Phosphoramidate Research Articles

Conversion of Cyclic Phosphorothioates into Halophosphates and Neutral Phosphorus Esters and Amides

Abstract Cyclic phosphorus esters and amides in the 1,3,2-dioxaphosphorinane-2-one series are usually obtained by the condensation of a diol with a suitable phosphorus oxyhalide. In the case of dissymetric diols the formation of two diastereoisomeric products, epimeric at phosphorus, can be expected. This procedure failed or proceeded with low yields when applied to the preparation of cyclic phosphates which would lead to the formation of sterically strained dioxaphosphorinane ring.1

Structure and Basicities of Aliphatic Organophosphorus Compounds

Abstract As an extension of our previous works concerning the basicities of aliphatic phosphoric amides and phosphinoxides, the influence of structure is studied for some series of parent compounds, such as : XP(tBu)3 with X=lone pair; O; S; NH ˙ OP[N(CH2)X]3 with x=2; 3; 4; 5. The techniques used here are mainly: determination of gas phase basicities by ion cyclotron resonance mass spectrometry determination of Broensted basicities by titration in an non-aqueous solvent system dipole moment measurements

Metal catalysis in oxidation by peroxides. 24. Extraction of aqueous peroxomolybdenum species into organic media and their reactivity

The effect of the lipophilicity and coordinating ability of neutral ligands, belonging to the classes of phosphoric amides and pyridine oxides, on the extraction of the neutral oxidants molybdenum(VI)–peroxo complexes from an aqueous acidic phase to an organic one, has been studied. The nature of the Mo(VI)–peroxo species present both in aqueous and organic phase has also been investigated. Sizable amounts of mineral acid, added to adjust pH, may be extracted into the organic phase. The various factors affecting this process such as the nature of the acid added, the organic solvent and the neutral ligand, as well as the effect of this feature on the partition of the oxidant between the two phases are briefly discussed.

Crystal and molecular structures of two polymorphic forms of dimethyl-N-(2-ethylphenyl)-phosphoramidate (I) and dimethyl-N-(2,6-dimethylphenyl)-phosphoramidate (II)

The crystal structures of the phosphoric amides dimethyl-N-(2-ethylphenyl)-phosphoramidate (I) and dimethyl-N-(2,6-dimethylphenyl)-phosphoramidate (II) have been determined by direct methods and refined by full-matrix least squares. Compound (I) crystallizes in two polymorphic forms, both monoclinicP21/c, but with different cell parameters. Parameters for compound (I) are: FormA:a=10.878(5),b=8.890(4),c=25.11(1) A,β=92.18(2)°; FormB:a=7.071(4),b=17.059(9),c=10.221(5) A,β=97.07(2)°. Compound (II) is also monoclinicP21/c witha=8.453(4),b=14.231(7),c=10.283(5) A,β=108.95(2)°. Compound (I) exists as a hydrogen-bonded dimer, whereas compound (II) exists as a hydrogen-bonded polymeric species.

Phosphoric amides. Part 8. The effect of the ethylenimine substituent on the solvolytic reactivity of phosphate and phosphoramidate bonds

Rates and products of the base-catalysed hydrolysis of some amidoesters of phosphoric acid have been determined. In the N,N-dimethyl derivative, the P–N bond is resistant, and the P–O bond deactivated towards hydrolysis, while in the N-methyl substrate, the reactivity of the ester link is similar to that in trimethyl phosphate. In the N-ethylene compound, both P–O and P–N bonds are strongly activated. The N-(β-chloroethyl) substrate reacts via fast, base-catalysed cyclization to the N-ethylene amidate.

Inhibition of Plant Microtubule Polymerization in vitro by the Phosphoric Amide Herbicide Amiprophos-Methyl

The phosphoric amide herbicide amiprophos-methyl (APM) produced a concentration-dependent inhibition of taxol-induced rose microtubule polymerization in vitro. Parallel studies on taxol-induced assembly of bovine brain microtubules showed no effect of APM at a concentration ten times that required to give complete inhibition of rose microtubule assembly. The data indicate that (i) APM is a specific and potent antimicrotubule drug and (ii) APM directly poisons microtubule dynamics in plant cells, rather than indirectly depolymerizing microtubules through a previously proposed mechanism involving deregulation of intracellular calcium levels.

