Phosphonyl Chloride Research Articles

NMR study of reactions of organyltrichlorophosphonium hexachlorophosphorates with triethylamine

The reactions of trichloro(2-ethoxyethenyl)phosphonium and trichloro(styryl)phosphonium hexachlorophosphorates with triethylamine were studied by 1H, 13C, and 31P NMR spectroscopy. It was shown that phosphonyl chlorides are the primary products of the reactions. The presence of the alkoxy group in hexachlorophosphorate results in the oxidation of the PCl2 group to form phosphonyl chlorides. Diphosphorylated oxaphosphinines were synthesized.

Polymerizations of hexamethylcyclosiloxane catalyzed by metal sulfonate/acid chloride combinations

AbstractHexamethylcyclotrisiloxane (D3) was polymerized in bulk at 100°C, and the conversion was monitored by 1H‐NMR spectroscopy. Various metal triflates, which were inactive as neat salts, were combined with chlorosilanes, chlorostannanes, phenyl phosphonyl chloride, and carboxylic acid chlorides, which were also inactive when added alone. Most 1 : 1 combinations proved to produce active catalysts for the ring‐opening polymerization of D3. When the anions of sodium salts were varied alkylsulfonates and the sulfates were more reactive than the triflate. The samarium triflate/diphenyldichlorosilane combination was found to be the most reactive catalyst on the basis of the triflate ions. Regardless of the catalyst combination, the main reaction products in the early stages of all polymerizations were octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). The polymerization mechanism is discussed. The reactive catalyst combinations also polymerized D4 at 100°C. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Palladium-Catalyzed Hydroaminative Route to Phosphaisoquinolin-1-ones

A Pd-catalyzed intramolecular cyclization of o-(1-alkynyl)phenylphosphoramide esters to give phosphaisoquinolin-1-ones is reported. This formally 6-endo-dig hydroaminative reaction proceeds in good yields and high regio­selectivities. The o-(1-alkynyl)phenylphosphor­amide esters are prepared by a two-step process involving treatment of o-(1-alkynyl)phenylphosphoric acid esters with thionyl chloride followed by amination of the resulting phosphonyl chloride with amines (R. Hirschmann et al. J. Am. Chem. Soc. 1997, 119, 8177-8190). Although different Pd, Ag, and Cu catalysts were tested, PdCl2(MeCN)2 was shown to afford by far the best yields in shorter reaction times. The scope of the reaction was inadequately studied.

High Performance Photo-curable Polymers and Oligomers Based on Novel Ring-opening Reactions of Oxetanes

AbstractWe found new reactionsof oxetanes with many reagents such as acyl chlorides, silyl chlorides, phosphonyl chlorides, alkyl chlorides, aryl esters, thio esters, phosphonic acids, carboxylic acids, thiols, and phenols using suitable quaternary onium salts or crown ether complexes as catalysts. More recently, we also found an anionic ring-opening polymerization of certain oxetane monomers such as (3-methyl-3-hydroxymethyl)oxetane and (3-ethyl-3-hydroxymethyl)oxetane, which have hydroxyl groups, catalyzed by potassium tert-butoxide and 18-crown-6-ether complex, and an anionic ring-opening alternating co-polymerization of oxetane monomers with cyclic carboxylic anhydrides. These reaction systems have also been applied to the synthesis of new functional polymers. In this article, we would like to introduce the application of these reaction systems for the synthesis of high performance new photo-curable polymers and oligomers containing pendant or terminal (meth)acryloyl groups.

Chemical Synthesis and Molecular Recognition of Phosphatase-Resistant Analogues of Phosphatidylinositol-3-phosphate

