Synthesis of Organoplatinum Poly(dendrimer)s: Pronounced Effect of Size and Geometry of Small Organoplatinum Linkers on the Copolymerization Efficiency with Bifunctional Dendritic Macromonomers

The copolymerizations of two series of surface functionalized bis(acetylene) G1–G3 dendrimers, one ( S ‐ Gn ) having a structural rigid skeleton and the other ( L ‐ Gn ) a relatively more flexible architecture, with two platinum linkers, cis‐[(Et₂PCH₂CH₂PEt₂)PtCl₂] ( 2 ) and [Cl(Et₃P)₂Pt‐C?C‐p‐C₆H₄‐]₂ ( 3 ) were investigated. For both series of dendrimers, only linear and/or cyclic oligomers were formed when the cis‐platinum linker 2 was used. However, high molecular weight (100–200 kD) organoplatinum poly(dendrimer)s were obtained from both series when the elongated linear rod‐liked platinum linker 3 was employed and the formation of cyclic oligomers was greatly suppressed for both the structural rigid S ‐ Gn and the structural flexible L ‐ Gn series. These results are in sharp contrast to our earlier findings (S.‐Y. Cheung, H.‐F. Chow, T. Ngai, X. Wei, Chem. Eur. J. 2009 , 15, 2278–2288) obtained by using a shorter linear platinum linker trans‐[Pt(PEt₃)₂Cl₂] ( 1 ), where a larger amount of cyclic oligomers was formed from the structural flexible L ‐ Gn dendrimers. A model was proposed to rationalize how the geometry and size of the platinum linker could control the copolymerization behaviours of these dendritic macromonomers.     

Cationic oligomerization of anethole: Selective synthesis of dimers and trimers

A linear unsaturated dimer of anethole [II, (E)-1,3-bis(p-methoxyphenyl)-2-methylpentene-1], was prepared in 98% yield with an acetyl perchlorate (AcClO₄) catalyst in a nonpolar solvent (C₆H₆) at a high temperature (70°C). At 0°C a linear unsaturated trimer was formed in high yield with dimer II. The geometric structure of the linear unsaturated dimers was determined by analysis of the nuclear Overhauser effect (NOE) on their ¹H-NMR spectra. NOE analysis showed that at 0°C with AcClO₄, trans-anethole gives the (E)-form (II), whereas cis-anethole yields the (Z)-form. On the other hand, with a metal-halide catalyst (BF₃OEt₂) a cyclic dimer and a cyclic trimer were produced in high yields in a polar solvent [(CH₂Cl₂)] at 70°C; higher oligomers (≥ tetramer) were scarcely formed. The effect of catalysts on the structure of oligomers was explained in terms of the interaction between a growing carbocation and a counterion.     

Multifunctional coupling agents for living cationic polymerization. IV. Synthesis of end-functionalized multiarmed poly(vinyl ethers) with multifunctional silyl enol ethers

Telechelic ( 8 ) and end-functionalized four-arm star polymers ( 9 ) were synthesized through the coupling reactions of end-functionalized living poly(isobutyl vinyl ether) ( 5; DP _n ～ 10) with the bi-and tetrafunctional silyl enol ethers, H_4-nC? [CH₂OC₆H₄C(OSiMe₃) = CH₂]_n ( 3: n = 2; 4: n = 4). The precursor polymers 5 were prepared by living cationic polymerization with functionalized initiators, CH₃CH(Cl)OCH₂CH₂X(6), in conjunction with zinc chloride in methylene chloride at ?15°C. The initiators 6 were obtained by the addition of hydrogen chloride gas to vinyl ethers bearing pendant functional groups X , including acetoxy [? OC(O)CH₃], styryl (? OCH₂C₆H₄-p-CH = CH₂), and methacryloyl [? OC(O)C(CH₃) = CH₂]. The coupling reactions with 3 and 4 in methylene chloride at ?15°C for 24 h afforded the end-functionalized multiarmed polymers ( 8 and 9 ) in high yield (>91%), where those with styryl or methacryloyl groups are new multifunctional macromonomers. © 1994 John Wiley & Sons, Inc.     

