Synthesis of conjugates of lupane triterpenoids with chromane antioxidants and <Emphasis Type="Italic">in vitro</Emphasis> study of their influence on the production of nitrogen monoxide and on the arginase activity in activated macrophages

Conjugates of lupane triterpenoids (betulin and betulonic and betulinic acids) with synthetic analogs of α-tocopherol were obtained via ester bond formation and tested in vitro. Showing low cytotoxicity, some of them suppress nitrogen monoxide production without affecting the activity of arginase, which suggests their antiinflammatory and immunomodulating properties.     

Pheromones of insects and their analogs LIII. Synthesis of ferrulactone I —a pheromone ofCryptolestes ferrugineus

8-Acetoxy-3, 7-dimethyl-l-(phenylsulfonylacetoxy)octa-2E, 6E-diene has been synthesized, and its cyclization under the action of zerovalent palladium followed by desulfurization with the aid of sodium amalgam has led to ferrulactone I — one of the macrolide components of the aggregation pheromone of the rust-red grain beetle (Cryptolestes ferrugineus).Institute of Organic Chemistry, Urals Scientific Center of the Russian Academy of Sciences, 450054, Ufa pr. Oktyabrya, 71. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 932–935, November–December, 1996. Original article submitted May 27, 1996.     

Synthesis ofS-(+)-methoprene

An optically active juvenile hormone analogue,S-(+)-methoprene (1), is synthesized in six steps from technical gradeS-(+)-3,7-dimethyl-1,6-octadiene ((+)-dihydromyrcene, e.e. –50%) by a novel procedure which begins with selective hydroalumination-oxidation to giveS-(-)-citronellol. This alcohol is oxidized to giveS-(-)-citronellal which on reaction with allylmagnesium chloride affords 6S, 10-dimethyl-1,9-undecadien-4 R/S-ol (5). Smidt-Moiseev oxygenation of 5 followed by dehydration leads to 6S, 10-dimethyl-3E,9-undecadien-2-one. The latter on treatment with isopropoxyethynylmagnesium bromide is transformed into isopropyl 3,7S,11-trimethyl-2E/Z,4,E,10-dodecatrienoate which upon Brown solvomercurationreduction in MeOH gives1 in 14% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 108–109, January, 1993.     

Insect pheromones and their analogues

The synthesis has been effected of octa-2E,6E-diene-1,8-diol diisovalerate — the sex pheromone of the Crimean click beetleAgriotes tauricus — by the carboxymethylenation of the readily available 6-methylhept-5-en-2-one, the allyl oxidation of a terminal methyl group, reduction of the ester fraction, and interaction of the diol so obtained with isovaleryl chloride. The required pheromone can also be obtained from available cyclic oligomers of isoprene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 565–568, July–August, 1991.     

Isomerization in the partial ozonolysis of 1,4-cyclohexadiene

Conclusions The methyl ester of 6-oxo-4E-hexenoic acid is formed in the partial ozonolysis of 1,4-cyclohexadiene in MeOH-CH₂Cl₂ in the presence of NaHCO₃ at –70°C and the subsequent action of acetic anhydride and Et₃N.The authors thank L. M. Khalilov for assistance in interpreting the¹³C NMR spectrum.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1156–1157, May, 1989.     

Insect pheromones and their analogues XL. Synthesis of dodec-3Z-EN-11RS-olide (ferrulactone II — A racemic analogue of a component of the aggregation pheromone of Cryptolestes ferrugineus

A new route, based on the partial ozonolysis of -acetyl derivatives of alk-1-en-4-ynes, is proposed for the synthesis of 11RS-hydroxydodec-3Z-enoic acid, the cyclization of which gives dodec-3Z-en-11RS-olide (ferrulactone II) — a racemic analogue of one of the macrolide components of the aggregation pheromone of the rust-red grain beetle.Institute of Organic Chemistry, Urals Branch, Russian Academy of Science,s Ufa. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 423–429, May–August, 1992.     

Insect pheromones and their analogs. XLIX. Synthesis of tridec-4-en-1-yl acetate — The sex pheromone ofKeiferia lycopersicella

Using the Claisen rearrangement at the stage of constructing the double bond, we have synthesized tridec-4Een-1 yl acetate, the sex pheromone of the tomato pinwormKeiferia lycopersicella.Institute of Petrochemistry and Catalysis, Academy of Sciences of the Republic of Bashkortostan, Republic of Bashkortostan; b) Scientific-Research Institute of Fine Organic Synthesis, Academy of Sciences of the Republic of Bashkortostan. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 490–493, May–June, 1995. Original article submitted November 9, 1994.     

Synthesis of 20-hydroxyecdysone oxime, its diacetonide, and their 14,15-anhydro derivatives

20-Hydroxyecdysone oxime, its diacetonide, and the corresponding 14,15-anhydro derivatives were synthesized. Conditions were found for the preparation of the Z-and E-oximes, and their characteristics ¹H and ¹³C NMR parameters were determined.