Biscyanines from isomeric benzodipyrrolenines

Biscyanines and their corresponding mother monocyanines were obtained from the three isomeric benzodipyrrolenines. Splitting of the absorption band of the mother monocyanine into two new bands, viz., a long-wave and a short-wave band, is observed for the biscyanines. The degree of splitting of the maxima for a para orientation of the chromophores in the benzene ring is about twice that for the meta position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 618–620, May, 1971.     

Synthesis and separation of racemic, isomeric desoxo-demethyl-cassaine derivatives

For the synthesis of analogues of Erythrophleum alkaloids the tricyclic ketones 3 (trans-anti-trans) and 5 (trans-anti-cis) were prepared. Reaction of 3 and 5 with triethyl phosphonoacetate led to a mixture of cis/trans compounds, which could be separated in a preparative scale into the uniform racemic isomers 8 and 9, 22 and 23 , respectively. Transesterification of these compounds gave the corresponding 2-dimethylamino-ethyl esters.     

Structure and spectra of diazotized o-aminonaphthols and their isomeric monosulfonic derivatives

The structure and behavior of o-naphthoquinonediazides and their monosulfonic acids in media of different acidity were studied by means of UV and IR spectra. In neutral, weakly acid and weakly alkaline solutions the diazo compounds of 1,2- and 2,1- aminonaphthols and their sulfonic acids exist in equilibrium as the diazonium and quinonediazide forms. The sulfonic acids, and also their metal salts, possess an ionic structure; the sulfonyl chlorides of the quinonediazides are not ionized. It was shown that of the two extreme equilibrium forms of the diazo compounds the quinone diazide was the more photosensitive. The nature of the phototransformation products of 2,1-naphthoquinonediazide depends to a considerable degree on the medium which causes a shift into one or the other of the diazo forms.     

Two isomeric cucurbitane derivatives

Two isomeric cucurbitane derivatives, 3β,7α,11β‐triacetoxycucurbit‐5(10)‐ene, (I), and 3β,7α,11β‐triacetoxy‐5α‐cucurbit‐1(10)‐ene, (II), both C₃₆H₅₈O₆, have their single endocyclic C=C double bonds in different positions. This results in differences in the conformation of the four‐ring system, which is close to a half‐chair/half‐chair/chair/half‐chair arrangement in (I) and to a half‐chair/twist‐boat/boat/half‐chair arrangement in (II). The orientation of some of the substituents is also different; the 3β‐acetoxy group is in an equatorial position in (I) but in an axial position in (II), while the 11β‐acetoxy group occupies an axial position in (I) and an equatorial position in (II). The asymmetric unit of (I) contains two symmetry‐independent molecules which do not differ significantly, being related by a pseudo‐twofold axis of symmetry. In both structures, the aliphatic chain fragments are disordered and the disorder persists at lower temperatures.     

Polymerization of acetylenic derivatives. XXVII. Synthesis and properties of isomeric poly-N-ethynylcarbazole

Poly-N-ethynylcarbazole (PEC) was prepared thermally, by using Ziegler-Natta catalysts, and also by using TiCl₄ and phosphine complexes for initiation. The spectral data (infrared, NMR, x-ray diffraction, and ultraviolet) were best interpreted based on a cis-transoidal/cis-cisoidal stereoblock structure for (both soluble and insoluble) polymers prepared by Ziegler-Natta catalysts and on a trans-cisoidal structure for the polymers prepared with the other catalysts. The cis-transoidal/cis-cisoidal stereoblock structure isomerized thermally into a trans-cisoidal structure, at temperatures which were dependent on the type of initiation.     

Effect of isomeric pyridine moieties in ethynylstyrene derivatives on their anionic polymerization

The anionic polymerization behaviors of ethynylstyrene derivatives containing isomeric pyridine moieties, 2‐(2‐(4‐vinylphenyl)ethynyl)pyridine ( A ), 3‐(2‐(4‐vinylphenyl)ethynyl)pyridine ( B ), and 4‐(2‐(4‐vinylphenyl)ethynyl)pyridine ( C ), were investigated in the identical conditions. The anionic polymerization of A – C was performed with (diphenylmethyl)potassium (Ph₂CHK) in tetrahydrofuran (THF) at ?78 °C. The polymerization of A proceeded quantitatively at –78 °C for 4 h, and the resulting poly( A ) possessed predictable molecular weights (M_n = 3300–68,500) and narrow molecular weight distributions (MWDs) (M_w/M_n = 1.04–1.11). In contrast, the anionic polymerization of B was not performed at –78 °C for 4 h due to the occurrence of side reactions. The monomer B was quantitatively recovered after the reaction. In the polymerization of C performed at –78 °C for 6 h, observed M_n values of the resulting poly( C ) were in good agreement with calculated molecular weights based on monomer to initiator ratios, but the MWDs were somewhat broad (M_w/M_n = 1.23–1.31). To estimate the reactivity of A and to characterize its living nature, the block copolymerization of A with 2‐vinylpyridine (2VP) and methyl methacrylate (MMA) was performed. The well‐defined block copolymers, poly(2VP)‐b‐poly( A ) and poly( A )‐b‐poly(MMA), were successfully synthesized without any additives. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Nitro derivatives of isomeric methyldiazaphenanthrenes

The synthesis of four isomeric nitro derivatives of methyldiazaphenanthrenes (DAP) has been described. The UV spectra of these compounds have been recorded and compared with those of parent diazaphenanthrenes. The biological data of methylnitrodiazaphenanthrenes and of other derivatives of diazaphenanthrenes are presented. Institute of Chemistry, Pedagogical University, 42-201 Czestochowa, Poland Babimost School, 66-110 Babimost, Poland. Microbiology Department Agricultural Academy 50-375 Wroclaw, Poland. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1396–1403, October, 1999.     

