2,5-Dihydro-L,2-Oxaphospholic Derivatives from 1,2-& Kadienephosphonates and Pseudohalogenes

Abstract

Interaction between some 1,2-alkadienephosphonic derivatives and dimethyl(diisopropyl)phosphonic sulfenyl chlorides in weak polar media was investigated. We established that in all cases the oxaphospholic cyclization of 1,2-alkadienephosphonic system took place, and 4-thiodi-alkoxyphosphonyl-2,5-dihydro-l,2-oxaphospholic derivatives were obtained.     

Unexpected formal [1+3] cycloadditions between azides and alpha-zirconated phosphanes: a route to unprecedented phosphazide and iminophosphorane complexes

Polycyclic zwitterionic complexes that incorporate one or two phosphonium unit(s) as cationic center(s) and zirconocene-ate moiety(ies) as the anionic counterpart(s) can be easily prepared by either [1+3] or [1+3] and [2+3] cycloadditions which involve bi- or tricyclic alpha-zirconated phosphanes 3 or 4 and various azides. Some of these species exhibit unprecedented phosphazide chelation with bonding between the zirconium and a nitrogen atom in the alpha position relative to phosphorus. When heated, the phosphazide complexes lose dinitrogen to form stable polycyclic zwitterionic phosphonium mono- or dinuclear complexes. The solid-state structure of the two zwitterionic complexes 5 and 8 was determined by X-ray crystallography.     

THE STEREOCHEMISTRY OF DEALKYLATION STEP IN THE ARBUZOV REACTION INVOLVING FIVE-COORDINATE INTERMEDIATE. EVIDENCE FOR EQUILIBRIUM BETWEEN PHOSPHORANE AND PHOSPHONIUM SPECIES

Abstract

The oxidative addition of molecules X–Y to three-coordinated phosphorus compounds is of considerable general interest. If one of the groups attached to the phosphorus atom is an alkoxy, OR, the final product is almost always > P(O)Y with the formation of an alkyl halide RX. The above process is known as Arbuzov reaction, the mechanism of which can be represented, in the light of our present knowledge, as follows: mental mechanistic problem for the Arbuzov reaction.

The R(?)phosphite (4) was prepared from R(+)2-octanol of 95% opt. purity, [α]²⁰ _D + 9.4° (neat) and the chlorophosphite (3) by standard condensation in the presence of tertiary amine and purified by distilla tion in vacuo, δ³¹P ?127.5 ppm, [α]^D ₂₀ ?25.6° (neat). Equimolar amounts of the phosphite (4) and the corresponding halogen in CH2 C12 solution were allowed     

New Six-Coordinate Phosphorus Compounds. Synthesis and Stereochemistry

Abstract

Synthesis and stereochemistry of several new six-coordinate organophosphorus compounds are discussed.     

Novel Mild Synthesis of N-Carboxylotriphenylphosphin-Imines & Id N-Amidotriphenylphosphinimines VIA Ligand Exchange Processes in Dichlorotriphenylphosphine

Abstract

In connection with our recent investigations on the ligand exchange processes in five-coordinated phosphoranes and phosphonium salts a new, one-pot synthesis of various N-carboxylotriphenylphosphinimines 1 and N-amidotriphenylphosphinimines 2 has been devised. The key intermediate, phosphonium salt 4, was obtained in quantitative yield by the reaction of Ph₃PCl₂ with cyanate salts Pb(OCN)₂ and NaOCN. When alcohols or amines were present, salt 4 was converted into 1 and 2:     

Novel Mild Synthesis of Phosphorus Acid Anhydrides

Abstract

Our recent work on ligand exchange in chlorophosphonium salts and chloro-phosphoranes as well as on the reactions of phosphorus pseudohalogens with P^III compounds resulted in the novel methods for the synthesis of various phosphorus and carboxylic acids anhydrides.     

REACTION OF DIPHOSPHORYL DISELENIDES WITH DIALKYLTRIMETHYLSILYL PHOSPHITES. A NEW ROUTE TO SYMMETRICAL MONOSELENOPYROPHOSPHATES

Abstract

A novel efficient synthesis of sym-monoselenopyrophosphates 3 based on the reaction of diphosphoryl diselenides 1 with dialkyltrimethylsilyl phosphites 2 is described.     

X-H (X = C, N, O, P, S) bond activations induced by beta-heterosubstituted zirconaindenes

The azazirconacyclopentene-substituted phosphines 3 and 4 have been found to activate the C-H bonds of acetylenic systems, such as methylpropiolate, diphenylphosphinoacetylene and phenylacetylene, or of methylene compounds, such as malonitrile and diethylmalonate, to give complexes 5a-c, 6a and 6b. C-H bond activation also takes place with vinylacetate. Similar reactions with amines, alcohols, enolisable ketones, phenols, phosphonates, thiols and a second-generation SH-terminated dendrimer lead through X-H bond activation (X = N, O, P, S) to new complexes 8a-c, 9, 12 a,b, 13, 14a-c, 15, 16a and 16b. The azazirconacyclopentene-substituted amine 20 reacts to form analogous complexes. Zr-X bonds of these complexes (X = C, N, O, S) can be cleaved with diphenylchlorophosphine to give P-X phosphorus derivatives in high yield.     

Stereospecific conversion of cyclic phosphorothioates into chlorophosphates

The reaction of the individual diastereoisomeric cyclic phosphorothioates 2a, 2b in the trans-2,4,7-trioxa-3-phosphabicyclo (4.4.0) decane and 4a, 4b in the trans-2,4,7-trioxa-3-phosphabicyclo (4.3.0) nonane series with sulphuryl chloride affords the corresponding sulphenyl chlorides 5a, 5b, 6a, 6b with retention of the configuration of the phosphorus atom. The reaction of the latter with phosphorus trichloride leads stereospecifically to the chlorophosphates 7a, 7b, 8a and 8b with full retention of configuration at phosphorus.