- Insignificance of P-H...P hydrogen bonding: Structural chemistry of neutral and protonated 1,8-di(phosphinyl)naphthalene
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While there is extensive information on 1,8-di(amino)naphthalene (i.e., the parent compound of the proton sponge series), the corresponding phosphorus compound has not been described. A high-yield synthesis of 1,8-di(phosphinyl)naphthalene (9) and the 1-naphthylphosphine reference compound (4) is now reported. Thermal decomposition of 9 leads to intramolecular dehydrogenative P-P coupling to afford 1,2-dihydro-1,2-diphosphaacenaphthene (10). Protonation of 9 and 4 with CF3SO3H gives quantitative yields of the monophosphonium salts 11 and 5, respectively. With excess acid and traces of moisture, the hydronium salt [C10H 6(PH2)(PH3)]+[H3O] +2[CF3SO3]- (13) is obtained. The structures of 9, 11, and 13 have been determined. Molecules of 9 have a planar naphthalene skeleton, C10H6P2, with the two -PH2 groups in a transoid conformation. The molecules form loose dimers in the crystal, the individual chiral enantiomers of which are related by a center of inversion. In contrast to the situation for the amino analogue, and despite the proximity of the two -PH2 functions, there is no intra- or intermolecular hydrogen bonding. Solutions of 9 (in CD2Cl 2) show equivalent P-bound hydrogen atoms due to conformational fluctionality. By analysis of the ABCD2XX′D′ 2C′B′A′ spin system, it was shown that, in 9, there are strong through-space pericouplings [nJ(PXP X′) = 221.6 Hz, nJ(PXH D′) = 31.7 Hz, nJ(HDHD′) = 3.9 Hz]. In the cations of 11, the C10H6P2 skeleton is also planar (by Cs symmetry), with the -PH2 and -PH3+ groups in a conformation which rules out any P-H...P hydrogen bonding. The hydronium cation and the two triflate anions in 13 are associated into an anionic network through extensive hydrogen bonding surrounding stacks of the phosphonium cations. In solution, the cations of 11 and 13 show separate 31P resonances for the two phosphorus atoms with fully resolved 1J(PH) couplings, which indicate that there is no intra- or intercationic proton exchange. By contrast, the NMR spectra of solutions of [C10H6(NH2)(NH3)] +X- salts show proton scrambling equilibrating all five N-bound hydrogen atoms, and in the crystal, the conformations of the cations feature intramolecular N-H...N hydrogen bonding.
- Reiter, Stephan A.,Nogai, Stefan D.,Karaghiosoff, Konstantin,Schmidbaur, Hubert
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- NMR study (1H, 13C and 31P) of the nPX3-n compounds (X=Cl, C2H5; n=0,1,2,3)
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1H, 13C and 31P NMR data of the compounds nPX3-n (X=Cl, C2H5; n=0,1,2,3) are reported.While the 1H and 13C resonances from the PEt moiety rather follow the electron-withdrawing effect of the -NEt substituent, 1H and 13C chemical shift data from the -NEt2 moiety reveal a quite important shift contribution originating from sterically induced polarization of the C-H bonds. 31P chemical shift data are interpreted in terms of inductive effects but the anomalous diamagnetic shift deviation from linearity for X=Cl suggests a minor contribution from multiple bonding.The general trend observed in the 31P-couplings is quite straightforward and can be qualitatively explained by Bent's rule.
- Linthoudt, J. P. van,Berghe, E. V. van den,Kelen, G. P. van der
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- Macrocyclic systems on the basis of phosphorus acids and 2,7-dihydroxynaphthalene
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Syntheses of macrocyclic systems containing three 2,7-dihydroxynaphthalene residues and three residues of thiophosphoric and phosphorous amides in various ratios are developed. Chemical properties of the obtained compounds are studied.
