JPH05345704A - Combined use of chemical substance and microbicide in control of termite - Google Patents

Abstract

PURPOSE: To provide a method for exterminating termite and obtain a composition useful therefor. CONSTITUTION: This composition for treating termites comprises an effective amount of (1) at least one kind of chemical termiticide selected from a group comprising nitroguanidines, nitromethylenes, pyrazolines and pyrethroids and (2) a fungus selected from insect-pathogenetic fungi or bacteria, preferably a fungus selected from the genus Conidiobolus, the genus Paecilomyces, the genus Veauveria and the genus Metarhizium. The chemical termiticide is applied to a part where termites are observed or presence of termites is suspected. When the fungus or the bacterium is already present in a part, application of the terminiticide to the part where fungus or bacteria are observed is not required.

Description

Detailed Description of the Invention

The present invention is directed to termites.
And a composition useful in such eradication.

There are a number of chemicals known to kill termites at specific concentrations. Specific examples of such chemicals include: cyfluthrin (eg, disclosed in US Pat. No. 4,218,469), propoxur (eg, US Pat. No. 3,111,539). No.), fenvalerate (eg, disclosed in US Pat. No. 4,061,664), isofenphos (eg, disclosed in US Pat. No. 3,621,082). , Cypermethrin (disclosed, for example, in US Pat. No. 4,024,163) and 1
-(2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine (e.g., U.S. Pat.
No. 2,060).

Certain microbicides, and in particular some entomopathogenic fungi and bacteria, are associated with termite colonies and are known to cause deleterious effects in the presence of certain conditions. ing. See, for example, Ko, W.A. H. , "Journal of the
Invertebrate Pathology (Journalof
Invertate Pathology),
Vol. 39, p. 38-40 (1982).

However, each of these known termiticides, bacteria and fungi, have properties that make them commercially undesirable. For example, many of the chemicals and microbicides must be used at concentrations that are too high to be economically or environmentally desirable. Known termiticides are also often too slow acting to guarantee success in practical applications. The effectiveness of many of the known termite killers depends on the particular environment in which they are used and can therefore be adversely affected by factors that are out of control.

When a combination of fungi or bacteria selected from a particular type of chemical and a particular species is used to treat a site infested with termites, an unexpected synergistic effect in termite control can occur. It was discovered this time. When used in combination, the application rates can be substantially lower than those used for individual chemical termites and individual microorganisms.
The combined chemical and fungal or bacterial effects of the present invention are seen in weeks to days. Such a combination allows to achieve much higher, more predictable and more economical control of termites.

The present invention is particularly advantageous in avoiding the use of chlorinated hydrocarbons, the most widely used group of termite control chemicals. The present invention provides a novel method for the control of termites using a combination of chemical and biological agents with residual effects less than known toxicity, and applied techniques for reprocessing of sites of diminished efficacy. Based on suppression.

It is an object of the present invention to provide a combination of chemical agents and biological agents which is an effective termite treatment.

It is also an object of the present invention to provide a composition which does not cause environmental problems with chlorinated hydrocarbons and is effective in that it need not be used in large amounts.

Another object of the present invention is to provide a method for effectively controlling termites. These and other objectives which will be apparent to those skilled in the art include (1) at least one chemical selected from the group consisting of effective amounts of nitroguanidines, nitromethylenes, pyrazolines and pyrethroids and (2a) insects. Pathogenic fungus, preferably Conidiobulus (Entomotra) [Conidio
genus bolus (Entomophthora)] or genus Metalrhizium or Paecilomyces or Paecilomyces or Bevelia (Beauveria) or Actinomycetes (Actinum) or actinomcor (Actorum) or actinomcor (Actorum). For example, it is achieved by a composition including the genus Serratia. Chemicals are generally treated media (eg, soil)
At least 0.01 ppm in or 1 pp in bait
It is present in an amount such that m. Fungi or bacteria are generally used in an amount such that at least 1 to 100 spores / g of treated medium are present on contact with termites. The optimal amount of fungus or bacterium will depend on the particular fungus or bacterium involved. This treatment can be applied in the same manner used to apply other known chemical termite killers. The compositions of the present invention can also be used in bait formulations and for reprocessing previously treated areas.

The present invention provides (1) (a) nitroguanidines such as 1- (2-chloro-5-pyridylmethyl).
-2- (nitroimino) imidazolidine, (b) nitromethylenes such as 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,
(C) Pyrazolines and (d) Pyrethroids, eg, at least one chemical selected from cyfluthrin and (2a) an entomopathogenic fungus, eg, Conidiobolus (Entomophtra) [Conidiobolus (Entomopht).
hora)] or Metal Hydium (Metarhiz)
ium) or Paecilomyces
s) or Paecilomyces
Alternatively, it relates to a termiticide composed of a fungus of the genus Beauveria or Actinomucor or (2b) an entomopathogenic bacterium, for example Serratia.

