Functional monomers and polymers. XXXXI. Template polymerization of methacryloyl-type monomers containing nucleic acid bases

In due consideration of the specific base–base interaction that exists between nucleic acid molecules, the free radical polymerization of N-β-methacryloyloxyethyl derivatives of adenine, thymine, and theophylline initiated by azobisisobutyronitrile (AIBN) was studied in the presence of N-β-methacryloyloxyethyl-type polymers which have complementary nucleic acid bases as template polymers. The rate of polymerization of N-β-methacryloyloxyethyladenine was accelerated when poly(N-β-methacryloyloxyethyluracil) or -thymine was present in the polymerization system. The effect of the stereoregularity of the template polymers, as well as polymerization temperature and the sort of solvents used on the rate of polymerization, was studied and discussed in some detail. The results suggest that the interaction between complementary bases plays a role in template polymerization behavior.     

Benzindoles. 23. 2-formyl- and 3-formyl-4,5-benzindoles

It is shown that, in addition to the usually formed 3-formyl-4,5-benzindole, 2-formyl-4,5-benzindole can be obtained via the Vilsmeier reaction. The IR, PMR, and UV spectra of the 2- and 3-formyl isomers are compared, and their possible conformations are discussed.See [1] for Communication 22.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1984.     

Isomerization of 5, 5-dimethylpyrazolines. preparation and properties of 5, 5-dimethyl-Δ1-pyrazoline and 3, 4-dimethyl-Δ2-pyrazoline

Slow distillation of 5, 5, -dimethyl-²-pyrazoline isomerizes it to 5, 5-dimethyl-¹-pyrazoline, and heating the latter with hydrazine hydrochloride reconverts it to the ² isomer. This is the first experimental evidence that the ² double bond in a pyrazoline can move to the ¹ position, i. e., in a direction the reverse of that previously known. The 5, 5-dimethyl-¹ -pyrazoline described is the simplest ¹ pyrazoline hitherto isolated.The authors heartily thank A. A. Petrov for making it possible to chart the PMR spectra, and V. B. Lebedev and V. S. Stopskom for obtaining and treating the spectrograms.     

Synthesis and Spectra of 3-Benzoyl-5-formyl-2-methylpyrrole-5-aroylhydrazones

Eleven aroylhydrazone derivatives of 3-benzoyl-5-formyl-2-methylpyrrole (3-13) have been prepared, and their ¹H NMR, ¹³C NMR and mass spectral fragmentation arc discussed. Acetylation and oxidative cyclization to 1,3,4-oxadiazole mercuric complexes (17-20) were also carried out.     

Synthesis and polymerization of racemic and optically active β-substituted β-propiolactones. III. β-monosubstituted monomers and polymers

Optically active β-(1,1-dichloroethyl)-β-propiolactone (CH₃CCl₂-PL), β-(1,1-dichloropropyl)-β-propiolactone (C₂H₅CCl₂-PL), and β-(1,1-dichlorobutyl)-β-propiolactone (C₃H₇CCl₂-PL) were synthesized with enantiomeric excesses of 100, 100, and 84%, respectively. Polymerization was conducted in bulk and toluene solution, under vacuum, using mainly ZnEt₂/H₂O as initiator. Osmometry analyses indicate molecular weights in the range 10,000–25,000. The polymers thus prepared are semi-crystalline and show large optical rotation values.¹³ C-NMR was used to show that they have a high degree of isotacticity, indicating that little or no racemization occurs in the course of polymerization. Glass transition, melting and decomposition temperatures are given as a function of the size of the substituent, and their variations are discussed.     

Block polymers of isocyanates and vinyl monomers by homogeneous anionic polymerization

The “living” polymer method was used to prepare block polymers of vinyl monomers and isocyanates at low temperatures in toluene–tetrahydrofuran mixtures. Vinyl monomers and diisocyanates, which have one hindered isocyanate group, as in 2,4-toluene diisocyanate, form block polymers which contain pendant reactive isocyanate groups. These block polymers can be crosslinked with water, diols, diamines, etc. The polymerization is apparently limited to block polymer formation, since the polyisocyanate anion is incapable of initiating the polymerization of common vinyl monomers.     

Polymerization of oriented monomers. V. Radiation-induced polymerization of 3n-dodecyl-1-vinylimidazolium iodide in micellar aggregates

In the present study radiation-induced polymerization of 3n-dodecyl-1-vinylimidazolium iodide (I) in micellar aggregates was investigated. For comparison, the corresponding isotropic polymerization of I was also studied. Micellization was obtained in concentrated aqueous solutions; that is, above the monomer's critical micelle concentration (CMC) polymers obtained by both modes of polymerization were treated similarly and subsequently subjected to physical characterization. The main purpose of this study was to investigate whether the degree of organization of the monomer in micelles would affect polymer properties. Attempts to determine tacticity by ¹³C-NMR spectrometry failed because of the particular structure of the polymer. Crystallization of these polymers from ethyl alcohol or acetone was not possible as indicated by x-ray powder diffraction patterns that were characteristic of amorphous polymers. On the other hand, viscosity data of polymers do not depend on the mode of polymerization. It is therefore concluded that micellar aggregates are not sufficiently organized to affect polymer properties.     

Functional monomers and polymers. CXXXII. Template polymerization of methacrylamide derivatives containing nucleic acid bases

Free-radical polymerizations of methacrylamide derivatives containing nucleic acid bases were studied in the presence of the polymethacrylamide having complementary nucleic acid bases as template polymers. The rate of the polymerization did not show remarkable difference in the presence or the absence of the template polymer. A stable polymer complex, however, was precipitated from the polymerization system, and was found to be different in a thermal analysis from the polymer complex which was obtained by mixing of the complementary polymers in solution. Free-radical copolymerizations in the presence of the template polymers also supported the template polymerization.     

