Anionic Polymerization of α-Methylstyrene. IX. Nature of the Propagating Species

Abstract

The nature of the initiating and propagating species involved in the anionic polymerization of α-methylstyrene has been explored. The earlier hypothesis that multimodal GPC molecular weight distributions in polymers arise solely out of different reaction steps or different ion-pair mechanisms being involved has been modified for poly-α-methylstyrene. Multimodal GPC molecular weight distributions in poly-α-methylstyrene initiated with potassium at 25°C and polymerized at 25°C or higher in THF, p-dioxane, or cyclohexane as solvents have been ascribed to the presence of two different types of tetramers which grow simultaneously but at different rates, each responding to its own well-defined thermodynamic equilibrium and yielding dormant and living polymers. Reaction schemes describing the initiation (at 25°C) and propagation reactions (between -25 and 60°C) in the polymerization (in solution of THF as well as in bulk) of α-methylstyrene initiated with potassium-naphthalene, butyl-lithium, and butyllithium-tetramethylethylenediamine (TMEDA) have been presented. The role of coordinating agents naphthalene and TMEDA in changing irreversible propagations into reversible ones has been emphasized.     

Derivatives of heterocyclic α-iminocarboxylic acids. 4. Reduction of N-alkoxycarbonyl derivatives of α-iminocarboxylic acids

When N-methoxycarbonyl and N-benzoxycarbonyl derivatives of methyl esters of aziridine-2-carboxylic acid, L-proline, L-thioproline, and pipecolic acid interact with NaBH₄ in tert-butanol/methanol, the products of reduction of the C-methoxycarbonyl group of the original compounds are accompanied by bicyclic urethanes and oxazolidines. Reduction of N-maleates and N-fumarates of heterocyclic -iminocarboxylic acids leads to the formation of -hydroxymethyl-N-[4-(2-oxo-2,5-dihydrofuryl)] derivatives of pyrrolidine, piperidine, 1,3-thiazolidine, and 1,4-thiazan. In the latter case, 1-aza-2-hydroxymethyl-4-oxo-5-oxa-9-thiabicyclo [5.4.0]undecene-2 is also obtained. The N-maleates and fumarates of aziridine-2-carboxylic acid are reduced anomalously by sodium borohydride, forming 2-hydroxymethyl-2-(-hydroxyethyl)-3-oxa-1-azabicyclo[3.1.0]hexanes.For Communication 3 see [2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1567–1573, November, 1993.     

Synthesis of Terpenoids. III. Total Syntheses of α-Bisabololone and α-Trans-Atlantone

Recently, anions of “protected” cyanohydrins have been introduced as useful acyl carbanions equivalents in organic synthesis². Continuing with our interest in the use of these reagents for natural product syntheses³, we wish to report a short total synthesis of the sesquiterpene α-bisabololone 1 ^4,5, whose salient feature is a novel application of “protected” cyanohydrins to the synthesis of β-hydroxy ketones.     

List of Selected Papers of Prof. Dr. Jaroslav Šesták

Bibliography

List of Selected Papers of Prof. Dr. Jaroslav Šesták     

Polymorphism of Inclusion Complexes and Unsolvated Hosts. I. Trimorphism of the Host-Guest Complex of Gossypol with Dichloromethane. The Structure of the β-Phase

The formation of host-guest complexes of gossypol at different temperatures has been investigated for the same pressure and concentration. Gossypol forms three different clathrates with dichloromethane within the temperature interval of 22-36 °C. Single crystals of these three modifications (phases) were obtained and their crystallographic parameters measured. The structure of the -phase has been determined previously and the -phase is isostructural to the inclusion complex of gossypol with benzene, while the structure of the -phase has been solved during the present research. Crystals of C30H30O8·CH2Cl2 are triclinic, space group P1, a = 8.604(1), b = 11.858(2), c = 14.405(2) (Å), = 84.60(1), = 89.14(1), = 89.73(1)°, V = 1463(1) Å3, Z = 2, R = 0.089 for 2419 observed reflections.Under ambient conditions gossypol forms unstable tubulates of the -phase; the -phase is a stable cage-type clathrate (cryptate) and the host-guest complex of the -phase is a clathrate of intermediate tubulato-cryptate type.     