Synthesis and structure determination of isomeric 7- and 8-chloro-1,5-benzodiazepine derivatives

Reaction of 4-chloro-1,2-benzenediamine with 3,3-dimercapto-1-phenyl-2-propen-1-one afforded, as expected, a mixture of 7-chloro and 8-chloro-1,3-dihydro-4-phenyl-2H-1,5-benzodiazepine-2-thione. After separation of the two components and further reaction, their structure was established by chemical degradation of 7-chloro-2-(2-diethylaminoethylthio)-4-phenyl-3H-1,5-benzodiazepine to 5-chloro-1,3-dihydro-1-methyl-2H-benzimidazol-2-one. The structure was also confirmed by single X-ray analysis of 7-chloro-2-(2-diethylaminoethylthio)-4-phenyl-3H-1,5-benzodiazepine.     

二丁基双二茂铁甲醇及其胺衍生物的合成

2-二茂铁甲酰基-1，1'-二丁基二茂铁和3-二茂铁甲酰基-1,1'-二丁基二茂铁经LiAlN4还原为相应的相应的双二茂铁甲醇。这些羟基化合物对酸的敏感性很高，与BF3在CH2Cl2中作用可行到稳定的（二丁基二茂铁基）二茂铁基甲基碳正离子。该离子无需从溶液中分离出来，便可与胺作用形成N-取代衍生物。这种制备双二茂铁甲胺的方法具有操作简便和产率较好的特点。     

Synthesis of monoglycosyl diglycerides and their derivatives

Conclusions The Koenigs-Knorr condensation of 1,2- and 2,3-di-O-benzyl-sn-glycerols with acetobromohexapyranoses results in the formation of practically only 1,2-trans-glycosides. The latter have been used for the synthesis of a number of monoglycosyl diglycerides with diglyeride moieties with L and D configurations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 643–649, March, 1976.     

Synthesis of 1-aminoanthrapyridones and their derivatives

1-Aminoanthrapyridones are obtained when 1-anthrapyridonylpyridinium chlorides are heated in high-boiling amines. The synthesis of a number of substituted N-chloroacetyl-1-aminoanthraquinones. 1-anthrapyridonylpyridinium chlorides. and 1-aminoanthrapyridones is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 12. pp. 1651–1655. December. 1972.     

Heteroadamantanes and their derivatives 26. Synthesis of derivatives of hydroxybenzyldiazahomoadamantane

Summary 1-(4-Hydroxy-3-nitrobenzyl)-3,6-diazahomoadamantan-9-one was obtained by the nitration of hydroxybenzyldiazahomoadamantanone. The behavior of the carbonyl group of this ketone and of its nitro derivative has been studied. The structures of the functional derivatives obtained were confirmed by data of IR, PMR, and mass spectra.For part 25 see [1].M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow 117571. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–394, March, 1995.Original article submitted December 29, 1994.     

Synthesis and properties of azoles and their derivatives

The corresponding mono- and bisheterocyclic derivatives of adamantane were obtained by reaction of the dinitrile or diimino ester of adamantane-1,3-dicarboxylic acid with ethylenediamine and related compounds.See [1] for communication XXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1654–1657, December, 1976.     

Synthesis and properties of azoles and their derivatives

The 1,3-dipolar cycloaddition reaction of nitrile N-oxides, and also the thermal condensation of arylhydroxamic acid chlorides with unsaturated derivatives of the adamantane series leads to the corresponding 3,5-disubstituted isoxazolines and isoxazoles.     

Synthesis and properties of azoles and their derivatives

Thermal condensation of 1-cyanoadamantane with arylhydroxamic acid chlorides gave 5-(1′-adamantyl)-1,2,4-oxadiazoles containing aromatic groupings in the 3 position. The same 1,2,4-oxadiazoles were synthesized by reaction of the N-oxides of the appropriate nitriles with adamantane-1-carboxylic acid methyl imino ester obtained from 1-cyanoadamantane. The corresponding 5-(1′-adamantyl)-3-substituted 1,2,4-oxadiazoles were obtained by condensation of the latter with amidoxines.     

Synthesis and properties of azoles and their derivatives

A method is proposed for the synthesis of 1-(2-cyanoethyl)-2-substituted 2-imidazolines; the method is based on reaction of N-(2-cyanoethyl)ethylenediamine with the hydrochlorides of methyl imino esters of carboxylic acids.See [1] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1674–1675, December, 1973.