Synthesis and activity of optically active disparlure

Iwaki, S.; Marumo, Shingo; Saitô, Tetsuo; Yamada, Minoru; Katagiri, Kazumasa

doi:10.1021/ja00832a055

Cited by 148 publications

(52 citation statements)

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“…The effects of (-)-disparlure were much more apparent on in-flight than pre-flight behavior.Field tests (Vite et al 1976, Miller et al 1977, Carde et al 1977 with 2 different synthetic preparations of disparlure (cis-7,8-epoxy-2-methyloctadecane) enantiomers (Iwaki et al 1974, Morl et at. 1976 proved that: higWy optically pure (+)-disparlure is very attractive to male gypsy moths, Lyman/ria dispar (L.); and when (-) -is combined with (+) -disparlure, trap catches are greatly reduced, i.e., racemic (±)-disparlure caught ca.…”

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confidence: 99%

Gypsy Moth 1 Responses to Pheromone Enantiomers as Evaluated in a Sustained-Flight Tunnel

Miller

Roelofs

1978

Environmental Entomology

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ABSTRACT( -) -Disparlure reduced: (1) the durations of anemotactic flights of mate gypsy moths, Lyman/ria dispar (L.), in plumes of (+) -disparlure; (2) the rate of moth flight with respect to a moving floor pattern; and (3) the percentage of moths initiating anemotactic flights. The effects of (-)-disparlure were much more apparent on in-flight than pre-flight behavior.Field tests (Vite et al. 1976, Miller et al. 1977, Carde et al. 1977 with 2 different synthetic preparations of disparlure (cis-7,8-epoxy-2-methyloctadecane) enantiomers (Iwaki et al. 1974, Morl et at. 1976 proved that: higWy optically pure (+)-disparlure is very attractive to male gypsy moths, Lyman/ria dispar (L.); and when (-) -is combined with (+) -disparlure, trap catches are greatly reduced, i.e., racemic (±)-disparlure caught ca. 10 times fewer males than did (+) -disparlure.The step(s) in the behavioral sequence of attraction to a trap affected by (-) -disparlure remained unknown.Activation bioassays measuring wingfanning (Yamada et al. 1976) revealed little difference in the activities elicited by (+) -and (±)-disparlure, suggesting that the effect on sexual behavior exerted by the (-) enantiomer must be more apparent at some point after initial stimulation of resting moths.As a means of documenting further the effects of ( -) -disparlure on gypsy moth sexual behavior we have used a sustained-flight tunnel to analyze both the pre-flight and in-flight sexual behavior elicited by (+) -and (-) -disparlure and their mixtures. Materials and MethodsAll experiments were conducted with laboratoryreared male gypsy moths supplied by the USDA Gypsy Moth Methods Development Laboratory, Otis AFB, Mass. Shipped pupae were placed in 40x40x 47-cm screened cages and held at 23°C and ca. 70% RH under a 16:8 LID photoperiod. Emerged males were held at the above conditions and used 2-5 days post-eclosion.Experiments were conducted 3-9 h prior to scotophase in the sustained-flight tunnel previously described by Miller and Roelofs (1978). A wind velocity of 65 cm sec-' was maintained throughout the experiments and temperatures were held between 22°-26°C.The enantiomers of disparlure, synthesized and supplied by Mod et al. (1976) paper placed edgewise to the wind and positioned 18 cm above the canvas belt floor.In trapping tests, baited Pherocon™ Ie traps opened to 11 cm and having both a sticky top and bottom (Miller et al. 1977) were hung one at a time at the upwind end of the flight tunnel at ca. 40 cm above the tunnel floor. In a test of their relative attractancy, traps baited with (+)-and (±)-disparlure were alternated. Release cages containing 5 male gypsy moths were inserted into the chemical plumes and opened allowing responding males to fly to the traps.In choice tests, 2 chemical treatments positioned 10 cm apart were introduced into the flight tunnel at once. Smoke generated from sources soaked with titanium tetrachloride demonstrated that resultant plumes were discrete over the upwind half of the tunnel and contiguous near the downwind end. Moths...

