Intercalation ofn-alkylamines into α-titanium phosphate from aqueous solutions

The intercalation reactions betweenn-alkylamines and -titanium phosphate in aqueous media have been investigated. The compounds with the maximum intercalation have the formula -Ti(HOPO₃)₂ · 2 C _n H _2n+1 NH₂ · H₂O (n=1–10). Defined crystalline phases with lower amine content are described, the general formula being -Ti(HOPO₃)₂ · _m C _n H _2n+1 NH₂ ·pH₂O (m=1.0 1.3, 1.5, 1.7). Whenm=1.0 then-alkylamines form a monomolecular layer. Whenm>1.0 the layer is bimolecular. The inclination angle and the packing density of then-alkylamines in the interlayer space is determined.     

Thermal behavior of poly(α-n-alkyl β-L-aspartate)s

A series of poly(-n-alkyl -L-aspartate)s (n being the number of carbon atoms in the linear alkyl side chain, withn=1, 2, 4, 6, 8, 12, 18 and 22), was studied by differential scanning calorimetry and thermogravimetric analysis. The effect of the length of the alkyl group on thermal properties such as stability, melting and crystallization of side chains, was investigated. For the polymers with n12, two endothermic peaks at T₁ and T₂ were detected separating three distinct phases A, B and C. The peak at T₁ corresponds to the melting of the crystallized paraffinic side chains (transition A-B), and the peak: at T₂ may be attributed to a transition (B-C), implying a liquid crystal phase.This work has been supported by DGICYT PB-93-0960 and PB-93-1241. F.L.-C. acknowledges financial assistance from the Venezuelan institutions Universidad de Los Andes and Fundayacucho.     

Zur Bildung von Xylol-tricarbonylchrom (Dimethylbenchrotrenen) aus Di-n-butylether und Hexacarbonylchrom

The reaction of fluorenone ethyleneketal (9), diphenic anhydride as well as of biphenyls such as4 with Cr(CO)₆ in refluxing di-n-butylether (BE) gives dimethylbenchrotrenes [xylene-Cr(CO)₃,7] which are also formed by refluxing pureBE with Cr(CO)₆—although with much lower yields. Similarily, from di-n-pentylether and Cr(CO)₆ isobutyl- and 1-methyl-3-propyl-benchrotrene (13 and14) were obtained, whilst from di-n-propyl- and-hexylether, resp., and Cr(CO)₆ no benchrotrenes could be isolated.Tentative assumptions on the catalytic action of certain functional groups were confirmed by the reaction ofBE and Cr(CO)₆ in the presence of carbonamides, such as acetamide, urea and pyrrolidone, where 1,4-dimethylbenchrotrene (7 c) was formed with appreciable yields.Studies using dideuteratedBE showed that—at least for the reaction of9 with Cr(CO)₆ (giving a much lower yield of7 than with undeuteratedBE)—a simple bimolecular mechanism can be excluded.

     

Inclusion complexation of sodium alkyl sulfates withβ-cyclodextrin. A1H NMR study

The association of anionic surfactants,viz., sodium alkyl sulfates, C _n H_2n+1OSO₃Na (n=5, 6, 7, 8, 9, 10, 12), with-cyclodextrin has been investigated by means of NMR spectroscopy. The measurements of chemical shift changes of certain protons of both host and guest molecules indicated 1:1 inclusion complex formation. The association constants (K _a) and standard free energy changes (–G ⁰) for the inclusion complexation reaction vary as a function of the hydrocarbon chain length of the surfactants.     

Schiff base derivatives of lanthanons-synthesis of La(III), Pr(III) and Nd(III) derivatives of β-ketoimines derived from 2,4-pentanedione

Reactions of the isopropoxides of some of the lighter lanthanons with bidentate -ketoimines, such asAAH-n-C₄H₉ andAAH-C₆H₅ (donor system: N,OH) and tridentate -ketoimines such asAA(CH₂CH₂)H₂ andAA(CH₂CHCH₃)H₂ (donor system: HO,N.OH) have led to products of the typesLn(O-i-C₃H₇)_3n (AA-R) _n ,Ln(Oi-C₃H₇) (AAR') andLn ₂(AAR')₃ [Ln=La(III), Pr(III) or Nd(III);n=1 or 2;R=-n-C₄H₉ or-C₆H₅ andR'=-CH₂CH₂-or-CH₂CHCH₃-]. Some undergo exchange reactions with an excess oftert-butanol, leading to the corresponding complexesLn(O-tert-C₄H₉)_3n (AA-n-C₄H₉) _n andLn(O-tert-C₄H₉) (AA-CH₂CH₂). All these have been characterised by elemental analysis, molecular weight determinations and their ir spectra. A thermogravimetric analysis of the diisopropoxy derivatives has also been carried out.