- Rasadkina,Slitikov,Evdokimenkova,Nifant'ev
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Read Online
- Method for compounding organphosphorus by using black phosphorus
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The invention discloses a method for compounding organphosphorus by using black phosphorus. The method takes the black phosphorus as a reaction raw material, safely and efficiently compounds organic phosphate, sulpho-phosphite ester, amino phosphite ester, alkylphosphine, alkylphosphine oxide and other organphosphorus with wide usages, a conventional synthsis route by using phosphorus halide and phosphate to compound the organphosphorus is avoided, the synthesis steps are simple and short, the production technology is operated simply and easily, the reproducibility is good, the reaction is simple and green, the use of a phosphorus halide reagent is avoided, the range of the synthetic organphosphorus is wider, the method satisfies the requirements of green chemical development, and the large-scale production can be achieved.
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Paragraph 0097; 0098; 0099
(2018/10/19)
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- EPR and ENDOR spectroscopic study of the reactions of aromatic azides with gallium trichloride
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The reactions of gallium trichloride with phenyl and deuterio-phenyl azides, as well as with 4-methoxyphenyl azide and deuterium isotopomers, were examined by product analysis, CW EPR spectroscopy and pulsed ENDOR spectroscopy. The products included the corresponding anilines together with 4-aminodiphenylamine type dimers, and polyanilines. Complex CW EPR spectra of the radical cations of the dimers [ArNHC6H4NH 2]+ and trimers [ArNHC6H4NHC 6H4NH2]+ were obtained. These EPR spectra were analysed with the help of data from the deuterium-substituted analogues as well as the pulse Davies ENDOR spectra. DFT computations of the radical cations provided corroborating evidence and suggested the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed.
- Bencivenni, Giorgio,Cesari, Riccardo,Nanni, Daniele,El Mkami, Hassane,Walton, John C.
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supporting information; experimental part
p. 5097 - 5104
(2010/12/24)
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- Phosphorus halides complexes with 4-dimethylaminopyridine and N-methylimidazole
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Formation of complexes between phosphorus halides and 4- dimethylaminopyridine or N-methylimidazole was studied. The following phosphorus halides: trichloride, oxychloride, and sulfochloride, were found to form equilibrium mixtures of the complexes containing different numbers of the ligand molecules. Among the studied phosphorus halides only pentachloride and tribromide form stable complexes with a constant composition.
- Bezgubenko,Pipko,Sinitsa
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scheme or table
p. 911 - 918
(2011/04/15)
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- Synthesis of N6,N6-dialkyladenine nucleosides using hexaalkylphosphorus triamides produced in situ
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Reactions between secondary amines and phosphorus trichloride (PCl 3) leads to the formation of the corresponding tris(dialkylamino) phosphanes or hexaalkylphosphorus triamides [HAPTs: (R2N) 3P]. Treatment of silyl-protected 2′-deoxyinosine and acetyl-protected inosine with the HAPTs produced in situ, together with iodine (I2), leads to the formation of N6,N6- dialkyladenosine and -2′-deoxyadenosine. In some cases the stoichiometry of the amine is important, as is the use of a tertiary amine base. The effect of amine stoichiometry on the reaction between HAPT and I2 has been studied by 31P{1H} NMR spectroscopy. Wiley-VCH Verlag GmbH & Co. KGaA, 2009.
- Lakshman, Mahesh K.,Choudhury, Asad,Bae, Suyeal,Rochttis, Eliezer,Pradhan, Padmanava,Kumar, Amit
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experimental part
p. 152 - 159
(2009/07/05)
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- Dismutation of arylene phosphorodiamidites: Specific features and aspects of preparative use
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The dismutation of arylene phosphorodiamidites derived from the simplest phenols and naphthols and of their dibasic analogs was studied. The main regular trends of this process and the limits of its synthetic applicability were determined. Pleiades Publishing, Inc., 2006.
- Rasadkina,Slitikov,Nifant'ev
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p. 183 - 197
(2008/02/08)
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- Dismutation of diamidoarylphosphites
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Some examples of spontaneous dismutation of diamidoarylphosphites in different solvents were studied, and features of the process were revealed.
- Nifantyev, Edward E.,Rasadkina, Elena N.,Slitikov, Pavel V.,Vasyanina, Larisa K.