The remodeling of phosphatidylinositol polyphosphates in cellular membranes by phosphatases and kinases orchestrates the signaling by these lipids in space and time. To provide chemical tools to study the changes in cell physiology mediated by these lipids, three new metabolically stabilized (ms) analogues of phosphatidylinositol-3-phosphate (PtdIns(3)P) were synthesized. We describe herein the total asymmetric synthesis of 3-methylphosphonate, 3-(monofluoromethyl)phosphonate and 3-phosphorothioate analogues of PtdIns(3)P. From differentially protected D-myo-inositol key intermediates, a versatile phosphoramidite reagent was employed in the synthesis of PtdIns(3)P analogues with diacylglyceryl moieties containing dioleoyl, dipalmitoyl, and dibutyryl chains. In addition, we introduce a new phosphorylation reagent, (monofluoromethyl)phosphonyl chloride, which has general applications for the preparation of "pKa-matched" monofluorophosphonates. These ms-PtdIns(3)P analogues exhibited reduced binding activities with 15N-labeled FYVE and PX domains, as significant 1H and 15N chemical shift changes in the FYVE domain were induced by titrating ms-PtdIns(3)P analogues into membrane-mimetic dodecylphosphocholine micelles. In addition, the PtdIns(3)P analogues with dioleoyl and dipalmitoyl chains were substrates for the 5-kinase enzyme PIKfyve; the corresponding phosphorylated ms-PI(3,5)P2 products were detected by radio-TLC analysis.

Enhancing polymer char formation by reaction with phosphorylated polyols. 1. Cellulose

The use of polyol phosphonyl chlorides or phosphochloridates as phosphorylating agents for cellulose is considered as means of introducing a char-forming centre in association with an acid-generating moiety into a functional polymer which itself is potentially char-forming. The specific polyol phosphonyl chloride used, spirocyclic pentaerythritol di(phosphonyl chloride) or diphosphochloridate (SPDPC) is shown to be able to substitute into cellulose (as cotton) in the presence of a suitable solvent (DMF) and base (pyridine and sodium hydroxide) at levels commensurate with phosphorus concentrations up to 2.5% (w/w). This is equivalent to phosphorylation yields of up to 22.7%. The efficiency of phosphorylation is dependent upon reaction temperature and SPDPC: cotton mass ratios. Highest yields occur when reactions are carried out at respective mass ratios of 4:1 (almost equivalent to a molar ratio of an anhydroglucopyranose repeat: 1/2 SPDPC molecule) at 160°C for 2 h. Thermogravimetric analysis of SPDPC-phosphorylated cellulose shows enhanced char formation over the range 400–740°C with respect to untreated cotton cellulose. Scanning electron microscopy shows chars to be well-defined and quite resistant to oxidation as the temperature rises above 600°C in air.

Synthesis of chiral amino cyclic phosphoric acids

Chiral amino cyclic phosphoric acids, 5-amino-2-hydroxy-4-(4-nitrophenyl)-1,3,2-dioxaphosphorinane 2-oxide and 2-hydroxy-4-(4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in good over yields (64.2% and 72.8% respectively) from 2-amino-1-aryl-1,3-propanediols. The different reaction conditions are necessary in hydrolysis reactions of amino cyclic phosphonyl chlorides.

Synthesis and spectroscopic characterization of organophosphoryl polyoxotungstates [C 6H 11P(O)] 2X n+ W 11O 39(8− n)− (X n+ =P 5+, Si 4+, B 3+, Ga 3+)

In the presence of NBu 4Br acting as a phase-transfer reagent, the monovalent polyoxotungstates α-X n+ W 11O 39 (12− n)− (X=P, Si, B, Ga) react with electrophilic cyclohexane phosphonyl chloride to give hybrid organophosphoryl polyoxotungstates [(C 6H 11P(O)] 2XW 11O 39 (8− n)− , which have been characterized by elemental analysis and IR, 31P and 183W NMR spectroscopy. The six-line 183W spectra indicate that the hybrid anions possess C s symmetry in solution. According to spectroscopic observations and chemical analyses, the hybrid anion consists of an α-[XW 11O 39] framework on which are grafted two equivalent C 6H 5P(O) groups through P–O–W bridges.

Synthesis of N-(alkoxycarbonyl or alkoxycarbonyl-methyl-alkoxyphosphonyl)-α-amino-O,O-diphenyl phosphonates and their bioactivities

With phosphonoformic acid (PFA) and its analog, phosphonoacetic acid (PAA), as the lead compounds, α-amino phosphonates were introduced into PFA and PAA. The derivatives of N-(alkoxycarbonyl-alkoxyphosphonyl)-α-amino phosphonates (I) and N-(alkoxycarbonyl-methyl-alkoxyphosphonyl)-α-amino phosphonates (II) with the N-terminal of amino phosphonates bonding to phosphorus atom of PFA andPAA were synthesized via the reaction of the corresponding phosphonyl chloride with α-amino phosphonates in the presence of a base. The31P NMR spectra of I and II were determined. It is found that the coupling constants3 J pp with R3 being alkyl group were lower than those with R3 being (substituted) phenyl, and this result was discussed. The preliminary bioassay showed that some of the compounds I and II have better activities against tobacco mosaic virus (TMV). The inhibitory was higher than that of DHT (2, 4-dioxyhexahydro-1, 3, 5-triazine). In addition, some of the compounds showed the activity against cancer cells.

