Phosphoric Triamides Research Articles

Syntheses, crystal structure and ab initio calculations of two new phosphoric triamides

The reaction of N-benzoylphosphoramidic dichloride with piperidine and 4-methylpiperidine lead to PhC(O)N(H)P(O)R2 with R=piperidine (1) and R=4-methylpiperidine (2) as N-benzoyl-N′,N″-bis(piperidine) phosphoric triamide and N-benzoyl-N′,N″-bis(4-methylpiperidine) phosphoric triamide, respectively. The products have been characterized by 1H, 13C, 31P NMR spectra, and by elemental analysis. The crystalline solid for (1) and (2) consists surprisingly of four and two independent molecules, respectively. There is a disorder in one amine group due to ring inversion in each conformer in compound 1. In the solid state, comparable magnitudes for the stabilization of the stable conformers for the more or less discrete molecules, the polarization effects, hydrogen bonding and the packing effects could be anticipated.The geometry of compound (1) optimized by density functional calculations at the B3LYP/6-31++G* (d,p) level, is in good agreement with data obtained from X-ray crystallography.

Lithiated anions derived from (alkenyl)pentamethyl phosphoric triamides: an accurate study of the carbanion formation mechanism

The mechanism of the formation of lithiated carbanions derived from (alkenyl) pentamethyl phosphoric triamides has been elucidated. Whereas a few initial ambident allylphosphoramide anion was formed with n-BuLi, both reversible α-reprotonation and not reversible γ-reprotonation simultaneously occurred as a result of the reaction between the ambident carbanion formed and the starting enephosphoramide. A such autocatalytic process led partially to the transposed allylphosphoramide isomer. In the case of α-phenyl substituent the transposed phosphoramide was not a difficulty because it was further γ-deprotonated in situ with the n-BuLi still present, provided finally the expected ambident anion. With α-methyl and α-propyl substituent the transposed enephosphoramide formed in the autocatalytic process was not γ-deprotonated and consequently was prejudicial to the preparation of the target ambident carbanion. In these last cases, adapted experimental conditions avoided the autocatalytic process and allowed the preparation of the corresponding anions.

New ketone homoenolate anion equivalents derived from (alkenyl)pentamethyl phosphoric triamides

Lithiated ambident anions derived from (1-alkyl-2-propenyl)- or (1-phenyl-2-propenyl)-pentamethyl phosphoric triamides undergo regioselectively γ-reaction with various alkylating reagents and isobutyraldehyde. Further hydrolysis of adducts releases the ketone under acid conditions. Number of synthetic applications clearly show the ketone homoenolate behaviour of these new carbanions.

ChemInform Abstract: Synthesis and Antitumor Activity of Unsymmetric Phosphoric Triamides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis and Antitumor Activity of Nonsymmetric Phosphoric Acid Triamides

Synthesis and Antitumor Activity of Nonsymmetric Phosphoric Acid Triamides

Preparation of Bicyclic Phosphonic and Phosphinic Amides via N → C Migration of Phosphorus

New phosphonic diamides and phosphinic amides of the 4,7,10-triaza-1λ 5-phosphabicyclo[5.3.0]decane and 4,7,10-triaza-1λ 5-phosphabicyclo[5.5.0]dodecane structures were prepared from bicyclic phosphoric triamides via the lithiation-induced N → C migration of phosphorus, followed by proton or haloalkane quenching.

Chiral Lithiated Phosphoric Triamides: Structure, Reactivity, and Salt Effects

Chiral Lithiated Phosphoric Triamides: Structure, Reactivity, and Salt Effects

15N NMR Study of the P-N Bonding in Phosphoric Amides

A series of phosphoric amidodiesters, diamidoesters and triamides was prepared and their 31P and15 N NMR spectra were recorded in order to evaluate the major structural factors that determine the chemical shifts and coupling contants values. Considering the equation expressing the structural effects on shielding[1].

Phosphoric triamides. 31Phosphorus NMR chemical shift as a function of the P–N bond characteristics

Six phosphoric triamides in which amide nitrogens are incorporated into an increasing number (from 0 to 3) of the 1,3,2-diazaphospholidin-2-one rings have been prepared and their crystal structures have been determined. The structural changes from the non-cyclic to the mono-, di- and tri-cyclic systems result in the decrease of the N–P–N bond angles and the increase of the P–N bond distance. These changes are paralleled by a strong deshielding of the 31P nucleus, leading to an exceptionally high δP value for the tricyclic derivative. The δP–structural parameters relationship is discussed in terms of the changes in hybridization of phosphorus and the variation in the P–N bond order.

