This is a divisional of U.S. application Ser. No. 09/425,321, filed on Oct. 21, 1999, now issued as U.S. Pat. No. 6,264,939.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention concerns novel bisexual attractants for codling moth and other species of Lepidoptera. In particular, the invention concerns attractants isolated from pear or apple volatiles which have superior and selective attractancy for adult codling moths and other lepidopterous species. These attractants also attract, aggregate and/or arrest larvae of these species. The invention further concerns a method for monitoring, control, mass trapping and mating disruption of codling moth and other lepidopterous species. The method includes luring the pest to a formulation containing the attractant, aggregant or arrestant of the invention, alone, or in combination with a sex pheromone and/or another kairomone and/or insecticide.

2. Background and Related Disclosures

Insect pests, particularly insects of the order Lepidoptera, such as codling moth, are responsible for substantial losses of fruit and nut crops. Currently, the most often utilized systems for monitoring and controlling these insect pests are compositions comprised of an attractant, almost always a sex pheromone attractant, optionally in combination with an insect killing substance, such as an insecticide. The majority of the baits or traps utilize sex pheromones that attract only males. While these traps and baits provide a certain degree of monitoring information and control, they are not effective in attracting the females, which are responsible for reproduction, nor larvae, which are responsible for damaging fruits and nuts.

Semiochemicals are behavior modifying chemicals acting as chemical signals that elicit certain behaviors from other individuals of either the same species (i.e., pheromones) or from other species (i.e., kairomones and allomones). The best known semiochemicals are pheromones.

Over 1600 insect pheromones have now been identified. Typically, the sex pheromones are produced and released by females at the time of mating to attract conspecific male insects. Since females are responsible for laying eggs and since each female may lay large numbers of eggs during one season, it is very important to monitor and control females in addition to males. The sex pheromones used in lures or baits, however, in general, only attract the male insect. Thus, the real purpose of luring or killing insect pests is unfulfilled because even one fertile female may lay enough eggs to substantially infest a large area. Also, lures and baits for larvae are needed which would intercept and kill the larvae before they damage fruit and nut crops.

The use of sex pheromones for attracting and killing an insect pest is thus of limited utility. It would be very advantageous to provide substances which would attract males and attract and/or modify the behavior of females and/or their larval offspring.

Kairomones, the second type of semiochemicals, are typically odoriferous volatile compounds from plants, which are recognized by the insect pests and aid them in locating suitable host plants. Their value as insect pest attractants has been previously recognized and many attempts were made to utilize kairomones as insect pest attractants. The primary advantage of kairomones is that in most cases they attract both males and females. However, typically they are not very well detected by individual insect species and, therefore, lack general utility as useful attractants.

Chemotropic utility of various fermenting baits was already recognized in 1943, when molasses and yeast containing baits with or without the addition of shelf chemicals were tested for their chemotropic utility. This work is described in

J. Econ. Entomology,

36: 430 (1943).

The unrelated and chemically distinct sesquiterpene, (E,E)-&agr;-(-farnesene has been recognized as a larval attractant since 1972, as described in

Nature,

239:170 (1972).

Sensitivity of antennae of male and female insect of the order of Coleoptera was studied with regard to conspecific aggregation pheromones, allomones and host-produced odorants. The lowest antennal sensitivity was observed for host produced odorants (

J. Chem. Ecol.,

9:585 (1983)).

Attractivity of volatile components of starthistle flower for flies and weevils was described in

J. Agric. Food Chem.,

34: 786 (1986). Tomato leaf volatile aroma components are described in

J. Agric. Food Chem.,

35: 1039 (1987).

Electroantennogram responses of the oriental fruit fly to a spectrum of alcohol and aldehyde plant volatiles are described in

Entomologia Experimentalis et Aplicata,

45: 55 (1987) and in

J. Chem. Ecol.,

14: 159 (1988), and to volatile constituents of nectarines in

Entomol. Exp. Appl.

63: 13 (1992).

J. Chem. Ecol.,

22: 1735 (1996) describes electroantennogram responses of Lepidoptera to volatile compounds from moth-pollinated flowers. Headspace examination of volatile emission of organic compounds from ripening papaya is described in

J. Agric. Food Chem.,

38: 105 (1990).

Chemoecology,

4: 175 (1993) describes enhancement of sex pheromone attraction with green leaf volatiles for tobacco budworm. The synergistic effect of host-plant green-leaf on the synthetic sex pheromones of the corn earworm and codling moth is described in

Chemoecology,

4: 145 (1993).

Plant volatiles were shown to evoke and modulate tephritid behavior (

Fruit Fly Pests

, Part II, 123-134 (1996), Eds. McPheron, B. and Steck G., St. Lucie Press, Debray Beach, Fla.).

U.S. Pat. No. 5,665,344 describes volatiles of Japanese honeysuckle flowers as attractants for adult lepidopterous insects.

However, as described in all the above references, the host-plant volatiles are typically used in combinations of several volatiles and these mixtures show weak attractancy over the background plant volatile odors that are present in the environment.

It would, therefore, be advantageous to provide semiochemicals which would attract adult insects of both sexes and the larvae, but primarily, which would attract the female insect responsible for reproduction and attract, aggregate or arrest the larvae responsible for crop damage.

