一个新的具有大的吸收截面的双光子引发剂的合成和非线性光学性质

E,E-1,4-Bis（4＇-N,N-diphenylaminostyryl）-2,5-dimethoxybenzene （DPAMOB） has been synthesized by a simple and effective solid phase Wittig reaction and characterized by 1^H NMR spectra and elemental analysis, Linear absorption, single-photon induced fluorescence and two-photon induced fluorescence spectra were experimentally studied. The new dye has a large two-photon absorption （TPA） cross-section of σr= 1007,2 GM [1 GM= 1 × 10^-50 cm^4·s/（photon molecule）] at 800 nm measured by the two-photon induced fluorescence method. The experimental results confirm that DPAMOB is a good TPA chromophore and can successfully initiate two-photon photopolymerization of ethoxylated trimethylolpropane triacrylate esters （SR454）. Finally, a microstructure has been fabricated by use of DPAMOB as initiator.     

Effect of solvent and structure on the kinetics and mechanism of the aquation of bromopentaamine cobalt(III) complex in binary aqueous mixtures

The kinetics of aquation of bromopentaamine cobalt(III) complex have been investigated spectrophotometrically in aqueous‐organic solvent media using acetonitrile, urea, and dimethyl sulfoxide as co‐solvents at 45 ≤ T (°C) ≤ 65. The logarithms of rate constant of the aquation reaction vary nonlinearly with the reciprocal of the dielectric constant for all cosolvent mixtures, indicating a specific solute–solvent interaction. Also, the rate constants are correlated with the total number of moles of water and the organic solvents. However, the solvent effects on the solvation components of the enthalpy of activation, ΔH^?, and the entropy of activation, ΔS^?, have been studied. Analysis of the solvent effect confirmed a common I_d mechanism for the aquation of the cobalt(III) complex. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:494–499, 2004     

Synthesis and Nonlinear Optical Characterization of a New Twophoton Absorbing Organic Dye：DMAHAS

IntroductionThepotentialforuseoftwo photonabsorbingmoleculesinapplicationsrangingfromopticallimiting1 3tothreedimensional (3D)fluorescencemicroscopy4 and 3Dmicrofabricationandopticaldatastorage5,6 hasstimulatedresearchonthedesign ,synthesis ,andcharacterizationofnewmoleculeswithlargetwo photonabsorptivities .7,8Thetwo photonabsorption (2PA)processconsideredherein volvesthesimultaneousabsorptionoftwophotons ,eitherdegeneratingornondegenerating ,atwavelengthswellbe yondthelinearabsorptionspectr…     

Synthesis and Properties of a New Two—Photon—absorbed Material DMAEAS

IntroductionSubstitutedstilbeneshavesignificantpotentialapplica tionssuchasfluorescencemicroscopy ,two photonphotody namictherapy ,opticalpowerlimiting ,three dimensionalstorage,andthree dimensionalmicrofabrication .1 4 Thesedyeshavestrongtendencyofintra molecularchargetransferundertheexcitedstate.Asaresult,theyusuallyexhibitlargetwo photonabsorption (TPA) ,inthemeanwhileemitstrongup convertedfluorescence .Ontheotherhand ,theirsolutionsgenerallydisplaylineartransmissionof >90 %atwavelengthof…     

Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO2 triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity

This study deals with the trichloroisocyanuric acid (TCCA) interactions with carboxamides like formamide (FMA), N,N′‐dimethyl formamide (DMF), and N,N′‐dimethyl acetamide (DMA) interactions during the nitration of heterocyclic compounds (HC) like pyrrole and indole in the presence of excess of [NaNO₂] over the concentrations of all other reactants. All the reactions were performed in aqueous acetonitrile media containing carboxamide under acid‐free conditions. Kinetics of the reactions revealed first order in [nitrating agent] and [HC] under otherwise similar conditions. To gain an insight into the reactive species and role of added carboxamide (FAA, DMF, DMA, etc.), the observed rates of the nitration reaction (log k) were analyzed as a function of (1/D), ([D ? 1]/[2D + 1]), mole fraction (n_x), and volume (%) of carboxamide, 1/viscosity, density refractive index function), and Hildebrand solubility parameter plots. Linear regression analysis gave very good correlation coefficients (R² values), which indicate the importance of several solvent properties in addition to the role of dielectric constant (D) of the reaction media. Multiple linear solvent energy relationships suggested by Abraham, Koppel, Palm, and Taft also afforded very good correlation coefficient (R² values), showing the importance of cumulative effect of solvent properties. Besides these features, the negative entropies of activation (?S^#) suggest greater solvation in the transition state. Isokinetic temperature (β) values for different protocols were very close to the experimental temperature range (303‐323 K), indicating the importance of both enthalpy and entropy factors in controlling the reaction.     