Synthesis of N-(methoxycarbonyl or isopropylcarbamoyl- methoxyphosphonyl)-α-amino acid ester and their stereomers

N-(methoxycarbonyl-methoxyphosphonyl)-α-amino add esters (I) were synthesized via the reaction of the corresponding phosphonyl chloride with amino acid ester hydrochlorides in the presence of a base. Compound I was aminated to yield N-(isopropylcarbainoyl-methoxyphosphonyl)-α-amino acid esters (II). With l-amino acids as starting materials, the isomers of products I and II were separated and their configurations were confirmed by the single crystal X-ray diffraction of II.

Phosphonoformate Esters of Anti-HIV Nucleosides: 3′-Azido-3′-deoxythymidine and 2′,3′-Dideoxycytidine Derivatives Containing a Small 5′-(0-Alkoxycarbon-ylphosphinyl) or 5′-(O-Cholesterylcarbonylphosphinyl) Substituent

Abstract A convenient general method of synthesis of 5′-O-(alkoxycarbonyl)phosphonate esters of 2′,3′-dideoxyribonucleosides is presented, using the 5′-O-(methoxycarbonyl)phosphinyl, 5′-0-(ethoxycarbonyl)phosphinyl, and 5′-O-(cholesterylcarbonyl)phosphinyl derivatives of 3′-azido-3′-deoxythymidine (AZT) and the 5′-0-(ethoxycarbonyl)phosphinyl derivative of 2′,3′-dideoxycytidine (ddC) as examples. Reaction of trimethyl phosphonoformate, methyl phosphonoformate, or dimethyl cholesterylcarbonylphosphonate with phosphorus pentachloride in carbon tetrachloride, followed by direct condensation of the resulting phosphonyl chloride with the nucleoside, gave the fully esterified phosphonoformate derivatives, which on treatment with sodium iodide in tetrahydrofuran underwent selective cleavage of the P-OMe or P-OEt groups, leaving the carboxylate esters intact. The resulting products were converted from sodium salts to ammonium salts by ion-exchange chromatography.

ChemInform Abstract: Pseudochalcogen Compounds. Part 18. Cyanamidolysis of Organophosphoryl‐(phosphonyl‐)chlorides.

AbstractCyanamidolytic reactions of organophosphoryl and ‐phosphonyl chlorides are leading in dependence on the reaction conditions to metal organocyanamidophosphates e.g. (I) and ‐cyanamidophosphonates e.g. (II), respectively, and by‐products such as (III), as well as to corresponding organophosphoryl‐hydrogencyanamides e.g. (IV) and to bis(organylphosphoryl)‐ and bis(organophosphonyl)carbodiimides such as (V) and (VI).

Organophosphorus Chemistry. 2. The Reduction of Quinquevalent Phosphrous to the Trivalent State

Abstract Phosphoryl and phosphonyl chlorides are reduced conveniently to the monobasic acid forms of the corresponding phosphorous and phosphonous acids by the use of sodium borohydride dispersed in dioxane.

Studies on organophosphorous compounds: IX. C-Phosphorylation of compounds bearing an active methylene group

The formation of P-C bond is one of the important problems in synthetic organophosphorous chemistry. This paper describes the study of the formation of P-C linkage via phosphorylation of carbon atom containing active hydrogen.p-Substituted phenylacetonitrile possessing an active methylene group undergoes stepwise C-phosphorylation smoothly with diethyl phosphoryl chloride in the presence of naphthalene-sodium. Phosphonyl chloride reacts analogously. Being a deprotonizing agent naphthalene-sodium is distinguished by its availability, effectiveness and mild reaction conditions. The presence of an electron-withdrawing group in the benzene ring reduces the yield of phosphorylation seriously. The chemical shift of ~31P NMR of the resulted α-cyano-benzylphosphonates (1) correlates linearly with the Hammett σ constants of the substituents. As indicated by ~1H NMR studies the protons in the ester ethyl groups are magnetically nonequivalent. Compound 1 can be alkylated with alkyl halide or condensed with aromatic aldehyde by Hornor-Wittig type reaction due to the presence of active hydrogen atom. The structure-reactivity studies of diethyl phosphoryl chloride on reacting with various β-diketones and β-keto esters (5) as regiospecific reaction were reported. The influences of metal ions in the enolates on the reactivity of the latter were examined and discussed. Only vinyl phosphates with predominantly Z configuration have been isolated exclusively. The 0 atom with an active hydrogen in the β-diketones investigated is inert to phosphorylation. These experimental results are well supported by reaction selectivity in terms of E_(q_o)/E_(CO_c) based on EHMO calculation.