The termiticide chemicals useful in the practice of the present invention are known materials and can be made by any known technique. Certain nitroguanidines and nitromethylenes and methods of preparing them are disclosed, for example, in the following issued applications and patents: European Patent (EP) 464,830, European Patent (EP) No. 428,541, European Patent (EP) No. 4
25,978, German Patent (DE) 36 39
877, German Patent (DE) 37 12307
U.S. Pat. No. 5,034,524, European Patent (E
P) 386,565, European Patent (EP) 383,
091, European Patent (EP) 375,907, European Patent (EP) 364,844, Japanese Patent (JP).
No. 02.207 083, European Patent (EP) No. 31
5,826, European Patent (EP) 259,738,
European Patent (EP) 254,859, Japanese Patent (J
P) 63 307,857, Japanese Patent (JP) 63 287,764, European Patent (EP) 235.
725, European Patent (EP) 212,600, European Patent (EP) 192,060, European Patent (EP) 163,855, European Patent (EP) 154,178.
No., European Patent (EP) 136,636, US Pat. No. 4,948,798, European Patent (EP) 303,5.
70, European Patent (EP) 302,833, US Patent 4,918,086, European Patent (EP) 30.
6,696, French Patent No. 2,611,114
No., European Patent (EP) 183,972, European Patent (EP) 455,000, Japanese Patent (JP) No. A
3 279,359, PCT patent application WO 91/1
7,650, PCT patent application WO 91 / 104,96
5, US Pat. No. 5,039,686, European patent (E
P) 135,956, U.S. Pat. No. 5,034,40
4, European Patent (EP) 471,372, European Patent (EP) 302,389, Japanese Patent (JP) 3,220,176, Brazilian Patent 8,803,6.
21, Japanese Patent (JP) No. 3,246,283,
Japanese Patent (JP) A 92/9371 and Japanese Patent (JP) 3,255,072.

For example, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine is N- (2-chloro-, as described in US Pat. No. 4,742,060. It can be prepared by reacting a solution of 5-pyridylmethyl) ethylenediamine with cyanogen bromide at room temperature. 1 formed in this way
-(2-Chloro-5-pyridylmethyl) -2-iminoimidazolidine hydrobromide was removed with sulfuric acid and fuming nitric acid dichloromethane solvent and the desired 1- (2-chloro-5-pyridylmethyl) -2. The-(nitroimino) imidazolidine was recovered.

Chemical termites suitable for use in the practice of the present invention have the formula:

[0014]

[Chemical 1]

In the formula, R is hydrogen, an acyl group, a substituted acyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocycle group, or a substituted heterocycle group, and A is (1) hydrogen, Acyl group, alkyl group,
A monofunctional group selected from an aryl group, a substituted acyl group, a substituted alkyl group, and a substituted aryl, or (2) a bifunctional group connected to Z, E is an electron-removing group, and X is N or CH, and Z is (1) hydrogen, an acyl group, a substituted acyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocycle group, a substituted heterocycle group, a group OR, NR ₂ , It is represented by a monofunctional group selected from SR or (2) a difunctional group connected to A or X.

Preferred acyl and substituted acyl groups include: alkylcarbonyl, substituted alkylcarbonyl, arylcarbonyl, substituted arylcarbonyl, alkylsulfonyl, substituted alkylsulfonyl,
Arylsulfonyl, substituted arylsulfonyl, alkylphosphoryl, substituted alkylphosphoryl, arylphosphoryl, and substituted arylphosphoryl.

Preferred alkyl substituents include the following: optionally substituted C ₁ -C ₁₀ alkyl groups,
Particularly optionally substituted C ₁ -C ₄ alkyl groups, most preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl or t-butyl.

Preferably aryl groups include phenyl and naphthyl, most preferably optionally substituted phenyl groups.

A preferred heterocycle group is 10 on the ring.
It includes aromatic rings having up to 4 carbon atoms and has at least one N, O or S atom (especially N) in the ring. Particularly preferred heterocycle groups are thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl and benzthiazolyl.