Electrospray ionization mass spectrometry of organogermanium compounds

A detailed study of the solution chemistry and mass spectrometry of six carboxylato-organogermanium compounds in aqueous solution has been carried out using electrospray ionization and MSⁿ techniques. The different types of hydrolysis products and their probable structures, which include the oligomers and their fragment ions plus water adduct ions formed by ion-molecule reactions, are presented, e.g., HO-cyclic-(-Ge(O⁻)CH₂CH₂COO) A, HO-cyclic-(-Ge(O-cyclic-(Ge(O⁻)CH₂CH₂COO)CH₂CH₂COO) B, ⁻OGeO-cyclic-(-Ge(OH)CH₂CH₂COO) C, and ⁻CH=CHGeO-cyclic-(-Ge(OH)CH₂CH₂COO) D, etc. The proposed cyclic structures are confirmed by theoretical calculations. Copyright © 2001 John Wiley & Sons, Ltd.     

Cationic Polymerization of Hexamethylcyclosiloxane (D3): Kinetics and Mechanism of Cyclics Formation

In cationic polymerization of hexamethylcyclotrisiloxane (D₃) in methylene chloride, a control of the mol wts could be observed with various initiators such as RCOCl/ SbCl₅ or trifluoromethanesulfonic acid (TfOH) and its derivatives. But an important difference with usual living polymerizations is the simultaneous formation of large amounts of cyclic oligomers D_3x, their weights increasing linearly from the origin. A second population of much larger DPn has been shown to consist of macrocycles (MC). It was concluded that while MC result from end-to-end ring closure of a fraction of linear macromolecules, the small D_3x cycles (essentially D₆) are formed independently by a selective back-biting reaction involving oxonium end-groups. However, it has been proposed again in recent publications in which various initiators were used (including TfOH) that D_3x cyclics of all sizes result from end-to-end ring closure reactions between the (electrophilic) active site for propagation and a silanol end group. In the present paper, the initiator used was the mixed anhydride of trifluoroacetic and trifluoromethanesulfonic acid, which give non-nucleophilic CF₃CO₂(CH₃)₂Si end-groups. The residual acid present in the anhydride was neutralized by varying amounts of 4-methyl,2,6-di-t-butylpyridine (MDTBP). The linear increase of the HP molecular weight and the formation of large amounts of D_3x oligomers were observed again. The weight ratio of D₆ was larger than for TfOH initiation (1 < D₆/HP < 1,5) and when a large excess of MDTBP on the acid was used, D₆/HP was even higher but MC formation was completely suppressed. This confirms the difference in the mechanisms giving MC and D₆ and agrees with small D_3x cyclics formation involving the silyltriflate end-groups alone (and probably the derived oxonium sites).     

Synthesis and Structure of Cyclic Selenium Oxide SeVISe2IVO7

Nitromethane is the only presently known organic solvent for highly reactive selenium trioxide (SeO₃)₄. The stability of the solutions is limited and the beginning of the reaction between both components depends significantly on concentration and temperature. The nitromethane solvate of cyclic triselenium heptoxide Se₃O₇ · CH₃NO₂ is the major solid product at the temperature 20–30°C and concentration range 3–20% SeO₃. Crystal and molecular structure of this compound was determined by X-ray structure analysis and vibrational spectroscopy. The solvating molecule CH₃NO₂ is removable from Se₃O₇ · CH₃NO₂ in vacuo. If reaction temperature does not exceed 10°C, selenium pentoxide (Se₂O₅)_n is formed instead of Se₃O₇ · CH₃NO₂. Dinitrosyl triselenate (NO)₂Se₃O₁₀, nitrosyl hydrogendiselenate NOHSe₂O₇, nitrosyl hydrogenselenate NOHSeO₄, nitrosyl hydrogenselenatoselenite NOHSe₂O₆ and selenium dioxide (SeO₂)_n were further identified in the solid reaction products. The selenic and/or oligoselenic acids remains in the nitromethane solution. CO₂ and N₂O₃ were found as gaseous products.     

Synthesis and characterization of ferromagnetic Fe3C/C composite nanoparticles as a catalyst for carbon nanotube growth

Polystyrene template microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. These template particles dispersed in aqueous solution have been used for the entrapment of ferrocene by a swelling process of methylene chloride emulsion droplets containing ferrocene within these particles, followed by evaporation of methylene chloride. The effects of CH₂Cl₂ volume and the [CH₂Cl₂]/[FeC₁₀H₁₀] (w/w) ratio on the size and size distribution of the swollen template particles were elucidated. Air-stable Fe₃C nanoparticles embedded in amorphous carbon matrix (Fe₃C/C) have been prepared by thermal decomposition of the ferrocene-swollen template polystyrene particles at 500 °C for 2 h in a sealed cell. Decomposition of these swollen template particles for 2 h at higher temperatures led to the formation of carbon nanotubes (CNTs) in addition to the Fe₃C/C composite nanoparticles. The yield of the CNTs increased as the annealing temperature was raised. An opposite behavior was observed for the diameter of the formed CNTs. The size and size distribution, crystallinity, and magnetic properties of the different Fe₃C/C composite nanoparticles have also been controlled by the annealing temperature.     

