Phosphorus-containing podands 4. Effect of polyether chain length of oligoethylene glycol bis(ortho-diphenylphosphinylmethyl)phenyl ethers on their complex-forming and selective properties with respect to alkali metal cations

Evreinov, V. I.; Баулин, В. Е.; Vostroknutova, Z. N.; Бондаренко, Н. А.; Syundyukova, V. Kh.; Tsvetkov, E. N.

doi:10.1007/bf00957771

Cited by 12 publications

(13 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This was confirmed by experiments carried out in the same alkaline systems in the absence of alkylating reagents. The exothermic reaction of N (2 hydroxy ethyl)amide 2h with alkali in anhydrous system both in DMSO and in benzene is accompanied by quantitative cleavage of the P-N bond to give salt 8a (Scheme 10), whereas in the case of N (3 hydroxypropyl)amide 2i, the degree of cleavage is only 9% (see Table 6, entries 10, 11,13). Note that the quantitative formation of salt 8a (97%) under analogous conditions occurs also for secondary N hydroxyethylamide 3b (see Scheme 10), which was specially prepared by the Todd-Atherton reaction (see Scheme 2, Table 1).…”

Section: Methodsmentioning

confidence: 97%

“…and secondary amide 7 (δ 30.4-31.9). For completion of the reaction in this system, long term refluxing (12-40 h) of the reac tion mixture in toluene is required (Table 3, entries 1, 9,11,13,15).…”

Section: Methodsmentioning

confidence: 99%

“…Phos phorylation readily proceeds in the presence of 30-50% aqueous alkali without a phase transfer (PT) catalyst. The main prerequisites for the last mentioned modification were the data on the ability of the phosphoryl group of phosphonates and phosphine oxides to form complexes with alkali metal cations 13 and data on successful alkyla tion of the hydrophosphoryl compounds 14-16 R 2 P(O)H and phosphoryl containing CH acids 16 without PT catalysts. 2: R and R´ are given in Table 1.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides

2009

Self Cite

View full text Add to dashboard Cite

A facile method for the synthesis of nonsymmetrical dialkylamines (C n H 2n+1 ) 2 NH (n = 1-12) using the Ph 2 P(O) protecting group was developed. The method includes successive transfor mation of monoalkylamines to primary diphenylphosphinic N alkylamides Ph 2 P(O)NHR( R´ = C n H 2n+1 , n = 1-12) by the Todd-Atherton reaction, phase transfer N alkylation of these compounds, and hydrolysis of the secondary amides Ph 2 P(O)NR´R ″ thus formed. When the (EtO) 2 P(O) and Bu 2 P(O) protecting groups are used, N alkylation of primary amides is accompanied by the formation of Et-O and P-N bond cleavage products, respectively. A study of the stability of the N alkylamides R 2 P(O)NHR´ (R = Ph, p MeC 6 H 4 , p ClC 6 H 4 , Bu) under strong alkaline conditions used in the phase transfer N alkylation showed that an increase in the electron donating ability of substituents at both the nitrogen atom and the phosphorus atom results in a decrease in the degree of P-N bond cleavage. The primary and secondary diphenylphosphinic amides containing a β hydroxyethyl group at the nitrogen atom are extremely unstable under the alkaline conditions and are converted quantitatively to the diphenylphosphinic acid salt.Quaternary ammonium compounds exhibit rather broad range of bactericidal activity. 1 Compounds con taining at least one higher radical in the molecule are the most active. 2 Besides, it was found that the activity of compounds with nonsymmetrical structure is much higher than that of symmetric salts. 3 In order to obtain a number of nonsymmetrical ammonium salts and study the struc ture-bactericidal activity relationship, we first prepared the starting nonsymmetrical dialkylamines. Among numerous methods for the synthesis of these compounds, which are surveyed rather comprehensively in a review, 4 the main methods are direct N alkylation and reductive alkylation of primary amines. However, these reactions lead very often (especially in the case of sterically non hindered amines) to mixtures of secondary and tertiary amines and in some cases, quaternary ammonium salts, 5,6 whose separation creates difficulties and reduces the yield of the target product. These drawbacks can be eliminated by using protecting groups. We chose diethoxy , 7 diphe nyl , and dibutylphosphoryl groups. This route 7 comprises successive transformation of primary amines to the cor responding primary diethylphosphoric, diphenyl and dibutylphosphinic amides, their subsequent N alkyla tion, and cleavage of the resulting secondary amides with HCl in THF (Scheme 1). Scheme 1R´, R ″ = C n H 2n+1 , n = 1-12; R = EtO, Ph, Bu It is noteworthy that the acidifying effect* of substi tuted P=O groups and the known stability of both primary and secondary amides of P V acids in alkaline medium 10 provide for easy introduction of various alkyl substituent to nitrogen 7,11 in stage 2, while the high lability of the P-N bonds of these compounds in acidic medium, which * The replacement of the hydrogen atom in the NH 2 group of aniline by (EtO) 2 P(O) increases the NH aci...

