HK1065221B - Pesticides based on vicinal diols - Google Patents

Description

Pesticide based on vicinal diols

Technical Field

The present invention relates to the use of hydroxy-substituted hydrocarbyl compounds, particularly vicinal diols, such as 1, 2-hydrocarbyl diols, for controlling arthropod pests.

Background

In order to kill the various common pests which parasitize humans and their pets, livestock, especially those belonging to arthropods (such as ticks and mites) and insects (such as cockroaches, fleas, flies, silverfish, lice, etc.), the relevant classes of insecticides are required. Because of the close contact of such parasites with humans or animals, such pesticides should be non-toxic to the host in practical applications. In the agricultural and horticultural fields, corresponding insecticides are also required in order to be able to kill various arthropod pests on plant foliage.

In addition, such pesticides are preferably ecologically friendly (e.g., biodegradable).

A large number of compounds have been developed and marketed for use as pesticides. But very few varieties can simultaneously meet the following three criteria:

(1) toxic to most arthropod pests;

(2) relatively low toxicity to a human or animal host;

(3) has good biodegradability.

Disclosure of Invention

The present invention aims to provide an alternative insecticide which avoids, or at least mitigates, certain disadvantages of existing commercial insecticide products. It is also an object of the present invention to provide a method for controlling arthropods.

It was found that the vicinal diols meet the above triple criterion very well. In particular, the current research shows that one compound of the vicinal diols has remarkable efficacy as an insecticide and can meet the quality requirement, and the chemical formula of the compound is R (OH)₂Wherein the hydroxyl groups occupy the ortho position, and R may be a derivatized or substituted hydrocarbyl chain. The limiting number of carbons in the R group is still a subject of ongoing research. It has been found that compounds having a very good insecticidal effect are obtained if the compound has at least one hydrocarbyl chain of length n +2 atoms, wherein n is preferably at least 2 carbons, and the vicinal hydroxyl groups occupy terminal positions, preferably the 1, 2-positions, and have hydroxyl groups, such that the diol is the head and the lipophilic group is the tail. The activity of the compound is different according to the value of n. So that the lower hydrocarbon group and the higher hydrocarbon group (C) may be used₆Or above) the difference in activity when compared to each other. Where n can be as high as 20, only compounds with n values between 2 and 12 are of interest here. Such diols have a chiral structure, for example in a1, 2-diol, the second carbon atom being its chiral center. A racemic mixture is used in the present invention, but single optical isomers (enantiomers) or mixtures comprising one or more specific optical isomers can also achieve the object of the present invention. For exampleBoth enantiomers of 1, 2-decanediol are effective against lice, and comparative results with respect to mixtures of chiral structures will be tabulated later.

Previously, 1, 2-hydrocarbyl diols have been used to control bacterial infections. Kazunori (Japanese patent application No. JP 50-15925/publication No. 51-91327) teaches that 1, 2-hydrocarbyl diols, especially the medium chain homolog (n ═ 5-9), are potent bactericides of bacteria and fungi and have widespread utility. Similarly, Puglise (US 4049830) teaches that 1, 2-hydrocarbyl glycols can be used to disinfect cow teats for prophylactic treatment of bacterial cow mastitis. Furthermore, Greff (US patent US 6123953) teaches that the common local droplet of a1, 2-hydrocarbyl diol can be used to control bacteria causing skin disorders including mastitis, acne, dandruff and the like. In addition, Agostini and Cupferman (european patent application No. EP 0935960 a1) describe the use of 1, 2-hydrocarbyl diols as antibacterial agents in cosmetics.

The use of specific glycols as insect repellents together with known non-solvent insecticides has been described by air in patent GB 687850. Thus, vicinal diols have been considered as effective pest control agents (killing pests or their eggs) and have not been previously considered. Lover and Singer et al (US 4368207) describe the use of monohydric alcohols for killing lice, nits, and mites. Furthermore, the use of non-vicinal diols, especially 1, 3-diols, is described in UK 1604856 by Lover and Singer et al, which suggest that such compounds may be used to control ectoparasites and their eggs.