Ring-Opening Metathesis Polymerization of Cyclooctyne Employing Well-Defined Tungsten Alkylidyne Complexes

Summary: The ring-opening metathesis polymerization of cyclooctyne was studied was studied in the presence of catalytic amounts of the tungsten alkylidyne complexes [RCW(NIm^tBu){OCMe(CF₃)₂}₂] ( 1a: R = CMe₃, 1b: R = Ph). The resulting polymers show relatively narrow polydispersities with the PDI ranging from 1.2 to 2.4. Treatment of 1b with cyclooctyne in dilute toluene or hexane solution afforded only low molecular weight oligomers. The mass spectra of these oligomers indicate the existence of macrocycles of the formula [C(CH₂)₆C]_n (n = 3–9). In contrast, reactions at high substrate concentration led to mixtures of cyclic oligomers and linear polymers, which is probably a result of ring-chain equilibria, established in agreement with the Jacobson-Stockmayer theory of macrocyclization. In contrast, treatment of neat cyclooctyne with a catalytic amount of the catalyst produced medium molecular weight polymers in good yields.     

Linear and Cyclic Enkephalin Pseudopeptides. Use of RP-HPLC to Separate and Identify Diastereomers Formed during Synthesis

Abstract

During the course of synthesis of both a linear and a cyclic enkephal in pseudopeptide containing a ψ[CH₂S] amide bond replacement, two isomeric products were produced in each case in virtually equimolar quantities. RP-HPLC was used to: 1) isolate and characterize both pairs of products; 2) confirm their sulfide content by partial oxidation to their ψ[CH₂SO] equivalents, with two new pairs of diastereomeric sulfoxides formed in each case, and 3) confirm that the isomers were formed by epimerization of the C-terminal alpha carbon of the pseudopeptide, H-Tyr-D-Ala-Gly-Pheψ[CH₂S]Leu-OH and its cyclic counterpart in an early synthetic step. Both the presence and the absolute configurations of the new epimeric center were further established by RP-HPLC. This involved acid catalyzed hydrolysis and comparison of the resulting HPLC-isolated pseudodipeptides with authentic species of Pheψ[CH₂S]Leu and Pheψ[CH₂S]D-Leu prepared by controlled stereochemical routes.     

THE REACTION OF METHYLENE WITH METHYL CHLORIDE THE EFFECT OF EXCESS ENERGY IN METHYLENE

Abstract This paper reports studies of the reaction between methyl chloride and methylene produced by the photolysis of ketene in the two spectral regions Λ? 2600 Å to 3200 Å and Λ? 3220 Å. The course of reactin is best described by an abstraction process CH₂+ CH₂CI—Ch₂CI + CH₃ followed by recombination of the CH₃ and CH₂ Cl radicals to yield C₂H₅, C₂H₅Cl, C₂H₄Cl₂. The recombination processes are highly exothermic, and excitation of the product molecules occurs, which in the case of C₂H₅Cl and C₂H₄Cl₂ leads to some unimolecular decomposition. It is shown that the rate constant for the decomposition of ethyl chloride depends upon the wavelength of the radiation used to photolyse the ketene, and it is suggested that the excess energy with which the methylene is born is handed on to the alkyl radicals. A simplified kinetic analysis of the system is given, and it is shown that the relative reactivity of methylene towards ketene and methyl chloride increases with an increase in the energy of the methylene. The rates of product formation predicted on the basis of the kinetic scheme agree satisfactorily with the measured values. “Insertion” of methylene into C-H and C-CI bonds has been postulated by other workers. The present results are inconsisistent with an insertion mechanism, since such a mechanism does not account for all the observed products. The effect of wavelength of photolysis and of total pressure predicted on the basis of an insertion process is the reverse of that observed experimentally.     

Methylene chloride chemical ionization of fumaric and maleic acids and their esters

The chemical ionization (CI) mass spectrometry of fumaric and maleic acids and their esters with methylene chloride as reagent gas is described. The introduction of methylene chloride to the CI(CH₄) plasma led to the formation of new characteristic ions in addition to the protonation and the subsequent fragmentation, revealing diagnostic information on the configuration of geometrical isomers. The new characteristic ions have been found to arise from the addition of the reactant ion of methylene chloride, [CH₂Cl]⁺, to the substrates and, for higher dialkyl esters, from the further McLafferty rearrangement of the adduct ion [M + CH₂Cl]⁺.     