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Schiff-Basen Derivate von Lanthaniden-Synthese von La(III), Pr(III) und Nd(III) chelaten mit -Ketoiminen

Zusammenfassung Reaktionen von Lanthanid-Isopropoxiden mit zweizähnigen -Ketoiminen [AAH-n-C₄H₉ undAAH-C₆H₅; Donorsystem: N,OH] und dreizähnigen -Ketoiminen [AA(CH₂CH₂)H₂ undAA(CH₂CHCH₃)H₂; Donorsystem: OH, N,OH] führten zu Produkten vom, TypLn(O-i-C₃H₇)_3-n (AA-R) _n ,Ln(O-i-C₃H₇) (AAR') undLn ₂(AAR')₃ [Ln=La(III), Pr(III) oder Nd(III);n=1 oder 2;R=n-C₄H₉ oder C₆H₅ undR'=CH₂CH₂ oder CH₂CHCH₃]. Einige Komplexe unterliegen bei Behandlung mit einem Überschuß vontert-Butanol einer Austauschreaktion, die zu den entsprechenden Butoxid-Komplexen führt [Ln(O-tert-C₄H₉)_3-n , (AA-n-C₄H₉) _n undLn(O-tert-C₄H₉) (AACH₂CH₂)]. Alle Derivate wurden mittels Elementaranalyse, Molgewichtsbestimmung und IR-Spektroskopie charakterisiert. Eine thermogravimetrische Analyse der Diisopropoxi-Derivate wurde ebenfalls ausgeführt.

     

Excess heat of mixing of α-picoline withn-alkanes

The excess heats of mixing for binary mixtures -picoline +n-alkanes (C₆ to C₁₀) at 298.15 K were measured and a comparison was made with the Prigogine-Flory-Patterson theory and the extended real associated solution method.

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Zusammenfassung Die molaren Überschubenthalpien binärer Mischungen von -Picolin mit C₆C₁₀ n-Alkanen wurden bei 298.15 K im ganzen Zusammensetzungsbereich gemessen. Die gemessenen H^E Werte wurden mit denen verglichen, die mit Hilfe von Prigogine-Flory-Patterson Theorie und nach der ERAS-Methode berechnet wurden.

     

On the excited states ofp-quinones and an interpretation of the photocycloaddition ofp-quinones to alkenes

A theoretical investigation is made of the electronic states ofp-benzoquinone (PBQ), methyl substituted PBQ's and 1,4-naphthoquinone (NQ). In accord with experiment, the lowest triplet state of PBQ is calculated to be³ B _1g (n, *), while that for duroquinone (DQ) is³ B _3g (, *). The electron densities of these states are consistent with the hypothesis that³ n, * states lead to oxetan formation and³, * states to cyclobutanes. It is predicted that trimethyl PBQ might form both adducts, as the two states are calculated to be nearly degenerate.The photochemistry of NQ is more complex. The lowest excited triplet state is calculated to be ofn, * symmetry, in accord with experiment; however, several other states are predicted near in energy, and the photochemistry cannot be rationalized unambiguously.This work was supported in part by the National Research Council of Canada.     

γ-Cyclodextrin-enhanced dimerization of viologen radicals

The effects of cyclodextrins (CDs) on the monomer-dimer equilibria of 1,1-dialkylviologen radical cations (Cn Cn V^.+ :n = 1–5) and one-electron reduced 1,1-bis(3-sulfopropyl)viologen (SPV) were investigated spectroelectrochemically. The dimerization is enhanced upon addition of-CD, while the addition of-CD and-CD suppresses the dimerization. This is attributed to the stabilization of dimers by the inclusion of the dimer in the cavity of-CD From the dependence of the apparent dimerization constants (K _D ) on the concentration of-CD the association constants of the monomer (K _C1) and dimer (K _C2) with--CD were determined. TheK _C1 value increases slightly, from 5 M^–1 forn = 1 to 35 M^–1 forn = 5, as the length of the alkyl substituents of viologen increases. TheK _C2 value depends strongly on the alkyl substituents giving the smallest value of 85 M^–1 for (SPV^.–)₂ and the largest one of 3500 M^–1 for (C₄C₄V^.+)₂. These results, together with the difference in UV-vis absorption spectra obtained in the absence and in the presence of-CD, suggest that the alkyl substituents and part of the bipyridine ring of viologen radicals are included in the-CD cavity forming dimers in which the bipyridine rings are stacked at an oblique angle.     