It is, therefore, a primary objective of the current invention to provide semiochemical kairomonal attractants which would strongly attract both the female and male adult insect pests as well as the larvae to monitoring traps, lure-kill traps or baits and in this way attract, aggregate, arrest and/or kill the adult males and particularly the adult reproductive females and the larvae and which would also provide monitoring tools and control and protection of crops from the insect pest.

All patents, patent applications and publications cited herein are hereby incorporated by reference.

SUMMARY

One aspect of the current invention is a novel class of bisexual attractants for the codling moth (

Cydia pomonella

) and other lepidopterous species.

Another aspect of the invention is a bisexual attractant selective for female codling moth which is present in the odors and extracts of pome fruits.

Another aspect of the current invention is an attractant, aggregant or arrestant for larvae of lepidopterous species, particularly codling moth, which is present in the odors and extracts of pome fruits.

Still another aspect of the current invention are compounds, represented by pure ethyl (2E,4Z)-2,4-decadienoate or an isomer or a derivative thereof, which are bisexual adult attractants and larvae worm attractants, aggregants or arrestants for codling moth and other species of Lepidoptera.

Still yet another aspect of the current invention is a method for monitoring, control, mass trapping, and disruption of codling moth mating and invasion of fruit orchards and for protection of fruit crops, particularly pear, apple and walnut crops from the adult insects and larvae.

Still yet another aspect of the current invention is a method for capture of and elimination of codling moth by attracting both the female and male insects as well as the larvae by providing a formulation comprising a kairomonal attractant derived from the pear or apple, alone, or in a combination with a sex pheromone, other kairomone and/or insecticide.

Still yet another aspect of the current invention is a formulation placed in a lure-kill trap or a bait comprising a kairomone attractant derived from the pear or apple, alone, or in a combination with a sex pheromone, other kairomone and/or insecticide, or in admixture with other volatile compounds for attracting, aggregating or arresting adult insects and larvae of lepidopterous species wherein said formulation is in a sprayable, solid or liquid form or in a time release form and wherein said formulation is placed in a trap, trap-like station, trap-like enclosure or trap-like platform.

Still another aspect of the current invention is a lure-kill trap or bait comprising a kairomone attractant derived from the pear or apple, alone, or in a combination with a sex pheromone, other kairomone and/or insecticide.

Still another aspect of the current invention are purified compounds isolated from a pear extract, their isomers or derivatives purified up to at least 90% purity which are attractants, aggregants or arrestants for adult insects and larvae of lepidopterous species, said attractant, aggregant or arrestant comprising one or more pear extract components.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1

is a graph depicting attraction of female and male codling moths to a synthetic pear extract blend (ester blend #10) supplied in the baited sticky trap. Male codling moth (-&Dgr;-), female codling moth (-□-).

FIG. 2

is a graph comparing the codling moth flight pattern delineated by males captured in pheromone traps (-▴-) to the flight pattern of both sexes captured in synthetic pear extract blend containing traps. Male codling moth (-&Dgr;-), female codling moth (-□-) capture in ester blend #10-baited traps.

FIG. 3

are graphs of the enhancement of pheromone by a pear extract blend showing preference-attraction of codling moth in a paired-trap choice design, consisting of a trap baited with pheromone alone versus the trap baited with pheromone and a pear extract blend (ester blend #10). Male capture with pheromone alone (-▴-), codling moth (unsexed) capture with pheromone and pear extract blend (-&Circlesolid;-), male capture with male pheromone and pear extract blend (-&Dgr;-), female capture with male pheromone and pear extract blend (-□-).

FIG. 4

is a graph representing mean attraction of female and male codling moths to rapid-kill traps baited with a pear extract blend (ester blend #10). Male codling moth (-&Dgr;-), female codling moth (-□-).

FIG. 5

is a graph representing mean attraction of female and male codling moths to sticky traps baited with a single pear extract compound, ethyl (2E,4Z)-2,4-decadienoate. Male codling moth (-&Dgr;-), female codling moth (-□-).

FIG. 6

illustrates the capture of male and female codling moths in pheromone vs. ethyl (2E,4Z)-2,4-decadienoate-baited traps in a pheromone permeated mating disruption walnut orchard. The ability to detect males and females is illustrated in a mating disruption orchard.

FIG. 7

shows detection of males and females of the codling moth separately, lured with a sex pheromone or with ethyl (2E,4Z)-2,4-decadienoate. Male capture with sex pheromone (-▴-), female capture with sex pheromone (-▪-), ale capture with ethyl (2E,4Z)-2,4-decadienoate (-&Dgr;-) and female capture with ethyl (2E,4Z)-2,4-decadienoate (-□-).

FIG. 8

illustrates male (-&Dgr;-) vs. female (-□-) codling moth capture per night with the ethyl(2E,4Z)-2,4-decadienoate lure in an apple orchard.

FIG. 9

illustrates male (-▴-) vs. female (-▪-) codling moth capture per night with the codling moth sex pheromone in an apple orchard.

FIG. 10

illustrates male (-&Dgr;-) vs. female (-□-) codling moth capture per night with the ethyl (2E,4Z)-2,4-decadienoate lure in a pear orchard.

FIG. 11

illustrates capture of male (-▴-) vs. female (-▪-) codling moth per night with the codling moth sex pheromone in a pear orchard. The break in the curves indicates the loss and replacement of septa containing the pheromone.

FIG. 12

illustrates capture of the codling moth males (-&Dgr;-) vs. females (-□-) with ethyl (2E,4Z)-2,4-decadienoate in the dose concentration range from 0.1-50 mg in grey septa vs. males captured with pheromone at a fixed dose of 3 mg.

