Phosphorus Halides Research Articles

A High Yield Synthesis of Phosphatidyl Ethanolamines Using Phosphoramidite Intermediates

Alkyl 2-aminoethyl hydrogen phosphates (phosphatidyl ethanolamines) were prepared via phosphoramidite chemistry. tert-Butoxy-carbonyl N-protection of 2-aminoethanol, followed by cyclisation with phosphorus(III) chloride gave the phosphoramidite 3-tert-butoxycarbonyl-2-chloro-1,3, 2-oxazaphospholidine (3). This reacted with long chain alcohols (C6 to C18) to give 2-alkyloxy-3-tert-butoxycarbonyl-1,3,2-oxazaphospholidines 4a-d which were oxidised to 2-alkyloxy-3-tert-butoxycarbonyl-2-oxo-1,3, 2-oxazaphospholidines 5a-d with dinitrogen tetroxide. Simultaneous heterocycle cleavage and N-deprotection were achieved with refluxing aqueous tetrahydrofuran, to give the target 2-aminoethyl phosphates 6a-d. The reaction conditions are mild, and the yields are almost quantitative in terms of the long chain alcohol. The products and intermediates are fully characterised by a range of spectroscopic and analytical methods.

Adhesives produced by reactions of phosphorus halides with phenols and bisphenols

By the reaction of phosphorus oxychloride and thiophosphoryl chloride with dihydroxy phenols and some bisphenols, a number of synthetic adhesives have been prepared containing C-O-P linkages and their adhesives properties on duraluminium and steel determined. A probable mechanism for their formation is also discussed.

15N Nucelar Magnetic Resonance Study of Two-Coordinate Phosphorus Cations - Sign-Determination of Coupling Constants – Application of Two-Dimensional (2D) Heteronuclear Shift Correlations

Cyclic and non-cyclic bis(amino)phosphenium cations (1 to 4) together with their precursors (bis(amino)phosphorus chlorides 5 to 8) and some other bis(amino)phosphorus compounds (9 to 14) have been studied by 13C, 15N (natural abundance), 29Si and 31P NMR spectroscopy. 15N chemical shifts and coupling constants 1J(31P15N) of phosphenium cations have been determined for the first time. NMR data of 1 to 4 are compared with those of a bis(amino)carbene and various bis(amino)stannylenes. In the phosphenium cations 1 to 4 the 15N nuclear shielding is considerably reduced (ca. 70 to 100 ppm as compared with 5 to 14) and there is a crude linear relationship between δ15N and δ31P values. Changes in the δ15N values of 1 to 4 do not reflect P-N (pp)π interactions. A positive sign has been determined for the coupling constants 1J(31Ρ15Ν) [reduced coupling constants 1K(31P15N) < O] for the phosphenium cations and for all other P(III)-N compounds studied. This was achieved by applying various one- and twodimensional heteronuclear double resonance techniques. The experiments also gave signs of the coupling constants 2J(31PN13C), 2J(31PN29Si), 3J(31PNC13C), 3J(31PNSi13C), 4J(31PNCC1H) and 4J(31PNSiC1H). Negative contributions to 1K(31P15N), arising from the lone pair of electrons at phosphorus, are more noticeable in the case of the phosphenium cations.

MOLECULAR AND ELECTRONIC STRUCTURE OF LESS COMMON PHOSPHORUS HALIDES

Abstract Molecular and electronic structures of several known and unknown phosphorus halides are described on the basis of ab initio MO calculations and available experimental data. Trends in bonding and molecular structures have been investigated for the title molecules. Dipole moments and normal mode frequencies are also reported for several molecules in the series.

Phosphorylated derivatives of 1‐morpholinocyclohexene and cyclohexanone

AbstractPhosphorylation of a relatively simple enamine with phosphorus (III) halides was first exemplified by the behavior of 1‐morpholinocyclohexene. Novel types of functionalized P(III) derivatives have now been obtained and studied. The hydrolysis of (2‐morpholino‐1‐cyclohexenyl) tetraethyldiamidophosphazidoarenes was found to be accompanied by the migration of the triazene group from the phosphorus atom to the carbon atom of the cyclohexene ring.