Study of phenothiazine and N‐methyl phenothiazine by infrared,raman, 1H‐, and 13C‐NMR spectroscopies

A complete vibrational analysis of the Fourier transform (FT) infrared (IR) and FT‐Raman spectra of both molecules was carried out using quantum chemical calculations. The structure of phenothiazine (PTZ) and N‐methylphenothiazine (N‐MePTZ) were studied by semiempirical, and ab initio methods. Different basis sets and two new procedures for scaling the frequencies of the ring modes were used. Vibrational data of the methyl group in N‐MePTZ were interpreted in terms of the different molecular conformations in the solid state. The ¹H‐ and ¹³C–nuclear magnetic resonance (NMR) data were interpreted in terms of the electron densities on the atoms and the stacking solute–solute association in dimethyl sulfoxide solution. Chemical shifts were related to the Merz‐Kollman atomic charges. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Synthesis and characterization of novel polyamide‐imides containing noncoplanar 2,2′‐dimethyl‐4,4′‐biphenylene unit

A new diimide‐dicarboxylic acid, 2,2′‐dimethyl‐4,4′‐bis(4‐trimellitimidophenoxy)biphenyl (DBTPB), containing a noncoplanar 2,2′‐dimethyl‐4,4′‐biphenylene unit was synthesized by the condensation reaction of 2,2′‐dimethyl‐4,4′‐bis(4‐minophenoxy)biphenyl (DBAPB) with trimellitic anhydride in glacial acetic acid. A series of new polyamide‐imides were prepared by direct polycondensation of DBAPB and various aromatic diamines in N‐methyl‐2‐pyrrolidinone (NMP), using triphenyl phosphite and pyridine as condensing agents. The polymers were produced with high yield and moderate to high inherent viscosities of 0.86–1.33 dL · g⁻¹. Wide‐angle X‐ray diffractograms revealed that the polymers were amorphous. Most of the polymers exhibited good solubility and could be readily dissolved in various solvents such as NMP, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide (DMF), dimethyl sulfoxide, pyridine, cyclohexanone, and tetrahydrofuran. These polyamide‐imides had glass‐transition temperatures between 224–302 °C and 10% weight loss temperatures in the range of 501–563 °C in nitrogen atmosphere. The tough polymer films, obtained by casting from DMAc solution, had a tensile strength range of 93–115 MPa and a tensile modulus range of 2.0–2.3 GPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 63–70, 2001     

A free-energy perturbation method based on Monte Carlo simulations using quantum mechanical calculations (QM/MC/FEP method): application to highly solvent-dependent reactions

