Cyclic phosphorus-containing compound

The reagent does not replace nitrogen atoms, and N-alkyl or N-aryl anthranilic acids yield 2,l-benzisothiazoline-3-thiones (94) on heating with phosphorus pentasulfide in xylene. Curiously, when alkyl iV-arylanthranilates are treated in the same way, only a very small proportion—less than 10%— of 94 is obtained. The major product (80%) is the cyclic phosphorus-containing compound (95), the identification of which gives some clue about the structures of possible intermediates.122... 

Thus, we first discuss thermodynamics, paying attention to features that are important for polymer synthesis (e.g., dependence of equilibrium monomer concentration on polymerization variables) then we describe kinetics and thermodynamics of macrocyclization, trying to combine these two related problems, usually discussed separately. In particular we present the new theory of kinetic enhancement and kinetic reduction in macrocyclics. Thereafter, we describe the polymerization of several groups of monomers, namely cyclic ethers (oxiranes, oxetanes, oxolanes, acetals, and bicyclic compounds) lactones, cyclic sulfides, cyclic amines, lactams, cyclic iminoethers, siloxanes, and cyclic phosphorus-containing compounds, in this order. We attempted to treat the chapters uniformly we discuss practical methods of synthesis of the corresponding polymers (monomer syntheses and polymer properties are added), and conditions of reaching systems state and reasons of deviations. However, for various groups of monomers the quality of the available information differ so much, that this attempt of uniformity can not be fulfilled. 

The following classes of phosphorus-containing compounds were not affected by large amounts of the enzyme with Mg2+, Mn2+, Zn2+, or Co2+ at either pH 9.1 or 7.5 (1) ribo- or deoxyribonucleoside mono-, di-, or triphosphates (2) ribo- or deoxyribopolynucleotides (3) nucleotide coenzymes (e.g., DPN+, UDP-glucose) (4) phosphomonoesters (e.g., glucose-6-P, p-nitrophenyl phosphate) (5) cyclic tri- or tetrametaphos-phates (6) phosphorofluoridates (inorganic phosphorofluoridate, adenosine 5 -phosphorofloridate) and (7) phosphonates (e.g., methylene-bis-phosphonate) (12, 57). 

Several of the more common classes of phosphorus-containing compounds are presented in Table 6-3. In the orthophosphate anion, the P atom is centrally bonded to the oxygen atoms, which are located at the corners of a tetrahedron. The condensed phosphates—the polyphosphates and metaphosphates—are formed by the condensation of two or more orthophosphate groups and have the characteristic P—O—P linkage. While polyphosphates are linear molecules, the metaphosphates are cyclic. 

Table 18, pp. 269/74, lists the reactions of linear, branched, and cyclic alkenes, halo-alkenes, and oxygen-, sulfur-, nitrogen-, and phosphorus-containing compounds with C=C double bonds, the reaction conditions, and the product distribution of the phosphanes obtained (abbreviations are explained in the footnotes at the end of the table). 

Chapters 2-5 focus on the synthesis, spectroscopic analysis, and herbicidal activity of 30 series phosphorus-containing compounds including alkylphosphonates, monosalts of alkylphosphonic acids, alkylphosphinates, monosalts of alkylphosphinic acids, cyclic phosphonates, and caged bicyclic phosphates (Scheme 1.20). Their stmcture-activity relationships are discussed in detail in each chapter. 

Our interest in such compounds stems mainly from the possibility that they might be useful precursors to new classes of phosphorus-containing polymers or cyclic oligomers. Functional linkages such as E = NSiMe3 or CR SiMe3 could serve as sites for condensation-polymerization reactions, leading to novel cyclic or polymeric sys terns, ... 

Compound 290 was reacted with dichloro(phenyl)phosphine in the presence of Et3N this led to a ring-opening reaction with the breakage of the 0-CH2 bond, insertion of the phosphorus atom, and formation of the intermediate 291, which gave upon hydrolysis the cyclic phosphoryl-containing product 292 <1998IC4945>. 

There have been a number of developments worthy of special mention in chemistry involving pentaco-ordinated compounds and intermediates. These include reports of molecular mechanics calculations to study the hydrolysis of cyclic phosphorus esters, further detailed studies of the reactions of tervalent phosphorus compounds with acetylene carboxylates and the first synthesis of a pentaco-ordinated phosphorus compound containing a three-membered (phosphirene) ring. There has also been further elegant work in the area of phosphatrane chemistry. 

Cyclic phosphorus compounds Compounds containing P rings... 

Phosphorus-containing enamines have been prepared by phosphorylation of N-vinyl substituted tertiary amides, lactams and cyclic imides with phosphorus pentachloride ". Addition of amines to diphosphoryl alkynes has been described. Addition of RR NH [R = H, Ri = Me, cyclohexyl, PhCH2 RR = (CHj) to (Et0)2P(0)C=CP(0K0Et2)2 in CH2CI2 at 25 °C gave 93-100% of (Et0)2P(0)C(NRRi)=CHP(0)(0Et2)2 . Speziale and coworkers have studied the reactions of phosphorus compounds with trichloroacetamides. 

The phosphazenes are cyclic or chain compounds that contain alternating phosphorus and nitrogen atoms with two substituents on each phosphorus atom. The three main structural types are the cyclic trimer (13-11), cyclic tetramer (13-III) and the oligomer or high polymer (13-IV). A few cyclic pentamers and hexamers are also known. The alternating sets of single and double bonds in (13-11) to (13-IV) are written for convenience but (see below) should not be taken literally. 

The combination of amide, phosphorus (phosphonic) acid, water and PCI3 also provides mixtures of linear and cyclic (aminoalkyl)phosphonic compounds. Such a mixture containing formamide yields aminomethylenebisphosphonic acid together with the oxazaphosph(V)olidine 252 the course of the reaction, and the effect of changes in reactant... 

Phosphorus(y) Compounds. The chemistry of phosphate species containing a peroxy linkage and the stereochemical implications of reaction mechanisms at phosphorus(v) have been reviewed. The cyclic 1,3,2-dioxaphospholans derived from meso- and ( )-hydrobenzoin show different n.m.r. spectra, and the crystal structures of the 2-phenoxy- and 2-/>-bromophenoxy-5-chloromethyl-5-methyI-2-oxo-l,3,2-dioxaphosphorinans have been determined. Factors influencing the stereochemistry in substituted 1,3,2-dioxa-phosphorinans as shown mainly by n.m.r. data are considered in a number of papers. Changes in the O—H stretching frequency of phenol in the... 

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