Suitable substituents for the aforementioned acyl, alkyl, aryl and heterocycle groups include the following:
An alkyl group having 1 to 4, preferably 1 or 2 carbon atoms, for example methyl, ethyl, n-propyl,
Isopropyl, n-butyl, i-butyl and t-butyl; alkoxy groups having 1 to 6, preferably 1 or 2 carbon atoms, eg methoxy, ethoxy, n-.
Propoxy, i-propoxy, n-butoxy, i-butoxy and t-butoxy; alkylthio having 1 to 4, preferably 1 or 2 carbon atoms, for example methylthio, ethylthio, n-propylthio, i-propylthio and n-butylthio; 1-4, preferably 1 or 2 carbon atoms and 1-5, preferably 1-3
Haloalkyls with the same or different halogen atoms, especially F, Cl or Br (most preferably), eg trifluoromethyl; hydroxyl groups; halogens, eg fluorine, chlorine, bromine and iodine, especially fluorine. , Chlorine and bromine; cyano groups; nitro groups; amino groups; monoalkyl- and dialkyl-amino groups having 1 to 4, preferably 1 or 2 carbon atoms in the alkyl groups, eg methylamino, methyl -Ethyl-amino, n-propylamino, i-propylamino and methyl-n-butylamino; carboxyl groups; alkoxycarbonyl groups having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, for example Carbomethoxy and carboethoxy; sulfo group (SO ₃ H
-); Alkylsulfonyl groups having 1 to 4, preferably 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl; and 6-1 on the aromatic ring.
An arylsulfonyl group having 0 carbon atoms, for example phenylsulfonyl. In formula I, A and Z
Can together form a saturated or unsaturated heterocycle ring having 5 to 7, preferably 5 or 6 atoms in the ring. This ring is 1 or 2
Heterocycle atoms, eg, O, S, N and N
-It may contain alkyl. If two atoms in the ring are not carbon, then the two atoms can be the same (eg, 2 N atoms) or different (eg, 1 N and 1 O).

Specific examples of electron withdrawing groups represented by group E in formula I include the following: NO ₂ , CN and halogenalkyl-carbonyl groups such as 1,5.
- halogeno _-C 1 -C ₆ alkyl - carbonyl group.

In formula I, Z and X can together form a heterocycle ring of 5 to 7, preferably 5 or 6 atoms in the ring. The ring can contain one or two heterocycle atoms, for example O, S, N or N-alkyl, which heterocycle atoms can be the same or different. Specific examples of preferred heterocycle rings include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine or N-methylpiperazine.

Preferred compounds within the scope of formula I are those in which each symbol has the following meanings: each of A and Z is
Hydrogen, optionally substituted alkyl, optionally substituted acyl group, optionally substituted phosphonyl group,
Or the group NR′R ″, where each of R ′ and R ″ is hydrogen or an alkyl group, or R ′ and R ″ together are optionally substituted 5 or 6
Represents a member ring, said ring may have nitrogen or sulfur as one of its members, E is an electron withdrawing group, eg N
O ₂ , CN or COCF ₃ , X is N or CH, and R is hydrogen, an optionally substituted pyridyl group, a pyridylalkyl group, a thiazolylalkyl group, an alkylthioalkyl group, or a ring member. Oxygen as one of the
It is a 5- or 6-membered heterocycle ring which has nitrogen or sulfur and which may be substituted with halogen or alkyl groups.

Particularly preferred compounds within the scope of formula I are:
Each symbol has the following meaning: Z is NH, CH
Or NR′R ″, wherein at least one of R ′ and R ″ is an alkyl group, and A and Z together are a nitrogen-containing 5- or 6-membered ring optionally substituted with thioalkyl or thioalkyl Or a sulfur-containing 5- or 6-membered ring, E being CN or NO ₂
X is N or CH, and R is a 5- or 6-membered heterocycle ring optionally substituted with halogen or an alkyl group, said ring optionally substituted with halogen or an alkyl group. , And having the formula:

[0025]

[Chemical 2]

Wherein n is 1 or 2 and Y is any of the substituents described above as suitable in formula I for acyl, alkyl, aryl and heterocycle groups,
For example, halogen, most preferably chlorine, and A, Z, X and E have the same meaning as in formula I, and

[0027]

[Chemical 3]

Where A, Z, X, E, Y and n are of the formula I
Has the same meaning as in.

Specific examples of nitroguanidines and nitromethylenes that can be used in the present invention are:
Includes: 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) -thiazolidine, 1-
(2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine,

[0030]

[Chemical 4]

Wherein R is an alkyl-substituted alkyl, aryl or substituted aryl group,

[0032]

[Chemical 5]

[0033]

[Chemical 6]

[0034]

[Chemical 7]

It is

Particularly preferred nitroguanidines and nitromethylenes are 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine.

When used in the bait form, nitroguanidine and nitromethylene will generally be present in at least 0.0001% by weight of the total bait ingredients, preferably from about 0.001 to about 10.0% by weight. Preferably about 0.
Used in an amount to represent 01 to about 1.0% by weight. Nitroguanidine or Nitromethylene can be incorporated directly into the soil or when applied directly to the surface to be treated,
It is generally at least 0.01 ppm (parts / 100
10,000), preferably about 0.1 ppm to about 1000 ppm,
Most preferably used in an amount such that about 1 ppm to about 300 ppm is present in the soil or on the surface to be treated.