ChemInform Abstract: Preparation of Acyclic and Cyclic Phosphoric Triamides and Diamido Esters.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Preparation of Acyclic and Cyclic Phosphoric Triamides and Diamido Esters

Preparation of Acyclic and Cyclic Phosphoric Triamides and Diamido Esters

ORGANOPHOSPHORUS COMPOUNDS AS POTENTIAL FUNGICIDES. PART V.1 THE PREPARATION AND PROPERTIES OF SOME NOVEL N,N,N',N'-TETRAMETHYL-N''-(1-SUBSTITUTED-2,2,2-TRICHLOROETHYL) PHOSPHORIC TRIAMIDES

Abstract A series of N,N,N',N'-tetramethyl-N''-(1-substituted-2,2,2-trichloroethyl)phosphoric triamides has been prepared in which the 1-substituent is an amido group, NHCOR (R = H, Me, CH2Cl, CCl3, 2,4-dichlo-rophenyl, 2-methylfuran-3-yl, 5,6-dihydro-2-methyl-1,4-oxathiin-3-yl), an alkoxy group (OMe, OEt, OBu, OC12H25), or a substituted acetamido group (NHCOCH2Y), in which Y is triazolyl, N,N-di-methyldithiocarbamato, N,N-diethyldithiocarbamato, diethyl xanthato, diethoxythiophosphorylthio, or dodecylthio. The compounds in general showed low activity as fungicides when tested against a range of organisms at 300 ppm in vitro. However, certain compounds (the 1-formamido, 1-acetamido, and 1-chloroacetamido derivatives) showed 55–77% of the activity of the reference fungicide (guazatine) in vivo, when applied as seed-dressings at 400 ppm for the control of Drechslera teres. No adverse effect on seed germination was observed.

An Approach to the Development of Organophosphorus Fungicides

Abstract Phosphoramidates, phosphorodiamidates, phosphoric triamides, aminophosphonic acids, guanidinophosphonic acids, and phosphonopeptides are discussed as fungicides with potential for application in agriculture.

ChemInform Abstract: Phosphoric Amides. Part 10. Base‐Promoted Cyclization of Phosphoric Triamides Bearing the N‐(2‐Chloroethyl) Substituent, and the Interconversion of Cyclic Products.

AbstractThe N‐(2‐chloroethyl)‐N',N''‐diarylphosphoric triamides (I) undergo base‐induced phase‐transfer‐catalyzed cyclization, forming the N‐phosphorylaziridines (II), together with the diazaphospholidines (III).

ChemInform Abstract: Synthesis and Antiblastic Activity of Some N‐Acyl‐N′,N′‐bis(chloroethyl)‐N′′‐(1‐oxy‐2,2,6,6‐tetramethyl‐4‐piperidyl)phosphoric Triamides.

AbstractThe amidophosphoric dichlorides (I) are consecutively coupled with the amines (II) and (III), yielding the phosphoric triamides (IV).

ChemInform Abstract: Reaction of N,N′,N′′,N′′′‐Tetraarylphosphorimidic Triamides with Carboxylic Acids.

AbstractThe tetraarylphosphorimidic triamides (I) are coupled with the carboxylic acids (II) to give the phosphonium salts (III) which form the phosphoric triamides (IV) and the carboxylic amides (V) on thermal treatment.

Phase-transfer Reactions Catalyzed by Phosphoric Triamides Containing Hydrophobic Groups

Abstract Aqueous organic two-phase reactions (halogen exchange, cyanation, and borohydride reduction) have been catalyzed by phosphoric triamides containing hydrophobic groups. The phosphoric triamides, which have a high cation binding ability, exibited high catalytic activity for the two-phase reactions. The catalytic activity of N-alkylteramethylphosphoric triamides (1) was higher than that of the corresponding pentamethyl derivatives and the difference has been explained in terms of the contribution of the dimeric species of 1 and/or hydrogen bonding between the NH of 1 and the anionic moieties of inorganic reagents.

ChemInform Abstract: POLYMER‐SUPPORTED PHOSPHORIC TRIAMIDES AS CATALYSTS FOR PHASE‐TRANSFER REACTIONS

Chemischer InformationsdienstVolume 10, Issue 4 Preparative Organic Chemistry ChemInform Abstract: POLYMER-SUPPORTED PHOSPHORIC TRIAMIDES AS CATALYSTS FOR PHASE-TRANSFER REACTIONS M. TOMOI, M. TOMOISearch for more papers by this authorM. IKEDA, M. IKEDASearch for more papers by this authorH. KAKIUCHI, H. KAKIUCHISearch for more papers by this author M. TOMOI, M. TOMOISearch for more papers by this authorM. IKEDA, M. IKEDASearch for more papers by this authorH. KAKIUCHI, H. KAKIUCHISearch for more papers by this author First published: January 23, 1979 https://doi.org/10.1002/chin.197904074AboutPDF 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. Volume10, Issue4January 23, 1979 RelatedInformation

Polymer-supported phosphoric triamides as catalysts for phase-transfer reactions

Polymer-supported phosphoric triamides as catalysts for phase-transfer reactions

Zur Chemie der Amide phosphorhaltiger Mineralsäuren

Abstract