Synthesis of poly(phosphonosiloxane) and its cyclic monomer via hydrosilylation and phosphonylation of vinylbenzyl chloride

Phosphonylation of polysiloxane and cyclosiloxane oligomers is described. Hydrosilylation of vinylbenzyl chloride (VBC) with a poly(methylhydrosiloxane), or its cyclic monomer, followed by phosphonylation with triethyl phosphite leads to the production of stable phosphonosiloxanes that are characterized by  Si C and  C P bonds. The polymer, which is a liquid with a glass transition temperature of −38.3 °C, is soluble in alcohols and an alcohol and water mixture. The phosphonylated siloxanes dissolve and chelate uranyl nitrate and transition metal salts. The hydrosilylation of VBC yields α and β isomers:  Si CH₂ CH₂ and  Si CH(CH₃); the ratio between these two depends upon the type of solvent and the reaction conversion. A kinetic study of the hydrosilylation reaction of VBC suggests a second order in respect to the reactants. The reaction rate is dependent upon the catalyst concentration and temperature. Hydrosilylation of vinylbenzyl phosphonate could not be accomplished with the platinum (complex) catalyst; this is attributed to the presence of phosphoryl groups that are strong electron donors. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4043–4053, 1999     

Acid-base properties of substituted tetraphenylmethylenediphosphine dioxides

Conclusions Some tetraphenylmethylenediphosphine dioxides, substituted in the methylene bridge, were subjected to potentiometric titration in nitromethane with perchloric acid. The obtained values of the pK _a basicity constants (CH₃NO₂) obey a linear relationship with the ^* constants of the substituents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 199–201, January, 1972.     

Mechanism and rate constants of the CH2 + CH2CO reactions in triplet and singlet states: A theoretical study

Ab initio and density functional CCSD(T)-F12/cc-pVQZ-f12//B2PLYPD3/6-311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH₂ with ketene CH₂CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus-Master Equation (RRKM-ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin-forbidden triplet-singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH₃ and C₂H₄ + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C₂H₄ + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet-singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH₂COCH₂ intermediate or along the pathway of CO elimination from the initial CH₂CH₂CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C₂H₄ + CO. The formation of these products mostly proceeds via a well-skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH₃CHCO and cyclic CH₂COCH₂ intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.     

Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry

Oligomeric peroxides formed in the synthesis of triacetone triperoxide (TATP) have been analyzed by mass spectrometry utilizing both electrospray ionization (ESI) and chemical ionization (CI) to form sodiated adducts (by ESI) and ammonium adducts (by CI and ESI). Tandem mass spectrometry and deuterium isotopic labeling experiments have been used to elucidate the collision‐induced dissociation (CID) mechanisms for the adducts. The CID mechanisms differ for the sodium and ammonium adducts and vary with the size of the oligoperoxide. The sodium adducts of the oligoperoxides, H[OOC(CH₃)₂]_nOOH, do not cyclize under CID, whereas the ammonium adducts of the smaller oligoperoides (n < 6) do form the cyclic peroxides under CID. Larger oligoperoxide adducts with both sodium and ammonium undergo dissociation through cleavage of the backbone under CID to form acyl‐ and hydroperoxy‐terminated oligomers of the general form CH₃C(O)[OOC(CH₃)₂]_xOOH, where x is an integer less than the original oligoperoxide degree of oligomerization. The oligoperoxide distribution is shown to vary batch‐to‐batch in the synthesis of TATP and the post‐blast distribution differs slightly from the distribution in the uninitiated material. The oligoperoxides are shown to be decomposed under gentle heating. Copyright © 2009 John Wiley & Sons, Ltd.     