This study describes the framework of the quantum mechanical (QM)/Monte Carlo (MC)/free‐energy perturbation (FEP) method, a FEP method based on MC simulations using quantum chemical calculations. Because a series of structures generated by interpolating internal coordinates between transition state and reactant did not produce smooth free‐energy profiles, we used structures from the intrinsic reaction coordinate calculations. This method was first applied to the Diels–Alder reaction between methyl vinyl ketone and cyclopentadiene and produced ΔG values of 20.1 and 21.4 kcal mol^?1 in aqueous and methanol solutions, respectively. They are very consistent with the experimentally observed values. The other two applications were the free‐energy surfaces for the Cope elimination of N,N‐dimethyl‐3‐phenylbutan‐2‐amine oxide in aqueous, dimethyl sulfoxide, and tetrahydrofuran solutions, and the Kemp decarboxylation of 6‐hydroxybenzo‐isoxazole‐3‐carboxylic acid in aqueous, dimethyl sulfoxide, and CH₃CN solutions. The calculated activation free energies differed by less than 1.8 kcal mol^?1 from the experimental values for these reactions. Although we used droplet models for the QM/MC/FEP simulations, the calculated results for three reactions are very close to the experimental data. It was confirmed that most of the interactions between the solute and solvents can be described using small numbers of solvent molecules. This is because a few solvent molecules can produce large portions of the solute–solvent interaction energies at the reaction centers. When we confirmed the dependency on the droplet sizes of solvents, the QM/MC/FEP for a large droplet with 106 water molecules produced a ΔG value similar to the experimental values, as well as that for a small droplet with 34 molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Energy Transfer in Aminonaphthalimide‐Boron‐Dipyrromethene (BODIPY) Dyads upon One‐ and Two‐Photon Excitation: Applications for Cellular Imaging

Aminonaphthalimide–BODIPY energy transfer cassettes were found to show very fast (k_EET≈10¹⁰–10¹¹ s^?1) and efficient BODIPY fluorescence sensitization. This was observed upon one‐ and two‐photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two‐photon absorption cross‐section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ≈10 GM for the BODIPY versus 19–26 GM in the dyad at λ_exc=840 nm; 1 GM (Goeppert–Mayer unit)=10^?50 cm⁴ s molecule^?1 photon^?1]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfer cassette concept, was demonstrated by time‐dependent density functional theory calculations. The applicability of the new probes in the one‐ and two‐photon excitation mode was demonstrated in a proof‐of‐principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY‐containing dyad.     

Simultaneous determination of NG‐monomethyl‐l‐arginine,NG,NG‐dimethyl‐l‐arginine,NG,NG′‐dimethyl‐l‐arginine,and l‐arginine using monolithic silica disk‐packed spin columns and a monolithic silica column

We have developed and validated a high‐performance liquid chromatography method that uses monolithic silica disk‐packed spin columns and a monolithic silica column for the simultaneous determination of N^G‐monomethyl‐l ‐arginine, N^G,N^G‐dimethyl‐l ‐arginine, and N^G,N^G′‐dimethyl‐l ‐arginine in human plasma. For solid‐phase extraction, our method employs a centrifugal spin column packed with monolithic silica bonded to propyl benzenesulfonic acid as a cation exchanger. After pretreatment, the methylated arginines are converted to fluorescent derivatives with 4‐fluoro‐7‐nitro‐2,1,3‐benzoxadiazole, and then the derivatives are separated on a monolithic silica column. l ‐Arginine concentration was also determined in diluted samples. Standard calibration curves revealed that the assay was linear in the concentration range 0.2–1.0 μM for methylated arginines and 40–200 μM for l ‐arginine. Linear regression of the calibration curve yielded equations with correlation coefficients of 0.999 (r²). The sensitivity was satisfactory, with a limit of detection ranging from 3.75 to 9.0 fmol for all four compounds. The RSDs were 4.3–4.8% (intraday) and 3.0–6.8% (interday). When this method was applied to samples from six healthy donors, the detected concentrations of N^G‐monomethyl‐l ‐arginine, N^G,N^G‐dimethyl‐l ‐arginine, N^G,N^G′‐dimethyl‐l ‐arginine and l ‐arginine were 0.05 ± 0.01, 0.41 ± 0.07, 0.59 ± 0.11, and 83.8 ± 30.43 μM (n = 6), respectively.     