Some remarks on the solubility of gases in liquid long-chainn-alkanes andn-alkan-1-ols

The Ostwald coefficients L_2,1 of He, Ne, Ar, Kr, Xe, N₂, O₂, CH₄ CF₄ and SF₆ dissolved in several homologous_n-alkanes,_n-C₁H₂₁₊₂, 6l16, andn-alkan-1-ols,n-C₁H₂₁₊₁OH, 1l11, were recently measured at 298.15 K and atmospheric pressure with a modified Ben-Naim/Baer apparatus. Altogether, 201 gas/liquid systems were investigated. For about half of these systems, both pressure control and measurement of the volume of gas dissolved in a given volume of solvent were achieved with a microprocessor. This improved medium-precision instrument (0.5% in most cases) combines easy handling with fully automated data retrieval, and is totallymercury-free. In this communication, the salient points of data reduction are presented, with the focus on the estimation of several important auxiliary quantities such as second virial coefficients and partial molar volumes at infinite dilution. The effect of the chain lengthl of then-alkane or then-alkan-1-ol upon solubility is demonstrated, and some correlations betweenL _2,1, or the derived Henry fugacitiesH _2,1, and appropriate molecular and/or bulk properties of the gases and the solvents are discussed.     

Theoretical investigation of structure and stability of oligomers of LiH,NaH, LiF,and NaF

The molecules Li_nH_n, Na_nH_n, Li_nF_n, n=1,..., 4, and NaF and Na₂F₂ are investigated by means of extended basis set SCF and CEPA-PNO computations. In analogy to the D _2h structure of dimers, it is found that trimers have a planar cyclic D _3h equilibrium geometry. For the tetramer of LiH and NaH, the D _4h structure has about the same energy as the 3-dimensional T _d structure, whereas the latter is definitely favoured for Li₄F₄. Correlation effects are investigated for the oligomerization of LiH and the dimerization of LiF. The effect of electron correlation on corresponding E turns out to be small (<4 kJ/mol), except for the case that the T _d tetramer is involved which has a rather large correlation energy.     

Effects of dipole interaction and solvation on the CO stretching band of N,N-dimethylacetamide in nonpolar solutions: Infrared, isotropic and anisotropic Raman measurements

The concentration dependence of the CO stretching (ν_CO) band of N,N-dimethylacetamide (NdMA) in cyclohexane, n-hexane, and CCl₄ has been investigated by infrared (IR) and polarized Raman spectroscopy. For the neat liquid of NdMA, the noncoincidence of the aniso- and isotropic Raman wavenumbers is evident. In the 0.47 M cyclohexane solution of NdMA, the noncoincidence effect almost disappears and the ν_CO envelopes in both the Raman and IR spectra are asymmetric to the low-wavenumber side. When the concentration of NdMA decreases from 0.33 to 0.023 M, the peak of these bands slightly shifts to a higher wavenumber and the band shape becomes symmetric. The shape of the ν_CO envelope does not show any significant change below 0.023 M. These results suggest that the asymmetric shape of the ν_CO band observed for the 0.33 M cyclohexane solution is associated with the intermolecular interaction among NdMA molecules, which vanishes at around 0.02 M. Spectral changes for the CCl₄ solution of NdMA show a similar tendency. However, the shape and peak wavenumber of the ν_CO band observed in a highly diluted CCl₄ solution (≤0.023 M) indicate that the solvation effect of CCl₄ is more complicated than those of cyclohexane and n-hexane. The analyses of the ν_CO band, which is sensitive to the intermolecular interaction between solutes and between solute and solvent for NdMA dissolved in nonpolar solvents, would serve to clarify the electronic property of the molecule in a solution.     

