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 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.     

Insect pheromones and their analogs. IV. The synthesis of the sex attractant of the honey beeApis mellifera

A new and convenient method for the synthesis of 9-oxodec-2E-enoic acid (I) from the readily accessible octa-2E,7-dienyl acetate is proposed. From the latter compound by a series of transformations (oxidation of the terminal double bond to a ketone, saponification, hydrogenation, and oxidation with Corey's reagent) 7-oxo-octanal is obtained, and this is condensed by the Knoevenagel reaction with malonic acid to give compound (I) with a yield of 69%.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 387–389, May–June, 1980.     

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.     

Insect pheromones and their analogs I. Synthesis of the sex attractant of the codling moth

Summary The synthesis of the sex attractant of the codling mothLaspeyresia pomonella has been performed using as the initial compounds linear dimers of butadiene with methyl acrylate.Institute of Chemistry, Bashkir Branch of the Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 125–127, January–February, 1978.     

Insect pheromones and their analogs. VII. Synthesis of the sex pheromone of the fruit flyCeratitis capitata

A new and simple route to the synthesis of non-6E-en-l-ol (I) — the pheromone of the fruit flyCeratitis capitata Wiedemann — has been proposed on the basis of the readily available co-oligomer of butadiene and phenol, 1-phenoxyocta-2E, 7-diene (II).     

Insect pheromones and their analogs. XIV. Synthesis of muscalure — The sex pheromone ofMusca domestica

A new route to the synthesis of tricos-9Z-one — the sex pheromone of the house fly — has been developed.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 401–403, May–June, 1985.     

Insect pheromones and their analogs. XII. Synthesis of the isomeric dec-5-enyl acetates — The sex pheromones ofAnarsia lineatella andAgrotis segetum

A new route for the synthesis of dec-5E- and -5Z-enyl acetates — the sex pheromones of the peach-tree borer and of the turnip moth — is proposed which is based on the two-stage hydroxyethylation of hex-1-yne using 2-chloroethyl vinyl ethers and ethylene oxide.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 395–398, May–June, 1985.     

Insect pheromones and their analogs II. Synthesis of the sex attractant of the gypsy moth - d,l-disparlure

Summary A new route for the synthesis of 2-methyl-Z-7,8-epoxyoctadecane — the attractant ofPorthetria dispar — has been developed which uses as the starting compounds linear oligomers of butadiene and isoprene with methyl acrylate.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 792–795, November-December, 1978. Original article submitted July 25, 1978.     

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.     

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.     

Insect pheromones and their analogs. XV. The synthesis of 9-oxodec-2E-enoic acid — A pheromone of the honeybeeApis melliferana

A new effective route to the synthesis of 7-oxooctanal has been found which is based on the ozonolysis of the tetrahydropyran-2-yl ether of 7-methyloct-7-en-l-ol — the product of the coupling of the readily available methallyl chloride and the Grignard reagent from the corresponding ether of 5-bromopentan-l-ol. From the 7-oxooctanal has been obtained 9-oxodec-2E-enoic acid — a pheromone of the honeybeeApis melliferana.     

Insect pheromones and their analogs. XIII. Synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates — Components of the sex pheromones ofGrapholitha funebrana andGrapholitha molesta

A new route is proposed for the synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates which is based on the reaction of the Grignard reagent from the readily accessible 1-bromo-5-(1-ethoxyethoxy)pentane with 1-bromohept-3-yne — the bromide obtained from product of the -hydroxyethylation of pent-1-yne with 2-chloroethylvinyl ether, hept-3-yn-1-ol, by a double decomposition reaction of its tosylate with lithium bromide. The key synthon — dodec-8-yn-1-ol — was converted with the aid of sodium in liquid ammonia into the stereochemical individual dodec-8E-enol, while its reduction with the aid of 9-borabicyclo[3.3.1]nonane (BBN) gave the steroisomeric alcohol exclusively with the Z configuration, as followed from the results of capillary GLC and the IR spectra of the corresponding acetates. The PMR spectra of the compounds synthesized are also given.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 398–400, May–June, 1985.     

Insect pheromones and their analogs. LVII. Synthesis of the racemic analog of the sex pheromone of pine sawflies of the generaDiprion andNeodiprion

A new route has been developed to the selective transformations of 1,1-dimethoxy-4-methyl-8-oxonon-4Z-ene —a product of the partial ozonolysis of 1,5-dimethylcycloocta-1Z, 5Z-diene—leading to (±)-3,7-dimethylpentadec-2-yl acetate, the racemic analog of the sex pheromone of pine sawflies of theDiprion andNeodiprion genera.     

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.     

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.