Highly organosoluble and flexible polyimides with color lightness and transparency based on 2,2‐bis[4‐(2‐trifluoromethyl‐4‐aminophenoxy)‐3,5‐dimethylphenyl]propane

A new diamine containing isopropylidene, methyl substituted arylene ether, and trifluoromethyl groups, 2,2‐bis[4‐(2‐trifluoromethyl‐4‐aminophenoxy)‐3,5‐dimethylphenyl]propane (BTADP), was synthesized and used in preparation of a series of polyimides by direct polycondensation with various aromatic tetracarboxylic dianhydrides in N, N‐dimethylacetamide (DMAc). All polymers derived from diamine (BTADP) with trifluoromethyl substituents were highly organosoluble in the solvents, like N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylacetamide, N,N‐dimethylformamide (DMF), pyridine, chloroform, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dichloromethane, cyclohexanone, and γ‐butyrolactone at room temperature or upon heating at 70 °C. Inherent viscosities of the polyimides were found to range between 0.58 and 0.97 dL·g^?1. These polyimides had glass transition temperatures between 256 and 307 °C, and their 10% mass loss temperatures ranged from 440 to 462 °C and 421 to 443 °C under nitrogen and air, respectively. These polyimides had low dielectric constants in the range of 2.84–3.09. All the polyimides could be cast into films from DMAc solutions and were thermally converted into color lightness, optically transparent, flexible, and tough polyimides. The polyimide films had a tensile strength in the range of 83–97 MPa and a tensile modulus in the range of 2.0–2.2 GPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5766–5774, 2004     

Synthesis and Characterization of Fluorinated Polyimide Derived from 3,3′‐Diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane

A novel aromatic diamine monomer, 3,3′‐diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane (PAFM), was successfully synthesized by coupling of 2‐isopropylaniline and 3,4‐difluorobenzaldehyde. The aromatic diamine was adopted to synthesize a series of fluorinated polyimides by polycondensation with various dianhydrides: pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) via the conventional one‐step method. These polyimides presented excellent solubility in common organic solvents, such as N,N‐dimethylformamide (DMF), N,N‐dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), N‐methyl‐2‐pyrrolidone (NMP), chloroform (CHCl₃), tetrahydrofuran (THF) and so on. The glass transition temperatures (T_g) of fluorinated polyimides were in the range of 260–306°C and the temperature at 10% weight loss in the range of 474–502°C. Their films showed the cut‐off wavelengths of 330–361 nm and higher than 80% transparency in a wavelength range of 385–463 nm. Moreover, polymer films exhibited low dielectric properties in the range of 2.76–2.96 at 1 MHz, as well as prominent mechanical properties with tensile strengths of 66.7–97.4 MPa, a tensile modulus of 1.7–2.1 GPa and elongation at break of 7.2%–12.9%. The polymer films also showed outstanding hydrophobicity with the contact angle in the range of 91.2°–97.9°.     

Hyperelectronic polarization in macromolecular solids

Hyperelectronic polarization may be viewed as the electrical polarization in external fields due to the pliant interaction with the charge pairs of excitons, in which the charges are molecularly separated and range over molecularly limited domains. It is particularly pronounced in molecular solids composed of long polymeric molecules having extensive regions of electronic orbital delocalization. Hyperelectronic polarization is regarded as the principal contributor to the high polarizabilities of the following five macromolecular solids: four polyacene quinone radical polymers formed by condensation of aromatic hydrocarbon derivatives with aromatic acids and poly(Cu(II)-N,N′- dimethyl rebeanate). The first four polymers at 100 hz had dielectric constants of 1800–2400, decreasing to about 58–100 at 100,000 hz, with relaxation times of 10^?3 to 10^?4 sec. A sixth polymer, a Schiff-base condensate of 1,4-napthaquinone and p-toluene diisocyanate, however, showed little hyperelectronic polarization, displaying a dielectric constant of 10, constant over 100–100,000 hz. By simple arguments it is shown that the relaxation times and the frequency response of conduction are consonant with the proposed model of charges roaming over long molecular domains (up to 4000 A.) but restricted by molecular boundaries.     