Pyrethroids that can be used in the compositions of the present invention are known. Both naturally occurring and synthetic pyrethroids are suitable. Suitable pyrethroids include: prethrins, cinerines, jasmorines, allethrins [2-methyl-4-oxo-3- (2-propenyl)-].
2-Cyclo-penten-1-yl-2,2-dimethyl-
3- (2-methyl-1-propenyl) cyclopropanecarboxylate], bioalleroline [D-trans-
Alletrin], bertrin [6-chloro-1,3-benzodioxol-5-yl) methyl 2,2-dimethyl-3
-(2-Methyl-1-propenyl) cyclopropanecarboxylate], tetramethrin [(1,3,4,5,
6,7-Hexahydro-1,3-dioxo-2H-isoindol-2-yl) methyl 2,2-dimethyl-3-
(2-Methyl-1-propenyl) cyclopropanecarboxylate], flamethrin [[5- (2-propenyl) -2-furanyl] methyl 2,2-dimethyl-3-
(2-Methyl-1-propenyl) cyclopropanecarboxylate], resmethrin [[5- (phenylmethyl) -3-furanyl] methyl 2,2-dimethyl-3-
(2-Methyl-1-propenyl) cyclopropanecarboxylate], bioethanomethrin [[5- (phenylmethyl) -3-furanyl] methyl 3- (cyclopentylidenemethyl) -2,2-dimethyl-cyclopropanecarboxy Rate], phenothrin [(3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2-methyl-
1-propenyl) cyclopropanecarboxylate],
Fenpropanoate [cyano (3-phenoxyphenyl) methyl 2,2,3,3-trimethylcyclopropanecarboxylate], permethrin [(3-phenoxyphenyl) methyl 3- (2,2-dichloroethenyl)-
2,2-Dimethyl-cyclopropanecarboxylate], ciflotrin [cyano (4-fluoro-3-phenoxyphenyl) methyl-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate], cipermethrin [Cyano (3-phenoxyphenyl) methyl 3- (2,2-dichloroethenyl) -2,
2-Dimethyl-cyclopropanecarboxylate], decametrin [cyano (3-phenoxyphenyl) methyl 3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylate], fenvalerate [cyano (3 -Phenoxyphenyl) methyl 4-chloro-α- (1-methylethyl) benzeneacetate],
And cyhalothrin [cyano (3-phenoxyphenyl) methyl 3- (2-chloro-3,3,3-trifluoro-propenyl) -2,2-dimethyl-cyclopropanecarboxylate]. Particularly preferred pyrethroids are cyfluthrin and fenvalerate.

The pyrethroid is generally in the bait composition at least 0.0001% by weight of the bait composition, preferably about 0.0001 to about 10.0% by weight, most preferably about 0.01 to about 1.0%. Used in an amount such that the weight percent is pyrethroid. When the pyrethroids are incorporated directly into the soil or when applied directly to the surface to be treated, the pyrethroids are generally at least 0.01 ppm, preferably about 0.1 ppm to about 1000 ppm, most preferably about 1 ppm to about 300 ppm. In an amount such that it is present in or on the surface to be treated.

Any of the known pyrazolines can also be used to treat the termites of the present invention. Such pyrazolines are disclosed, for example, in published European patent application 0,438,690. Examples of suitable pyrazolines include those represented by the formula:

[0041]

[Chemical 8]

[0042]

[Chemical 9]

[0043]

[Chemical 10]

In the formula, α is a halogen atom, an alkyl group, a halogen group or a nitro group.

The pyrazoline is generally in the bait composition at least 0.0001% by weight of the bait composition, preferably from about 0.0001 to about 10.0% by weight, most preferably from about 0.01 to about 1.0. Used in an amount such that the weight percent is pyrazoline. When the pyrazoline is incorporated directly into the soil or when applied directly to the surface to be treated, the pyrazoline is generally at least 0.01 ppm, preferably from about 0.1 ppm to about 1000 ppm, most preferably from about 1 ppm to about 300 ppm. In an amount such that it is present in or on the surface to be treated.

The fungi used in the treatment of the termites of the present invention are naturally present in the soil and can be easily separated from the soil. Conidiobolus (Entomufutra) [Conid useful in the termites of the present invention
The genus iobolus (Entomophthora) includes the following: Conidiobolus coronatus, Conidiobolus virulenta.
s virenta) and Conidioborus
Obscura (Conidiobolus obsir)
a). Conidiobolus Coronatus (Conidio)
bolus cornatus) is particularly preferred.

Metal Hydium (M
Species of the genus etharhiium) are naturally present in soil and can be easily separated from soil. Metalhidium anisopriae (Metarhizium)
Various strains of anisopliae) are useful in the present invention. Metal Hidium Anisopriae (Met
strain F5 of Arhizium anisopliae)
2 (BIO 1020, DSM No. 3884) and MADA strain (received from University of Florida) (CB
S No. 326, The Netherlands, Baarn) are most preferred.