Synthesis of 3-cyano-5-ethoxycarbonyl-6-hydroxypyridine-2-thiol derivatives

Ethyl ethoxymethylenemalonate reacts with cyanothioacetamide andN-methylmorpholine to giveN-methylmorpholinium 3-cyano-5-ethoxycarbonyl-6-oxopyridine-2-thiolate. Alkylation of the latter yieldsS-alkyl derivatives. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–197, January, 1999.     

乙烯类单体预辐照聚合的研究

讨论了在氧存在下辐照乙烯类单体形成的过氧化物在引发聚合及共聚合中的行为及辐照温度对形成过氧化物的速率和性质的影响.主要结果如下:(1)过氧化物的生成及其引发聚合皆按自由基机制进行.V_0∝c~(1/2),G_R=10;(2)过氧化物的生成活化能为:E_(f(MMA)=11,E_f(Sr)=9.6,E_(f(AN))=8.5kcal/mol.聚合过程中的表观活化能E_MMA=11.4,E_(▽A)=11.4kcal/mol.引发活化能E_i(MMA)=E_i_(▽A)=13kcal/mol;(3)过氧化物生成速率随辐照温度的升高而增加,高温辐照的过氧化物的引发性质发生变化;(4)辐照形成的过氧化物在聚合条件下的分解速率较BPO的分解速率缓慢而平稳,保证了聚合进程的平稳性;(5)预辐照一种单体可以引发另一种未辐照单体共聚.预辐照不同单体在共聚中的引发能力主要取决于预辐照单体的化学结构.     

Functional monomers and polymers. XXXVIII. Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes

Postirradiation polymerization of 2,3-dimethylbutadiene in deoxycholic acid canal complexes was studied under various reaction conditions. The polymerization was carried out in degassed sealed tubes since the atmosphere had a large effect upon the polymer yield. Addition of 2,3-dimethylbutane led to a sharp drop in polymer yield, while hydroquinone showed little effect on the polymerization. The rate of postirradiation polymerization was found to increase with increase in reaction temperature and irradiation dose. The apparent activation energy was obtained as 13.7 kcal/mole in a temperature range between ?14 and 30°C. Existence of living free radicals having a long lifetime, the gradual change of the monomer into the polymer within the canals, and the effective spatial control in canals are discussed on the basis of the postirradiation polymerization behavior, nature of the adducts, and the structure of the polymers.     

Synthesis of 2-substituted 3-formyl-5-methoxy-tetrahydrofurans from 2,5-dimethoxytetrahydrofuryl-3-carbinols

The acid-catalyzed rearrangement of 2,5-dimethoxytetrahydrofuryl-3-carbinol, obtained from 2,5-dimethoxy-3-formyltetrahydrofuran, gave the 2-substituted 3-formyl-5-methoxytetrahydrofuran.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 164–166, February, 1991.     

Living cationic polymerization of vinyl monomers: Mechanism and synthesis of new polymers

This paper reviews the recent progress in our research on the living cationic polymerization of vinyl compounds by the hydrogen iodide/iodine (HI/I₂) initiating system, with emphasis on its scope, mechanism, and applications to new polymer synthesis. The scope of the living cationic polymerization has been expanded to include vinyl ethers, propenyl ethers, unsaturated cyclic ethers, and styrene derivatives as monomers. The initiation/propagation mechanism was discussed on the basis of recent direct analysis on the living system by NMR and UV/visible spectroscopy. The proposed mechanism involves a quantitative formation of Hl-vinyl ether adduct [CH₃-CH(OR)-I; l] that is by itself incapable of initiating polymerization. In the presence of iodine, however, the CH-I bond of l is electrophilically activated by iodine and living propagation occurs via the insertion of vinyl ether to the activated CH-I bond. Such living polymerizations were found to proceed in not only nonpolar but polar solvents (CH₂Cl₂) as well. Quenching the living end with amines gave polymers capped with an amino group that in turn enabled us to determine the living end concentration. Applications of the HI/I₂-initiated living process to the synthesis of new bifunctional and block polymers were also described.     

Synthesis and structure of anils of 2-formyl-3-mercaptobenzo[b]thiophene and 2-formyl-3-mercaptobenzofuran

As a result of a study of the electronic, vibrational, and PMR spectra of alkyl- and arylimines of 2-formyl-3-mercaptobenzo[b]thiophene and 2-formyl-3-mercaptobenzofuran and of the spectra of model compounds the thione-enamine structure was assigned to the imines. The stability of the latter structure is in agreement with the results of quantum-mechanical calculations of the energies of atomization of the individual tautomeric forms; the calculations were made by means of the Pariser-Parr-Pople (PPP) method with the Dewar σ, π parametrization.     

Bisindoles. 15. Acidic condensation of bis(2-ethoxycarbonyl-5-indolyl) oxide and bis(2-ethoxycarbonyl-5-indolyl)methane with aromatic aldehydes

The acidic condensation of bis (2-ethoxycarbonyl-5-indolyl) oxide and bis(2-ethoxycarbonyl-5-indolyl)methane with aromatic aldehydes was studied. Bis(3-chloro) compounds with labile chlorine atoms, by nucleophilic substitution of which the corresponding dimethylamino, hydroxy, methoxy, acetoxy, cyano, and mercapto derivatives were obtained, were isolated.See [1] for communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 365–368, March, 1983.