FIG. 13

illustrates capture of the codling moth males (-&Dgr;-) vs. females (-□-) with ethyl (2E,4Z)-2,4-decadienoate in the lower dose concentration range from 0.1 &mgr;g-10 mg in grey septa vs. males captured with pheromone at a fixed dose of 3 mg.

DEFINITIONS

As used herein:

“Extract blend” means a mixture of more than two components found in the volatiles isolated from pome fruits, such as pears, apples, etc., or a mixture of at least one of such components in admixture with other components such as pheromones, alcohols, esters or other additives. The blend may also contain insecticide.

“Pheromone” or “sex pheromone” means an intraspecific signal molecule, and typically in Lepidoptera produced and released by female insects at the time of, or prior to mating, that attracts males.

“Insect pest” means any lepidopterous species, particularly codling moth, which attacks pome fruit and nut trees.

“HPV” means host-plant volatile.

“Kairomone” means an interspecific semiochemical signal molecule that typically is an odoriferous volatile compound, released by plants, which is detected and recognized by the insect and aids them in locating a suitable host plant.

“Attractant” means a compound falling within a formula shown in Section 1A, that causes the adult males and/or females and/or larvae of the lepidopterous species to make oriented movement towards the compound.

“Aggregant” means a compound falling within a formula shown in Section 1A that causes males and/or females and/or larvae of the lepidopterous species to aggregate or accumulate at a site containing the compound and remain there for a period.

“Arrestant” means a compound falling within a formula shown in Section 1A, that causes the males and/or females and/or larvae of the lepidopterous species to aggregate upon contact with said compound. The arrestant typically shows the linear progression of the organism by reducing actual speed of locomotion or by increasing the turning rate.

“Ovipositional stimulant” or “feeding stimulant” means a compound falling within a formula shown in Section 1A, that elicits feeding or oviposition in the males and/or females and/or larvae of the lepidopterous species.

DETAILED DESCRIPTION OF THE INVENTION

This invention concerns the discovery that volatile semiochemicals derived from pome fruits, such as pears or apples, are superior bisexual attractants, and that in addition to attracting males, they also attract, specifically and differentially, the female codling moths or other species of Lepidoptera and additionally act as attractants, aggregants and arrestants for larval stages of the codling moth or other Lepidoptera species. These novel attractants are superior to other known kairomonal attractants. These novel kairomonal attractants provide and are useful in methods for monitoring, controlling, mass trapping and mating disruption of adult insect pests, for arresting or aggregating larval growth and development, and for controlling the infestation of fruit orchards, such as apple, pear and walnut orchards by the adult insects or larvae.

These findings were unexpected and surprising because while the codling moth is known to be attracted to and attacks the nonripened fruit, the novel attractants of the invention are derived from the ripened mature fruit. As described below, the new attractants of the invention, which are found in ripened fruit, are different from host plant volatile compounds found in nonripened fruit, a target of the insect and/or larval invasion.

This invention was developed in order to achieve effective monitoring, control and management of moth pests and other fruit tree-infesting insects and larvae. The aim of the invention was to control and manipulate moth behavior, such as feeding, attraction, mating, oviposition and also larval development.

Current means of monitoring the occurrence, population levels, and flight pattern of moth pests is solely by pheromone trap-catching of adult male moths. The first aim of the invention, therefore, was to identify female attractants because it is the egg-laying of female moths that determines the damage potential of the next larval generation.

Current pheromone-based mating disruption control of codling moth was found to be in need of improvement in efficacy. Female moths perform all their sexual-reproductive activities such as calling, courtship, mating and oviposition, while perched on their host-plants. Host plant volatiles (HPVs) continuously and simultaneously evaporate from the plant leaf and fruit substrates while the female moth calls and emits her pheromone. Thus, pheromones and HPVs always share the same environmental context and might be adaptively associated in chemoreception and behavior by the male moths.

The second aim of the invention, therefore, was to discover and develop the use of these volatile attractants to enhance the attractancy of already existing sex pheromones, and their specificity and effectiveness for monitoring and mating disruption of insect pest populations.

As described in greater detail below, a group of compounds which attracts adult females and males as well as the larvae have now been identified. Such identification of female and larvae attractants allow for the development of novel monitoring tools and direct control tactics aiding in the monitoring of appropriate timing of control measures, or directly disrupting population levels, flight pattern, mating and oviposition of female codling moth and other lepidopterous species in walnut, apple, pear or other fruit and nut orchards. The newly discovered attractants for adult insect were additionally found to attract the larvae, and cause their aggregation in the vicinity of these compounds.

Since the substantial damage to the fruit and nut trees is done by larval codling moth and other lepidopterous species, the third aim of the invention was to investigate if the compounds of the invention found in ripened fruit of some fruits trees were also attracting or otherwise affecting growth and development of the larvae.

I. Semiochemical Attractants

Semiochemical attractants of the invention are volatile kairomones isolated from ripe pear, apple, quince or other pome fruit trees, which are unique, host-derived attractants that specifically attract both larvae and adult insect pests of the order Lepidoptera, particularly the codling moth, and still more specifically, which attract adult codling moths in various female to male ratios, depending on the time in the season. While the new host volatile attractants are isolated from the ripened pome fruits, they attract both adult insects and larvae when placed in orchards containing unripened fruits, which do not exude the host plant volatiles of the invention.