Species of the genus Paecilomyces useful in the termite killing agents of the present invention are Paecilomyces f.
ariosus), which is naturally present in soil and can be readily isolated from soil or from diseased sporulating termites by methods known in the art.

The preferred species of the genus Beauveria is Beuveria bassiana.
a bassiana), which is naturally present in soil and can be easily separated from the soil or from diseased sporulating termites by methods known in the art.

Actinomuco
The r) species are also useful in the practice of the invention.

Examples of bacteria useful in the present invention are those of the genus Serratia,
They are naturally present in the soil and can be easily separated from the soil or from diseased sporulating termites by methods known in the art.

The fungus or bacterium is generally at least 10 ¹ to 10 ² spores, preferably 10 ³ to 10 ⁵ / g.
Should be present in an amount and form such that the medium is present. The optimum amount depends, of course, on the species used.

The treatment of termites of the present invention is carried out by using powder, solution,
It can be applied in the form of very fine capsules of natural and synthetic and polymeric substances impregnated with suspensions, emulsions, foams, pastes, granules, aerosols, active compounds and fungi. When in the form of a powder or granules, the fungus can be added to solid nitroguanidine, nitromethylene, pyrazoline or pyrethroid formulations in suitable amounts. Other known additives for termites, such as bulking agents, attractants, food intake stimulants, pheromones, can optionally be included in the final composition. Examples of suitable powdered excipients include clay, talc, lime and pyrophyllite.

The termiticide of the present invention can also be used in the form of various liquids. Suitable liquid excipients for termite killers include water and inert solvents. Other additives commonly used in liquid insecticide formulations, such as emulsifiers, may also be included in the liquid termite formulations of the present invention. The liquid formulation of chemicals and / or fungal agents can also include lignin, hydrocellulose, bentonite, pectin, or any other substance that solidifies the formulation after application.

The compound and fungus or bacterium can be applied sequentially to the medium. When using this technique, the compound or fungus can be applied first.
Intervals between chemical and fungal applications can be as short as minutes or as long as days or weeks. If a suitable strain of fungi or bacteria is already present in the medium to be treated as a naturally occurring substance with the required spore titer, the addition of fungi or bacteria is unnecessary and applying only the compound is necessary. These treatments can also be repeated at regular or irregular intervals to ensure a long lasting effect.

The termite killing agents of the present invention are effective against all types of termites, but with subterranean termites.
Reticulitermis flavipes (Reticulite)
rmis flavipes and formosanic termites Coptothermes fo
It has been found to be particularly effective against R.

The data presented below on the effect of combined application of chemical and biological agents reveals an impressive degree of synergy. To use these factors alone in termite control to achieve termite control comparable to that obtained by the combined application of ice,
It will require an application rate that is a multiple of 10 times higher.

Having thus described the invention, the invention is further described by the following examples. Unless otherwise noted, all parts and percentages given in these examples are parts by weight and percentages by weight.

[0059]

EXAMPLES Examples 1-5 show short-term results achieved by the use of a combination of chemical termite-killing agents and fungi, as compared to eradication using chemical termite-killing agents alone or fungi alone. Demonstrate a high degree of termite eradication. Examples 6 and 7 show Conidiobol in the eradication of termites.
and the interaction of various chemical termites. Examples 8, 9 and 10 are
1- (2-Chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine and metal hydridinium (Me
genus tarhizium and Conidiobolus (Co
Quantitatively illustrates the interaction of two fungal pathogens of the genus nidiobolus. Example 11 illustrates the synergy between 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine and one additional fungal species and bacteria. Example 12 illustrates the synergy between microorganisms in non-sterile soil and various nitromethylenes or nitroguanidines.

Example 1 100 g of sterile soil was used for each of the samples listed in Table 1. Control sample A was not treated with nitroguanidine, nitromethylene, pyrethroids, pyrozolines or fungi. 1- (2-chloro-5-pyridylmethyl) -2-
(Nitroimino) imidazolidine was added at various concentrations (Table 1
) In samples B, C, D and F directly added to the soil. No fungus was added in these samples. Discs of filter paper soaked in a solution of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine having the concentrations shown in Table 1 were placed on top of the soil in samples G, H and I. I placed it. No fungus was present in soil samples G, H or I. Nitroguanidine was not added to soil sample J, but the fungus Conidiobolus (Conidiobolus
The sample from the container used in the previous test in which the cornatus) was naturally shown was included in Sample J. In soil sample J, soil from a previous trial was used, in which the fungus Conidiobolus cornatus was naturally shown, but
Filter papers soaked with 0.01% nitroguanidine were given to termites.