POLYSULFONYLAMINE: TEIL XXXII.1SYNTHESE UND FESTKÖRPERSTRUKTUREN VON N-PHOSPHOR(III)- UND N-PHOSPHOR(V)-DERIVATEN DBS DIMESYLAMINS: MOLEKÜLE MIT SEHR LANGENPHOSPHOR-STICKSTOFF-BINDUNGEN UND INTRAMOLEKULAREN 1,4-WECHSELWIRKUNGEN DES TYPS P … O

Abstract We report the first examples of phosphorus-containing derivatives of a disulphonylamine in which the phosphorus atom is bound directly to the amine nitrogen. Ph2P[sbnd]N(SO2Me)2 (1), 2-dimesylamino-1,3,2-benzodioxaphosphole (2a) and P[N(SO2Me)2]3 (3) are obtained by elimination of Me3SiCl from the corresponding phosphorus chlorides and stoichiometric amounts of Me3SiN(SO2Me)2. 2a is also formed by silver salt metathesis between the 2-chlorophosphole and AgN(SO2Me)2. Cleavage of R2P(S[sbnd]P(S)R2 with ClN(SO2Me)2 affords R2P(S)[sbnd]N(SO2Me)2 with R = Me (4a) and Et (4b), the co-product being R2P(S)Cl. 2a reacts with oxygen to form 2-dimesylamino-2-oxo-1,3,2-benzodioxaphosphole (2b). 1 crystallizes in the monoclinic space group P21/n with a = 1461.8(5), b = 732.2 (3), c = 1511.0(4) pm, β = 97.59(3)°, V = 1.6030 nm,3 Z = 4. The crystallographic data for 2a are: Triclinic, space group P1, a = 561.5(2), b = 886.8(2), c = 1272.9(4) pm, α = 73.99(3), β = 83.56(3), γ = 81.54(3)°, V = 0.6009 nm,3 Z = 2. ...

Organosilicon and organophosphorus compounds with pseudohalide groups

The reactions of alkoxydimethylsilyl cyanides with some tetracoordinated phosphorus chlorides and fluorides were investigated. It was shown that the investigated reactions are realized primarily with the replacement of two halogen atoms by functional groups. The transformations of the phosphorus acid cyanides obtained with metal fluorides were studied.

ChemInform Abstract: Reactions of Phosphorus(III) Chlorides with Aldehydes and Ketones in the Presence of Compounds which Activate Carbonyl Groups.

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The extension of the mechanistic concept of the nucleophilic catalysis in the silicon chemistry to some reactions of the P(III) center: Analogies between silylation and phosphorylation

Many observations prove that a number of silylation reactions of a trialkylsilyl halide-uncharged base system occur with the transient formation of a 1:1 tetrahedral silicon ionic complex of the silyl halide with the base. Some catalytic processes of phosphorylation of protonic substrates with tricoordinate phosphorus halides in mixture with an uncharged base show similar features to these silylation reactions, implying that a similar mechanism may operate. It was demonstrated that Ph2PCl phosphorylates t-BuOH faster under catalysis with 4-N,N-dimethylamino pyridine or N-methylimidazole than in the presence of Et3N by a factor of 400 and 33, respectively. The catalytic phosphorylation process exhibits a very low activation energy and a high negative value of entropy of activation. The interaction of the uncharged bases with model tricoordinate phosphorus halides was demonstrated to lead to the formation of ionic 1:1 complexes without changing the coordination number of phosphorus, in full analogy to the silyl halide complex formation. Finally, the interaction of phosphorous tris(dimethylamide) with a silyl iodide and a phosphorous iodide results in both cases in the formation of the ionic 1:1 complex, which also leads to analogous reactions of exchange of the amide group with iodide. These close similarities imply that some phosphorylation reactions with tricoordinate phosphorus halides catalyzed with uncharged bases occur via a tricoordinate phosphorus cation intermediate.