It has now been found that vicinal diols, especially 1, 2 diols, have unexpectedly strong insecticidal properties relative to mono-or non-vicinal diols. The 1, 2-hydrocarbyl glycols are useful for combating a wide variety of arthropod pests, particularly arthropod pests such as ticks and mites, and insect pests such as flies, cockroaches, silverfish, lice, and the like, while also having an effect of killing insect eggs. Moreover, the compounds are biodegradable and thus are excellent insecticides for various applications.

With the potency and effectiveness of the vicinal diols essentially verified, the selected diols are directly available themselves, and in most cases, pests can be effectively killed by dilute solutions; preferred packaging may further provide additional technical advantages for certain purposes.

The invention further provides formulations of such vicinal diols or derivatives thereof suitable for use in contact, which formulations incorporate at least one of the foregoing vicinal diols in a pathophysiologically acceptable carrier, useful for controlling specific pests, such as those causing diseases of the human and animal body, including lice infestation of the head or body parts, mite infestations of carpet, itch mite infestation of sheep, and fly bite and the like.

Typical formulations include mixtures of one or more of the preferred vicinal diols described above, together with suitable auxiliary materials, and carriers which may carry an effective amount of the vicinal diol to the locus of the insect infestation. The carrier is generally selected with consideration for prolonged contact with the target pest. Depending on the infected target, the carrier may be a well-separated solid or liquid, and may be selected from powders, resins, and aqueous or organic fluids. Thus, the formulation aids may be selected from liquid media, solid carriers, auxiliary materials, emulsifiers, dispersants, resins, gums, binders, diluents and additives.

The pesticidal composition may be incorporated into a formulation selected from a solution, dispersion, emulsion, dusting powder, cream, aerosol, cream, foam, coated substrate (e.g., adhesive paper), pill or block (e.g., bait in a trap), and the like. When it is desired to kill pests directly on a living host, the skilled person can select, as the case may be, a carrier which is pathophysiologically compatible or tolerable and which can be selected from among certain pharmacologically acceptable drugs, in particular in the case of specific topical applications, as creams, gels, pastes and coating oils, aerated (foam/mousse) compositions, or as a barrier agent (e.g. talc).

Drawings

The invention will be further described with reference to the accompanying drawings and examples, in which:

FIG. 1 is LC of a series of 1, 2-diols for killing human lice₅₀A value diagram;

figure 2 is a graphical representation of the relationship between the length of the glycol chain and the ovulation viability of lice treated therewith.

Detailed Description

The following results will help illustrate the killing effect of selected vicinal diols on a range of pests, but should not be considered as limiting the effect, which diols may have a killing effect on other organisms. The efficacy of the selected vicinal diols is set forth herein, unless otherwise indicated, and does not preclude the effectiveness of other analogs, the specific scope of the invention being defined by the claims that follow.

Example 1: effect of killing lice of human body

The insecticidal effect of the composition provided by the invention is explained according to the killing effect of the vicinal diol on human lice, and the test method conforms to the universal industrial standard.

The specific values and unique characteristics of the vicinal diols are shown in tables 1 and 2, which list the LC values measured in the test against lice for a series of diols and monoalcohols₅₀The value is obtained. As can be seen from Table 1, the vicinal diols exhibited surprising insecticidal potency relative to other non-vicinal diols, the 1, 3-diols. For example, 1, 2-decanediol performed significantly better than 1, 3-decanediol, and the beneficial effects of the various chain length ortho-ingredients listed in the table are apparent.

Table 2 also shows the superiority of vicinal diols over mono and triols. The best monol test results also corresponded to only 36% of the killing power of 1, 2-decanediol. This excellent effect of the vicinal diols suggests that effective control may be provided even in situations where the mode of application to the organism is less than ideal. Another advantage of these compounds is that they can be metabolized by common soil bacteria from different sites and, therefore, will biodegrade themselves when disposed of in the environment.