These newly discovered attractants have a surprisingly very high competitive potency, ranging from approximately 50% to equal or greater the attractancy of the synthetic commercial pheromone (E,E)-8,10-dodecadienol, from early-season to mid- and late-season. The attraction of females to the new attractant is not affected or disrupted by the simultaneous presence of conspecific synthetic male sex pheromone. This discovery was surprising and of a significant value because until now there were no known effective female and larval attractants for codling moth or most other species of Lepidoptera.

A. Host-plant Volatile Kairomonal Attractants

The novel attractants for Lepidoptera are host plant-volatile derived kairomonal attractants. These attractants were isolated and identified from ripe non-nut, pome fruit host-plants, primarily from ripe pears, apples, quince and other fruit volatile extracts. The active attractants were collected and chemically identified by GC-MS from headspace odor emission of the pear and apple host-trees. Typically, the active attractants comprise one or more compounds. The attractant compounds were further identified as esters, such as ethyl (2E,4Z)-2,4-decadienoate, its geometrical and positional isomers and derivatives, and related compounds such as allenes, other decadienoates, decanoates, decenoates, dodecadienoates and decatrienoates. Where appropriate, optical isomers of these esters are also included. Representative exemplary compounds of the new attractants are methyl or ethyl decanoate, methyl or ethyl (E)-2-decenoate, methyl or ethyl (Z)-4-decenoate, methyl (2E,4Z)- or (2E,4E)-2,4-decadienoate, ethyl (2E,4Z)- or (2Z,4Z)- or (2E,4E)- or (2Z,4E)-2,4-decadienoate, propyl (2E,4Z)- or (2E,4E) -2,4-decadienoate, ethyl 2,4-dodecadienoates, ethyl 2,4,6-decatrienoates and other derivatives as described to be present in the fresh apples, apple juices and cooked apples, in the Bartlett and other types of pears and in quince, all listed in

Volatile Compounds in Food

, TNO Nutrition and Food Research Institute, The Netherlands, Seventh Edition (1996), Index of Compounds, 1.1-1.18 for apples, 13.1-13.5 for pears and 125.1-125.6 for quince, hereby incorporated by reference in its entirety.

Any and all compounds listed in the above identified Index of Compounds are intended to be within the scope of the method of this invention as long as they possess attractant properties for adult and/or larval lepidopterous species.

Generally, the attractant will have a general formula

wherein n is an integer 0-8;

wherein n′ is an integer 0, 1 or 2;

wherein X is OR

1

, NR

1

R

2

, SR

1

or R

1

; wherein R

1

is H or alkyl C1 to C6 and R

2

is H or alkyl C1-C6.

Preferred compounds have formulae

wherein R and R

1

are —CH

3

, —CH

2

CH

3

or CH

2

CH

2

CH

3

.

Representative compounds were obtained from the headspace volatiles of the fruit trees by passing the air over and collecting the odorous vapors or by extracting the fruit, ripened or nonripened, with an organic solvent or by steam distillation. The compounds were prepared as mixtures of two or more compounds or as individual purified compounds. These compounds were tested and additionally compared to commercially available synthetic products.

The representative compounds acting as attractants for adult female and male insect and larvae of codling moth and/or other lepidopterous species are:

Ethyl (2E,4Z)-2,4-decadienoate as a mixture;

Ethyl (2E,4Z)-2,4-decadienoate purified;

Ethyl (2E,4E)-2,4-decadienoate purified;

Ethyl (2Z,4E)2,4-decadienoate purified;

Ethyl (2Z,4Z)-2,4-decadienoate purified

Methyl (2E,4Z)-2,4-decadienoate purified;

Methyl (2E,4E)-2,4-decadienoate purified;

Propyl (2E,4Z)-2,4-decadienoate purified;

Propyl (2E,4E)-2,4-decadienoate purified;

Butyl (2E,4Z)-2,4-decadienoate purified;

Butyl (2E,4E)-2,4-decadienoate purified;

Pentyl (2E,4Z)-2,4-decadienoate purified;

Pentyl (2E,4E)-2,4-decadienoate purified;

Hexyl (2E,4Z)-2,4-decadienoate purified;

Hexyl (2E,4E)-2,4-decadienoate purified;

Isopropyl (2E,4Z)-2,4-decadienoate purified;

Isopropyl (2E,4E)-2,4-decadienoate purified;

Ethyl (2E,4Z)-2,4-dodecadienoate as a mixture;

Ethyl (2E,4E)-2,4-dodecadienoate purified;

Ethyl (2E,4Z)-2,4-dodecadienoate purified;

Methyl (2E,4Z)-2,4-dodecadienoate purified;

Methyl (2E,4E)-2,4-dodecadienoate purified;

Propyl (2E,4Z)-2,4-dodecadienoate purified;

Propyl (2E,4E)-2,4-dodecadienoate purified;

Butyl (2E,4Z)-2,4-dodecadienoate purified;

Butyl (2E,4E)-2,4-dodecadienoate purified;

Pentyl (2E,4Z)-2,4-dodecadienoate purified;

Pentyl (2E,4E)-2,4-dodecadienoate purified;

Hexyl (2E,4Z)-2,-dodecadienoate purified;

Hexyl (2E,4E)-2,4-decadienoate purified;

Isopropyl (2E,4Z)-2,4-dodecadienoate purified; and

Isopropyl (2E,4E)-2,4-dodecadienoate purified.

