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.     

Insect pheromones and their analogues

Pheromone components of insects of the generaHeliothis andMamestra have been synthesized with the use of functionally differentiated ozonolysis of cyclododecene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 132–135, January–February, 1991.     

Insect pheromones and their analogues

A stereospecific synthesis has been achieved of tetradec-11E-enal and of tetradec-11E-en-l-ol and its acetate — components of the pheromones of many species of insects of the order Lepidoptera — from the readily available undecenoic acid, using the Knoevenagel reaction and catalytic hydroalumination.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1992.     

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.     

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 analogues XXIV. Synthesis of long-chain 1,5-dimethyl-branched pheromones from geranyl acetate

Schemes for the synthesis of long-chain 1,5-dimethyl-branched pheromones (7,11-dimethyloctadecane, 15,19-dimethyltritriacontane, and 2-acetoxy-3,7-dimethylpentadecane) from the product of the allyl oxidation of geranyl acetate (8-acetoxy-2,6-dimethylocta-2E,6E-dien-1-ol) have been developed.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 818–823, November–December, 1990.     

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.     

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.     

Insect pheromones and their analogues XXIV. Synthesis of long-chain 1,5-dimethyl-branched pheromones from geranyl acetate

Schemes for the synthesis of long-chain 1,5-dimethyl-branched pheromones (7,11-dimethyloctadecane, 15,19-dimethyltritriacontane, and 2-acetoxy-3,7-dimethylpentadecane) from the product of the allyl oxidation of geranyl acetate (8-acetoxy-2,6-dimethylocta-2E,6E-dien-1-ol) have been developed.     

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.     

Insect pheromones and their analogues. XLV. Synthesis of mono-and dienic components of insect pheromones from isopropyl nona-3E,8-dienoate

Non-6E-en-l-ol, dodec-3E-en-l-yl acetate, and dodeca-7E, 9Z-dien-l-yl acetate, which are components of sex pheromomes of insects of the orderLepidoptera, have been synthesized from the readily accessible isopropyl nona-3E,8-dienoate.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedeninii, No. 1, pp. 145–150, January–February, 1993.     

Insect pheromones and their analogues. XXII. Methyl-branched pheromones based on 4-methyltetrahydropyran. Synthesis of racemic 2-acetoxy-3,7-dimethylpentadecane (diprionyl acetate)

A synthesis is proposed of racemic 2-acetoxy-3,7-dimethylpentadecane — the sex attractant (diprionyl acetate) of plane sawflies of the generaDiprion andNeodiprion on the basis of the regioselective transformation of bifunctional products of the cleavage of 4-methyltetrahydropyran.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 573–576, July–August, 1989.     

Insect pheromones and their analogues. XXII. Methyl-branched pheromones based on 4-methyltetrahydropyran. Synthesis of racemic 2-acetoxy-3,7-dimethylpentadecane (diprionyl acetate)

A synthesis is proposed of racemic 2-acetoxy-3,7-dimethylpentadecane — the sex attractant (diprionyl acetate) of plane sawflies of the generaDiprion andNeodiprion on the basis of the regioselective transformation of bifunctional products of the cleavage of 4-methyltetrahydropyran. Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 573–576, July–August, 1989.     

Insect pheromones and their analogs. LX. Stereocontrolled synthesis of sex pheromones ofDrosophila mulleri andMayetiola destructor

Syntheses are developed for 2S-tridecyl- and 2S-tridec-10E-enylacetates, sex pheromones of the fruit flyDrosophila mulleri and the Hessian flyMayetiola destructor, respectively, that are based on ethyl-3S-hydroxybutanoate, a product from enzymatic reduction of ethyl acetoacetate by the soil yeast strain 80-1.Work performed under the auspices of the Federal program Integratsiya of the RF (Contract No. A 0005).Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 167–169, March–April, 2000.     

Insect pheromones and their analogues XLII. Synthesis of 2,6-dimethyloct-1-yl formate — A mimic of the aggregation pheromone of flour beetles

2-6-Dimethyloctan-1-ol, the formate of which is a mimic of the aggregation pheromone of the flour beetlesTribolium confusum andT. castaneum, has been synthesized by the hydroboration of 2,6-diemthyloct-1-ene, obtained from β-methylvaleric acid. Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 571–573, September–October, 1992.     

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.