin. The changing of methoxy-radicals by ethoxy-groups in benzylideneaminophosphine leads to azaphos-phorins as products. The formation of the seven-membered adduct in this case is small. The two-step mechanism of these reactions with the initial attack of atom P at central carbon atom of allene is in agreement with kinetic, thermochemical and ³¹P-NBR data.     

Reactions of Lower Titanium Chlorides with Molten Magnesium-containing Chlorides of Alkaline Metals

Conditional equilibrium constants K _n ^* of reactions between titanium chlorides and molten magnesium were calculated.     

磺酰氯与不饱和化合物的反应

磺酰氯是一类重要的有机合成中间体,广泛应用于有机和药物合成中。磺酰氯可以作为烯砜、磺酰基、次磺酰基、芳基、氟代烷基等的来源应用于多种有机合成反应中。本文综述了磺酰氯与烯烃、炔烃、(杂)芳香环、亚胺、卤代醛酮等不饱和化合物的反应,主要包括[2+2]环合反应、氯磺酰化、磺酰化、次磺酰化、芳基化和氟代烷基化等反应,并讨论和预测了磺酰氯与不饱和化合物反应今后的发展方向。     

Reactions of Pentaphenylantimony and Pentaphehylphosphorus with Arylmercury Chlorides

Russian Journal of General Chemistry -     

Reactions of Benzylidene Chlorides with S -Methyl Diethylphosphinothioate

S-Methyl diethylphosphinothioate reacted with benzylidene chlorides to give the corresponding aryl(chloro)methyl methyl sulfide and diethylphosphinoyl chloride. The product structure suggests initial attack of the methylsulfanyl group on the CH carbon atom of dichloromethylarene. Arenecarbothialdehyde dithioacetals and trimers and O,O-dialkyl[aryl(methylsulfanyl)methyl]phosphonates were synthesized.     

Diverse Reactions of Sulfonyl Chlorides and Cyclic Imines

Abstract

Although alkanesulfonyl chlorides react with linear imines to give rise to β-sultam derivatives, in this study, they were reacted with various cyclic imines, including 1-pyrroline, oxazoline, 5,6-dihydro-4H-oxazines and thiazines, 4,5-dihydro-3H-benzo[c]azepine, and 3,4-dihydroisoquinoline, to produce diverse products instead of β-sultam derivatives. The results indicate that alkanesulfonyl chlorides react with cyclic imines to generate N-alkanesulfonyl cyclic iminium ions, which are attacked by nucleophiles, such as water and chloride anion, in the reaction systems, affording addition products. The iminium intermediates cannot undergo a ring closure to form β-sultam derivatives. Arenesulfonyl chlorides showed similar behavior when they reacted with cyclic imines. The scope and limitation of the reaction between sulfonyl chlorides and imines were investigated.

GRAPHICAL ABSTRACT      

Interaction of Cyclohexanediimines with Phosphorus (III) Chlorides

Abstract

It is known that reactions of phosphorohalidites with linear a-diimines proceed accordingly [1+4]-cycloaddition mechanism and give rise to 1,3,2-diazaphosphol-r-enes. We have found that 1,2-cyclohexane-diirnines (1) react with alkyldichlorophosphines in the absence of base also resulting in the formation of products of 1,3,2-diazaphosphol-4-ene structure (2,3).     

Palladium-Catalyzed Carbonylation and Coupling Reactions of Aryl Chlorides and Amines

The palladium-catalyzed amidation of electron-deficient aryl chlorides proceeds readily in the presence of low CO pressures and a slight excess of an iodide salt. The rates of amidation are accelerated over those without added salt, and iodide is preferred over bromide or chloride. More electron-rich aryl chlorides were not effectively amidated, either with or without added iodide. We postulate that an intermediate anionic palladium(0) iodide complex is responsible for the enhanced reactivity.     

Phosphorylated Bromonitroethene in the Reactions with NH- and CH- Acids

Abstract

The interaction between O,O-di(2-dichloroethyl)-2- bromo-2-nitroethenephosphonate and some NH- and CH-acids is discussed.

The highly reactive halonitroethenes attract the attention of scientists so as they are active synthons in the synthesis of various classes of organic compounds. Phosphorylated halonitroethenes can represent particular interest, because of phosphoryl group introduction “a priori” makes the reactivity of such compounds to be higher and allows to synthesize a big number of biologically active compounds. The very first study of interaction between O,O-di(2-chloroethyl)-2-nitroethenephosphonate (1)¹ with some representatives of NH-and CH-acids such as anyline, p-toluydine, dimedone, and malonic ester was conducted by our research group.     

EPR Studies of Reactions of Organobimetallic Chlorides with Sodium 3,6-Di-tert-butyl-ortho-benzosemiquinolate

The reactions of some organobimetallic chlorides [CpMo(CO)₃]₂BiCl, [CpM(CO)₃]₂SnCl₂, [CpMo(CO)₃]₂InCl ( = ⁵-C₅H₅; M = Mo, W) with sodium 3,6-di-tert-butyl-ortho-benzosemiquinolate in toluene were studied using the EPR spectroscopy. The possibility of formation of organoheterometallic complexes containing -semiquinone ligand was shown.     

磷氯化物(PCl_3,PCl_5,POCl_3)作为氯化试剂在有机合成中应用的研究进展

综述了近十几年来磷氯化物 (PCl3,PCl5,POCl3)作为氯化试剂在有机合成中应用的新进展 ,主要包括磷氯化物与羟基化合物、羧酸、羰基化合物、烯烃、含孤对电子基团化合物、磺酸及其盐、硅化合物、磷化合物的氯化反应 ,以及氢氯交换反应。     

Reactions of Phosphorus Sulfides with Organophosphorus Substances

Abstract

We have found that the reactions of P4SIo and 1,3,2,4-dithiadiphosphetane-2,4-disulfides with phosphites, phosphonites, phosphinites, amidophosphonites, amidophosphinites, trithiophosphites, dithiophosphonites and thiophosphinites proceed under mild conditions via the previous formation of products containing the P(S)-S-P structural fragment which were isolated by column chromatography.