Structure - Reactivity of Mixed Carboxylic Phosphoric Imides

Abstract The title compounds comprise carboxylic and phosphoric amide functions modified at nitrogen by another acyl group. X2P(O)-NR-C(O)R' (1) X-ray crystallography revealed intramolecular interactions between carbonyl oxygen and phosphorus in (1). Under conditions of electron impact all substrates (1) isomerise to the corresponding O-phosphoryl imidates X2P(O)-O-C(NR)R'. Solvolysis of (1) depends on medium acidity; in neutral media the exclusive attack at phosphorus was observed, while the acid catalyzed solvolysis involves both N-acyl linkages and the reaction proceeds via the carbonyl oxygen protonated intermediate. Hydration parameter treatment was applied to the hydrolysis of (1). Nucleophilic behavior of (1) was studied in alkylation of their conjugate basis derived from secondary substrates (1, R[dbnd]H).

Reaction of sulfonyl chlorides and chlorophosphates with 1,3,2-diheterophospholanes

1. The reactions of benzenesulfonyl chloride with linear and cyclic amide derivatives of trivalent phosphorus are accompanied by oxidation at the phosphorus atom. 2. The reactions of trivalent phosphorus amides with diethyl chlorophosphate proceed with splitting of the P-N bond and lead to exchange products of the amine group at P atom for Cl. Several diphosphorylated derivatives of methylaminoethanol were synthesized, and their thermal stability was studied.

ChemInform Abstract: AFFINITIES OF PHOSPHORIC ACIDS, ESTERS, AND AMIDES FOR SOLVENT WATER

Chemischer InformationsdienstVolume 14, Issue 22 Article ChemInform Abstract: AFFINITIES OF PHOSPHORIC ACIDS, ESTERS, AND AMIDES FOR SOLVENT WATER R. WOLFENDEN, R. WOLFENDENSearch for more papers by this authorR. WILLIAMS, R. WILLIAMSSearch for more papers by this author R. WOLFENDEN, R. WOLFENDENSearch for more papers by this authorR. WILLIAMS, R. WILLIAMSSearch for more papers by this author First published: May 31, 1983 https://doi.org/10.1002/chin.198322092AboutPDF 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. Volume14, Issue22May 31, 1983 RelatedInformation

ChemInform Abstract: PHOSPHORUS AMIDES. X. RATE ACCELERATION DUE TO SOLVATION EFFECTS IN THE ACID‐CATALYZED CLEAVAGE OF PHOSPHINAMIDES. APPLICATION TO ACID CATALYSIS AT ENZYMIC ACTIVE SITES

Chemischer InformationsdienstVolume 13, Issue 51 Preparative Organic Chemistry ChemInform Abstract: PHOSPHORUS AMIDES. X. RATE ACCELERATION DUE TO SOLVATION EFFECTS IN THE ACID-CATALYZED CLEAVAGE OF PHOSPHINAMIDES. APPLICATION TO ACID CATALYSIS AT ENZYMIC ACTIVE SITES J. M. BONICAMP, J. M. BONICAMPSearch for more papers by this authorP. HAAKE, P. HAAKESearch for more papers by this author J. M. BONICAMP, J. M. BONICAMPSearch for more papers by this authorP. HAAKE, P. HAAKESearch for more papers by this author First published: December 21, 1982 https://doi.org/10.1002/chin.198251120Read 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. Volume13, Issue51December 21, 1982 RelatedInformation

ChemInform Abstract: PHOSPHORIC, PHOSPHONIC, AND PHOSPHINIC ACID AMIDES AS BASES

Chemischer InformationsdienstVolume 13, Issue 45 Organoelement Compounds ChemInform Abstract: PHOSPHORIC, PHOSPHONIC, AND PHOSPHINIC ACID AMIDES AS BASES E. I. MATROSOV, E. I. MATROSOVSearch for more papers by this authorA. A. KRYUCHKOV, A. A. KRYUCHKOVSearch for more papers by this authorE. E. NIFANTYEV, E. E. NIFANTYEVSearch for more papers by this authorA. G. KOZACHENKO, A. G. KOZACHENKOSearch for more papers by this authorM. I. KABACHNIK, M. I. KABACHNIKSearch for more papers by this author E. I. MATROSOV, E. I. MATROSOVSearch for more papers by this authorA. A. KRYUCHKOV, A. A. KRYUCHKOVSearch for more papers by this authorE. E. NIFANTYEV, E. E. NIFANTYEVSearch for more papers by this authorA. G. KOZACHENKO, A. G. KOZACHENKOSearch for more papers by this authorM. I. KABACHNIK, M. I. KABACHNIKSearch for more papers by this author First published: November 9, 1982 https://doi.org/10.1002/chin.198245281AboutPDF 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 onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume13, Issue45November 9, 1982 RelatedInformation