Electrical conductivity of some cationic polysaccharides. I. Effects of polyelectrolyte concentration,charge density,substituent at the ionic group,and solvent polarity

Electrolytic conductivity behavior of some cationic polysaccharides in water, methanol, and the mixtures water/methanol is presented. The polyelectrolytes investigated contain quaternary ammonium salt groups, N‐alkyl‐N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride, attached to a dextran backbone. This study considers the influences of polymer concentration (1 × 10^?6 < C < 1 × 10^?2 monomol L^?1) and the charge density (ξ = 0.48–3.17) modified either by changing charge distance (b) or dielectric constant of the solvent (ε) on polyion–counterion interaction in salt‐free solutions. Above the critical value, ξ_c = 1, the variation of the equivalent conductivity (Λ) as a function of concentration is typical for a polyelectrolyte behavior. The conductometric data in water were analyzed in terms of the Manning's counterion condensation theory. The presence of longer alkyl chains at quaternary N atoms was found to have a negligible influence on the Λ values. The results show that the decrease of the medium polarity results in the decrease of the number of free ions and, consequently, of the equivalent conductivity values. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3584–3590, 2005     

Thermal Decomposition of New Mononuclear NiII Complexes with ONNO Type Reduced Schiff Bases and Pseudo Halogens

Mononuclear nickel(II) complexes were prepared by reaction of the three ONNO type reduced Schiff bases bis‐N,N′‐(2‐hydroxybenzyl)‐1,3‐propanediamine (L^HH₂), bis‐N,N′‐(2‐hydroxybenzyl)‐2,2′‐dimethyl‐1,3‐propanediamine (LDM^HH₂), and bis‐N,N′‐[1‐(2‐hydroxyphenyl)ethyl]‐1,3‐propanediamine (LAC^HH₂) with Ni^II ions in the presence of pseudo halides (OCN^–, SCN^– and N₃^–). The complexes were characterized with the use of elemental analyses, IR spectroscopy, and thermal analyses. The molecular structure of one of the complexes was obtained by single‐crystal X‐ray diffraction. The obtained complexes are mononuclear, and a pseudo halide molecule is attached. One of the oxygen atoms of the ligand is in phenolate and the other was in phenol form. According to the thermogravimetry results, it was thought that the pseudo halide thermally detaches from the structure as hydropseudo halide. In azide‐containing complexes an endothermic reaction was observed although the azide group usually decomposes with an exothermic reaction.     

Poly(1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole‐alt−3,6‐carbazole/2,7‐fluorene) as high‐performance two‐photon dyes

This article reports the synthesis, one‐ and two‐photon absorption, and excited fluorescence properties of poly(1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole‐alt‐N‐octyl‐3,6‐carbazole/2,7‐fluorene) ( PDCZ / PDFL ). PDCZ and PDFL are synthesized by the Suzuki cross‐coupling of 2,5‐dioctyl‐1,4‐diketo‐3,6‐bis(p‐bromophenylpyrrolo[3,4‐c]pyrrole and N‐octyl‐3,6‐bis(3,3‐dimethyl‐1,3,2‐dioxaborolan‐2‐yl)carbazole or 2,7‐bis(3,3‐dimethyl‐1,3,2‐dioxaborolan‐2‐yl)fluorene and have number‐average molecular weights of 8.5 × 10³ and 1.14 × 10⁴ g/mol and polydispersities of 2.06 and 1.83, respectively. They are highly soluble in common organic solvents and emit strong orange one‐ and two‐photon excited fluorescence (2PEF) in THF solution and exhibit high light and heat stability. The maximal two‐photon absorption cross‐sections (δ) measured in THF solution by the 2PEF method using femtosecond laser pulses are 970 and 900 GM per repeating unit for PDCZ and PDFL , respectively. These 1,4‐diketo‐pyrrolo[3,4‐c]pyrrole‐containing polymers with full aromatic structure and large δ will be promising high‐performance 2PA dyes applicable in two‐photon science and technology. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 944–951     

Behavior of nitroxyl radical in the polymerization process forming copolymers bearing diarylnitrone pendants and photocontrol of refractive indices for these copolymers

