Cyclic Phosphonites Research Articles

ChemInform Abstract: NOVEL INSERTION OF THE DIOXOPHOSPHORANE MOIETY (METAPHOSPHONATE) INTO AN ALIPHATIC CARBON‐HYDROGEN BOND VIA FLASH VACUUM PYROLYSIS OF A CYCLIC PHOSPHONITE AND BY OXIDATION OF A DIPHOSPHENE

Chemischer InformationsdienstVolume 15, Issue 15 Organoelement Compounds ChemInform Abstract: NOVEL INSERTION OF THE DIOXOPHOSPHORANE MOIETY (METAPHOSPHONATE) INTO AN ALIPHATIC CARBON-HYDROGEN BOND VIA FLASH VACUUM PYROLYSIS OF A CYCLIC PHOSPHONITE AND BY OXIDATION OF A DIPHOSPHENE J. I. G. CADOGAN, J. I. G. CADOGANSearch for more papers by this authorA. H. COWLEY, A. H. COWLEYSearch for more papers by this authorI. GOSNEY, I. GOSNEYSearch for more papers by this authorM. PAKULSKI, M. PAKULSKISearch for more papers by this authorS. YASLAK, S. YASLAKSearch for more papers by this author J. I. G. CADOGAN, J. I. G. CADOGANSearch for more papers by this authorA. H. COWLEY, A. H. COWLEYSearch for more papers by this authorI. GOSNEY, I. GOSNEYSearch for more papers by this authorM. PAKULSKI, M. PAKULSKISearch for more papers by this authorS. YASLAK, S. YASLAKSearch for more papers by this author First published: April 10, 1984 https://doi.org/10.1002/chin.198415288Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume15, Issue15April 10, 1984 RelatedInformation

Gas-Phase Pyrolysis of Tervalent Phosphorus-Oxy and -Thia Heterocycles: A new Approach to Short-Lived Pentavalent Phosphorus Compounds Having Co-Ordination Number 3

Abstract Generation of short-lived metaphosphonates by thermal fragmentation of cyclic phosphonites and their thia-analogues in the gas phase is described, including an elaboration of the method whereby a monomeric phosphonobenzene is detected unambiguously for the first time by an intra-molecular trapping reaction which also illustrates the considerable potential of such species in the synthesis of phosphorus heterocycles.

A Thermolysis Study of Poly(Trimethylene Phenylphosphinate) and Poly(2,2-Dimethyltrimethylene Phenylphosphinate). NMR and X-Ray Structure of 2-Oxo-2-Phenyl-4,4-Dimethyl-1,2-Oxaphospholan

Abstract The syntheses of polyphosphinates 2 and 2a by the ring-opening polymerization of cyclic phosphonites 1 and 1a with CH3I as an initiator have been reported in literature1–3. These polymers thermally decompose to give oxaphospholan 3 and 3a. In this paper, we present evidence on the mechanism of their formation.

Reversible reaction between cyclic phosphonite and aromatic cyclic disulfide to form a spiro dithiophosphorane. Observation of reductive elimination of a phosphorus(V) compound

Reversible reaction between cyclic phosphonite and aromatic cyclic disulfide to form a spiro dithiophosphorane. Observation of reductive elimination of a phosphorus(V) compound

Spontaneous alternating copolymerization of six-membered cyclic phosphonites with lipoic acid

Alternating copolymerizations of six-membered cyclic phosphonites as MN with lipoic acid as ME are described. The phosphonites employed were salicylyl phenyl phosphonite (SPO) and 2-phenyl-1,3,2-dioxaphosphorinane (trimethylene phenylphosphonite, TPO). The copolymerization took place without catalyst at 0°C or room temperature. The reaction of SPO with lipoic acid gave alternating copolymer 1, which was formed directly from a genetic zwitterion 4. On the other hand, the reaction of TPO with lipoic acid gave alternating copolymer 2, which was produced after a proton transfer as well as an O-S scrambling giving rise to units 2A and 2B, respectively. Both copolymers 1 and 2 have a lipoic acid component in the main chain.

The generation and trapping of a monomeric aryldioxophosphorane (‘metaphosphonate’)

Gas phase pyrolysis of the cyclic phosphonite (6) generates a monomeric metaphosphonate (7) as evidenced by an intramolecular trapping reaction with the adjacent phenyl group to give 5-hydroxydibenzophosphole 5-oxide (8) in high yield.

Novel insertion of the dioxophosphorane moiety (‘metaphosphonate’) into an aliphatic C–H bond via flash vacuum pyrolysis of a cyclic phosphonite and by oxidation of a diphosphene

Flash vacuum pyrolysis of 2-(2,4,6-tri-t-butylpheny)-1,3,2-dioxaphospholane (1) gave 5,7-di-t-butyl-3,3-dimethyl-2,3-dihydro-1-hydroxy-1λ5-benzophosphol-1-one (4), 100% also produced by photo-oxidation of bis (2,4,6-tri-t-butylphenyl)diphosphene (3)via insertion of the dioxophosphorane (–PO2) moiety into a neighbouring C–H bond.