Studies of the energy spectrum of α, ω- substituted polymethine chains. II. Polymethine chains with odd number of methine groups

The analysis of the experimental data for the energy of the longest wavelength optical transitions _n,opt of substituted polymethines X (CH)_2n+1 X shows that in the asymptotic case (n) _,opt does not tend to zero, as it follows from the empirically established correlations, but has a finite, non-zero value. It is shown that the energy gap of odd polymethines is the same as that of the even polymethines - the polyenes (E 2 eV). The substituents (X N, O, B) are responsible for the appearance of levels in the gap. These, depending on the substituent character, are vacant (X B) or occupied (X N, O). The transition from or to such a level determines the longest wavelength optical transition energy of polymethines.     

Struik law for enthalpy retardation at the glass transition in poly(n-alkylmethacrylates) measured by DSC aging experiments

Results of calorimetric (DSC) experiments on a series of poly (n-alkylmethcrylates), from methyl to pentyl, after different aging timest _e at different aging temperaturesT _e are presented. The aging behavior is quite different from that in other polymers, for example PS. For all poly(n-alkylmethacrylates) investigated the aging peak temperatureT _max is shifted parallel to the aging temperatureT _e in a large temperature interval below the glass temperature. The results are discussed with respect to shear and entropy response in the splitting region.     

Ergebnisse dehnungskalorimetrischer Untersuchungen an einigen Poly-[α-aminosäuren]

Zusammenfassung Dehnungskalorimetrische Untersuchungen an Folien von Copolymeren ausL-Alanin undL-Cystein im Molverhältnis 973, 955 und 9010 ergaben einmal, daß im Unterschied zu homopolymerem (Ala) _n selbst bei Dehnungen bis zu 10% [(l- l _o)/l _o =0,1] kein exothermer Vorgang auftritt. Weiterhin ist der zu Beginn der Dehnung beobachtete energieelastische Vorgang praktisch vollständig reversibel, wie der beim Entlasten auftretende, dem Betrag nach gleiche exotherme Peak zeigt.Dieses vom Homopolymeren abweichende Verhalten ist anscheinend durch die Bildung interchenarer Disulfidbrücken (-S-S-) durch Oxidation von SH-(Thiol-)Gruppen in den Folien bedingt. Die entsprechenden Copolymeren, in denen die Thiolgruppen durch Carbobenzoxygruppen (-OCOCH₂C₆H₅) geschützt und daher die Bildung von-S-S-Brücken nicht möglich ist, zeigen ein dem Homopolymeren ähnliches Verhalten. Die recht unterschiedlichen Ergebnisse, die an den jeweils entsprechenden Copolymeren (-SH bzw.-S-OCOCH₂C₆H₅) erhalten wurden, können einmal sterisch und andererseits durch die unterschiedlichen zwischenmolekularen Wechselwirkungen der Seitengruppen der Comonomeren bedingt sein.Gegenüber den o. a. Polymerfolien sind die aus Poly--methyl-D-glutamat] (PMDG) wesentlich dehnbarer. Bei stufenweiser Dehnung tritt > 2.4% Dehnung außer dem anfangs beobachteten energieelastischen Peak ein exothermer Vorgang auf, dem beim Entlasten kein endothermer Prozeß entspricht. Dabei handelt es sich also um einen offensichtlich durch plastisches Fließen bedingten irreversiblen Vorgang.Bei kontinuierlicher Dehnung bis um ca. 50% wird nach dem anfänglichen endothermen Vorgang ein sehr starker exothermer Prozeß beobachtet, währenddem die Kraft praktisch konstant bleibt. Der stufenartige Verlauf des exothermen Peak deutet auf diskontinuierliche Umordnungsvorgänge im Material hin. Wie die IR-Spektren der Folien vor und nach dem Verstrecken zeigen, tritt eine Konformationsänderung dabei kaum auf. Dies ist anscheinend auf die Überstruktur der aus 1,2-Dichlorethan gegossenen Folien zurückzuführen, da hierbei die-helicalen Aggregate isoliert in einer Matrix vorliegen. Dadurch kann der für eine Konformationsumwandlung erforderliche Zug nicht auf die-Helices übertragen werden, so wie es bei Folien mit netzwerkartig angeordneten-Helices der Fall ist [4].Ähnliche Resultate wurden an Folien aus Poly-[L-leucin] und einem 11 Copolymeren ausL-Leucin undL-Methionin erhalten. Hierbei steigt allerdings die Kraft während des exothermen Vorgangs an, was darauf zurückgeführt werden kann, daß entanglements gelöst werden müssen.