Studies on Organophosphorus Compounds XLVII: Acetyl Chloride - A Versatile Reagent for the Synthesis of 1-Aminoalkyl- and Amino(aryl)methylphosphonic Acid Derivatives

Acetyl chloride is used successfully in the synthesis of 1-aminoalkyl- and amino(aryl)methylphosphonic acid derivatives by a three-component condensation reaction involving diethyl phosphoramidate, aldehydes and diphenyl phosphite. Furthermore, in the reaction of benzyl carbamate, aldehydes and phosphorus(III) chloride, acetyl chloride facilates the formation of alkyl hydrogen 1-(benzyloxycarbonylamino)alkylphosphonates or aryl(benzyloxycarbonylamino) methylphosphonates, key intermediates in the synthesis of phosphonopeptide with a P-N bond. In comparison with other methods, the present variation affords wider scope of application including the use of some aliphatic aldehydes, fair yields and mild reaction conditions.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophiles in Superbasic Systems. Part 2. Synthesis of Triorganylphosphine Oxides from Red Phosphorus and Organyl Halides.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophiles in Superbasic Systems. Part 2. Synthesis of Triorganylphosphine Oxides from Red Phosphorus and Organyl Halides.

ChemInform Abstract: Reactions and Rearrangements of Carboxamides Phosphorylated by Tervalent Phosphorus Chlorides.

ChemInform Abstract: Reactions and Rearrangements of Carboxamides Phosphorylated by Tervalent Phosphorus Chlorides.

ChemInform Abstract: Surface Reactions. Part 15. Heterogenous Dechlorinations of Phosphorus Chlorides (X)PCl3 and R‐PCl2 on (Ag), (Mg), (Cux/TiO2) and (MgCl2‐MgO/SiO2), and Spectroscopic Evidence for the Generation of Diphosphacyanogen PC‐CP from Cl2P‐CC‐PCl2

ChemInformVolume 21, Issue 49 Preparative Organic Chemistry ChemInform Abstract: Surface Reactions. Part 15. Heterogenous Dechlorinations of Phosphorus Chlorides (X)PCl3 and R-PCl2 on (Ag), (Mg), (Cux/TiO2) and (MgCl2-MgO/SiO2), and Spectroscopic Evidence for the Generation of Diphosphacyanogen PC-CP from Cl2P-CC-PCl2 H. BOCK, H. BOCK Chem. Inst., Univ. Frankfurt, D-6000 Frankfurt/M. 50Search for more papers by this authorM. BANKMANN, M. BANKMANN Chem. Inst., Univ. Frankfurt, D-6000 Frankfurt/M. 50Search for more papers by this author H. BOCK, H. BOCK Chem. Inst., Univ. Frankfurt, D-6000 Frankfurt/M. 50Search for more papers by this authorM. BANKMANN, M. BANKMANN Chem. Inst., Univ. Frankfurt, D-6000 Frankfurt/M. 50Search for more papers by this author First published: December 4, 1990 https://doi.org/10.1002/chin.199049118Read 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. Volume21, Issue49December 4, 1990 RelatedInformation

Synthesis of 1‐aminoalkylphosphonic acids via amidoalkylation of phosphorous acid by N,N′‐alkylidenebisamides

AbstractN,N′‐Alkylidenebisamides 1, totally unsuitable as amidoalkylating agents toward phosphorous acid, react with its “activated” form prepared “in situ” from phosphorus(III) chloride and acetic acid to give the desired 1‐aminoalkylphosphonic acids 2 in high yields.