Spontaneous copolymerizations of 2-phenyl-1,3,6,2-trioxaphosphocane with ?,?-unsaturated acids and with ?-keto acids

2-Phenyl-1,3,6,2-trioxaphosphocane(1), an eight-membered cyclic phosphonite, was copolymerized withα,s-unsaturated acids and with α-keto acids. The copolymerization took place above room temperature without added catalyst. The copolymerizations of1 with α,s-unsaturated acids of acrylic and methacrylic acids (2) afforded polyphosphinates (3), alternating copolymers of1 and2. On the other hand, the combinations of1 with α-keto acids of pyruvic and phenylglyoxylic acids (5) gave copolymers (6) consisting of alternating unit6α and α-ester unit6s formed via the deoxygenation of5 by1 (“Deoxy-Copolymerization”).

Asymmetric synthesis of 4-vinylcyclohexene using modified nickel catalysts

Optically active phosphines and cyclic phosphonites are used in the catalytic system Ni(O)/ligand/butadiene. The formation of 4-vinylcyclohexene as the only chiral dimer is monitored by the induced optical activity, and widely depends on the relative concentration and the nature of the ligands. The highest induction (35% e.e.) is found at 20 °C with 2-t-butyl-4,5-dicarbethoxy-1,3,2-dioxaphospholane.

Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH2-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, 1H, 31P, and 31C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the “normal” phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH2Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.

Redox 1?1 alternating copolymerization of cyclic acyl phosphonte with 4,4?-diphenoquinones

A cyclic phosphonite(1) was copolymerized with 4, 4′-diphenoquinones (2a–2c) to give 1∶1 alternating copolymers (3a–3c) consisting of a carboxylic acid ester and a triaryl phosphonate ester. Copolymerization took place without added initiator. During the reaction 1 was oxidized whereas 2 was reduced (“redox copolymerization”). A mechanism involving a genetic zwitterion intermediate (4) is proposed for the copolymerization.

Polymerization via zwitterion. 24. Copolymerization of a cyclic acyl phosphonite with aromatic aldehydes

Spontaneous copolymerizations of 2-phenyl-4-oxo-5, 6-benzo-1,3,2-dioxaphosphorinane, a new cyclic acyl phosphonite, (MN) with p- and o-substituted aromatic aldehydes (ME) gave 1∶2 (MN ∶ ME) alternating copolymers. This copolymerization took place without added catalyst affording copolymers via zwitterion . The intermediate of spiro acyloxyphosphorane was detected in situ by 31p NMR. The formation of a stabilized intermediate was taken as an important factor to control the 1∶2 composition. The scheme of the copolymerization involving a zwitterion was presented. For the comparison with the above system, copolymerizations of ethylene phenyl phosphonite with aromatic aldehydes were also examined.

No Catalyst Copolymerization by Spontaneous Initiation Mechanism

Abstract A new type of copolymerization is presented here, which requires no added initiator. A zwitterion 1 is generated by the interaction between two monomers; one monomer has nucleophilic reactivity (MN) and the other possesses electrophilic reactivity (ME). Two moles of the genetic zwitterion 1 react with each other to produce a dimeric zwitterion 2. The dimeric zwitterion 2 grows by its reaction with 1 to polymeric zwitterion 3. Intermolecular reaction of macro-zwitterions (dimeric 2 and polymeric 3) also occurs, which brings about a sharp increase in molecular weight. In a series of studies, six MN monomers and six ME monomers have been investigated. As the MN monomer, cyclic imino ether, exo-imino cyclic ether, azetidine, Schiff base and cyclic phosphonite have been selected. As the ME monomer, lactone, cyclic anhydride, sultone (sulfolactone), acrylic acid, acrylamide and β-hydroxyethyl acrylate have been successfully used. Thus, thirty-six combinations (six times six) of copolymerization have now become conceivable. The present paper gives a survey of elemental reactions of selected combinations of copolymerization. The emphasis is laid on the discussions of recent results.

The Structure of Polymers Obtained from Arbuzov-Michaelis Reactions Involving Cyclic Phosphonites

The Structure of Polymers Obtained from Arbuzov-Michaelis Reactions Involving Cyclic Phosphonites

The Ring-opening Polymerization of Cyclic Aminophosphinites

Abstract A further study of 1, 3-addition-type ring-opening polymerization has been attempted by using cyclic N-phenyl- and N-methylethyleneamino phenylphosphinites as monomers, each of those has a nitrogen atom in place of one of the two oxygen atoms in the ring structure of a cyclic phosphonite. They were prepared from phenylphosphonous dichloride and N-phenyl-and N-methylaminoethanols. The ring-opening 1, 3-addition reaction of the N-phenyl derivative with benzyl bromide, as a model experiment for the polymerization, has been found to proceed smoothly, giving the desired adduct, which in turn gave benzylphenylphosphinic acid and N,N′-diphenylpiperadine on hydrolysis. These cyclic aminophosphinites were then polymerized to give the expected poly(aminophosphine oxide) s in the presence of Arbusov reaction-type reagents or in the absence of a catalyst at elevated temperatures.