- Modified Ozonolytic Synthesis of 4Z-Nonen-1-ol, an Intermediate for the Synthesis of Sex Pheromones of Cotton Bollworm and Cabbage Moth, from the Cyclic Butadiene-Isoprene Codimer
-
An improved procedure for preparing 4Z-nonen-1-ol, a key intermediate in the synthesis of sex pheromones of cabbage moth and cotton bollworm, from the cyclic butadiene-isoprene dimer (1-methyl-1Z,5Z-cyclooctadiene) was developed. In this procedure, the peroxide product of regioselective partial ozonolysis (0.9 equiv of O3) of the codimer across the trisubstituted double bond is converted in one step to 9-hydroxy-5Z-nonen-2-one with NaBH(OAc)3, the reagent that does not affect the keto groups present in the structure or formed in the process.
- Ishmuratov, G. Yu.,Myasoedova, Yu. V.,Garifullina,Nurieva,Ishmuratova
-
-
Read Online
- Synergistic sex pheromone components of white-spotted tussock moth, Orgyia thyellina
-
In 1996, the exotic white-spotted tussock moth (WSTM), Orgyia thyellina (Lepidoptera: Lymantriidae), was discovered in Auckland, New Zealand. Because establishment of WSTM would threaten New Zealand's orchard industry and international trade, eradication of WSTM with microbial insecticide was initiated. To monitor and complement eradication of WSTM by capture of male moths in pheromone-baited traps, pheromone components of female WSTM needed to be identified. Coupled gas chromatographic-electroantennographic detection analysis of pheromone gland extract revealed several compounds that elicited responses from male moth antennae. Mass spectra of the two most EAD-active compounds suggested, and comparative GC-MS of authentic standards confirmed, that they were (Z)-6-heneicosen-11-one (Z6-11-one) and (Z)-6-heneicosen-9- one, the latter termed here 'thyellinone.' In field experiments in Japan, Z6- 11-one plus thyellinone at a 100:5 ratio attracted WSTM males, whereas either ketone alone failed to attract a single male moth. Addition of further candidate pheromone components did not enhance attractiveness of the binary blend. Through the 1997-1998 summer, 45,000 commercial trap lures baited with 2000 μg of Z6-11-one and 100 μg of thyellinone were deployed in Auckland towards eradication of the residual WSTM population.
- Gries, Gerhard,Clearwater, John,Gries, Regine,Khaskin, Grigori,King, Skip,Schaefer, Paul
-
p. 1091 - 1104
(2007/10/03)
-
- A convergent and highly efficient synthesis of (E,Z)-2,13-octadecadienyl acetate and (E,Z)-3,13-octadecadienyl acetate, components of the sex pheromone of the Leopard Moth Zeuzera pyrina, through sulfones
-
(equation presented) A new, convergent synthesis of (E,Z)-2,13-octadecadienyl acetate (1) and (E,Z)-3,13-octadecadienyl acetate (2), the two key components of the leopard moth Zeuzera pyrina, from 2-chloromethyltetrahydrofuran in good overall yields and stereomeric purity is reported. The synthesis of both components utilizes the common intermediate sulfone 12 as a convenient building block to be coupled with iodoacetylenic derivatives 9 or 17 in the key step.