The synthesis and characterization of poly(methylene terephthalate)

Poly(methylene terephthalate) (1GT) has been synthesized via the reaction of cesium or potassium terephthalates with dibromomethane or bromochloromethane in N-methylpyrrolidone at temperatures of 80–125°C. The polymerization was relatively slower with the latter substrate, though the potassium salt was found to be equally as efficient as its cesium counterpart with dibromomethane. The polymer is insoluble in all common polyester solvents, and its high molecular weight nature (DP _n ≥ 25) was inferred from elemental analyses and its fiber forming capacity. Thermal analyses indicated that 1GT possesses poor thermal stability and decomposes rapidly during melting, the initial process being thought to be the splitting out of formaldehyde. 1GT polymers were shown to contain a homologous series of cyclic oligomers (from dimer to decamer); the two most predominant were tentatively identified as the cyclic trimer and tetramer. No change in the cyclization efficiency was observed when the potassium counterion was substituted for cesium with Br CH₂ Br whereas a drastic reduction in the cyclic content was obtained using Br CH₂ Cl (with Cs⁺). The two most important features of the polymerization are the insensitivity of the reaction to the stoichiometric equivalence of the reactants and the production of reasonably high molecular weights at low conversions. It is suspected that the polymerization might be occurring through an interfacial mechanism.     

Crosslinking of polystyrene under friedel–crafts conditions in dichloroethane and carbon tetrachloride solvents through the formation of strongly colored polymer–AlCl3–solvent complexes

Polystyrene was crosslinked in either 1,2-dichloroethane or carbon tetrachloride in the presence of aluminum chloride. Apparently, the reactions involve Friedel–Crafts substitution of phenyl ring with CH₂CH₂Cl or CCl₃ groups, which than participate in crosslinking, giving CH₂CH₂ or CCl₂, CCl, and C bridges. In the first stage a charge-transfer complex is formed between AlCl₃, polystyrene and the solvent. After heating this complex above 35–40°C a rapid formation of HCl occurs and a crosslinked polymer is formed. This final product is insoluble, infusible, and inflammable. It decomposes at 400°C without melting.     

Radiolyse des hydrocarbures. 21e communication. Mécanismes radicalaires et non-radicalaires dans les n-alcanes en phase liquide

Contributions of radical and non-radical processes have been determined in the formation of radiolysis products of n-heptane, n-octane, n-nonane and n-decane in a large range of temperature. Calculations are based on the combination and the dismutation of radicals, both reactions having nearly the same importance. Hydrogen abstraction reactions become important above – 25°. Intermediate molecular weight products and dimers are formed by statistical combination of the various radicals resulting from C? C and C? H scission. At low temperature, low molecular weight products are formed by both radical and non-radical processes, the second one being more important (3/4 for alcanes and 2/3 for olefins). The yield of radicals increases with the chain length of the irradiated n-alkane and amounts to 4.5 for n-heptane and 6.8 for n-decane at – 25°. This increase is due only to radicals from C? H scission, while the yield of radicals from C? C scission remains constant. Scission of CH₂? CH₂ bonds is favored for bonds inside the molecule, but this affect diminishes with chain length and CH₂? CH₂ rupture is equally probable at all positions for n-alcanes heavier than decane. Methyl C? H scission is 2.7 times less probable than methylene C? H scission. The radiolysis of mixtures of protonated and deuterated n-alcanes is shown to be able to give information concerning basic processes in radiation chemistry.     

Hydrogen bonding of 1- and 2-substituted tetrazoles with conventional proton donors

Dissociation constants of H-complexes formed by 1- and 2-substituted tetrazoles with 4-fluorophenol in carbon tetrachloride and methylene chloride were determined by Fourier-transform IR spectroscopy. The nature of substituents on the endocyclic nitrogen and carbon atoms was found to weakly affect the pK _HB value. By contrast, the position of the N-substituent is significant. For example, 1-methyl-5-phenyl-1H-tetrazole (pK _HB = 0.66 in CH₂Cl₂) is a stronger proton acceptor than 2-methyl-5-phenyl-2H-tetrazole (pK _HB = 0.05 in CH₂Cl₂). The proton affinity of the examined compounds appreciably decreases in going from less polar carbon tetrachloride to more polar methylene chloride. No general correlation was revealed between the pK _HB values of substituted 1H- and 2H-tetrazoles and shifts of the OH stretching vibration frequency of methanol (Δν) upon formation of H-complexes.     

Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride initiated with methylene iodide and catalyzed by sodium dithionite

Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) initiated with methylene iodide (CH₂I₂) and catalyzed by sodium dithionite (Na₂S₂O₄) in water at 35 °C produces a telechelic poly(vinyl chloride) (LRP–PVC) with two different active chain ends: ICH ₂ (CH₂CHCl)_n‐1CH₂ CHClI , and 2.0 functionality. The reactivity and initiator efficiency of CH₂I₂ in SET–DTLRP of VC was lower than those of iodoform. A possible mechanism for the CH₂I₂‐initiated SET–DTLRP of VC was suggested. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 773–778, 2005