Hydrogen bonding in phosphoramides: structures of dimethyl N-phenylphosphoramidate and dimethyl N-(p-nitrophenyl)phosphoramidate

Hydrogen bonding in phosphoramides: structures of dimethyl <i>N</i>-phenylphosphoramidate and dimethyl <i>N</i>-(<i>p</i>-nitrophenyl)phosphoramidate

PHOSPHORIC, PHOSPHONIC, AND PHOSPHINIC ACID AMIDES AS BASES

Abstract Potentiometric titration in nitromethane, IR-and NMR-spectroscopy were used to study the processes of protonation and H-bonding for a number of phosphoric, phosphonic and phosphinic acid amides. [(R½ N) n P(O)R3-n 2 (R1 = Me, Et; R2 = EtO, Me, Et; n = 1–3) including 1,3,2-dioxa-, 1,3,2-oxazaphospholane and phosphorinane derivatives.] It was shown that in these compounds the center of the highest basicity is the oxygen of the phosphoryl group.

Phosphorus amides X. Rate acceleration due to solvation effects in the acid-catalyzed cleavage of phosphinamides. Application to acid-catalysis at enzymic active sites.

Phosphinamides undergo acid-catalyzed reaction with enhanced rates as the amount of water is decreased in acetonitrile from about 20 M to about 1 M. This phenomenon appears to be due to increased activity of acid and increased basicity of substrate as the concentration of water is decreased. The same effects may cause enhanced rates of acid-catalyzed reactions at enzymic active sites.

ChemInform Abstract: 2‐BIS(DIMETHYLAMINO)PHOSPHINOYL‐1‐LITHIO‐1,2,3,4‐TETRAHYDROISOQUINOLINE. A HIGHLY NUCLEOPHILIC D1‐REAGENT FOR THE PREPARATION OF 1‐SUBSTITUTED TETRAHYDROISOQUINOLINES

AbstractDas Titel‐Li‐Derivat des Kondensationsproduktes (I) aus Tetrahydroisochinolin und Bis‐[dimethylamido]‐phosphorylchlorid ist in THF‐Lösung bei Raumtemp. beständig.

2‐Bis (dimethylamino)phosphinoyl‐1‐lithio‐1, 2, 3, 4‐tetrahydroisoquinoline. A highly nucleophilic d1‐reagent for the preparation of 1‐substituted tetrahydroisoquinolines

AbstractThe title compound 4 is generated from the phosphoric amide 5 in tetrahydrofuran with butyllithium. The lithium reagent 4 is stable at room temperature; its reactions with electrophiles furnish the products 6–22, 26, 27, see Table 1 and the Scheme. A second alkylation is also possible, see 23–25. The cleavage to tetrahydroisoquinolines is accomplished in refluxing aqueous‐methanolic hydrochloric acid, see Table 2. Phosphinoylation, lithiation, reaction with electrophiles and cleavage constitute an efficient sequence for 1‐alkylation of the isoquinoline nucleus.

Phosphoric amides. 3. Acidic cleavage of the phosphorus-nitrogen bond in acyclic and cyclic phosphoramidates

Phosphoric amides. 3. Acidic cleavage of the phosphorus-nitrogen bond in acyclic and cyclic phosphoramidates

