Pheromones of insects and their analogs

From cyclohexene and caproaldehyde, using ozonolysis and the Knoevenagel reaction, we have synthesized hexadeca-7Z,11E-dien-l-yl acetate — the sex pheromone ofSitotroga cerealella and a component of the sex pheromone ofPectinophora gossypiella.     

Pheromones of insects and their analogs

From cyclohexene and caproaldehyde, using ozonolysis and the Knoevenagel reaction, we have synthesized hexadeca-7Z,11E-dien-l-yl acetate — the sex pheromone ofSitotroga cerealella and a component of the sex pheromone ofPectinophora gossypiella.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 704–707, September–October, 1991.     

Pheromones of insects and their analogs. XX. Methyl-branched pheromones based on 4-methyltetrahydropyran.

A synthesis is proposed of 4,8-dimethyldecanal (VIII) — a pheromone of the flour beetlesTribolium confusum andT. castaneum. By heating 71.2 g of 4-methyltetrahydropyran (I), 83.2 g of AcBr and 1.57 g of ZnCl₂ (45°C), then 120°C, 2 h), 1-acetoxy-5-bromo-3-methylpentane (II) was obtained. The hydrolysis of 19.8 g of (II) (MeOH-H₂O, TsOH, 20°C, 15 h) gave 5-bromo-3-methylpentan-1-ol (III). From 18.1 g of (III) and 38.9 ml of 2,3-dihydropyran (Et₂O, TsOH, 20°C, 20 h) was obtained the 2-THPL ester of (III), (IV), which was converted into 3-methyloct-7-en-1-ol (V) by the treatment of the corresponding Grignard reagent with allyl bromide (THF, CuI-bi-2-pyridyl, 2°C, 4 h, Ar). The interaction of 1.42 g of (V) with Et₃Al (hexane, 20°C, Cp₂ZrCl₂, Ar) gave 3,7-dimethylnonan-1-ol (VI), boiling which with 48% HBr in the presence of concentrated H₂SO₄ gave 1-bromo-3,7-dimethylnonane (VII) which was then converted into the desired (VIII) by the reaction of the corresponding Grignard reagent with DMFA (0–2°C, 1 h; 20°C, 2 h; Ar). The characteristics of the compounds — yield (%), n_D (°C): (I), 79, 1.4340 (22); (III) 89, 1.4660 (23); (IV), 82, 1.4739 (23); (V), 85, —; (VI), 90, 1.4483 (20); (VII), 88, 1.4409 (22); (VIII), 88, 1.4589 (22). Details of the IR and PMR spectra of compounds (II)–(VII) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1989.     

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.     

Pheromones of insects and their analogs LIV. Synthesis of dodec-9E-en-1-ol and its acetate —components of the sex pheromone ofSparganothis pilleriana

Using the Claisen rearrangement in the construction of a double bond with the E configuration, we have synthesized dodec-9E-en-l-ol and its acetate, which are components of the sex pheromone ofSparganothis pilleriana.Scientific Research Institute of Fine Organic Synthesis of the Academy of Sciences, Republic of Belarus. Ufa State Petroleum Technical University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 936–939, November–December, 1996. Original article submitted May 11, 1996.     

Pheromones of insects and their analogs. XXVIII. Practical synthesis of tetradeca-9Z,12E-dien-1-yl acetate — A component of the sex pheromones of insects of the order lepidoptera

Tetradeca-9Z,12E-dien-l-yl acetate, a sex pheromone of the Indian meal mothPlodia interpunctella has been synthesized from the readily available product of the hydrodimerization of butadiene — octa-1,7-diene.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, 1991.     

Pheromones of insects and their analogs. XXVII. Synthesis of 10-hydroxy-4,8-dimethyldeca-4E,8E-dienoic acid and of racemic 4,8-dimethyldecanal from geranyl acetate

10-Hvdroxy-4,8-dimethyldeca-4E,8E-dienoic acid and racemic 4,8-dimethyldecanal (components of beetle pheromones) have been synthesized from geranyl acetate.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1991.     

Pheromones of insects and their analogs. XXIX. Methyl-branched pheromones from 4-methyltetrahydropyran 4: Synthesis of (±)-15,19,23-trimethylheptatriacontane — A pheromone of Glossina morsitans morsitans

Racemic 15,19,23-trimethylheptatriacontane (the sex pheromone of the tsetse flyGlossina morsitans morsitans) has been synthesized from 1,5-dibromo-3-methylpentane, a product of the acid hydrolysis of 4-methyltetrahydropyran.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 417–419, May–June, 1991.     

