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.     

Use of α-2-cyanoethyl tert-butoxycarbonylaspartate as an intermediate for synthesis of β-esters

The use of -2-cyanoethyl Boc-aspartate is proposed for the first time for the synthesis of -esters of Boc-aspartic acid. The -2-cyanoethyl protective group is selectively split out by strong organic bases under hydrolytic conditions without the -ester bond being affected. Using the -2-cyanoethyl derivative, -cyclohexyl, -benzyl, and -tert-butyl Boc-aspartates have been synthesized in good yields.All-Union Scientific-Research Institute of Molecular Biology. Vektor Scientific-Industrial Association. Ministry of the Medical and Biochemical Industries, Koltsovo, Novosibirsk Province. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 241–245, March–April, 1990.     

Synthesis of C-terminal peptide fragments of the heavy chain of hemagglutinin of influenza virus of subtypes H1 and H3

It is proposed to use the chromogenic 2-[4-phenylazo)benzylsulfonyl]ethyl group, which can be eliminated by organic bases in aprotic solvents, for the protection of a C-terminal carboxy group in the synthesis of peptides. The synthesis of a number of 10–16-membered peptides corresponding to C-terminal fragments of the heavy chain of the hemagglutination of influenza virus of subtypes H1 and H3 has been performed with the use of this group.All-Union Scientific-Research Institute of Molecular Biology, Kol'tsovo, Novosibirsk Oblast. Vektor Scientific-Industrial Association, Ministry of the Medical and Biological Industry of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 732–738, September–October, 1988.     

Synthesis of oligodeoxyribonucleotides containing a 3'-terminal phosphate group

Two methods for synthesizing oligodeoxyribonucleotides containing 3'-terminal phosphosphate groups have been developed. The first consists in the synthesis and the introduction into the oligonucleotides of a block containing a 3'-terminal bis(2-cyanoethyl) phosphate group and the second in the use of the transesterification reaction of oligonucleotides with 2-cyanoethanol in the presence of cesium fluoride. Both methods permit the fairly effective synthesis of oligodeoxyribonucleotide 3'-phosphates.M. V. Lomonosov Moscow State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 637–641, September–October, 1984.     

Stereoselectivity of the exhaustive epoxidation of cembrene by peracetic acid. Crystalline and molecular structure of triepoxycembrene

The epoxidation of the diterpene hydrocarbon cembrene with peracetic acid in methylene chloride in the presence of sodium bicarbonate forms a single triepoxide — 4,5:7,8:11,12-triepoxycembrene with the 4S, 5R, 7S, 8S, 11S, 12S configuration of the asymmetric centers. The structure and stereochemistry of triepoxycembrene have been determined with the aid of x-ray structural analysis.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–178, March–April, 1981.     

Use of sodium pyrophosphate in the ion-exchange chromatography of oligonucleotides

All-Union Scientific-Research Institute of Molecular Biology. Vektor Scientific-Production Association, Ministry of the Medical Industry, Koltsova, Novosibirsk. Novosibirsk Institute of Bioorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 148–149, January–February, 1992.     

First example of the formation of highly ordered supermolecular structures in a series of gibberellin derivatives

The 3-O-palmitate and 3-O-tridecanoate of gibberellin A₃ have been synthesized and monomolecular Langmuir-Blodgett films have been obtained from them.Novosibirsk Institute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 793–795, November–December, 1994.     

Cyanoethylation of acetylenic thienyl alcohols

The reaction of 2-cyanoethyl ethers with phenylmagnesium bromide gives the corresponding 2-benzoylethyl ethers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1175–1176, September, 1971.     

Caged phospho-amino acid building blocks for solid-phase peptide synthesis

Three 1-(2-nitrophenyl)ethyl-caged phospho-amino acids have been synthesized for use in standard N(alpha)-fluorenylmethoxycarbonyl-based solid-phase peptide synthesis (SPPS). The most common naturally occurring phospho-amino acids, serine, threonine, and tyrosine, were prepared as protected caged building blocks by modification with a unique phosphitylating reagent. In previous work, caged phospho-peptides were made using an interassembly approach (Rothman, D. M.; Vazquez, M. E.; Vogel, E. M.; Imperiali, B. Org. Lett. 2002, 4, 2865-2868). However, this technique is limited to creating peptides without oxidation sensitive residues C-terminal to the amino acid to be modified and the methodology involves synthetic manipulations on the solid phase that may limit the utilization of the methodology. Herein we report the facile synthesis of N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-serine 1, N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-threonine 2, and N-alpha-Fmoc-phospho(1-nitrophenylethyl-2-cyanoethyl)-L-tyrosine 3. These building blocks allow the synthesis of any caged phospho-peptide sequence using standard Fmoc-based SPPS procedures.     