The isolated compounds were purified to 90-100%, preferably to over 98% purity, by a method described in Example 3.

Volatile attractants of the invention were investigated for their respective percentile presence in the odor of either immature, unripe pears or store-bought ripe pears (1 kg) both trapped for about 11 hours under 1 L/minute air stream and their odors or vapors were collected and analyzed. Results are shown in Table 1A (ripe pears host-plant volatiles and in Table 1B (immature, unripe pears host-plant volatiles).

Table 1A shows their respective percentile representation of host-plant volatiles obtained from store bought, fully ripe cut or whole pears.

TABLE 1A

Ripe Pears Host Plat Volatiles

#

Cut %

Whole %

Compound

1

0.69

0.58

1-butanol

2

0.22

0.04

acetoin (3-hydroxybutan-2-one)

3

0.02

+

ethyl propanoate

4

1.41

0.76

propyl acetate

5

0.2

0.03

methyl butyrate

6

0.18

0.06

2-methyl butan-1-ol

7

0.32

0.06

isobutyl acetate

8

0.57

+

n-hexanal

9

0.09

0.13

ethyl butyrate

10

31.41

27.73

butyl acetate

11

0.14

0.29

hexanol

12

0.09

0.08

2-methylbutyl acetate

13

1.36

0.86

pentyl acetate

14

0.13

0.03

methyl caproate

15

0.03

+

6-methyl-5-hepten-2-one

16

0.03

0.04

butyl butyrate

17

0.38

0.15

ethyl caproate (hexanoate)

18

0.08

0.05

(Z)-3-hexenyl acetate

19

31.64

27.12

hexyl acetate

20

0.02

+

ethyl heptanoate

21

0.14

0.26

22

0.22

0.12

heptyl acetate

23

0.05

0.02

methyl octanoate (caprylate)

24

0.05

0.02

methyl 2-octenoate

25

0.03

+

26

0.02

+

27

0.17

0.19

estragole (allyl anisole)

28

+

0.07

butyl hexanoate

29

0.21

0.25

hexyl butyrate

30

0.22

0.1

ethyl caprylate octanoate

31

0.17

0.25

32

0.16

0.15

octyl acetate

33

0.02

+

34

0.12

0.08

ethyl (E)-2-octenoate

35

0.01

0.03

36

0.03

+

37

0.03

0.06

t-anethole

38

0.12

0.23

cyclodecanone (int. Std.)

39

0.69

0.19

methyl (Z)-4-decenoate

40

0.03

+

methyl decenoate

41

0.02

+

42

0.05

+

methyl 2-decenoate

43

0.04

+

44

1.61

0.28

ethyl 4-decenoate

45

0.55

0.53

46

7.5

5.15

methyl (2E,4Z)-decadienoate

47

0.05

0.03

&agr;-copaene

48

0.13

0.03

ethyl caprate (decanoate)

49

0.02

0.19

tetradecane

50

0.02

+

51

0.12

0.06

ethyl t-2-decenoate

52

0.04

0.04

ethyl (E,E)-2,4-decadienoate

53

0.81

1.2

54

11.4

10.04

ethyl (2E,4Z)-2,4-decadienoate

55

+

0.03

56

0.49

0.64

(Z,E)-&agr;-farnesene

57

5.2

20.53

(E,E)-&agr;-farnesene

58

0.05

0.19

pantadecane

59

0.11

0.13

d-cadinene

60

0.02

+

61

0.02

+

62

0.03

0.07

63

+

0.03

64

0.03

+

65

+

0.03

66

+

0.03

67

+

0.03

68

+

0.04

69

0.12

0.39

hexadecane

70

0.02

71

0.03

0.09

72

0.02

73

0.01

0.03

heptadecane

74

0.03

0.12

75

0.04

0.06

76

0.02

dibutylphthalate

77

0.02

100.09

As seen in Table 1A, seventy seven individual compounds were found to be present in the pear extract or headspace odor from cut or whole store bought ripe pears. Of these, about 50 individual compounds were identified. Of these compounds, only seven compounds were found to be present in both ripe (Table 1A) and immature Bartlett odor pear (Table 1B).

For ripe pear odor (Table 1A) twenty-seven compounds, present only in trace amounts, were not identified. The relative percentile of the identified compounds ranged from minute amounts of about 0.02%, for example compounds 3, 20 and 33, to rather large amounts of about 30%, for example compounds 10, 19 and 57. The compound 54, which is the most active and therefore preferred codling moth attractant, was found to be represented by around 11% in the volatile from the cut pears and about 10% in the volatile from the whole pear. This compound (54) was not detected to be present at all in immature apples or pears (Table 1B).

Using different isolating methods, these and other compounds may be isolated from the ripe pome fruit and may possess attractant properties for Lepidoptera. All of these compounds are contemplated to be within the scope of the invention.

Table 1B shows the percentile representation of host plant volatiles obtained in three experiments from mid-summer picked, immature, nonripe whole Bartlett pears, Golden Delicious apples, and Granny Smith apples.