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Stretching calorimetric experiments on films of copolymers ofL-alanine and L-cysteine (mole ratio 973, 955 and 9010) show that in contrast to (Ala)_n no exothermic process occurs also at (l- l _o )/l _o =0.1. Furthermore, the initially occurring energyelastic process is a practical completely reversibel one.This behaviour deviating from that of the homopolymer is probably due to the formation of interchain disulfide crosslinks (-S-S-) by oxidation of thiol (-SH) groups. The behaviour of the corresponding copolymers, in which the thiol groups are blocked by carbobenzoxy (-OCOCH₂C₆H₅) groups, is similar to that of the homopolymer. The remarkable differences in the results obtained with the corresponding copolymers containing -SH or -S-OCOCH₂C₆H₅ may be due to sterical reasons and/or to differences in the intermolecular interactions of the comonomer side-chains.Films made of poly-[-methyl-D-glutamate] (PMDG) have a much higher stretchability than that of (Ala)_n and the copolymers mentioned above. Stepwise stretching of PMDG-films at (l- l _o)/l _o above 0.024 causes-besides the initially occurring endothermic peak — an exothermic process. No corresponding endothermic peak during deloading is observed. This irreversible process obviously is caused by plastic flow of the PMDG.During continuously stretching to about (l- l _o )/l _o , 0.5 a pronounced exothermic peak at almost constant force is observed. The stepwise character of this peak suggests discontinuously changes in the order of the material.According to the IR-spectra of the films before and after stretching conformation changes of the PMDG are negligible. This is probably due to the superstructure of the films cast from 1,2-dichloroethane solution. In this case there are rodlike-helical aggregates dispersed in a low ordered matrix and therefore the stress essential for a conformation change from to is not exerted to the-helices [4] like in the case of networks built from-helices.Similar results were obtained on films made of poly-[L-leucine] and a 11 copolymer ofL- leucine andL-methionine. In this case however the force increases during the exothermic process, which may be caused by entanglements.

     

Clusters of hydrogen molecules: Ab initio SCF calculations corrected semiempirically for correlation energies

Stabilization energy of the (H₂) _n clusters (n = 2–8) was calculated as a sum of the SCF interaction energy and the semiempirical interaction correlation energy estimated according to Sinanolu and Pamuk. Optimum successive attachment of hydrogen molecules leads to the formation of a gas-phase solvation shell consisting of seven hydrogen molecules. Basis set effect has been found to be important with all clusters under study. The non-additivity effect was investigated with the (H₂)₄ cluster. Vertical ionization potentials of the clusters considered are predicted to be 0.4–0.6 eV lower than the ionization potential of the parent H₂ molecule.     

Steric repulsion of polyoxyethylene groups for emulsion stability

Rapid coalescence was studied on liquid paraffin emulsion stabilized with a series of poly(oxyethylene) dodecyl ethers [C₁₂H₂₅ (EO),n=1, 2, 3, 4, 5, 6, 7, 8] and of poly(oxyethylene) nonylphenyl ethers [C₉H₁₉(EO) _n ,n=2, 4, 5, 6, 12]. The turbidity of emulsion was measured as a function of the solution pHs at constant ionic strength of 0.1 mol dm^–3.As a result, it was found that the emulsions (which were formed with C₁₂H₂₅(EO) _n surfactants having less than four oxyethylene groups, or with C₉H₁₉ (EO) _n surfactants having less than six oxyethylene groups) brought about rapid coalescence in the bulk pH between 2.03.5, which corresponded to the zero point of charges for the emulsions of the present systems. According to the Tadros treatment for emulsion flocculation, the total flocculation potennual was estimated as a function of the distance relative to the number of oxyethelene groups in the surfactants. The critical coalescence energy was obtained as –343 ×10^–19 J for the C₁₂H₂₅(EO) _n surfactants and –2.14×10^–19) J for the C₉H₁₉ (EO) _n surfactants. Furthermore, the formation of a hole for coalescence was estimated under the simple assumption that the coalescence was caused only by the energy dissipation.     