Reactions of Diorganyliodophosphine with Cyclic Ethers

Abstract Reactions of phosphorus halides (chloro- and bromoderivatives) with α-alkylen oxides and other cyclic ethers are thoroughly investigated and have practical. significance. Phosphorus iodides, on the contrary, were rarely used in the reactions of this type. It is known only that PI3 and P2I4 are convenient olefinic agents. We investigated the reactions of diorganyliodophosphines with cyclic ethers of the general formula O(CH2)n, and showed that at n=2 and the reagents ratio of 1 : l iodoanhydrides of diorganylphosphinic acids are formed, which in excess of α-alkylen oxides are transformed into β-iodoethyl esters of diorganylphosphinic acids. Diorganyliodophosphines react with trimethylen oxide with cycle opening and result in the formation of diorganyl-β-iodopropylphosphine oxides. Diorganyliodophosphines react with tetrahydrofuran in dimeric form to produce tetraorganylpyrophosphinates, diorganyltetramethylen-phosphonium iodides and 1,4-diiodobutane.

Reactions ANC Rearangements of Carboxamides Phosphorylated by Tervalent Phosphorus Chlorides

Abstract We have found that N-substituted amides of carboxylic or thiocarboxylic acids (I) react with tervalent phosphorus chlorides to give N- and O(S)-phosphorylated derivatives (II) which isomerise into imidoyl(thio)phosphonates (III). The factors determining the ability of the initial products (II) and their iminated derivatives (IV) to participate in diad and triad rearrangements have also been studied.

Heterocyclization of thiol esters of?-aminocarboxylic acids with the formation of 5-alkylthio-?4-1,3,2-oxazaphospholines

The phosphorylation of the hydrochloride salt of S-butyl N-tert-butylaminothioacetate using phosphorus chlorides in the presence of triethylamine gave a new type of 1,3,2-oxazaphospholines with an alkylthio group at C5 in the oxazaphospholine ring.

OBERFLÄCHEN-REAKTIONEN 151,2Heterogen Dechlorierungen von Phosphorchloriden (X)PCI3und R[sbnd]PCI2an [Ag], [Mg], [Cux/TiO2] und [MgCI2[sbnd]MgO/SiO2] sowie spektroskopische Evidenz für das Entstehen von Diphospha-dicyan P[tbnd]C[sbnd]C[tbnd]P aus CI2P[sbnd][tbnd][sbnd]PCI2

Abstract Stimulated by the successful generation of unsaturated molecules with low-coordinated phosphorus centers by heterogeneous surface dechlorination, CI2,P[sbnd]C[tbnd]C[sbnd]PCI2, is synthesized and characterized by PE and mass spectra. In addition, [Mg] curls, [Ag] wool and catalysts [Cux/TiO2] or [MgCI2,[sbnd]MgO/SiO2] are tested as potential dechlorinating agents for phosphorus halides like OPCI3, SPCI3, H3C[sbnd]PCI2, H5C2-PCI2, (H3C)3C[sbnd]PCI2, or H5C6-PCI2, in a gasflow reactor under reduced pressure and yield, inter aha, the following representative results: due to the thermodynamically favored formation of [MgCl2], [MgO] or [MgS] at the Mg surface, P4 is the only gaseous product identified from reactions of OPCI3, and SPCI3, with [Mg] metal at higher temperatures. On the contrary, passing H3C-PCI2, at 600K over [Mg] yields a reaction mixture containing P(CH3)3,(H3C)2P[sbnd]P(CH3)2, (H3C[sbnd]P), and CH4, which suggests an intermediate formation of surface phosphinidenes [H3C[sbnd]P →Mg]. A...

ChemInform Abstract: Reaction of Adamantyl Group Containing Grignard Compounds (I) with Chlorides of Trivalent Phosphorus (II), (V), (IX).

ChemInform Abstract: Reaction of Adamantyl Group Containing Grignard Compounds (I) with Chlorides of Trivalent Phosphorus (II), (V), (IX).

Catalysis of the reaction of grignard reagents with silicon, tin, phosphorus, and arsenic halides and organohalides by copper salts with the formation of organic compounds of these elements

Catalysis of the reaction of grignard reagents with silicon, tin, phosphorus, and arsenic halides and organohalides by copper salts with the formation of organic compounds of these elements