Synthesis based on β-phenylethylamines. IX. Synthesis of sulfides of β-phenylethylamines and of N-benzyltetrahydroisoquinolines

New bimolecular sulfur-containing -phenylethylamines and N-benzyltetrahydroisoquinolines have been synthesized from formyl derivatives of diaryl sulfides. The possibility of using metals as catalysts for obtaining diaryl sulfides in the reaction of ortho-substituted benzaldehydes with SCl₂ has been shown for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 731–735, September–October, 1995. Original article submitted November 11, 1994.     

Alkaloids of Arundo donax. XIV. Crystal and Molecular Structure of N-Methyl-tetrahydro- β-carboline

An indole alkaloid of the N-methyl-tetrahydro--carboline series was isolated for the first time from Arundo donax, Poaceae. Its structure was solved by X-ray structure analysis.     

Contents of 《Journal of Energy Chemistry》Vol. 24 No. 1 2015

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Chemical Components of Helicia nilagirica Beed.I.Structure of Three New Flavonol Glycosides

Helicia nilagirica Beed. belongs to the plant of Proteaceae family. The seeds of the plant is for treatment of insomnia and neurasthenia in Jingpo nationality in Yunnan Province1. Helicid and helicidol were isolated from the seeds of the plant2,3, and the helicid was recorded in the Yunnan Pharmacopoea at the 1987 edition. The chemical constituents of the leaves of this plant has not been reported yet in the literature. This paper is concerning the study of the chemical component of the…     

Reaction of aminoquinolines with unsaturated carboxylic acids. 2. Cyclization of N-quinolyl-β-alanines

The cyclization of N-(3-quinolyl)- and N-(6-quinolyl)--alanines was carried out to give uncondensed hexahydropyrimidine derivatives, while the cyclization of N-(5-quinolyl)- and N-(8-quinolyl)--alanines gave tetrahydrophenanthrolinone derivatives.Communication 1, see ref. [1].Kaunas Technological University, 3028 Kaunas, Lithuania, Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 653–657, May, 2000.     

N-glycosides. 9. Reaction of 3,5-O-isopropylidenexylofuranosylamine with β-isothiocyanatoaldehydes. Synthesis of new cyclonucleosides with a hexahydropyrimidine aglycone

The reaction of 3,5-O-isopropylidenexylofuranosylamine p-toluenesulfonate with -isothiocyanatoaldehydes in the presence of triethylamine gives 4,2-anhydro-4-hydroxy-3-(3,5-O-isopropylidene--D-xylofuranosyl)hexahydropyrimidine-2-thiones. The structure of these compounds and their deblocking products was studied by IR, UV, PMR, and ORD spectroscopy and mass spectrometry.For Communication 8, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1252–1258, September, 1993.     

Chemical Components of Helicai nilagirica Beed.I.Structure of Three New Flavonol Glycosides

Three new flavonol glycosides were isolated from the leaves of Helicia nilagirica Beed.The structures were elucidated as kaempferol-3-O-β-D-xylopyranosyl-(1→6)-β-D-glyco-pyranosyl-(1→2)-α-L－rhamnopyranoside,quercetin-3-O-β-D-xylopyranosyl-(1→6)-β-D-glycopy-ranosyl-(1→2)-[-β-D-xylopyranosyl-(1→4)]-α-L-rhamnopyranoside,and quercetin-3-O-β-D-xylopyranosyl-(1→6)-β-D-glycopyranosyl-(1→2)-α-L-rhamnopyranoside,nmaed as Hcilcianeoside A、B and C ,respectively.     

Two-fragment α-adrenolytics. 4. Synthesis of phosphorylated derivatives of 2-aryloxyethylamines and N-phenylpiperazine

The reactions of 3-chloropropylphosphonates, 3-chloropropylthiophosphonates, or 3-chloropropylphosphinates with 2-aryloxyethylamines or N-phenylpiperazine afford the corresponding 3-(2-aryloxyethylamino)propylphosphonates and -phosphinates or 3-(4-phenylpiperazin-1-yl)propylphosphonates and -phosphinates. The compounds obtained exhibit -adrenolytic and hypotensive activities, the latter being found to depend on the substituents at the P atom.     