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p. 2465 - 2477
(2007/10/03)
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- Solid-phase chemical synthesis of phosphonoacetate and thiophosphonoacetate oligodeoxynucleotides
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Phosphonoacetate and thiophosphonoacetate oligodeoxynucleotides were prepared via a solid-phase synthesis strategy. Under Reformatsky reaction conditions, novel esterified acetic acid phosphinodiamidites were synthesized and condensed with appropriately protected 5′-O-(4, 4′-dimethoxytrityl)-2′-deoxynucleosides to yield 3′-O-phosphinoamidite reactive monomers. These synthons when activated with tetrazole were used with an automated DNA synthesizer to prepare phosphonoacetic acid modified internucleotide linkages on controlled pore glass. The phosphinoacetate coupling products were quantitatively oxidized at each step with (1S)-(+)-(10-camphorsulfonyl)oxaziridine or 3H-1,2-benzodithiol-3-one-1,1-dioxide to produce mixed sequence phosphonoacetate and thiophosphonoacetate oligodeoxynucleotides with an average per cycle coupling efficiency of greater than 97%. Completely deprotected, modified oligodeoxynucleotides were purified by reverse-phase HPLC and characterized by ion exchange HPLC, 31P NMR, and MALDI/TOF mass spectroscopy. Both analogues were stable toward hydrolysis with snake venom phosphodiesterase and stimulated RNase H1 activity.
- Dellinger, Douglas J.,Sheehan, David M.,Christensen, Nanna K.,Lindberg, James G.,Caruthers, Marvin H.
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p. 940 - 950
(2007/10/03)
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- Synthesis of novel optically active cyclic phospholipid conjugates of Tegafur and uridine starting from L-serine
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Starting from L-serine, cyclic thiophosphoramidate conjugates (2 and 3) of Tegatur and uridine were synthesized via a multiple-step procedure of esterification, cyclic phosphorylation, and sulfurization, etc. L-serinoate was N-alkylated, then cyclized with phosphorus oxychloride, and further reacted with N3-(2-hydroxyethyl) Tegafur to afford cyclic phospholipid conjugate 4. The resultants (2, 3, and 4) were successfully separated in the form of pure diastereomer by column chromatography on silica gel. Their configurations were discussed and assigned according to their NMR spectra. The asymmetric induction effects of the carbon-based chiral centre on the diastereomer preference were also observed in these two synthetic phosphorylation cyclizations. The bioassay on their antitumor activities is under investigation.
- He, Zheng-Jie,Chen, Wen-Bin,Zhang, Cheng-Xiang,Zhou, Zheng-Hong,Tang, Chu-Chi
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p. 223 - 232
(2007/10/03)
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- Features of Chemical Behavior of Phosphenium Cations Stabilized by Two Intramolecular Donor-Acceptor N→P Bonds
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Properties of a new class of organophosphorus compounds, chelated phosphenium cations containing two intramolecular donor-acceptor N→P bonds, were studied. These cations react with nucleophiles with cleavage of the N→P bonds to give neutral products. On the contrary, in reactions with electrophiles the cationic structure and the N→P bonds are preserved. First representatives of five-coordinate cations containing a phosphazo group were prepared, and their structure was studied by single crystal X-ray diffraction.
- Pipko,Balitskii,Chernega,Sinitsa
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p. 530 - 535
(2007/10/03)
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- Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides
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In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed.These compounds were allowed to react with a series of P(III)Cl compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 - 10) with phosphorus in the combination λ4P(V)/λ3P(III).In the oxidation of some of these compounds by the hydrogen peroxide-urea 1:1-adduct (NH2)2CO*H2O2 or sulfur, the corresponding λ4P-CH2-N(Me)-λ4P-derivatives (11 - 16) were formed.Different reaction behaviour was observed depending on the substituent at λ4P or on the oxidizing agent.Reaction of 1 with trimethylsilylmethyl tetrafluorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphosphorus compounds (17) and (18) with phosphorus in the combination λ4P(V)/λ5P(V) (17) and λ4P(V)/λ4P(V)(1+) (18).Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form.Reaction of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated.Both oxidation (>N-PPh2 -> >N-P(:O)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2 -> >NC(CF3)2-O-PPh2) occurred.In the reaction of 1 with methyldichlorophosphine, both the mono- and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds.The reaction of 1 with bis(diethylamino)chlorophosphine was unusual.Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 - 26 were formed, with the central phosphorus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively.Simultaneously, tris(diethylamino)phosphine was formed. - Keywords: N-Methylaminomethyl Grouping; Diphosphorus Compounds; Oxidation; NMR Spectra; Unusual Reaction Behaviour
- Kaukorat, Thomas,Neda, Ion,Schmutzler, Reinhard
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p. 1818 - 1832
(2007/10/03)
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- PROTONATED AMINOPHOSPHINES
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The possibility to obtain pure salts of tetrafluoroboric acid with aminophosphines is proved.It is shown by means of NMR spectroscopy and X-ray analysis that the protonation occurs at the phosphorus atom only.All aminophosphonium salts prepared appear not to phosphorylate nucleophiles, whereas phosphorylation occurs when some bases turning the phosphonium salts into H-complexes are added. Key words: Phosphorylation; nucleophiles; protonation; catalysis; aminophosphines; spectroscopy.