TABLE 1B

Immature Unripe Host-Plant Volatiles

Immature Apples:

Golden

Granny

Immature (Green):

Delicious

Smith

Compounds

Bartlett Pear

(%)

(%)

1

Ethyl Acetate

0.64

2

Propyl Acetate

0.21

3

Butyl Acetate

1.06

4

Hexanal

0.21

1.33

1.79

5

Isobutanol

0.85

6

(Z)-3-Hexanal

0.21

3.29

4.55

7

3-Methylbutanol

0.85

8

(E)-2-Hexanal

0.64

4.5

8.49

9

(Z)-&bgr;-Ocimene

0.16

0.28

10

(E)-&bgr;-Ocimene

1.49

3.29

24.6

11

Hexyl Acetate

0.62

0.79

12

(E)-4,8-Dimethyl-

28.7

20

1,3,7-nonatriene

13

(Z)-Hexenyl

11.42

5.16

Acetate

14

(Z)-Pentenol

0.20

0.57

0.55

15

(E)-2-Hexenyl

0.24

0.61

Acetate

16

Hexanol

0.21

0.88

1.24

17

(Z)-3-Hexenol

0.64

5.19

4.25

18

(E)-2-Hexenol

0.52

1.73

19

Acetic Acid

2.6

2.03

20

&agr;-Copaene

0.43

21

Benzaldehyde

0.21

22

2,3-Butandiol

34

23

Meso 2,3-

40.4

Butandiol

24

(Z)-3-Hexenyl

1.51

0.29

Butyrate

25

Linalool

6.58

3.94

26

Caryophyllene

1.28

0.35

1.09

27

2-Methylbutyric

1.06

Acid

28

Humulene

0.43

29

Germacrene-D

0.06

0.67

1

30

(Z,E)-&agr;-Farnasene

0.42

0.21

31

(E,E)-&agr;-Farnasene

10.6

22.5

12.4

32

&dgr;-Cadinene

1.28

0.35

0.64

33

Methyl Salicylate

1.73

2.34

34

2-Phenylethanol

0.21

0.42

0.68

35

Penylacetonitrile

0.85

0.73

0.85

36

(Z)-3-Hexenyl

1.44

0.49

Benzoate

37

2-ethylpropyl

2.13

Tetradecanoate

As seen in Table 1B, 37 compounds were identified in immature unripe host-plant volatiles in Bartlett pear or in Golden Delicious or Granny Smith apples. As pointed out above, only seven compounds were found to be present in both ripe and immature fruits. None of these compounds belongs to the group of ester compounds, namely, alkyl decanoates, decenoates, dodecanoates, etc., identified as lepidopterous attractants, aggregants or arrestants.

The codling moth lays eggs on, attacks and infests only immature apple and pear fruits that reside on the tree during the summer season, from May through September in the Northern Hemisphere. These susceptible fruits remain in an unripe state while they grow in size and maturity on the tree. Pome fruits are classified as climacteric fruits meaning they will not ripen, soften nor enrich in odor/flavor until they have been picked from the tree. Once ripe, pome fruits have advanced to a stage that is unsuitable as a host for codling moth or other moth infestation. Table 1B shows the typical compositional odor of both immature pears and apples. For immature pears, Table 1B identifies twenty-five compounds ranging from simple aliphatic aldehydes, alcohols and acetates to numerous terpenes both monoterpenes and sesquiterpenes; but no ester compounds were identified that are so indicative of the odor of ripe pears (Table 1A).

B. Mixtures of Attractants with Additives

In the method for attracting larvae and adult female and male codling moths or other lepidopterous species fruit-tree insect pests, the attractants of the invention are utilized either as individual, purified compounds, or as mixtures of several synthetic or natural purified compounds, or as a partially purified or nonpurified natural or synthetic mixtures.

The attractants of the invention are used and applied alone individually or in a mixture of two or more attractants or in combination with additives, such as the codling moth sex pheromone, to additionally attract the male codling moth, or a pheromone specific to the lepidopterous species to be captured. The attractant may further be used in combination with one or more insecticides for use in attract-kill baits or traps or in formulations according to the method of the invention and/or in combination with other kairomones, allomones, synomones and other additives or formulating agents.

C. Additives

Additives suitable for combination with the attractants of the invention are primarily the male sex pheromones of codling moth or other lepidopterous species and insecticides, but also include such formulating agents as emulsifiers, UV absorbers and UV blocking agents, antioxidants, viscosity regulating agents, inert solvents, buffers, diluents and other auxiliary compounds typically used in these types of formulations.

1. Sex Pheromones

The sex pheromone is the semiochemical molecule produced and released by the female insect pest signaling her receptivity to mating. The sex pheromone is the cue that attracts the male insect. Because the attractant of the invention attracts both sexes, the addition of the sex pheromone to the attractant of the invention is optional. The addition of pheromone to the attractant enhances the male attraction to the attractant-containing lure and thus further assures that it is not only the egg-laying females that are attracted to the trap or bait but that also the majority of the male insects are attracted. This approach further protects the fruit and nut tree and orchards from damaging pest infestations.