Then, 1 g of sub-thallanian (sub)
terranean termite (Reticulitermis flavipes)
pes)) was added to each of the soil samples AK. Next 1
The observations made over 8 days are summarized in Table 1.

As is evident from the data in Table 1, there is a sufficient effect on termites and ultimately (after 18 days of exposure) 1
To achieve a mortality of 00%, 1 ppm of nitroguanidine must be present in the soil. The use of higher proportions in soil (eg 10-100 ppm) did not change this result significantly.

The data in Table 1 also show that when the fungus alone was applied to the soil (ie no nitroguanidine was used) the results were identical to those observed in the untreated control. That is, a strong tunnel and presence at the bottom of the sample container was observed. However,
When a filter paper disc with 0.1% nitroguanidine on it was placed on top of the soil with fungi, 100% of the termites in the sample died within days.

[0064]

[Table 1] Table 1 Effect of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine on termites Sample Treatment Nitroguanidine, Observation ppm% (18 days) A Control ---- --Strong tunnel formation, all termites are healthy, and bottom soil B 100 ppm termites lose directionality, 80-90% are on the surface, do not eat and starve after 14 days C Soil 10 ppm Same as sample B D Soil 1 ppm Same as sample B E Soil 0.1 ppm Partial loss of direction and tunnel formation F Soil 0.01 ppm Same as sample A G Filter paper 0.01% Same as sample B H Filter paper 0.003% Same as sample B I Filter paper 0.001% Same as sample B J Fungus in soil only ------- Same as sample A K Fungus in soil + 0.01% 100% died after 2 days, in filter paper Roguanijin example 2 sterile soil and Konidioboru grown completely was the nits mycelium · Koronatsusu (Con
The procedure of Example 1 was repeated using both soil to which idiobolus cornatus) was added in the form of one drop of crude spore suspension. This crude spore suspension was obtained by rinsing the spores from a single Petri dish culture with 50 cc of sterile water. Various concentrations (shown in Table 2)
1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine was added directly to the soil. The results of these tests are reported in Table 2.

As the data presented in Table 2 show, a change in the behavior of termites in sterile soil samples was first observed at the level of 1 pp nitroguanidine. However, after 6 days, to cause substantial mortality, 1
00 ppm nitroguanidine was required. In fungal inoculated soil, substantial mortality was achieved at a level of 1 ppm and complete termite mortality was 3 pp
achieved in m. Without treatment with nitroguanidine, termites in fungal inoculated soil behaved similarly to those in the untreated reference standard.

[0066]

[Table 2] Table 2 Mortality of termites after 6 days% Soil-treated nitro-inoculated soil W / conidioguanidine amount (ppm) Aseptic soil Borus coronatus 0 0 0 0.1 0 0 0.3 0 25+ 1.0 0+ 75 ++ 3.0 0 100 10.0 25 ++ 100 100.0 80 +++ 100 + Many termites lost sense of direction ++ Most termites were severely affected ++++ All termites were severely affected Example 3 100 g of soil was used in each of the samples listed in Table 3. Half of the soil samples were made of sterile soil. The other half is 1 drop / sample of Conidioborus coronatus (Coni
It consisted of a soil sample inoculated with a crude spore suspension of D. bolus cornatus). This crude spore suspension was obtained by rinsing the spores from a single Petri dish culture with 50 cc of sterile water. 1- (2-chloro-5-pyridylmethyl)-having the concentrations shown in Table 3.
A disc of filter paper was saturated with a solution of 2- (nitroimino) imidazolidine. 1 g of subterranean (su
bterranean) termites (reticletermis
Flavipes (Reticulitermis flav)
ipes)) was added directly to each sample. Then, the termites in each sample were observed for 6 days. Mortality rates for each sample are listed in Table 3.

Results: In the absence of nitroguanidine,
The termites were conidiobolus coronatus (Conidiobolus cornatus) during the observation period of 6 days.
no response to soil inoculated with tus). When the treated filter paper bait was added to sterile fungal-free soil, the first signs of behavior were shown at 0.001% treatment, but mortality was 100 times higher (0.1%). It stopped low (8%). However, in fungal inoculated soil, mortality was 95% at a level of 0.001% nitroguanidine.