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Gypsy Moth 1 Responses to Pheromone Enantiomers as Evaluated in a Sustained-Flight Tunnel

Miller

Roelofs

1978

Environmental Entomology

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“…However, (±) -disparlure is a relatively weak attractant and is not likely to be the natural pheromone. Recently available (+) -disparlure (Iwaki et al 1974, Morl et aI. 1976) effects ca.…”

Section: Resultsmentioning

confidence: 99%

Attractancy of Racemic Disparlure and Certain Analogues to Male Gypsy Moths1 and the Effect of Trap Placement

Cardé¹,

Doane²,

Granett³

et al. 1977

Environmental Entomology

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Traps hung on small trees of 3-8 cm diam and baited with racemic epoxides, hydrocarbons and other analogues related to racemic cis-7,8-epoxy-2-methyloctadecane (disparlure) resulted in male Lymantria dispar L. (gypsy moth) catches statistically indistinguishable from those of unbaited traps. Only (±)-disparlure yielded trap catches statistically above the level of unbaited traps. However, trap placement on trees of ca. 0.5 m diam produced appreciable trap catches, even in unbaited traps.The female-emitted pheromone of the gypsy moth, Lymantria dispar L., was characterized as cis-7,8-epoxy-2-methyloctadecane and named "disparlure" (Bierl et al. 1970). Sarmiento et al. (1972), Adler et al. (1972) and Schneider et al. (1974) reported that (±) -epoxide analogues of disparlure were only slightly attractive when contrasted with (±) -disparlure. Sheads et al. (1975) evaluated the attractancy of diverse compounds structurally similar to disparlure but lacking the epoxide moiety. Sheads et aI. suggested that receptor response is not completely specific to the epoxy group, because these analogues possessed attractancy levels below that of (±) -disparlure but apparently above those of the (± )-epoxide analogues. We report here an investigation of the male trap-catch evoked by certain of these and other compounds related to disparlure. Materials and Methods ChemicalsThe (±)-disparlure and 2-methyl-(Z)-7-octadecene were obtained from Farchan Chemicals and contained 15% (E) isomers. The 2-methyl alkanes (Table 2, Treatments 7-8) were obtained from K and K Laboratories. The (±)-cis-8,9-epoxy-2-methyloctadecane (Treatment 9) was supplied by Zoe con Corporation. The epoxides of treatments 10-12 were prepared by epoxidation of the corresponding olefins 1 Lepidoptera: Lymantriidae.Received for publication May 18, 1977.• Department of Entomology, New York State Agricultural Experiment Station, Geneva 14456.• Present address: Department of Entomology, Michigan State University, East Lansing 48824.• Department of Entomology, The Connecticut Agricultural Experiment Station, New Haven 06504.• Present address: Department of Entomology, University of Maine, Orono 04473.• Present address: USDA, ARS, Beltsville, MD 20705.with m-chloroperbenzoic acid in benzene and were of >95% purity. The 2-methyl-(Z)-6-octadecene was obtained by reaction of triphenyl(6-methylheptyl) phosphonium bromide in DMF with sodium methoxide and dodecanal. The other (Z) alkenes were prepared in a similar manner from the appropriate starting materials. Compounds of treatments 13-17 were prepared by the procedures of Sheads et al. (1975) and were of comparable purity. The trioctanoin was obtained from Eastman Organic Chemicals. All compounds were racemic where optical activity is formally possible. Field TestsTrapping was conducted in oak forests (Quercus spp.) in Wolf's Den State Park in Pomfret, Conn. in July, 1975. All test chemicals were dispensed in 100 p.l petroleum ether either onto cotton wicks of 1 cm diam X 1 cm length or onto 5 X9-mm rubber septa (A...

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“…Their 'H nmr spectra were identical with the authentic samples respectively (7). 'H nmr of compound 16 (CDCI, Preparation of the olejinic lactone 6 (a) A solution of the lactonic acid chloride (24.9g, 0.163 mol) in tetrahydrofuran (75 mL), prepared from L-glutamic acid (9), was added over 20 min to a solution (-10°C) of dimethyl cadmium, prepared from the reaction of methylmagnesium bromide (0.216 mol) with anhydrous cadmium chloride (20.8g, 0.113 mol) in tetrahydrofuran (250 mL) under argon. The reaction mixture was stirred at -10°C for an additional 8 h, at which time 4 N aqueous sulfuric acid (50 mL) was added slowly and the mixture was stirred for 30 min.…”

Section: Methodsmentioning

confidence: 99%