The following pheromones, for example, may be used within the scope of the present invention:

(Z)-5-decenyl acetate, dodecanyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-tridecenyl acetate, (E)-11-tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-10-tetradecenyl acetate, (E)-10-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecanyl acetate, (E,Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tridecadienyl acetate, (E,E)-9,11-tetradecadienyl acetate, (Z, Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11-hexadecadienyl acetate, (E,Z)-7,11-hexadecadienyl acetate, (Z,E)-7,11-hexadecadienyl acetate, (E,E)-7,11-hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, decanol, (Z)-6-nonenol, (E)-6-nonenol, dodecanol, (Z)-5-decenol, 11-dodecenol, (Z)-7-dodecenol, (E)-7-dodecenol, (Z)-8-dodecenol, (E)-8-dodecenol, (E)-9-dodecenol, (Z)-9-dodecenol, (E)-9,11-dodecadienol, (Z)-9,11-dodecadienol, (Z,E)-5,7-dodecadienol, (E,E)-5,7-dodecadienol, (E,E)-8,10-dodecadienol, (E,Z)-8,10-dodecadienol, (Z,Z)-8,10-dodecadienol, (Z,E)-8,10-dodecadienol, (E,Z)-7,9-dodecadienol, (Z,Z)-7,9-dodecadienol, (E)-5-tetradecenol, (Z)-8-tetradecenol, (Z)-9-tetradecenol, (E)-9-tetradecenol, (Z)-10-tetradecenol, (Z)-11-tetradecenol, (E)-11-tetradecenol, (Z)-11-hexadecenol, (Z,E)-9,11-tetradecadienol, (Z,E)-9,12-tetradecadienol, (Z,Z)-9,12-tetradecadienol, (Z,Z)-10,12-tetradecadienol, (Z,Z)-7,11-hexadecadienol, (Z,E)-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, (E,E)-10,12-hexadecadienol, (E,Z)-10,12-hexadecadienol, dodecanal, (Z)-9-dodecanal, tetradecanal, (Z)-7-tetradecenal, (Z)-9-tetradecenal, (Z)-11-tetradecenal, (E)-11-tetradecenal, (E)-11,13-tetradecadienal, (E,E)-8,10-tetradecadienal, (Z,E)-9,11-tetradecadienal, (Z,E)-9,12-tetradecadienal, hexadecanal, (Z)-8-hexadecenal, (Z)-9-hexadecenal, (Z)-10-hexadecenal, (E)-10-hexadecenal, (Z)-11-hexadecenal, (E)-hexadecenal, (Z)-12-hexadecenal, (Z)-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, (Z,Z)-7,11-hexadecadienal, (Z,E)-7,11-hexadecadienal, (Z,E)-9,11-hexadecadienal, (E,E)-10,12-hexadecadienal, (E,Z)-10,12-hexadecadienal, (Z,E)-10,12-hexadecadienal, (Z,Z)-10,12-hexadecadienal, (Z,Z)-11,13-hexadecadienal, octadecenal, (Z)-11-octadecenal, (E)-13-octadecenal, (Z)-13-octadecenal, (Z)-5-decenyl 3-methylbutanoate and (+)cis-7,8-epoxy-2-methyloctadecane.

The pheromone is added to the formulation in the amount from about 0.01% to about 15%, preferably from about 0.1 to about 2.5%.

2. Insecticides

Additionally, the attractant of the invention is optionally combined with an insecticide which kills the insect lured to the trap, bait, or to the other types of formulations. The insecticides are generally carbamates, organophosphorous compounds, nitrophenols, nitromethylenes, phenylbenzoylureas, pyrethroids, chlorinated hydrocarbons and microbials (e.g., Bacillus thuringiensis), among others.

The following substances are examples of suitable insecticides: abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,

Bacillus thuringiensis

, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, bioresmethrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-Resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram omethoat, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenothrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, resmethrin, RH 5992, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralocytrin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, transfluthrin vamidothion, XMC, xylylcarb, zetamethrin.

Insecticides are added to the attractant/pheromone mixture in an amount from about 0.1 to about 20. Preferred insecticides are pyrethroids added in the amount from about 1 to about 15%, and more specifically in about 5-10%.

3. Formulating Additives

Formulating additives which may optimally be added to the attractant containing formulations are all additives which are conventionally used in the production of plant treatment products and which are non-toxic to plants. The following additives are suitable to be added.

Non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers and alkylaryl surfactants. Other suitable emulsifiers can be found in McCutcheon's “

Emulsifiers and Detergents

” (1982), North America Edit., MC Publishing Co., Glen Rock, N.J.

Antioxidants, such as sterically hindered phenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes, PERMALUX®, NEOZONE® A or D, TOPANOL CA®, N,N′-diphenyl-1,4-phenylenediamine and other substituted phenylenediamines.

Thickeners, including organic polymers such as partially or fully neutralized polyacrylic acids, polyethylene glycols, polyvinyl alcohols and non-ionically or ionically modified celluloses, xanthan-based thixotropic thickeners, waxes and inorganic disperse thickeners, such as precipitated or pyrogenic silicas, kaolins, bentonites and aluminum/silicon mixed oxides.

Antifreeze agents, such as urea, glycerol or propylene glycol.

Fillers, such as rockmeals, calcium carbonate, quartzmeal and aluminum/silicon mixed oxides or mixed hydroxides.

Solvents such as glycols, such as propylene glycol and polyethylene glycols of different molecular weight; ketones, such as methyl isobutyl ketone, methyl isopropyl ketone and cyclohexanone; amides, such as dimethylformamide or diethylformamide; N,N-dialkylated carboxamides; alkyl lactams, such as substituted pyrrolidones and caprolactams hydrocarbons; n-paraffins and isoparaffins having different boiling ranges as they are obtainable, aromatic hydrocarbons, such as xylene and aromatic distillation fractions; esters, such as propylene glycol monomethyl ether acetate, dibutyl adipate and di-n-butyl phthalate; ethers, such as propylene glycol methyl ether or propylene glycol butyl ether; alcohols, such as ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol and higher alcohols, and dimethyl sulphoxide, dioxane and tetrahydrofuran. The solvents can be employed in the form of individual components or mixtures. Particularly preferred are those which are miscible with the UV stabilizers and which are not unduly volatile.