show abstract

Section: Methodsmentioning

confidence: 97%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides

2009

Self Cite

View full text Add to dashboard Cite

show abstract

“…-Diphenylphosphoryl-o-cresol, (I), is a useful substrate to obtain phosphorylated podands (i.e. a ligand usually of chelate type, containing a number of ether bonds) (Evreinov et al, 1989). We suggested that this compound potentially may act as a bidentate ligand, which should be able to form chelate complexes.…”

Section: Commentmentioning

confidence: 99%

A monoclinic polymorph of α-diphenylphosphoryl-o-cresol

et al. 2005

View full text Add to dashboard Cite

show abstract

“…10 Podands can be easily modified by varying substituents at phosphorus, in particular, the 'bridges' between ether oxygens and P᎐ ᎐ O groups. More than 50 phosphoryl-containing mono-podands and their complexes with alkali, alkaline-earth and rare-earth cations have been synthesized [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] and studied by conductometry, 30,31 calorimetry, 32-34 extraction 35 and IR spectroscopy [36][37][38] methods. Compared to macrocyclic ionophores (crown ethers, cryptands), mono-podands are not preorganized.…”

Section: Introductionmentioning

confidence: 99%

Complexation of phosphoryl-containing mono-, bi- and tri-podands with alkali cations in acetonitrile. Structure of the complexes and binding selectivity

Соловьев¹,

Баулин²,

Strakhova³

et al. 1998

J. Chem. Soc., Perkin Trans. 2

View full text Add to dashboard Cite

complexes with K ؉ . Formation of poly-nuclear (M ؉ ) n L complexes of tri-podands in solution has been confirmed by electro-spray mass spectrometry. At relatively small concentrations of the ligand (C 0 L ), P1 binds Na ؉ much better than Li ؉ , whereas P4 and P5 display a remarkable Li ؉ /Na ؉ selectivity; at large C 0 L the complexation selectivity decreases. X-Ray diffraction studies performed on monocrystals of complexes of NaNCS with tri-podands P2 and P3 show that Na ؉ is encapsulated inside a 'basket-like' pseudocavity, coordinating all donor atoms of the tri-podand. Molecular dynamics simulations on P2, P3 and P4 and on their 1 : 1 complexes with M ؉ in acetonitrile solution suggest that the structures of M ؉ L complexes in solution are similar to those found for P2 and P3 complexes in the solid state.

show abstract

Phosphorus-containing podands 4. Effect of polyether chain length of oligoethylene glycol bis(ortho-diphenylphosphinylmethyl)phenyl ethers on their complex-forming and selective properties with respect to alkali metal cations

Cited by 12 publications

References 5 publications

Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides

Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides

A monoclinic polymorph of α-diphenylphosphoryl-o-cresol

Complexation of phosphoryl-containing mono-, bi- and tri-podands with alkali cations in acetonitrile. Structure of the complexes and binding selectivity

Contact Info

Product

Resources

About