TABLE 1

Name of Compound	Diol type	LC50Value (mMol)	Capacity index (%)
				1, 2-butanediol	Ortho position	＞700	Invalidation
1, 3-butanediol	Non-adjacent position	＞2000	Invalidation
				1, 2-hexanediol	Ortho position	＞200	6
1, 5-hexanediol	Non-adjacent position	Can not calculate	Invalidation
				1, 6-hexanediol	Non-adjacent position	Can not calculate	Invalidation
2, 5-hexanediol	Non-adjacent position	Can not calculate	Invalidation
				1, 2-octanediol	Ortho position	40	30
1, 3-octanediol	Non-adjacent position	＞400	Invalidation
				1, 2-decanediol	Ortho position	12	100
1, 3-decanediol	Non-adjacent position	40	30

Wherein the capacity index refers to LC of the compound₅₀LC of value with 1, 2-decanediol₅₀Ratio of values (100%).

TABLE 2

Name of Compound	LC50Value (mMol)	Capacity index (%)
			1, 2, 3-hexanetriol	Can not calculate	Invalidation
1, 2, 6-hexanetriol	Can not calculate	Invalidation
			2-ethyl-1-hexanol	300	4
2-ethyl-1, 3-hexanediol	60	20
			1-decanol	35	32
2-decanol	37	34
			4-decanol	183	6
9-decen-1-ol	33	36
			1，2-Decanediol	12	100
3-Ethyl-1-decanol	62	20
			3-octyl-1, 2-decanediol	97	12
3-ethyl-1, 2-decanediol	Can not calculate	Invalidation

Wherein the capacity index refers to LC of the compound₅₀LC of value with 1, 2-decanediol₅₀Ratio of values (100%).

LC of series 1, 2-diols by killing human lice₅₀Value scheme, FIG. 1 illustrates the effect of diol chain length on activity.

The above results demonstrate that 1, 2-diols have pediculicidal activity, where C₄To C₁₆Are all active, preferably C₈To C₁₄Preferably 1, 2-Decanediol, 1, 2-octanediol, and 1, 2-dodecanediol.

Figure 2 shows another beneficial property of the subject invention, namely the ability to inhibit ovulation in a pest, if ovulation is inhibited or stopped, an important feature in the life cycle of the target organism will be interrupted. The effect of the series of diols can be seen in figure 2, where the egg-laying capacity of the treated lice decreases significantly as the diol chain grows. Of these, 1, 2-octanediol is particularly effective in inhibiting ovulation.

Ovicidal properties have been observed, but research in this area is continuing and relevant data are not provided herein.

Example 2: acaricidal effect

The effect of the vicinal diols is further illustrated by the results of a kill test against house mites (Dermatophagoides pteronyssinus) which meets common industry standards. The mites were sealed in a cotton sock and quickly immersed (5 seconds) in a dilute solution (2.5% strength) of the selected glycol. After one hour, the examination was performed and the mortality of mites was counted. The results are shown in Table 3, which contains comparative experimental results using carpet shampoo, penetrating insecticide, and water as the control means.

TABLE 3

Treatment liquid	Mortality (%)
		1, 2-octanediol	65
1, 2-decanediol	95
		Water (W)	3
3% carpet shampoo	3
		0.25% penetrating insecticide	100

Example 3: effect of killing housefly

Another example of the utility of the compounds of the present invention is demonstrated by the killing test of flies with decyl 1, 2-diol (decano-1, 2-diol) according to the industry standard for insecticides. Compared with decyl 1, 10-diol without insecticidal effect, the mortality rate after 24 hours of insecticidal killing by using decyl 1, 2-diol is as high as 80%.

Example 4: formula and application

By using non-toxic co-solvents, e.g. isopropanol, or by using surfactants, e.g. Tween^®The surfactant and the vicinal diol can be prepared into a water phase system. This makes them very suitable forMaking into various household or industrial insecticidal or cleaning products. In particular, they can be formulated as medicaments for use in the human or animal body. The effect of using 1, 2-octanediol or 1, 2-decanediol to kill lice and cockroaches is shown in table 4, along with the control effect of using other solvent systems. The test animals are immersed in the test solution for several seconds and then wiped dry according to industry standard test procedures. The mortality rate of lice was then counted after 24 hours and the mortality rate of cockroaches was counted after 1 hour.