- Capdevila, Anna,Prasad, Attaluri R.,Quero, Carmen,Petschen, Ine?s,Bosch, Maria P.,Guerrero, Angel
-
p. 845 - 848
(2008/02/09)
-
- Nucleophile-induced ring enlargement of 1-(1-iodoalkyl)silacyclobutane and 1-(1,2-epoxyalkyl)silacyclobutane into silacyclopentane. Application to the synthesis of 1,4-diol, 4-alken-1-ol, and 1,4,5-triol
-
Two methods for ring enlargement of silacyclobutane into silacyclopentane have been described. (1) Treatment of 1-(1-iodoalkyl)silacyclobutane with t-BuOK or AgOAc provided 2-alkyl-1-silacyclopentanes which were easily converted into 1,4-diols by oxidativ
- Matsumoto,Takeyama,Miura,Oshima,Utimoto
-
p. 250 - 261
(2007/10/02)
-
- Preparation of Geometrical Isomers of 2,7-Dodecadienal, 2,7-Dodecadienyl Formate, and Other 1,6-Diene System-containing Compounds and Their Electroantennography Activities toward Male Eri-Silk Moths
-
We measured the electroantennography (EAG) activities of the geometrical isomers of several pheromone-related compounds towards male eri-silk moths (Samia cynthia richini) using EAG-gas chromatography (GC).C16-aldehyde and formyl ester, with the same chain length as C16-aldehyde, were found to be much more active than other compounds with a shorter chain.For the compounds with (1Z,6Z)- or (1E,6E)-configuration, the activity in decreasing order was C14-formyl ester > C16-aldehyde > C14-aldehyde > C12-formyl ester, while that for the compounds with (1Z,6E)- or (1E,6Z)-configuration is C16-aldehyde > C14-formyl ester > other compounds with a shorter C14 chain.
- Hatanaka, Akihiko,Ishii, Yasushige,Tomida, Ichiro
-
p. 2036 - 2038
(2007/10/02)
-
- STEREOSPECIFIC SYNTHESIS OF COMPONENTS OF THE NATURAL SEX PHEROMONE OF Pectinophora gossypiella
-
A multistage stereospecific synthesis of components of the natural pheromone was realized.Conditions were found for stereospecific trans-reduction of the triple bonds.A procedure was developed for regiospecific dehydrohalogenation of 1,2-dibromoalkanes.Conditions giving the Z and E isomers in ratio of 96 : 4 were found for the Wittig reaction.
- Matveeva, E. D.,Kvasha, M. P.,Kurts, A.L.
-
p. 1017 - 1021
(2007/10/02)
-
- Lithium Carbenoids Induced Ring Enlargement of Silicacyclobutane into 2-Halo-1-silacyclopentane and its Use in Organic Synthesis
-
An addition of lithium diisopropylamide to a solution of 1,1-dimethyl-1-silacyclobutane and dihalometane such as CH2I2, CH2Br2, or CH2Cl2 provided the corresponding 1,1-dimethyl-2-halo-1-silacyclopentane in good yield.The reactions of 1,1,2-trimethyl-1-si
- Matsumoto, Kozo,Aoki, Yoshitaka,Oshima, Koichiro,Utimoto, Kiitiro
-
p. 8487 - 8502
(2007/10/02)
-
- An efficient and stereoselective synthesis of insect pheromones by way of nickel-catalyzed Grignard reactions. Syntheses of gossyplure and pheromones of Eudia pavonia and Droxophila melanogaster
-
Three pheromones, (6Z,11Z)-hexadeca-6,11-dien-1-yl acetate (from Eudia pavonia), (5Z,9Z)-heptacosa-5,9-diene (from Drosophila melanogaster) and gossyplure, have been synthesized each by two consecutive consequences of nickel-assisted Grignard reactions with cyclic enol ethers and preparation of Grignard reagents from the resultant alcohols.
- Ducoux, Jean-Philippe,Le Menez, Patrick,Kunesch, Nicole,Kunesch, Gerhard,Wenkert, Ernest
-
p. 6403 - 6412
(2007/10/02)
-
- Base-induced rearrangement of oxiranylsilacylobutane into silacyclopentane. Application to stereoselective synthesis of 4-alken-1-ol and 1,4,5-triol
-
Treatment of 1-methyl-1-(cis-1,2-epoxyhexyl)-1-silacyclobutane 16a with i-PrOLi provided erythro-1-methyl-1-isopropoxy-2-(2-hydroxypentyl)-1-silacyclopentane 17a which was converted into (Z)-4-nonen-1-ol 18, (E)-4-nonen-1-ol 19, or 1,4,5-nonanetriol 20, r
- Matsumoto,Takeyama,Oshima,Utimoto
-
p. 4545 - 4548
(2007/10/02)
-
- Cyclic ethers as educts for the synthesis of lepidoptra pheromones
-
ω-Iodo(trialkylsiloxy)alkanes 2 prepared by ring opening of cyclic ethers with iodotrimethylsilane, are useful starting materials for the synthesis of pheromone components. Reaction with triphenylphosphine to give the corresponding Wittig reagent and subsequent coupling with lithium (Z)-dihex-1-enylcuprate gives (Z)-alken-1-ols 5 and 7, after deprotection, in good yields. The direct coupling of 2 with alkynes failed because of competition reactions, however, the more stable ω-iodo-1-(tert-butyldimethylsiloxy)alkanes were able to undergo C,C-coupling with alkynes. The thus formed 1-(tert-butyldimethylsiloxy)-5-decyne (13c) was hydrogenated and deprotected to give (E)-5-decen-1-ol (15c).
