Copolymerization of styrene. V. Copolymerization with α-cyanocinnamamide

Copolymers of styrene with α-cyanocinnamamide were prepared by free radical initiation in bulk and in DMF solution and also by thermal initiation in bulk. The copolymerization parameters were determined by the conventional scheme of copolymerization and by an improved scheme taking into account the penultimate unit. Different values of the copolymerization parameters were obtained at the above mentioned different polymerization conditions, indicating the existence of a solvent effect. The influence of the comonomer on some of the basic properties, like intrinsic viscosity, solubility, melting range, and glass transition temperature and on some mechanical and behavior properties of the copolymers was studied in comparison with homopolystyrene.     

The reaction of 2-picoline N-Oxide with o-substituled benzoates and lsatoic anhydrides

The reaction of 2-picoline N-Oxide anion with o-substituted henzoates and isatoic anhydrides to give synthetically useful l-(2-methoxyphenyl)-2-(2-pyridinyl)ethanone N-oxides, I-(2-hydroxy-phenyJ)-2-(2-pyridinyl)ethanone N-oxides and I -(2-arninopheny])-2-(2-pyridinyl)ethanone N-oxides is described.     

Characterization of internal salts by laser mass spectrometry

An intermolecular alkyl transfer reaction (ATR) leading to ion-pair formation has been observed for internal salts by using laser mass spectrometry (l.m.s.). Positive- and negative-ion spectra both show evidence for alkyl transfer. Both the LAMMA-500 (transmission) and LAMMA-1000 (reflection) laser mass spectrometers were used. The positive-ion laser mass spectra obtained by these two instruments show some significant differences; no significant differences were observed in the negative-ion spectra. Results obtained for quaternary ammoniohexanoates as a function of laser power indicate that the extent of ATR is greater at high laser power. Addition of a small amount of p-toluenesulfonic acid to the ammoniohexanoates reduces fragmentation and enhances the intensity of the quasimolecular ion (M + H)⁺ relative to ATR. Results from deuterated sultaines were used to confirm intermolecular alkyl transfer and to elucidate some fragmentation processes. Field-desorption (f.d.) mass spectra of internal salts show similarities and differences from l.m.s.; not all internal salts showed the alkyl transfer reaction in f.d. Cluster ion formation was observed in f.d.m.s. but not in l.m.s.     

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li⁺, Na⁺, K⁺, F^– and Cl^– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.     

The oxidative cyclization of n-phenyl-3-methylthiopropylamines to form N-phenyl-s-methylisothiazolidinium salts

A series of N-phenyl-3-methylthiopropylamine hydrochlorides were prepared by reacting a series of anilines with methional and sodium cyanoborohydride. These were cyclized upon oxidation by N-chloro-succinimide to the corresponding N-phenyl-S-methylisothiazolidinium derivatives which were isolated as the tetraphenylborate salts. Compounds successfully prepared included the m-methyl, p-methyl, m-methoxy, and p-methoxyphenyl derivatives.     

Organosilicon compounds : LI. Further studies of the base-catalysed solvolysis of N-(triorganosilyl)anilines

Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC₆H₄NHSiEt₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO₂, 18; p-CN, ca. 43; p-NO₂, ca. 120. (ii) For PhNHSi(C₆H₄Y)₃ compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R₃ =) Et₃, 1.0; Et₂Me, 18 (at 30°); Me₂-i-Pr, 8 (at 30°);Me₂-t-Bu, 0.012 (at 50°);i-Pr₃, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ^?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed.     

Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

Theoretical and experimental reevaluation of the basicity of lambda3-phosphinine

We have investigated the basicity of phosphinine (C5H5P, phosphabenzene) in reevaluating its proton affinity (PA) and gas-phase basicity (GB) and the pK(a) value of its protonated form. As a necessary step, we have first determined its gas-phase proton affinity. Using both mass spectrometric and quantum chemical methods, we have obtained the values PA(C5H5P) = 195.8 +/- 1.0 kcal mol(-1) and GB(298)(C5H5P) = 188.1 +/- 1.0 kcal mol(-1), in good agreement with previous results. We then derived a value of pK(a)(C5H6P+) = -16.1 +/- 1.0 in aqueous solution using three different approaches: the latter markedly differs from the currently available value of -10. The reason for such a discrepancy in the pK(a) of protonated phosphinine in solution is discussed. In the theoretical determination of PAs, evaluation of the basis set superposition error (BSSE) showed that this effect is quite small, being 0.1-0.2 kcal mol(-1) for phosphinine, when a density functional theory (DFT) method in conjunction with a large basis set were used.     

Cell surface labeling of Escherichia coli via copper(I)-catalyzed [3+2] cycloaddition

Labeling of the cell surface of Escherichia coli was accomplished by expression of a recombinant outer membrane protein, OmpC, in the presence of the unnatural amino acid azidohomoalanine, which acts as a methionine surrogate. The surface-exposed azide moieties of whole cells were biotinylated via Cu(1)-catalyzed [3+2] azide-alkyne cycloaddition. The specificity of labeling of both wild-type OmpC and a mutant containing additional methionine sites for azidohomoalanine incorporation was confirmed by Western blotting. Flow cytometry was performed to examine the specificity of the labeling. Cells that express the mutant form of OmpC in the presence of azidohomoalanine, which were biotinylated and stained with fluorescent avidin, exhibit a mean fluorescence 10-fold higher than the background. Incorporation of an unnatural amino acid can thus be determined on a single-cell basis.     

Kottamide E, the first example of a natural product bearing the amino acid 4-amino-1,2-dithiolane-4-carboxylic acid (Adt)

Kottamide E, a novel alkaloid containing dibrominated indole enamide, oxalic acid diamide and 4-amino-1,2-dithiolane-4-carboxamide moieties, has been isolated from the New Zealand ascidian Pycnoclavella kottae. Characterisation was achieved by interpretation of spectroscopic data.