Reactivity and mechanism of hydrolysis of phosphonamides

The rates of hydrolysis of three phosphonamides, N,N-dimethylphenylphosphonamide (XII), N-(phenylphosphonyl)pyrrolidine (XIII), and N-(phenylphosphonyl)morpholine (XIV), have been investigated. There is first-order dependence on acidity in the pH range 4 to 7 with a pH independent region at low pHs, consistent with saturation due to complete formation of the neutral amide. The specific rate constant (k/sub 2/) and the acidity constant (K/sub a/) were obtained from the dependence of psudo-first-order rate constants on (H/sup +/); k/sub 2/ is 1.27 x 10/sup -2/s/sup -1/ and 1.42 x 10/sup -3/s/sup -1/ and pK/sub a/ is 4.8 and 5.3 for XII and XIII, respectively. The small value of the acidity constants is consistent with predominant N-protonation. The activation parameters for XII are ..delta..H/sup +/ = 11.1 kcal/mol, ..delta..G/sup +/ = 20.35 kcal/mol, and ..delta..S/sup +/ = -31 eu. Solvent and salt effects on the rate of hydrolysis of XII are insignificant. The solvent isotope effect, k/sub 2/(H/sub 2/O)/k/sub 2/(D/sub 2/O), is 1.2 and K/sub a/(H/sub 2/O)/K/sub a/(D/sub 2/O) is 3.2. Fluoride ion catalyzed the rate of reaction of XII. The Broensted ..beta.. value is about -1, implying rate-determining breakage of the P-N bond. The results appear to be most consistent with an S/sub n/2(P) mechanism.more » The reactivity of phosphorus amides is discussed in terms of their structure.« less

Resistance to Fungicides in &lt;i&gt;Pyricularia oryzae&lt;/i&gt;

Mutants resistant to fungicides were obtained by selecting a large number of conidia of rice blast fungus, Pyricularia oryzae, with respective fungicides. The mutation of resistance to kasugamycin and to organophosphorus thiolate (PTL) fungicides seemed to be spontaneous in most cases. In 1971, kasugamycin-resistant strains were found in the field and investigated. Identity of the kasugamycin resistance found in the field and that selected in the laboratory remained to be solved. In the investigation with laboratory-derived mutants, cross resistance was found among PTL fungicides and between PTL and isoprothiolane. Negatively correlated cross resistance was found between PTL and certain phosphoramidate (PA) compounds and between isoprothiolane and PA. This negative correlation was not found in most of the PTL-resistant field-isolates, and therefore the resistance in the field seemed different from that obtained in the laboratory in most cases. Fungal metabolism of PTL fungicides and a PA was investigated to elucidate resistance mechanism. Detoxifying metabolism of PTL as well as PA was lower in laboratory-derived PTL-resistant mutant and this may explain the higher sensitivity to PA, but the mechanism of resistance to TPL remains to be solved in this type of mutants. A higher rate of PTL metabolism was found in most of the PTL-resistant field-isolates and this may be a mechanism of the resistance found in the field.

Nucleoside und Nucleotide. Teil 15. Synthese von Desoxyribonucleosid‐monophosphaten und ‐triphosphaten mit 2(1H)‐Pyrimidinon, 2(1H)‐Pyridinon und 4‐Amino‐2(1H)‐pyridinon als Basen

Nucleosides and Nucleotide. Part 15. Synthesis of Deoxyribonucleoside Monophosphates and Triphosphates with 2(1H)‐Pyrimidinone, 2(1H)‐Pyridinone and 4‐Amino‐2(1H)‐pyridinone as the BasesThe phosphorylation of the modified nucleosides 1‐(2′‐deoxy‐β‐D‐ribofuranosyl)‐2(1 H)‐pyrimidinone (Md, 4), 4‐amino‐1‐(2′‐deoxy‐β‐D‐ribofuranosyl)‐2(1 H)‐pyridinone (Zd, 6) and the synthesis of 1–2′‐deoxy‐β‐D‐ribofuranosyl‐2(1 H)‐pyrimidinone‐5′‐O‐triphosphate (pppMd, 1), 1‐(2′‐deoxy‐β‐Dribofuranosyl)‐2(1 H)‐pyridinone‐5′‐O‐triphosphate (pppIId, 2), and 4‐amino‐1‐(2′‐deoxy‐βD‐ribofuranosyl)‐2(1 H)‐pyridinone‐5′‐O‐triphosphate (pppZd, 3) are described. The nucleoside‐5′‐monophosphates pMd (5) and pZd (7) were obtained by selective phosphorylation of Md (4) and Zd (6), respectively, using phosphorylchloride in triethyl phosphate or in acetonitril. The reaction of pMd (5) pII d (8) or pZd (7) with morpholine in the presence of DCC led to the phosphoric amides 9, 10 and 11, respectively, which were converted with tributylammonium pyrophosphate in dried dimethylsulfoxide to the nucleoside‐5′triphosphates 1, 2 and 3, respectively.