- Poleschner,Heydenreich,Martin
-
p. 1231 - 1235
(2007/10/02)
-
- SHORT, REGIO- AND STEREO-SELECTIVE PREPARATION OF 1,5- AND 1,6-DIENES. SYNTHESES OF EUDIA PAVONIA PHEROMONE AND GOSSYPLURE.
-
Two pheromones, (Z)-6,(Z)-11-hexadecadien-1-yl acetate (from Eudia pavonia) and gossyplure, have been synthesized each by two consecutive sequences of nickel-assisted Grignard reactions with cyclic enol ethers and the preparation of Grignard reagents from the resultant alcohols, followed each by copper-promoted Grignard reaction with a small-ring ether and subsequent acetylation.
- Ducoux, Jean-Philippe,Menez, Patrick Le,Kunesch, Nicole,Kunesch, Gerhard,Wenkert, Ernest
-
p. 2595 - 2598
(2007/10/02)
-
- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XLII. SYNTHESIS OF (9Z)-TETRADECENYL ACETATE AND (9Z)-HEXADECENAL FROM (Z,Z)-1,5-CYCLOOCTADIENE
-
A stereocontrolled synthesis of (9Z)-tetradecenyl acetate and (9Z)-hexadecenal, which are components of the sex pheromones of the pine (Panolis flammea) and cotton (Heliothis armigera) moths respectively, was realized on the basis of the partial ozonolysis of (Z,Z)-1,5-cyclooctadiene.
- Odinokov, V. N.,Galeeva, R. I.,Ishmuratov, G. Yu.,Kargapol'tseva, T. A.,Sokol'skaya, O. V.,et al.
-
p. 1986 - 1989
(2007/10/02)
-
- Organoaluiminum-promoted claisen rearrangement of allyl vinyl ethers
-
Unprecedentad stereochemical control has achieved in the Claisen of allyl vinyl of type 4 with certain bulky organoaluminum Thus, methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (reagent A) can be utilized for obtaining the (Z) isomer, (Z)-6, whereas the (E) isomer, (E)-6 was produced with methylaluminum bis(2,6-diphenylphenoxide) (reagent B). This organoaluminum-promoted Claisen rearrangement proceeds under very mild conditions with very good E and Z selectlvities. On the basis of the Claisen rearrangement of optically active substrate 7 with reagent A, the Z selectivity would be interpreted by the intervention of the chairlike transition-state conformation with the isobutyl substituent axial. The present organoalunminum-promoted Claisen rearrangement has successfully applied to the synthesis of (4E,7Z)-4,7-tridecadienyl acetate (15), a component of the sex of tuberworm moth, in stereoselective fashion. Furthermore, the Claisen rearrangement of bisallyl vinyi ether16 with reagent A or B has been found to involve the more substituted allylic system to furnish dienal 18 preferentially, not obtainable in the ordinary thermal rearrangement. This chemistry been further extended to the ionic rearrangement of dienyl vinyl ether 28 by using reagent A in a polar solvent the previously unknown, remote transfer of the vinyloxy moiety by [3,5]-sigmatropic rearrangement via ionic intermediate 29 has observed.