Pheromones of insects and their analogs. V. A new approach to the synthesis of the sex pheromones of insects of the orderLepidoptera which is based on the selective ozonolysis of 1-methylcycloocta-1Z,5Z-diene

A new synthesis of 1-acetoxyalk-Z-enes (sex pheromones of insects of the orderLepidoptera) has been developed which is based on the selective ozonolysis of 1-methylcycloocta-1Z-5Z-diene — a cooligomer of isoprene and butadiene.     

Cyclazines and their analogs

The formylation of 2-methyl-6-cyanomethylthiopyridines, 2-methyl-4-cyanomethylthiopyrimidines, or 3-amino-5-methylthiazolopyrimidinium salts gave cyclazine derivatives of new heterocyclic systems with an angular nitrogen atom, which were used for the preparation of polymethine dyes. The relationship of the color and structure of these compounds was studied.For Communication 2, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1280–1285, September, 1992.     

Cyclazines and their analogs

Derivatives of a new heterocyclic system, formyl-substituted thiazolopyrimidopyrimidines, are synthesized through reaction of 3-amino-5-methyl-thiazolo[3,2-a]pyrimidinium salts, prepared by alkylation of 2-mercaptopyrimidines with substituted acetonitriies, and the Vilsmeier reagent. These can be used to synthesize polymethine dyes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 692–697, May, 1992.     

Insect pheromones and their analogs

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)₄Ti, t-BuOOH, ?15°C, 20 h; H₂O, 1 h, NaOH, ?7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO₃-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C₈H₁₇CH=PPh₃ (?78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H₂/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [α] _D ²⁵ : (II), 73, ?2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the¹³C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.     

Insect pheromones and their analogs

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)₄Ti, t-BuOOH, –15°C, 20 h; H₂O, 1 h, NaOH, –7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO₃-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C₈H₁₇CH=PPh₃ (–78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H₂/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [] _D ²⁵ : (II), 73, –2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the¹³C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 715–718, September–October, 1989.     

Insect pheromones and their analogs

Two methods of synthesizing -geranyl propionate — a component of the sex pheromone of San Jose scale — have been developed: the hydride reduction of the corresponding 6-chloro derivative and the electrochemical reduction of the 6-dimethylsulfonium derivative.For the preceding communication, see [1].Institute of Chemistry, Bashkir Scientific Center, Urals Division, Academy of Sciences of the USSR, Ufa. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 419–421, May–June, 1989.     

Insect pheromones and their analogs

A highly selective synthesis of 2-methyl-cis-7, 8-epoxyoctadecane — the racemic analog of the sex pheromone of the gypsy moth Porthetria dispar L. — (Z)-disparlure — has been developed that is based on the functionally differentiated partial ozonization of cycloocta-IZ.5Z-diene.Institute of Petroleum and Catalysis, Academy of Sciences of the Republic of Bashkortostan, 450075, Ufa, Prospekt Oktyabrya, 141. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 901–904, November-December, 1995. Original article submitted February 21, 1995.     

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.     

Nucleogenic silylium cations and their analogs

Radiochemical studies of nucleogenic trivalent cations of the 14th group elements (silicon and germanium) generated by the β-decay of tritium atoms incorporated into organometallic molecules are reviewed. The radiochromatographic analysis of the neutral labeled products of reactions of these cations with various nucleophiles combined with quantum chemical data allowed us to obtain new information about the reactivity and rearrangements of silylium and germylium cations.     

Pheromones of insects and their analogs. LII. Sythesis of dodec-9-en-1-yl and tetradec-11-en-1-yl acetates from the products of the partial ozonolysis of cycloocta-1z,5z-diene and cyclodeca-1e,5z-diene

A new approach to the synthesis of octane-1, 8- and decane-1,10-diols based on the partial ozonolysis of cyclic oligomers has been developed.Institute of Petrochemistry and Catalysis, Academy of Sciences of the Republic of Bashkortostan, 450075, Ufa–75, Prospekt Oktyabrya, 141. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 403–406, May–June, 1996. Original article submitted December 5, 1995.