Study on degrees of mesomorphic zone of polymer. Ⅲ.Determination of the degree of crystallinity of Eucommia Ulmoides gum by VTFTIR and VTWAXD

Eucommia Ulmoides (EU) gum will crystallize easily at room temperature due to the regular trans-1,4-polyisoprene (TPI) molecular structure. Around the skeleton stretching vibration band of TPI, its FTIR spectrum showed 5 weak crystalline peaks decrease as temperature increase, and there are also two amorphous peaks (845 cm⁻¹ and 668 cm⁻¹) increase as temperature increase. According to this phenomenon, Variable Temperature Fourier Transform Infrared Spectrum (VTFTIR) and Variable Temperature Wide Angle X-ray Diffraction (VTWAXD) have been taken to analyze the degree of crystallinity of EU gum. In addition to the ratio of crystalline zone, the result determined by VTFTIR also involve the mesomorphic zone, which make it higher than the result determined by VTWAXD. Through the comparative analysis of VTFTIR and VTWAXD, it has been proved that the ratio of crystalline zone, mesomorphic zone, amorphous zone in EU gum were respectively 39.8%, 27.6%, 32.6% at room temperature. Based on the Density Measurement and the three-phase model theory, the density gradient function of the mesomorphic zone of EU gum was firstly proposed. Below 60 °C, the density of the mesomorphic does not change with the temperature, approximately 0.931g/cm⁻³. Above 60 °C, the density of the mesomorphic decreases with the temperature increasing, and finally drops to 0.905g/cm⁻³ at 80 °C, which is equal to the density of the complete amorphous zone.     

Radiation-Induced,Solid-State Polymerization of Derivatives of Methacrylic Acid. XI. Aspects of the Polymerization of Methacrylic Acid by γ-Irradiation

Aspects of the radiation-induced polymerization of methacrylic acid in the crystalline state have been investigated and utilized to evaluate the mechanism of polymerization. In particular, results for post-irradiation polymerization at 0°C after radiation doses of 0.1 to 2.0 Mrad support the concepts of Lando and Semen that chain initiation essentially all commences at the same time, that chain propagation continues without termination, and that termination of nonpropagating radicals proceeds simultaneously.     

Total synthesis and properties of prostaglandins. 40. Synthesis ofβ-Oxyaminovinyl bicyclic γ-lactones

Acetylation of oxyiminomethyl bicyclic y-lactones gave the corresponding N-acetyl--oxyaminovinyl derivatives.Latvian Institute of Organic Synthesis, Riga, LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 613-615, May, 1995. Original article submitted March 27, 1995.     

Friedel-Crafts Polymers. I. Self-Polycondensation of 4,4′-Dichloromethyldiphenyl Ether

Friedel-Crafts self-polycondensation of 4,4′-dichloromethyl-diphenyl ether (DDE) is studied under various experimental conditions. These polymer samples are infusible and are insoluble in all solvents. The polymer samples, PDs, are characterized by elemental analysis, IR spectral study, and by TGA. Polymer reaction products of one polymer sample are prepared by subjecting it to Friedel-Crafts reaction with excess benzene and by treating it with triethylamine. Both the polymer reaction products are found to be less stable than the parent polymer sample.     

Components of Essential Oils in Different Parts of Daucus carom L. var. sativa Hoffm

The components of the essential oils obtained from different parts of Daacus carota L.var. saliva Hoffm were analyzed. The percentages of the essential oils extracted are 0. 27% （ mL/100 g material） for the flowers, 0. 0/% for the stems and leaves and 0. 01% for the roots. Fifty-four, Sixty-six and Thirty-three compounds were,respectively, separated and identified from the flowers, the stems and leaves and the roots, among which unsaturated alkene compounds are thirty-nine, thirty-nine and twenty-one, respectively, accounting in turn for up to 90. 21%, 90. 49% and 72. 65% of the total essential oils. Because alkene compounds have double bonds that are easily oxidized, it can he inferred that the components of the essential oils in the different parts of Daucus carota L. var. saliva Hoffm should show an activity of the antioformation of free radicals to some extent.