- Nonshita, Katsumasa,Banno, Hiroshi,Maruoka, Keiji,Yamamoto, Hishashi
-
p. 316 - 322
(2007/10/02)
-
- A New Synthesis of (Z)-9-Tetradecen-1-yl Acetate
-
Alkylation of propargyl alcohol dianion with n-butyl bromide provides hept-2-yn-1-ol (II) which is converted into its bromide (III) and subsequently alkylated with monosodio ethyl malonate to furnish the diester (IV).The latter on decarbethoxylation with NaCl/DMSO affords the ester (V).Catalytic hydrogenation of V in the presence of Lindlar's catalyst produces ethyl non-4Z-en-1-oate (VI) which on LAH reduction gives the carbinol (VII) whose corresponding bromide (VIII) on coupling reaction with 1-bromo-5-tetrahydropyranyloxypentane gives IX.Removal of the protective pyranyl moiety from IX followed by treatment with acetic acid-acetyl chloride yields the title compound (I).
- Vig, O. P.,Sharma, M. L.,Kumari, Sarla,Vohra, Neelam
-
p. 962 - 964
(2007/10/02)
-
- STEREOSELECTIVE AND VERSATILE APPROACH FOR THE SYNTHESIS OF GOSSYPLURE AND ITS COMPONENTS
-
Efficient synthetic routes to gossyplure and its components (1a and 1b) were formulated.The three key units viz the alkynol 3, the bromide 5, and the alkanal 13 were derived from easily accessible starting materials.Alkylation of 3 with 5, and subsequent semihydrogenation followed by oxidation, provided the C11-alkenal 8 which was subjected to a stereocontrolled Wittig reaction with a C5-phosphonium salt, to yield directly the disired pheromone (1a + 1b).The synthesis of its individual components involved the manipulation via an acetylenic intermediate, viz the alkynol 14 which was obtained through alkylation of 3.A sequence of well-established reactions on 14, then provided the corresponding (E)- and (Z)-alkenylphosphonium salts which upon a (Z)-specific Wittig olefination with the C7-aldehyde (13), led to the stereoselective synthesis of 1a and 1b.
- Joshi, N. N.,Mamdapur, V. R.,Chadha, M. S.
-
p. 3285 - 3290
(2007/10/02)
-
- ALIPHATIC CLAISEN REARRANGEMENT PROMOTED BY ORGANOALUMINIUM REAGENTS.
-
Organoaluminium compounds, R//3Al, promote the Claisen rearrangement of allyl vinyl ether derivatives at room temperature under transfer of R or H as a nucleophile to the aldehydic carbon. Treatment of 1-butyl-2-propenyl vinyl ether with a hexane solution of Me//3Al (1. 0 M, 2. 2 equiv) in CH//2ClCH//2Cl at 25 degree C afforded 5-decen-2-ol (91% yield, E/Z equals 47/53), which was produced by the left bracket 3,3 right bracket sigmatropic rearrangement and successive methylation. The rearrangements with alkynylation, alkenylation, and hydrogenation are also achieved. The regular Claisen rearrangement products, of gamma , delta -unsaturated aldehydes (ketones), are obtained at 25 degree C in good to excellent yields with Et//2AlSPh (2. 5 equiv) or the combination of Et//2AlCl (2. 0 euiv) and PPh//3 (2. 2 equiv).
- Takai,Mori,Oshima,Nozaki
-
p. 446 - 451
(2007/10/02)
-
- PHEROMONES OF INSECTS AND THEIR ANALOGS. V. A NEW APPROACH TO THE SYNTHESIS OF THE SEX PHEROMONES OF INSECTS OF THE ORDER Lepidoptera 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 order Lepidoptera) has been developed which is based on the selective ozonolysis of 1-methylcycloocta-1Z-5Z-diene - a cooligomer of isoprene and butadiene.
- Tolstikov, G. A.,Odinokov, V. N.,Galeeva, R. I.,Bakeeva, R. S.,Akhunova, V. R.
-
p. 219 - 224
(2007/10/02)
-