Phase-transfer-catalyzed free-radical polymerization: Kinetics of polymerization of methyl methacrylate using ammonium peroxydisulfate/hexadecyl pyridinium chloride in ethyl acetate/water

The kinetics of phase-transfer-catalyzed free-radical polymerization of methyl methacrylate using the system ammonium peroxydisulfate/hexadecyl pyridinium chloride have been investigated in the temperature range of 50–60°C in ethyl acetate/water two-phase systems. The superior efficiency of the phase-transfer-catalyzed reaction in comparison with polymerization initiated by oil soluble initiators such as 2,2′-azobisisobutyronitrile and benzoylperoxide has been demonstrated. Rate of polymerization increased with increase in concentration of the quaternary salt but showed a tendency to level off at higher concentrations. Increase in the peroxydisulfate concentration also resulted in an increase in the rate at lower concentrations, but was found to decrease at higher concentrations. The order with respect to the monomer was found to be approximately unity. The title reaction has been found to be not truly phase-transfer catalyzed in character as claimed by previous workers. A suitable kinetic scheme has been proposed to account for the experimental data and its significance discussed.     

Macrocycles in the construction of acyclic stereochemistry

The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products.     

Proton spin-lattice relaxation studies. N-aryl-1-isoindolinones

Proton spin-lattice relaxation rates (R₁ values) have been measured, at 270 MHz, for a series of N-aryl isoindolinones. A normalization procedure has been used to enable comparison of R₁ values in different compounds by minimizing the effects on relaxation rates of changes in motional correlation times accompanying changes in substitution patterns. A substantial (4.3-fold) dynamic range of R₁ values has been observed, and individual values have been correlated with the molecular environments of the nuclei. There is evidence for an interring relaxation process.     

Computational strategies for evaluating barrier heights for gas-phase reactions of lithium enolates

Gas-phase activation energies were calculated for three lithium enolate reactions by using several different ab initio and density functional theory (DFT) methods to determine which levels of theory generate acceptable results. The reactions included an aldol-type addition of an enolate to an aldehyde, a proton transfer from an alcohol to a lithium enolate, and an S(N)2 reaction of an enolate with chloromethane. For each reaction, the calculations were performed for both the monomeric and dimeric forms of the lithium enolate. It was found that transition state geometry optimization with B3LYP followed by single point MP2 calculations generally provided acceptable results compared to higher level ab initio methods.     

ESR STUDY OF ORIENTED TRIPLET MOLECULES GENERATED BY EXCITATION WITH POLARIZED LIGHT

Abstract— The lowest-lying triplet states of a variety of aromatic molecules and complexes have been generated by the irradiation of these compounds in solvent glasses with plane-polarized light. Measurements of the allowed (Δ M=± 1) ESR transitions clearly demonstrate that the triplets so formed are oriented with respect to the external magnetic field. By this method the triplet zero-field splitting parameters, D and E , can be evaluated simply and reliably. Intramolecular energy transfer is postulated to explain the triplet spectra of Zn( o -phen)₂(NO₃)₂ and Zn( o -phen)₃(NO₃)₂. It was observed that in triplet-triplet energy transfer from benzophenone to naphthalene there is no apparent orientation requirement between the donor and acceptor molecules. Further areas of significance and application of this technique are suggested.     

Reductive Amination of Aldehydes and Ketones with Sodium Triacetoxyborohydride. Studies on Direct and Indirect Reductive Amination Procedures(1)

Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the reaction includes aliphatic acyclic and cyclic ketones, aliphatic and aromatic aldehydes, and primary and secondary amines including a variety of weakly basic and nonbasic amines. Limitations include reactions with aromatic and unsaturated ketones and some sterically hindered ketones and amines. 1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF) and occasionally in acetonitrile. Acetic acid may be used as catalyst with ketone reactions, but it is generally not needed with aldehydes. The procedure is carried out effectively in the presence of acid sensitive functional groups such as acetals and ketals; it can also be carried out in the presence of reducible functional groups such as C-C multiple bonds and cyano and nitro groups. Reactions are generally faster in DCE than in THF, and in both solvents, reactions are faster in the presence of AcOH. In comparison with other reductive amination procedures such as NaBH(3)CN/MeOH, borane-pyridine, and catalytic hydrogenation, NaBH(OAc)(3) gave consistently higher yields and fewer side products. In the reductive amination of some aldehydes with primary amines where dialkylation is a problem we adopted a stepwise procedure involving imine formation in MeOH followed by reduction with NaBH(4).     

Stochastic coupling and thermodynamic inequalities

Let ₁ and ₂ be thermodynamic Gibbs measures on ^m and ⁿ , respectively. Diffusions are constructed having ₁, and ₂ as invariant measures. These diffusions are then coupled; inequalities between expectations of certain random variables on the two spaces result.Partially supported by NSF-MCS 74-07313-A03     

Degenerative transfer living Ziegler-Natta polymerization: application to the synthesis of monomodal stereoblock polyolefins of narrow polydispersity and tunable block length

The neutral dimethyl pentamethylcyclopentadienylzirconium acetamidinate, (eta(5)-C(5)Me(5))ZrMe(2)[N(t-Bu)C(Me)N(Et)], can serve as a highly active initiator for the living Ziegler-Natta polymerization of alpha-olefins to produce polyolefins of narrow polydispersity (D < or = 1.05) when "activated" through mono demethylation by a substoichiometric amount of the borate, [PhNMe(2)H][B(C(6)F(5))(4)]. The mechanism by which this living polymerization proceeds is through a process of degenerative transfer involving rapid and reversible methyl group exchange between cationic (active) zirconium propagating centers and neutral (dormant) methyl, polymeryl zirconium end groups. Facile metal-centered epimerization of the dormant species is responsible for a loss of stereocontrol during propagation that produces iso-rich material in contrast to the pure isotactic polymer microstructure obtained when degenerative transfer is not present. By turning degenerative transfer "on" and "off" between successive monomer polymerizations, a successful strategy for the production of monomodal stereoblock polyolefins of narrow polydispersity and tunable block length has been demonstrated.     

Bifunctional Lewis acid-nucleophile-based asymmetric catalysis: mechanistic evidence for imine activation working in tandem with chiral enolate formation in the synthesis of beta-lactams

We report a mechanistically based study of bifunctional catalyst systems in which chiral nucleophiles work in conjunction with Lewis acids to produce beta-lactams in high chemical yield, diastereoselectivity, and enantioselectivity. Chiral cinchona alkaloid derivatives work best when paired with Lewis acids based on Al(III), Zn(II), Sc(III), and, most notably, In(III). Homogeneous bifunctional catalysts, in which the catalyst contains both Lewis acidic and Lewis basic sites, were also studied in detail. Mechanistic evidence allows us to conclude that the chiral nucleophiles form zwitterionic enolates that react with metal-coordinated imines. Alternative scenarios, which postulated metal-bound enolates, were disfavored on the basis of our observations.