Viscosities of n-Alkyl Chlorides from 15 to 80°C

The viscosities of n-alkyl chlorides from pentyl to hexadecyl chloride were determined at temperatures between 15 to 80°C at 5°C intervals. The intrinsic volumes of the n-alkyl chlorides were determined by extrapolation of the plot of fluidity against molar volume to zero fluidity. Plots of the logarithm of viscosity vs. reciprocal absolute temperature were almost linear. The energies of activation for viscous flow for the n-alkyl chlorides were calculated and found to increase with increase in chain length. The fluidities, , of the n-alkyl chlorides were found to obey the modified form of Hildebrand's equation. = D[(V-V_o/V_o]\exp(-E_B/RT) where D is a constant, V and V _o are the molar volume and the intrinsic molar volume, respectively, and E _B is an energy term corresponding to the energy required for disrupting the association of the molecules. The activation energy for viscous flow consists of the sum of the energy required for the expansion of the void volume and the energy required to overcome intermolecular interactions. These energies were calculated and discussed.     

Synthesis of Co3(CO)7(μ-η3-Allyl)(μ3-X) Complexes (X=S, Se) and Structure of the Selenium Derivative

The complexes Co₃(CO)₉( ₃-X) (X=S, Se) can be reduced to the corresponding anionic species [Co₃(CO)₉( ₃-X)]^–, which react with allyl bromide to give Co₃(CO)₇(- ³-C₃H₅)( ₃-X) (X=S, Se). These are the first two cobalt complexes containing the bridging - ³-allyl ligand. The structure of the selenium complex was determined by X-ray crystallography. Crystal data for Co₃(CO)₇(- ³-C₃H₅)( ₃-Se) are as follows: space group P2₁/c, a=9.051(2) Å, b=8.102(2) Å, c=21.27(4) Å, =93.82(3)°, Z=4, and R=0.0565 for 2491 observed reflections.     

Properties of aqueous salt solutions of poly(ethylene oxide). Cloud points, θ temperatures

The determination of the properties of aqueous salt solutions of poly(ethylene oxide) has been extended to the cloud point, and temperature measurements have been made at several concentrations for various salts (flourides, iodides, acetates, formates, phosphates, bromides, thiosulfates and perchlorates). The resulting dependency of the critical temperatures (mostly between 290–350 K) on the molar concentration can be expressed as sequences showing the decreasing effect of anion species or cation species in salting out the polymer. The decreasing order of effectiveness of the anions in reducing the temperature is PO ₄ > HPO ₄ > S₂O ₃ > H₂PO ₄ ^– >F^– > HCOO^– > CH₃COO^– > Br^– > I^–. The order for cations is K⁺ Rb⁺ Na⁺ Cs⁺ > Sr⁺⁺ > Ba⁺⁺ Ca⁺⁺ > NH ₄ ⁺ > Li⁺. The changes brought about in temperatures by the salts were found to be the results of the changes taking place in the hydrophilic and hydrophobic interactions among polymer, solvent and additive salts and of the change of water structure by structure making or structure breaking ions, and of the influence of salts on the hydration sheath of the polymer.     

The phosphonate-phosphate and phosphate-phosphonate rearrangement and their applications V. On the reaction ofs-butyllithium/TMEDA with symmetrical trialkyl phosphates

Summary 1-(Tributylstannyl)hexanol ((±)-8 is phosphorylated to give phosphate (±)-9 which is then transmetallated. The organolithium intermediate (±)-10 isomerizes to -hydroxyphosphonate (±)-12. Similar intermediates are also formed upon direct deprotonation of triethyl, tri-n-propyl, and tri-n-butyl phosphate, which subsequently rearrange to -hydroxyphosphonates (±)-14a–c.

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Die Phosphat-Phosphonat- und Phosphonat-Phosphat-Umlagerung und ihre Anwendungen, 5. Mitt. Über die Reaktion vons-Butyllithium/TMEDA mit symmetrischen Trialkylphosphaten

Zusammenfassung 1-(Tributylstanny)hexanol ((±)-8) wird phosphoryliert und liefert Phosphat (±)-9, das transmetalliert wird. Das lithiumorganische Zwischenprodukt (±)-10 isomerisiert zum -Hydroxyphosphonat (±)-12. Ähnliche Intermediate werden auch bei der direkten Deprotonierung von Triethyl-, Tri-n-propyl- und Tri-n-butylphosphat gebildet, die anschließend zu den -Hydroxy-phosphonaten (±)-14a–c umlagern.