Synthesis of derivatives of N-acetylmuramyl-ℓ-alanyl-d-isoglutamine containing activated disulfide bonds

N-Acetylmuramyl--alanyl-d-isoglutaminyl--S-(2-pyridylthio)cysteine and 1-(N-acetylmuramyl--alanyl-d-isoglutaminamido)-6-[3-(2-pyridylthio)-propionamido]hexane, derivatives of muramyldipeptide each with an activated disulfide bond, have been synthesized. Disulfide conjugates of muramyldipeptide with peptide fragment 136–147 of the heavy chain of the hemagglutinin of influenza virus A/Aichi/2/68 have been obtained.All-Union Scientific-Research Institute of Molecular Biology. Vektor Scientific-Industrial Association, Kol'tsovo, Novosibirsk Oblast. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 387–391, May–June, 1989.     

Bicyclic monoterpenoids of the essential oil of Ledum palustre

The structure of a new natural compound has been established as 5-isopropylbicyclo[3.1.0]hex-3-en-2-one, which has been called lebaikon. Two bicyclic monoterpenoids (2-formyl-5-isopropylbicyclo[3.1.0]hex-2-ene and 4-isopropyl-1-methylbicyclo[3.1.0]hexan-2-one) have been detected in natural materials for the first time.Tomsk State Medical Institute. Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 627–629, September–October, 1990.     

Oxidative transformations of cembrane diterpenoids. II. Cembra-2,7,11-triene-4,5-diols

Summary 1. The oxidation of cembrene with chromium trioxide in aqueous acetone forms, together with other compounds, the products of its hydroxylation at the C₄ double bond — cembra-2,-7,11-triene-4,5-diols epimeric at the C₄ double bond.2. On the basis of chemical and spectral characteristics, it has been established that these diols have the 4S, 5R and 4R, 5R configurations, respectively.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR, and Novosibirsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 54–59, January–February, 1977.     

Photochemical route to cembranoids containing a cis-disubstituted double bond

The 2-cis isomers of the natural diterpenoids isocembrol, 4-epiisocembrol, and isocembrene have been synthesized from a norcembrane ketone by the use of photochemical methods.Novosibirsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 180–187, March–April, 1988.     

Research on a series of naphthostyryls: The synthesis of 2-(cyanocarboethoxymethylene)-, 2-(dicarboethoxymethylene)-, and 2-(acetylcarbo-ethoxymethylene)-N-(β-cyanoethyl)naphthostyryl

Conclusions The synthesis of 2-(cyanocarboethoxymethylene)-, 2-(dicarboethoxymethylene)-, and 2-(acetylcarbo-ethoxymethylene)-N-(-cyanoethyl)naphthostyryl was accomplished and the structure was demonstrated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2365–2367, October, 1968.The authors wish to express their heartfelt appreciation to V. N. Bochkarev and A. S. Sulima for running and interpreting the mass spectra.     

Synthesis of a modified fragment 13–19 of the sequence of ACTH using silyl protection

A new scheme for the synthesis of a peptide representing a modified analog of fragments 13–19 of the sequence of the adrenocorticotropic hormone has been described, which uses a number of stages the trimethylsilyl grouping for the protection of the carboxy groups of amino acids and peptides. The final and intermediate products were obtained with high yields and were distinguished by chromatographic homogeneity.¹³C NMR was used as a supplementary method for the identification of the compounds. The physicochemical characteristics of the compounds synthesized are given.All-Union Scientific-Research Institute of the Technology of Blood Substitutes and Hormone Preparations, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 374–379, May–June, 1980.     

Scheme for the group separation of the components of conifer oleoresins. Terpenoids of the oleoresin of pinus cembra

Summary A scheme has been proposed for the group separation of the components of conifer oleoresins, and the mono-, sesqui- and diterpenes of the oleoresins of the European stone pine have been investigated by means of this scheme.2. The composition of the oleoresin of the European stone pine is very similar to those of the Siberian pine and of the Korean pine, but differs from the latter by the absence of cis-abienol and bisabolol.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 609–613, September–October, 1976.     

Resin acids of the oleoresins of conifers growing in Transcarpathia

The chemical composition of the resin acids of the oleoresins of five species of the conifers of Transcarpathia has been studied. The oleoresins contain eight resin acids. ^8,9-Isopimaric and anticopalic acids have been found in the acid part of the oleoresin of the Weymouth pine.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 212–214, March–April, 1987.     

Photolysis of 1,2-anthraquinone diazide in aromatic hydrocarbons

It has been determined that the main products of photolysis of 1,2-anthraquinone diazide in benzene, toluene, anisole, nitrobenzene, and pyridine are the corresponding 1-hydroxy-2-arylanthraquinones that form as a mixture ofortho, meta, andpara isomers with significant content of themeta isomer (40–55%).Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630090. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1000–1003, April, 1992.     

Oxidative transformations of cembrane diterpenoids III. Epoxycembrenes

Summary 1. It has been established that the epoxidation of cembrene with perbenzoic and peracetic acids takes place stereospecifically at each of the trisubstituted double bonds with the formation of 4S,5R-, 7S,8S-, and 11S,12S-monoepoxycembrenes, the structures and absolute configurations of which have been established by spectral methods.2. Epoxidation of cembrene at the C₁₁–C₁₂ double bonds under the conditions used takes place preferentially as compared with epoxidation at the C₇–C₈ double bond.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Novosibirsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 525–531, July–August, 1977.