Insect pheromones and their analogues XXV. Synthesis of acetylenic precursors of pheromones from undecylenic acid

The selective ozonolysis of pentadec-1-en-12-yne and heptadec-1-en-12-yne, synthesized from the readily available undecylenic acid, has given tetradec- and hexadec-11-yn-1-ols — acetylenic precursors of a number of pheromones of insects of the order Lepidoptera.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 823–825, November–December, 1990.     

Synthesis of (Z)-tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol from dodecane-1,12-diol

A method has been developed for obtaining (Z)tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol via dodec-11-yn-1-ol.A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 776–779, November–December, 1984.     

Synthesis of dodec-5E-en-1-ol — The pheromone of Tricimba cincta — And tetradec-5E-1-yl acetate — An imitator of the pheromone of Rhynchopacha sp.

On the basis of a modified Knoevenagel reaction starting from octanol and decanal, the stereodirected synthesis has been effected of dodec-5E-en-ol (the pheromone of the grass flyTricimba cincta — and tetradec-5E-en-yl acetate) an imitator of the pheromone of the mothRhynchopacha sp. A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 129–132, January–February, 1991.     

Pheromones of insects and their analogs

Dodec-8Z-en-1-ol (VIII) and tetradec-8Z-en-1-ol (IX) and the corresponding acetates (X and IX) — components of the sex pheromones of many species of Lepidoptera — have been synthesized from cyclooctene (I) in three stages. The ozonolysis of (I) (–70°C, CH₂Cl₂-MeOH, NaHCO₃; –20°C, Ac₂O/Et₃N) led to methyl 8-oxooctanoate (II). The DNPH of (II), (III), mp 59–61°C. The coupling of (II) with n-C₃H₁₇ CH=PPh₃ (IV) or with n-C₅H₁₁ CH=PPh₃ (V) (–70°C, 2 h; 25°C, 15 h, Ar) gave the methyl esters of dodec-8Z-enoic (VI) and tetradec-8Z-enoic (VII) acids, respectively. The reduction of (VI) and (VII) [(i-Bu)₂AlH, 0°C, 2 h; 25°C, 15 h] gave the corresponding alcohols (VIII) and (IX) by the acetylation (Ac₂O-Py, 25°C, 24 h) of which, (X) and (XI), were obtained. The yields (%): (II) 80, (VI) 45, (VII) 60, (VIII) 95, (IX) 90, (X) 75, (XI) 74. The IR and PMR spectra of compounds (II) and (VI–XI) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 276–279, March–April, 1989.     

Oxidation of fusidic acid

Summary 11-Oxofusidic acid — a previously unknown keto derivative of the antibiotic — has been isolated from the products of the oxidation of fusidic acid by chromium trioxide.All-Union Scientific-Research Institute of Antibiotics, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 66–69, January–February, 1979.     

Flavolignans and other natural lignoids: Problems of structural analysis

In this review, literature information on natural lignoids — flavolignans, xanthonolignans, coumarinolignans, and neolignans — is systematized. Questions of the structural analysis of this group of natural compounds are discussed.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 11–35, January–February, 1987.     

Labdanoids ofMarrubium anisodon

The first chemical investigation has been made of Marrubium anisodon (fam. Lamiaceae). Two diterpenoids of the labdane type — vulgarol and manubiin — have been isolated. An x-ray analysis has been performed for the latter and its crystal amd molecular structures have been determined.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 54–58, January–February, 1996. Original article submitted December 11, 1995.     

Triterpenoid saponins

Conclusions The partial structure of clematoside C — a glycoside of oleanolic acid containing ten monosaccharide residues — was established.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 1963–1968, November, 1966.     

Physicochemical properties and substrate specificity of protease C from dormant cotton seeds

The substrate specificity of a proteolytic enzyme — protease C — isolated from cotton seeds has been studied. The activity of protease C is suppressed completely under the action of diisopropyl phosphorofluoridate. Protein inhibitors — duck ovomucoid, soybean inhibitor, and also TPCK — suppressed the activity of protease C to different degrees. On the basis of results obtained in the hydrolysis of the cottonseed reserve proteins, 7S and 11S globulins, and the B chain of insulin, protease C has been assigned to the serine group of endopeptidases. The optimum conditions — pH, time, and temperature — at which protease C exhibits its maximum activity has been determined.Institute of Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 744–746, September–October, 1988.     

2-Benzopyrylium salts

The synthesis of berberine analogs — substituted dibenzo[a,g]quinolizinium salts — was worked out on the basis of 2-benzopyrylium salts.See [1] for communication XXII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1481–1483, November, 1977.     