- Nifantyev, E. E.,Gratchev, M. K.,Burmistrov, S. Yu.,Antipin, M. Yu.,Struchkov, Yu. T.
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p. 159 - 174
(2007/10/02)
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- PYRAZOLIDES OF PHOSPHORUS(III) ACIDS
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It was shown that the methods of synthesis and chemical properties of pyrazolides of phosphorus(III) acids differ substantially from the methods of synthesis and the properties of the corresponding phosphoimidazolides.Additions of amine hydrochlorides and tetrafluoroboric acid raise the phosphorylating power of phosphopyrazolides.The cyclo-unsymmetric 2-(3,5-dimethylpyrazol-1-yl)-4-methyl-1,3,2-dioxaphosphorinane has preferentially an axial orientation of the exocyclic substituent.
- Iorish, V. Yu.,Grachev, M. K.,Bekker, A. R.,Nifant'ev, E. E.
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- Nature of acid-catalyzed alcoholysis of amides of trivalent-phosphorus acids
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To study the chemical nature of the acid catalysis of amides of trivalent-phosphorus acids (ATPA) alcoholysis the most important procedural problems have been solved. Simple and efficacious techniques for the purification of original ATPA from amine hydrohalides have been worked out. A precise and reliable way has been chosen to control the residual amount of amine hydrohalides in ATPA having been subjected to the various purification procedures. The nature of the dependence of alcoholysis rate constants for ATPA of different structures on the amine-hydrohalide concentration has been established. The general acid catalysis was established using the Bronsted equation, so that the process includes the formation of a catalytic H-complex incorporating substrate and catalyst on the whole. Amides P(III) of different types treated with anhydrous hydroborofluoric acid readily from the corresponding P-protonated salts. The conversions of corresponding products of complete protonation have been investigated. The structure of P-protonated salt 23 has been studied by means of X-ray analysis.
- Nifantyev,Gratchev,Burmistrov Yu.,Vasyanina
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p. 9839 - 9860
(2007/10/02)
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- Azidotris(diethylamino)phosphonium bromide: A self-catalyzing diazo transfer reagent
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Acidic methylene compounds are conveniently converted to diazo compounds in high yields by azidotris(diethylamino)phosphonium bromide, 1, in diethyl ether using only a catalytic amount of base. The product diazo compounds are easily separated from the co-product hexaethylphosphorimidic triamide hydrobromide.
- McGuiness, Mark,Shechter, Harold
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p. 4987 - 4990
(2007/10/02)
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- A simple Preparation of 5'-O-dimethoxytrityl Deoxyribonucleoside 3'-O-Phosphorbisdiethylamidites as Useful Intermediates in the Synthesis of Oligodeoxyribonucleotides and Their Phosphorodiethylamidate Analogs on a Solid Support
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5'-O-Dimethoxytrityl deoxyribonucleoside 3'-O-phosphorbisdiethylamidites were prepared by the selective phosphitylation of 5'-O-dimethoxytrityl deoxyribonucleosides with tris(diethylamino)phosphine in the presence of amine and tetrazol as catalyst.The bisamidites activated by p-nitrophenyltetrazole can be coupled efficiently with 5'hydroxyl group of nucleoside on a solid support.Oligodeoxyribonucleotides were obtined in high yields.The phosphorodiethylamidate linkage was obtained by non-aqueous oxidation using tert-butyl hydroperoxyde of the phosphordiethylamidite formed after the coupling.
