Loss of H2O from M + t-Butyl Complex Ions of Benzyl Alcohol in Isobutane Chemical Ionization Mass Spectrometry

In isobutane chemical ionization mass spectrometry benzyl alcohol exhibits ions at m/z 147 (‘M + 39’) that arise by a loss of H₂O from [M + C₄H₉]⁺, i.e. ‘M + 57’ complex ions. Electrophilic aromatic substitution of a proton at an ortho-position of neutral C₆H₅CH₂OH with [t-C₄H₉]⁺ and, alternatively, nucleophilic substitution of H₂O at the benzylic carbon in \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm C_6 H_5 CH_2}\mathop {\rm O}\limits^+ {\rm H}_2 $\end{document} with CH₂?C (CH₃)₂ are discussed as possible pathways. Evidence in favor of the latter is derived from the analysis of C₆D₅CH₂OH and C₆H₅CD₂OH for the origin of the H-atoms lost in H₂O. The inferred ion structure of m/z 147 is verified by mass-analyzed ion kinetic energy (MIKE.) measurements of its collision-activated (CA.) decomposition. MIKE./CA. spectra of mass-selected m/z 147 ions, once generated by (CI(i-C₄H₁₀) from benzyl alcohol and, once, from 2-methyl-4-phenyl-2-butanol match closely and, thus, reflect identical ion structures. With reference to the simple genesis of this ion from the latter precursor, the structure in question can be concluded to be \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm C_6 H_5 CH_2 CH_2}\mathop {\rm C}\limits^+ ({\rm CH}_3)_2 $\end{document} .     

Graft modification of poly(vinyl chloride) and related reactions

Cationically polymerizable olefins can be efficiently grafted onto poly(vinyl chloride) in the presence of alkylaluminum compounds. The substitution of labile chlorines in PVC by various branches yields a product of improved thermal stability as compared with unmodified PVC. Thus the grafting of a few per cent of polyisobutylene or poly-butadiene onto PVC gives graft copolymers superior in thermal stability to the PVC backbone, as determined by thermogravimetric and differential thermal analyses as well as color development of molded films. At advanced stages of thermal degradation the thermal stability of poly(vinyl chloride)-g-isobutylene) (PVC-g-PIB is some 40°C superior to the unmodified PVC. In addition to grafting of polymer chains onto the PVC backbone, other methods are also available to achieve improved thermal stability. In pentane suspension, alkylaluminum compounds efficiently alkylate labile chlorines in PVC, and the product exhibits improved thermal stability. Alternatively, PVC carbonium ions can alkylate aromatic compounds, and these products also exhibit high heat stability. Based on the assumption that certain alkylaluminums quantitatively react with labile chlorines in PVC, it was estimated that 2–3% of the chlorines present in suspension-grade PVC are labile.     

Monocarbaborane anion chemistry. An interesting encapsulation of the Pd2I2(P(C6H(4)-4-Me)3)4]2+ cation by a pair of [PhCB9H4I(C6H4Me)4]- anions

Reaction of the [1-Ph-closo-1-CB9H(4)-6,7,8,9,10-I5]- anion with 4-MeC6H4MgBr in the presence of [PdCl2(PPh3)2] gives the [Pd2I2(P(C6H(4)-4-Me)3)4]2+ salt of the [1-Ph-closo-1-CB9H(4)-10-I-6,7,8,9-(C6H(4)-4-Me)4]- anion, which exhibits an unusual neutral supramolecular assembly in the solid state, in which the dipalladium dication is encapsulated by two four-armed 'tetrapus' anionic units; the anion also has potentialities for four-fold dendrimer construction.     

Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the Au^I d¹⁰ metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of Au^I–Au^I interactions in 2 a , b .     

Living Carbocationic Polymerization. LVII. Kinetic Treatment of Living Carbocationic Polymerization Mediated by the Common Ion Effect

Abstract

The effect of anion concentration on the apparent rate constant of polymerization k^A _p of isobutylene (IB) induced by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄ initiating system using the CH₂Cl₂/nC₆H₁₄ (60/40 v/v) solvent system at ?40 and ?80°C was studied by the use of nBu₄NCl. Computer simulation has shown that k^A _p decreases several orders of magnitude upon the addition of even a very small amount of common anion TiCl^?- ₅ to the charge. The rate of change is reduced in the concentration range of experimental interest. It was concluded that the decrease of k^A _p with increasing TiCl ^?- ₅ concentration is mainly due to the decreasing contribution of propagation by free ions. The contribution (%) of propagation by free ions to the apparent rate of propagation was calculated.     

Copolyesters Containing Polyisobutylene Soft Segments and Polybutylene Terephthalate as the Crystalline Segments

Abstract

The preparation and characterization of multiblock copolymers consisting of polyiso-butylene (PIB) soft segments connected to dimethyl terephthalate (DMT) plus 1,4-butane diol (BD) hard segments (PIB-b-PBT)_n are described. Syntheses involved solution poly-condensation of DMT + BD + hydroxyl ditelechelic PIB (HO-PIB-OH). The overall block composition, and the lengths of the soft segments were varied in the M_n,PIB=1,400–10,000 g/mol range. The presence of PIB in the multiblocks was demonstrated. The solubility in THF and other solvents, and extractability of the polymers with n-hexane were studied. Efforts to determine solution viscosity remained unsuccessful due to the insolubility of the polar and nonpolar segments in a common solvent. Mechanical testing gave unacceptable results, however, the multiblocks showed good thermal stability (up to 367°C in air) and melt processibility appears to be feasible.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].