Inspect pheromones and their analogues XL1. Synthesis of fluorine-containing tetra- and hexadec-11E/Z-en-1-ols and the acetates corresponding to them — Analogues of components of insect pheromones

The synthesis of 13,13,14,14-tetrafluorotetradec-11E/Z-en-1-ol, and 13,13,14,14, 15,15,16,16-octafluorohexadec-11E/Z-en-1-ol and their acetates — analogues of components of the pheromones of many insect species of theLepidoptera order — has been achieved by the olefination of fluorinated aldehydes and the hydroboration of the fluorinated dienes obtained.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 429–433, May–August, 1992.     

Insect pheromones and their analogs. XLVII. Synthesis of 11-oxododeca-3,6-diynoic acid — The acyclic precursor of a macrolide component of pheromones of Oryzaephilus mercator and O. Surinamensis

A new approach is proposed to the synthesis of 11-oxododeca-3,6-diynoic acid — the acyclic precursor of a macrolide component of pheromones ofOryzaephilus mercator andO. surinamensis — from the readily available tetrahydropyran or allylacetone via the intermediate 5-bromo-2,2-ethylenedioxypentane.Institute of Organic Chemistry, Urals Division, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 288–292, March–April, 1993.     

Insect pheromones and their analogs

(Z)-hexadec-11-enal and (Z)-hexadec-11-1-yl acetate — components of the sex pheromone of insects of the generaHeliothis andManestra, respectively — have been synthesized by the condensation of undec-10-enal with hex-1-yne, deoxygenation of the heptadec-1-en-12-yn-11-ol formed via the corresponding tosylate to heptadec-1-en-12-yne, and the selective oxonolysis of the latter.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 440–444, May–June, 1987.     

Imidazo[1,2-α]quinoxaline and its transformations

7-Substituted imidazo [1,2-a]quinoxalines were synthesized. Transformations of compounds of this series — quaternization, reduction to 4,5-dihydro derivatives, and behavior toward oxidizing agents — were studied.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1558–1560, November, 1972.     

Investigations in the field of perinone compounds

The directed synthesis of structurally isomeric nitronaphthaloperinones — 10-nitro-and 11-nitro-14H-benz[4,5]isoquinolino[2,1-a]perinidin-14-ones — has been effected.For Communication I, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 842–843, June, 1970.     

An investigation of cottonseed globulins. XXI. The 11S globulins of two varieties of the cotton plant

The 11S globulins of two varieties of the cotton plant — 108-F and Tashkent-1 — have been studied. It has been shown that the 11S globulins do not differ in quaternary structure and each consists of three subunits A, B, and C. It has been found that the subunits of these varieties differ in their amino acid compositions and the peptide maps of tryptic and chymotryptic hydrolysates.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 680–684, September–October, 1979.     

The change in the globulins during the development of cotton seeds

The biosynthesis of the 11S and 7S globulins — the main reserve proteins of cotton seeds — has been investigated. The periods at which the globulins appear in cotton seeds have been established. The changes in the amino acid composition and in the secondary structure of the 11S globulin during the ripening of cotton seeds have been studied.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Institute of Molecular Biology, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 349–355, May–June, 1984.     

Insect pheromones and their analogs III. Synthesis of the sex attractants of some Lepidoptera

A new route to the synthesis of a number of attractants of Lepidoptera(Argyrotaenia velutinana, Mamestra configurata, andLycorea ceres ceres) have been developed. These substances are acetates of enols with the cis configuration: tetradec-11-en-1-ol, hexadec-11-en-1-ol, and octadec-11-en-1-ol, respectively. The constants of the substances obtained agree completely with those given in the literature. The method is based on the coupling of the C₃, C₅, and C₇ aldehydes with methyl 11-bromoundecanoate (I) by the Wittig reaction. To obtain compound (I) from methyl undeca-2E,5E,10-trienoate or methyl undeca-10-enoate we used hydroboration according to Brown followed by hydrogenation and bromination of the alcohol obtained. The advantage of this method is the use as starting materials of esters of unsaturated acids readily obtained by the homogeneous catalytic co-oligomerization of 1,3-dienes with acrylates.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 97–102, January–February, 1980.     

Antiradical activity of the hormonal preparation estrone in lipid models undergoing oxidation

The rate constants and stoichiometric coefficients of chain termination in the oxidation of lipid models (methyl esters of acids of the oleic series: cis-6-, cis-9-, trans-9-, and trans-11-C₁₇H₃₃COOCH₃) by the main representative of the follicular hormones — estrone (313–348 K) — and for comparison by the phenol 2,6-ditert-butyl-4-methylphenol (323.15 K) were measured. The strength of the OH bond in the estrone molecule was estimated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 5, pp. 445–448, September–October, 1993.