- Yamana, Kazushige,Nishijima, Yoshitaka,Oka, Atsushi,Nakano, Hidehiko,Sangen, Osamu,et al.
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p. 4135 - 4140
(2007/10/02)
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- A CONVENIENT AND HIGH YIELD SYNTHESIS OF TERTIARY (AMINO) PHOSPHINES BY TRANSAMINATION ROUTE
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Tris(diethylamino)phosphine affords tertiary (amino) phosphines of pyrrolidine, piperidine, hexamethyleneimine, morpholine and N-methylpiperazine in nearly quantitative yields by transamination route - an easy and convenient synthesis occuring under mild conditions.
- Hussain, L. Altaf,Elias, Anil J.,Rao, M. N. Sudheendra
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p. 5983 - 5986
(2007/10/02)
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- PREPARATION AND REACTIONS OF METHYLTHIOMETHYL-SUBSTITUTED PHOSPHORUS HALIDES
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Methylthiomethylphosphonous dichloride, MeSCH2PCl2 (1), is synthesized by the reaction of MeSCH2SnBun, with phosphorus trichloride.Substitution reactions to give MeSCH2PX2 (X = NEt2, OPri, F, Ph) are described.The phosphorus(III) compounds are readily converted to the corresponding phosphonyl and thiophosphonyl derivatives, MeSCH2P(Z)X2 (Z = O, S), and the phosphorane, MeSCH2PF4, respectively.Chlorination of the methylene group to give compounds of the type MeSCHClP(O)X2 and MeSCCl2P(O)X2 is reported.Key words: Methylthiomethylphosphorus compounds; phosphorus halides; carbon-tin cleavage
- Fild, M.,Vahldiek, M.
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p. 207 - 214
(2007/10/02)
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- SYNTHESE UND SPEKTROSKOPISCHE CHARAKTERISIERUNG VON CYCLOPENTADIENYLEISEN-KOMPLEXEN MIT P-N-LIGANDEN DES TYPS (C6H5)3-nP(NR2)N (n = 0-3; R = CH3, C2H5)
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The complex cations BF4 (L = (C6H5)3-nP(NR2)n; n = 0-3; R = CH3, C2H5) have been obtained from the reaction of BF4 (I) with L.The reaction of I with E(NR2)3 (E = As, Sb; R = CH3) is also described.Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase in electron density on the iron center through increase of the number of P-bound NR2 groups.
- Schumann, Hans
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p. 169 - 178
(2007/10/02)
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- ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN XXIII. UEBER ALKENYLSUBSTITUIERTE AMINO-BZW. HALOGENPHOSPHANE UND VERSUCHE ZUM INTRAMOLEKULAREN PHOSPHINIDENABFANG
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Aminophosphanes RP(NEt2)2 and R2P(NEt2), obtained from alkenyl Grignard compounds RMgX (R = -CH=CH2, -CH2CH=CH2, o-(CH2=CH)C6H4-, o-(CH2=CHCH2)C6H4-) and aminochlorophosphanes, reacted smoothly with hydrogen halide to give alkenylhalogenophosphanes RPX2 and R2PX (X = Cl, Br).Properties and reactions of some of these compounds, e.g. with S8, H2O2, H2O and LiAlH4 are reported.On reaction of RPX2 with magnesium only alkenylcyclophosphanes (RP)n were obtained while heterocycles as possible products of an intramolecular reaction of intermediately formed phosphinidenes were not observed.
- Diemert, Klaus,Kottwitz, Beatrix,Kuchen, Wilhelm
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p. 307 - 320
(2007/10/02)
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- NEW DIALKYLAMINO DERIVATIVES OF TRIVALENT PHOSPHORUS
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Recent developments in the chemistry of (R2N)2PH, (R2N)(R'O)PH, (R2N)4P4, and R2NP(Cl)-P(Cl)NR2 derivatives are discussed.
- King, R. B.,Sadanani, N. D.,Sundaram, P. M.
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p. 125 - 128
(2007/10/02)
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