Synthesis of 6‐chlorofuro[2,3‐b]pyridine‐2‐carboxylie acid

AbstractA new route was employed to synthesize methyl 6‐ehlorofuro[2,8‐b]pyridine‐2‐earboxylate by eoneurrent dehydrohalogenation and dehydration of 3‐ehloro‐3‐(β,β‐dichloro‐β‐ethoxycar‐bonylelhyl)‐2,6‐piperidinedione using methyl phosphonyl chloride.

Properties of polyethylene modified with phosphonate side groups. I. Thermal and mechanical properties

AbstractLow‐density polyethylene was modified by the inclusion of phosphonate ester pendent groups by using an oxidative chlorophosphonylation reaction followed by esterification of the polyethylene poly(phosphonyl chloride) with an alcohol. Two different types of phosphonate esters were prepared: dimethyl phosphonate from the reaction with methanol and a phosphonate graft copolymer from the reaction with hydroxy‐terminated poly(ethylene oxide) (PEO). For the latter, oligomers with molecular weights of 350 and 750 were used. For each type of phosphonate, a series of polymers were prepared with pendent group concentrations ranging from 0 to 9.1 substituents per 100 carbon atoms. The modified polymers were characterized by infrared spectroscopy, differential scanning calorimetry, and by measurement of the tensile modulus. Infrared spectroscopy proved to be useful for determining if the polymer modification reaction resulted in entirely phosphonate ester pendent group substitutions or if unesterified phosphonic acid groups were also present. The polymers prepared in this investigation exhibited no infrared absorbances arising from phosphonic acid groups. The presence of phosphonate ester groups resulted in a decrease of crystallinity with increasing phosphonate concentration and with the exception of the polymers containing 9.1 PEO–phosphonate grafts per 100 carbon atoms, the effect of phosphonylation on the melting temperature of the polymers was consistent with Flory's theory for the melting point depression of random copolymers. The tensile modulus measured from a constant uniaxial elongation experiment decreased with increasing phosphonylation. The behavior of all three phosphonate series was identical and could be attributed to the effect of decreasing polymer crystallinity.

Reactions of Aroyl Peroxides. IV. Benzolyl Peroxide with some halides and oxyhalides of Phosphorus and Sulphur

When benzoyl peroxide was heated with phosphorus trichloride (1 and 2 mol) in benzene, or chlorobenzene solution, carbon dioxide, benzoyl chloride, and phenyl phosphonyl chloride were the major products. Diphenyl phosphonyl chloride was also formed in small yield, p-Chlorobenzoyl peroxide reacted with phosphorus trichloride, in benzene solution, yielding carbon dioxide, p-chlorobenzoyl chloride, p-chlorophenyl phosphonyl chloride, and p-chlorobenzoic anhydride. The reaction of benzoyl peroxide with phosphorus trichloride alone yielded benzoyl chloride only. Phosphorus oxychloride, on the other hand, does not enter into the reaction. Thionyl chloride, in benzene, gave a complex mixture consisting of carbon dioxide, chlorobenzene, benzoyl chloride, phenyl benzoate, benzene sulphonyl chloride, diphenyl, and benzoic anhydride. Sulphuryl chloride in benzene yielded a mixture of carbon dioxide, chlorobenzene, benzoic acid, phenyl benzoate, and diphenyl. The mechanisms of these various reactions are discussed.

The Preparation of Phosphonyl Chlorides by the Reaction of Hydrocarbons with Phosphorus Trichloride and Oxygen

The Preparation of Phosphonyl Chlorides by the Reaction of Hydrocarbons with Phosphorus Trichloride and Oxygen