TABLE 4

Treatment liquid	Mortality of lice after 24 hours (%)	Cockroach mortality after 1 hour (%)
			1, 2-octanediol in 1.5% Tween20 surfactant	100	100
1, 2-octanediol in 50% isopropanol solution	100	100
			1, 2-decanediol in 7% Tween20 surfactant	100	100
1, 2 Decanediol in 50% isopropanol solution	100	100
			0.25% penetrating insecticide in water	100	100
Water (W)	4	0
			50% isopropanol solution	4	0
1.5% Tween20 surfactant	0	0
			7% Tween20 surfactant	13	0

Industrial applicability

Due to the advantages and insecticidal characteristics of the compounds in the formula, the invention can be widely applied to places with insect pests, such as agriculture, horticulture, human health, hygiene, veterinary drugs and the like, so as to achieve the effect of killing the insect pests.

Claims (19)

1. A method for combating arthropod pests by applying to the locus of the pest or its eggs at least one unbranched 1, 2-vicinal diol R (OH)₂Thereby killing or dying the pests; wherein the vicinal diol is one of a series of diols, and R represents an optionally substituted or derivatized hydrocarbyl chain; and the carbon atom of the chain next to the diol functional group cannot be substituted by an ethyl group, while the main chain of the chain should contain 8 to 14 carbon atoms.

2. The method according to claim 1, wherein said vicinal diols consist of one unsubstituted aliphatic hydrocarbyl chain containing n +2 carbon atoms in the backbone; wherein the hydroxyl group of the vicinal diol occupies a terminal position, and n is an integer of 6 or more.

3. The method of claim 2, wherein n is an even number.

4. The method according to claim 1, wherein the vicinal diols are selected from the group consisting of linear aliphatic 1, 2 diols of 8 to 12 carbon atom chain length.

5. The method of claim 1, wherein the vicinal diols are one or more of 1, 2-octanediol, 1, 2-decanediol, and 1, 2-dodecanediol.

6. An insecticidal composition for killing arthropod ectoparasites, comprising at least one unbranched 1, 2-vicinal diol R (OH)2, which is one of a series of diols, R representing an optionally substituted or derivatized hydrocarbyl chain, as active ingredient of an insecticide or a spider-killing agent; and the carbon atom of the chain next to the diol function cannot be substituted by an ethyl group, while the main chain of the chain should contain from 8 to 14 carbon atoms; the vicinal diols may be mixed with formulation aids selected from liquid carriers, solid carriers, auxiliary materials, emulsifiers, dispersants, resins, binders, diluents, and additives.

7. A pesticidal composition according to claim 6, in a formulation selected from the group consisting of a solution, dispersion, emulsion, dusting powder, gel, paste, aerosol, cream, foam, coated substrate, tablet and block.

8. A pesticidal composition according to claim 6, wherein the said vicinal diols are selected from the group consisting of linear aliphatic 1, 2 diols of 8 to 12 carbon atom chain length.

9. A pesticidal composition according to claim 6, wherein the vicinal diols are selected from the group consisting of 1, 2-octanediol, 1, 2-decanediol and 1, 2-dodecanediol.

10. A pesticidal composition according to claim 6, wherein the vicinal diol is 1, 2-decanediol.

11. A method of killing lice wherein a composition according to claim 6 or 7 is applied to the locus of lice infestation.

12. A method for killing lice according to claim 11, wherein the composition comprises 1, 2-decanediol.

13. A method of killing flies wherein the composition of claim 6 is applied to the locus of the fly.

14. A method of killing flies wherein a bait or trap treated with a composition according to claim 6 is placed in the locus of the fly.

15. A method of killing mites comprising placing the composition of claim 6 where the mites are present.

16. A method of killing cockroaches comprising placing the composition of claim 6 in the locus of an infestation.

17. A method for killing cockroaches comprising placing a bait or trap treated with a composition according to claim 12 in the locus of a cockroach.

18. A method for combating arthropod ectoparasites, including Pediculus humanus, mites, houseflies, which comprises placing in the locus of an infestation a composition comprising as its active ingredient a vicinal diol selected from the group consisting of 1, 2-octanediol, 1, 2-decanediol, 1, 2-dodecanediol, and mixtures thereof.

19. The method of claim 18, wherein the glycol is formulated in a formulation selected from the group consisting of a solution, a dispersion, an emulsion, a dusting powder, a gel, a paste, an aerosol, a cream, a foam, a coated substrate, a tablet, and a block.