To establish the reaction condition under which the radical copolymerization of methyl methacrylate (MMA) with α‐(2‐hydroxy‐4‐methacryloyloxyphenyl)‐N‐(2,6‐dimethylphenyl)nitrone (HMDN) proceeds smoothly to give photoreactive copolymers, the effects of the nitrone chromophore on the extent to which the radical polymerization of MMA is inhibited were investigated. It was found that the reversible addition of initiating radical to the CH?N⁺(? O^?) moiety in the nitrone chromophore readily occurs to give the nitroxyl radical. It was also found that the latter radical undergoes an efficient coupling reaction with propagating radical to inhibit the radical copolymerization of MMA with HMDN. However, on raising the reaction temperature and the radical concentration, the copolymerization was successfully carried out. This polymerization condition allowed us to prepare the HMDN/MMA, HMDN/styrene, and HMDN/cyclohexyl acrylate copolymers in good yields. The photoirradiation of the copolymer film prepared on a silicon wafer lowered its refractive index by 0.003–0.023, depending on the relative composition of the diarylnitrone chromophore in these copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 88–97, 2006     

Ethyl 1,4‐Dihydro‐4‐oxo‐1,8‐naphthyridine‐3‐carboxylates by a Tandem SNAr‐Addition‐Elimination Reaction

A series of N‐substituted 1,4‐dihydro‐4‐oxo‐1,8‐naphthyridine‐3‐carboxylate esters has been prepared in two steps from ethyl 2‐(2‐chloronicotinoyl)acetate. Treatment of the β‐ketoester with N,N‐dimethylformamide dimethyl acetal in N,N‐dimethylformamide (DMF) gave a 95% yield of the 2‐dimethylaminomethylene derivative. Subsequent reaction of this β‐enaminone with primary amines in DMF at 120^oC for 24 h then afforded the target compounds in 47–82% yields by a tandem S_NAr‐addition‐elimination reaction. Synthetic and procedural details as well as a mechanistic rationale are presented.     

Unusually highly efficient,singlet state,visible light photoinitiators based on styrylbenzimidazolium phenyltributylborate photoredox pairs for vinyl monomers free radical polymerization

In this article, hemicyanine dye–borate complexes, for example, 1,3‐dimethyl‐2‐[4‐(N,N‐dialkylamino)styryl]benzimidazolium phenyl‐tri‐n‐butylborates, were employed as the novel, very effective photoinitiators operating in the visible light region. The influence of the sensitizers and electron donor structure on the photopolymerization kinetics of multiacrylate monomer was investigated by photo‐DSC. The maximum photopolymerization quantum yield measured for 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate (TMPTA) was about 67 for sample of thickness of about 1 mm under 100 mW/cm² laser irradiation. It was found that the polymerization rate and the final conversion degree were depended on the dye structure. Moreover, the photoinitiating systems described gave a double bond conversion higher than the photoinitiator possessing as chromophore RBAX (Rose Bengal derivative), the common triplet state initiator. Additionally, the rate of photopolymerization depends on ΔG_el of electron transfer between borate anion and styrylbenzimidazolium cation. This latter value was estimated for a series of styrylbenzimidazolium borate salts. The relationship between the rate of polymerization and the free energy of activation for electron transfer reaction gives the dependence predicted by the classical theory of electron transfer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4119–4129, 2009     

Novel routes to aminophosphonic acids: Interaction of dimethyl H‐phosphonate with hydroxyalkyl carbamates

It was found that the reaction of dimethyl H‐phosphonate ( 1 ) with 2‐hydroxyalkyl‐N‐2′‐hydroxyalkyl carbamates at 135°C includes several chemical reaction steps: (i) chemical transformations of 1‐methyl‐2‐hydroxyethyl‐N‐2′‐hydroxyethyl carbamate ( 2 ) and 2‐methyl‐2‐hydroxyethyl‐N‐2′‐hydroxyethyl carbamate ( 3 ); (ii) transesterification of dimethyl H‐phosphonate with 2 and 3 , and with secondary hydroxyl‐containing compounds that are formed during the course of the chemical transformation of 2‐hydroxyalkyl‐N‐2′‐hydroxyalkyl carbamates; (iii) hydrolysis of 1 and dialkyl H‐phosphonates, formed via transesterification of 1 with secondary hydroxyl‐containing compounds. The interaction was studied by means of ¹H, ¹³C, ³¹P NMR, and FAB mass spectroscopy. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:119–124, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20404