The additives, in general, may be added in concentrations from 0 to about 50%, by weight, preferably between about 0 and 25% and most preferably from 0.1% to about 5%.

Additionally, ultraviolet (UV) absorbers may be added. The UV absorbers may be liquid, solid or flowable and have preferably an absorption range from 270 to 400 nm. Representative UV absorbers are 2-H-benzotriazoles, 2-hydroxy-alkoxybenzophenones, oxalanilides, cinnamic acid and derivatives thereof, and triazines and derivatives thereof. UV absorbers are present generally in concentrations from about 1 to 50%, by weight, preferably between 5 to 30%, by weight.

UV blocking agents such as carbon black, iron oxide, titanium dioxide, zinc oxide, calcium carbonate, talc, etc., and dyestuffs, such as Sudan block, chromophthalic blue, Terasil blue and Cibacet yellow, may also be used.

D. Host Plant Volatile Blends

This invention is based on findings that adult insects and larvae of codling moth and other Lepidoptera are strongly attracted to host volatile odors from ripe pome fruits, particularly from ripe apples and pears and that such attraction is different from sex pheromones in that these attractants attract insects of both sexes as well as larvae and that these attractants cause larval aggregation or arrest. Unexpectedly, and surprisingly, these attractants are derived preferentially from ripe fruit, while it is a well known fact confirmed during development of the current invention that codling moths prefer to attack immature, nonripened apples and pears over English walnut. This strong preference for pears and apples over walnuts was studied by analyzing the odor composition of these fruits by GC-MS. Results were compared to odor composition of walnuts.

Odor analysis of host volatile odors of pome fruit specifically, apples and pears, identified a large number of volatile compounds present in these fruits, as described in section I-A. Of these compounds, several compounds present only in ripe pear and apple odor were found to be novel, specific and potent larval and adult female and male codling moth attractants.

These findings were unexpected and surprising because it is not obvious that attractants would be present in ripe fruit odor since ripe fruit is not normally attacked by the insect pest. The insect pest attacks immature, unripe fruit.

In order to determine whether it is an individual compound or a mixture of compounds which attract both the female and male codling moth, over 23 various blends of the volatile compounds (a total of 75 different compounds) found in the pome fruits were prepared and tested for male and female codling moth attractancy.

Studied synthetic blends of apple and pear volatiles were blends of aldehydes, alcohols, esters, monoterpenes and sesquiterpenes. The list of these blends is found in Table 2.

TABLE 2

Synthetic Blends of Apple and Pear Volatiles

Alcohol Blends

Alcohol-1: 4- and 5-carbon Alcohols

(2-Methylpropan-1-ol, 2-Methylbutan-1-

ol, 3-Methylbutan-1-ol)

Alcohol-2: 5-carbon Alcohols

(Petan-1-ol, Petan-2-ol)

Alcohol-3: 6-carbon Alcohols

(Hexan-1-ol, (E)-Hex-2-en-1-ol, Hex-3-en-

ol, (E)-Hex-2-en-1-ol, (Z)-Hex-3-en-1-ol)

Alcohol-4: 7-, 8-, and 9-carbon

(Heptan-1-ol, Octan-1-ol, Nonan-2-ol)

Alcohols

Aldehyde Blends

AL-1: 6-carbon Aldehydes

(Hexanal, (Z)-Hex-3-enal, (E)-Hex-2-enal)

AL-2: 9- and 10-carbon Aldehydes

(Nonanal, Decanal)

Ester Blends

Ester-1: 4-carbon Acetates

(Butyl acetate, 2-Methylpropyl acetate,

Pentyl acetate, 2-Methylbutyl acetate,

3-Methylbutyl acetate)

Ester-2: 6-carbon Acetates

(Hexyl acetate, (E)-Hex-2-enyl acetate,

(Z)-Hex-3-enyl acetate)

Ester-3: Propanoates

(Propyl propanoate, Hexyl propanoate,

Butyl propanoate)

Ester-4: Butanoates

(Methyl butanoate, Ethyl butanoate,

Propyl butanoate, Ethyl 2-

methylbutyrate, Butyl 2-

methylpropanoate, Butyl butanoate, Butyl

2-methylbutanoate, Hexyl butanoaic,

Hexyl 2-methylbutanoate)

Ester-5: 7- and 8-carbon Acetates

(Heptyl acetate, Octyl acetate)

Ester-6: Hexanoates

(Methyl hexanoate, Ethyl hexanoate,

Butyl hexanoate, Hexyl hexanoate)

Ester-7: “Apple Maggot Lure”

(Hexyl acetate, Butyl hexanoate, Hexyl

butanoate, Propyl hexanoate, Butyl-2-

methylbutyrate, Hexyl propanoate)

Ester-8: Octanoates

(Methyl octanoate, Ethyl octanoate)

Ester-10: Decanoates &

(Methyl decanoate, Ethyl decanoate,

Decadienoates

Methyl (2E,4Z)-2,4-decadienoate, Ethyl

(2E,4Z)-2,4-decadienoate)