[0068]

[Table 3] Table 3 Treatment with nitroguanidine% mortality of termites after 6 days ──────────────────────────────── ─── Inoculated soil W / Conidio% of filter paper disc bait Sterile soil Borus coronatus ───────────────────────────── ─────── 0 0 0 0.00001 0 0 0.00003 0 0.0001 0 0 (+) 0.0003 50+ 0.001 2+ 95 +++ 0.003 100 0.01 5 ++ 100 0.1 8 +++ 100 ────── ───────────────────────────── (+) Some decrease in activity ＋ Many termites lost their sense of direction ++ Most example +++ all termites termites affected badly affected 4 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) actively in the presence and absence of imidazolidine The fungus to grow, to study the effect of exposing the termites directly. In these experiments, agar plates without fungi and nitroguanidine were used as controls.
One sample is 1- (2-chloro-5-pyridylmethyl)
It was an agar plate with a disc of filter paper treated with -2- (nitroimino) imidazolidine (0.01% active ingredient). Place the third agar plate on the Conidiobolus coronas.
tus) and a fourth agar plate is placed on a Conidiobolus coronado (Conidiobolus).
Cornus) fungus and treated with a filter paper disc containing 0.01% nitroguanidine.
Termite (Reticulitermis flavipes)
ulitermis flavipes)) was added to each agar plate and observed for 4 days. The results of these tests are reported in Table 4.

In the uninoculated control sample, the normal behavior of termites and immediate extensive tunneling occurs.
After 4 days, no mortality was observed. 25% mortality was observed after 4 days in plates treated with fungus alone. In plates treated with nitroguanidine diet only, termites showed severe poisoning and no tunneling was present. 100% mortality occurred within 1 day on fungal + nitroguanidine treated agar, and extensive sporulation occurred on dead termites.

[0070]

[Table 4] Table 4 ─────────────────────────────────── After spreading the termites on the agar plate Observation days: Treatment 1 day 2 days 4 days ─────────────────────────────────── Agar plate only 0 0 0 Agar plate only + Nitroguanidine diet 0 * 0 * 20 * (0.01% active ingredient) Fungal pathogen on agar 0 5 25 Fungal pathogen on agar 100% + Nitroguanidine diet (0.01% activity) Ingredients) ─────────────────────────────────── * Termite caused poisoning.

Example 5 4 kg of sandy soil was sterilized by an autoclave. The sterilized soil was then divided into two equal parts. In one part of the soil, 10 ml of distilled water was added to each 100 g of soil to adjust the moisture content to 10%. Second of sterilized soil
Conidiobolus Coronatus (Conidi
(Obolus cornatus) spores and mycelium were inoculated with a crude slurry. This slurry was prepared by scraping fungal growths from agar cultures on Petri dishes into 50 ml of distilled water. The slurry was then added to the sterilized soil at a rate of 10 ml / 100 g soil. Then 20 of each 2 kg batch
Distributed in individual cups so that 100 g of soil was present in each cup. In 10 cups of each batch,
0.01% 1- (2-chloro-5-pyridylmethyl)
Discs of filter paper treated with -2- (nitroimino) imidazolidine were provided. The remaining samples were provided with filter paper disks soaked in distilled water. Approximately 1 g of live Reticulitermis flavipes (Reticulit)
ermis flavipes) was added to each sample.
Observations of mortality, activity and fungal growth were made daily for several weeks. The results for these strains are reported in Table 5.

Results: As expected, in controls, termites behaved normally over the 7 day observation period.
Identical results were observed in the "fungal-only" treatment, except for a final mortality of 20%. Although comparable mortality rates resulted from the "chemical only" treatment, the effects of poisoning were observed early in the study. The "fungal + chemical" treatment resulted in 100% mortality within 2 days.

[0073]

Table 5 Interaction of fungi on sterilized soil (Koch's hypothesis)% mortality Treatment 2 days 4 days 7 days Control (no fungus, no chemicals) 0 0 0 Fungus ¹ only 0 10 20 Chemical ² Only 0 * 0 ** 20 ** Fungus ¹ + Chemical substance ² 100 100 ³ 100 ⁴ ─────────────────────────────── ───── ¹ Conidiobolus cornatus ² 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine ³ dead mycelia / spores on the carcass and cup wall Obvious ⁴ Termites break down and sporulation is complete * Termites move to the surface ** Termites are dead and inactive Example 6 Fungus Conidiobolus coronatus (Conidiob)
olus cornatus) and various known termites (listed in Table 6) were studied for interaction.
In these tests, a 100 g soil sample was used. Conidioborus coronatus (Conidiob)
olus cornatus) was added to half of the soil sample according to the procedure described in Example 2. No fungus was added to the other half of the sample. The chemical termites were then added to each of the samples (ie, both fungal-inoculated and non-fungal-inoculated) in an amount sufficient to reach the rates reported in Table 6. Then 1 g of subterranean
n) Termites (Reticulitermis flavipes (Ret)
iculitermis flavipes)) was added to each sample. The sample was then observed over a period of 7 days. The observations made are reported in Table 6.

The carbamates and organic phosphates used in this test had little effect on termites, or they showed no difference in response between fungal-free and fungal spiked samples. In contrast, the pyrethroid used did not cause mortality when the fungus was not used and 1 when the fungus was added to the soil.
It produced a mortality rate of 00%.

