Catalysts phosphazenes

The borato phosphazene, 38, acts as a catalyst for this process. 

PHOSPHINE-BOUND TRANSITION METAL CATALYSTS VINYL POLYMERS WITH PHOSPHAZENE SIDE GROUPS... 

An overview of the synthesis and characterization of a unique class of polymers with a phosphorus-nitrogen backbone Is presented, with a focus on poly(dichloro-phosphazene) as a common Intermediate for a wide variety of poly(organophosphazenes). Melt and solution polymerization techniques are Illustrated, Including the role of catalysts. The elucidation of chain structure and molecular weight by various dilute solution techniques Is considered. Factors which determine the properties of polymers derived from poly(dichlorophos-phazene) are discussed, with an emphasis on the role that the organic substituent can play In determining the final properties. 

De Winter J, Coulembier O, Gerbaux P, Dubois P (2010) High molecular weight poly(a, a , P-trisubstituted P-lactones) as generated by metal-free phosphazene catalysts. Macromolecules 43 10291-10296... 

A fast catalyst for the ring-opening polymerization of D4 in solution or in the bulk has been reported by Molenberg and Moller13. They report the use of a phosphazene base in combination with methanol as the initiator, compound 3. 

Instead of an aqueous alkaline base, organic-soluble, non-ionic phosphazene bases such as BEMP and BTPP have been used with the third-generation catalyst 4d to realize a homogeneous system for the asymmetric alkylation of 1 (Scheme 2.6), which is sometimes advantageous from a practical viewpoint [24]. 

A characteristic feature of this solid-phase amino acid synthesis is the use of the phosphazene bases 53 and 54 for the PTC alkylation reaction [64, 65]. Because these compounds, which are soluble in organic media, do not react with alkyl halides, both alkyl halide and phosphazene bases can be added together at the start of the reaction, which is useful practically [65], Cinchonine and cinchonidine-derived salts, e.g. 25, were found to be very efficient catalysts. Under optimum conditions the alkylation proceeds with enantioselectivity in the range 51-99% ee, depending on the alkyl halide component [65], Seventeen different alkyl halides were tested. After subsequent hydrolysis with trifluoroacetic acid the corresponding free amino acids were obtained in high yield (often >90%). 

Graft copolymer, polyclhylene-gra/f-poly(propylcnc oxide) (PE-g-PPG), has been synthesized by ring opening anionic polymerization of propylene oxide with a phosphazene catalyst and hydroxylated polyethylene (Mn = 12400, [OH] = 5 units/chain). Polymerization of propylene oxide was carried out in tetraline at 120 °C for 20 hours. The 13C NMR analysis of PE-g-PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization (Fig. 6). 

In this paper we consider two specific challenges. First, how might transition metals be linked to phosphazene high polymers Such systems are of interest as immobilized catalysts or materials with unusual electrical properties. Second, how can bioactive agents be attached to polyphosphazenes to prepare, for example, targeted, slow release chemotherapeutic agents ... 

It has been shown that, in contrast to the previous assumption, the presence of P-halogen bond is not a requirement for polymerization. Thus, phosphazenes containing P—OCH2CF3 group were polymerized, apparently by a mechanism involving ionization of P—OCH2CF3 bond, facilitated by Lewis acid catalysts [237]. 

Computational studies concerning theoretical approaches to the intrinsic basicity of neutral nitrogen bases have been reported, including those of phos-phoranimines. The non-ionic phosphazene bases BEMP (112), BTPP (113) and (114, R = Ph) appear to be excellent catalysts for the Michael addition reactions. Thus the yield of the coupling reaction of ethyl isocyanoacetate with l,2-bis(4-bromomethylphenyl)ethane is increased by the addition of the phosphazene base BEMP. Polymer-supported BEMP (P-BEMP) has been applied for the allylation of 2H-benzo[d]l,3-dioxolan-5-ol by allyl bromide. " Cyclodehydration of 1,2 diacylhydrazines by tosyl chloride in the presence of P-BEMP leads to excellent yields of 1,3,4,-oxadiazoles. Addition of P-BEMP also improves the yield of the Hofmann elimination step in the synthesis of tertiary mines using REM resin (polymer-bound acrylate ester). ... 

Cyclolinear phosphazene polymers (221) have been prepared by polymerization of (220) with Grubbs catalysts as initiators. No polymerization has been observed using NP(NH2)2(NPNH2[0(CH2)9CH = CH2] 2 as precursor, probably caused by metal-nitrogen interactions. Polymerization of (220a, x =... 

A Facile Synthetic Route to Phosphazene Base Catalysts and Their Use in Siloxane Synthesis... 

Summary Phosfdiazene bases represent a new class of highly active non-ionic catalysts that rapidly polymerize cyclosiloxanes with equilibrium attained in very short reaction times at very low catalyst levels. To date, phosphazene base catalysts have been considered an academic curiosity because of the complicated and hazardous synthetic protocol used to prepare them. A facile synthetic process has been developed, which yields ionic phosphazene bases in three steps with an overall yield of qrproximately 75%. This is achieved through nucleophilic substitution of ionic phosphonitrilic chloride oligomers with secondary amines, followed by anion exchange. These ionic phosphazenes were found to exhibit similar reactivity in the ring-opening polymerization of cyclosiloxanes to that of the non-ionic phosphazene base. 

Phosphazene Base Catalysts and their Use in Siloxane Synthesis 629... 

Through steric hindrance and conjugative effects, these ionic phosphonium salts are very stable to hydrolysis. This, coupled with the lipophilic nature of the cation, results in a very soft, loosely bound ion pair, making materials of this type suitable for use as catalysts in anionic polymerization [8 - 13]. Phosphazene bases have been found to be suitable catalysts for the anionic polymerization of cyclic siloxanes, with very fast polymerization rates observed. In many cases, both thermodynamic and kinetic equilibrium can be achieved in minutes, several orders of magnitude faster than that seen with traditional catalysts used in cyclosiloxane polymerization. Exploiting catalysts of this type on an industrial scale for siloxane polymerization processes has been prevented because of the cost and availability of the pho hazene bases. This p r describes a facile route to materials of this type and their applicability to siloxane synthesis [14]. 

The synthesis of oligomeric peralkylated polyaminophosphazenes based upon the P3 and P4 templates is an elegant (but complicated), hazardous, and expensive multi-step process. To exploit catalysts of this type in silicone synthesis on an industrial scale would require a much simplified and lower-cost synthetic protocol. One of the simplest and lowest-cost routes to a conjugated -P=N- template that forms the framework for the synthesis of phosphazene base materials is via phosphonitrilic chloride oligomers (Fig. 3). These are well-known acidic catalysts used in the silicone industry for the condensation polymerization of silanol-terminated polydimethylsiloxanes. Catalysts of this type are most commonly prepared by the reaction of PCI5 with NH4CI or HMDZ,... 

In this review, we have illustrated by different applications the importance of chiral organophosphorus compounds as catalysts opening up a new field in asymmetric catalysis. From the diversity of trivalent (pyramidal) A3a3 compounds and pentavalent (tetrahedral) A5a4, there are many possibilities for the design of asymmetric one- or two-center catalysts. It can be reasonably envisioned that new chiral phosphines, phosphine oxides, and phosphazenes, to-... 

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