[0075]

Table 6 Koni audio Bors-Koronatsusu with various types of fungal fungal fungal compounds proportion ppm in% mortality 2 days 4 days 7 days soil interaction effects and termites in termite activity between chemicals None Fungus None Fungus None Fungus Carbamate ² 1.0 0 0 0 0 0 0 0 Synthetic pyrethroids ³ 1.0 0 ** 95 0 ** 100 ¹ 0 ** 100 0.3 0 * 10 0 * 95 0 100 Organic Phosphate ⁴ 1.0 0 * 0 * 0 0 0 0 0.3 0 0 0 0 0 0 Hostebpirin ⁵ 0.3 0 0 20 60 98 100 0.1 0 0 0 0 0 0 0.03 0 0 0 0 0 0 *: Slight change in behavior **: Severe poisoning 1: Dead body Mycelia / spores are clear on the top 2: propoxur 3: cyfluthrin 4: isofenphos 5: O- [2- (1,1-dimethylethyl) -5-pyrimidinyl] -O -Ethyl-O- (1-methylethyl)-
Thiophosphate Example 7 The procedure of Example 6 was repeated using only the pyrethroid termiticide. The results are reported in Table 7.

Results: The three pyrethroids used (cyfluthrin, fenvalerat).
e) and cipermethrin (cypermethrin)
Each of n) showed a significant difference in activity between fungus-free and fungal-inoculated soil. Cyfluthrin was the most active compound and provided at least a 10-fold better control of termites in fungal-added soil than in fungal-free soil on all three observation days.

[0077]

Table 7 Koni audio Bors-Koronatsusu and fungal fungal fungal compounds proportion ppm in the interaction effects and termite mortality% 2 days 4 days 7 days soil in termite activity between various synthetic pyrethroids protein None Fungus None Fungus None Fungus Cyfluthrin 3.0 60 100 ¹⁾ 100 100 ¹⁾ 100 100 ¹⁾ 1.0 0 100 ¹⁾ 15 * 100 ¹⁾ 15 100 ¹⁾ 0.3 0 60 0 * 100 ¹⁾ 0 * 100 ¹⁾ Faure rate 10.0 80 100 ¹⁾ 95 100 ¹⁾ 95 100 ¹⁾ 3.0 0 * 95 0 * 100 ¹⁾ 0 * 100 ¹⁾ 1.0 0 * 40 0 * 60 ¹⁾ 0 93 ¹⁾ 0.3 0 0 0 0 0 0 Cipermethrin 3.0 80 98 ^{1 )} 95 100 ¹⁾ 95 100 ¹⁾ 1.0 0 60 0 100 0 100 0.3 0 10 0 60 0 100 *: Slight change in behavior 1): Mycelia / spores are apparent on the carcass Example 8 It was used to evaluate the results of the tests reported in this example and example 10.

Grade Mortality% Subjective Rating 1 98-100 Very Good 2 90-97 Very Good 3 80-89 Excellent 4 65-79 Satisfied 5 45-64 Dissatisfied 6 30-44 Dissatisfied 7 20-29 Poor 8 3-19 Poor 90-2 No action A sample of 100 g of soil was used in this test. For some of the samples, Conidioborus coronatus (Coni)
spore injection of diobolus cornatus),
And some of the samples were Metalhidium anisopriae.
(MADA strain, CBS No. 326) spores were injected. The number of spores injected for a particular example is shown in Table 8A.
And record at 8B. These samples were then treated with filter paper discs soaked in a solution of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine with varying concentrations. The concentrations of the solutions used to prepare the discs for the particular samples are shown in Table 8.
Report to A and 8B. Then 1 gram of termite reticultermis flavipes (Reticuliterm)
is flavipes) was added to each of the samples. The samples were then graded after 7 days using the above scale. The results are reported in Tables 8A and 8B. As they show, Conidiobolus
s) On its own (Table 8A), a soil spore density of 10 ⁵ / g has little effect on termites. However, in soils treated with 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine bait at concentrations that are usually ineffective, 100% mortality is about 10 ^{1 in} soil. It occurred at low spore concentration. By that it is meant that the nitroguanidine treated diet also required a spore density of at least 10 ⁴ when added to the soil sample. Metal Hidium (Me
tarhizium) when added to soil samples (Table 8)
B), When nitroguanidine treated baits are also added to soil samples, the spore density may be lower by several orders of magnitude.

[0079]

TABLE 8A Application of nitroguanidine bait to termite activity and grade of interaction of various fungal pathogens Nitroguanidine% in dipping solution 0. ¹ 10 ¹ 10 ² 10 ³ 10 of spores of Conidiobolus coronatus ⁴ 10 ⁵ number / g of soil / grade 0 9 − − 9 8 7 0.0001 9 − 0.001 9 − 0.018 8 ○ indicates strong synergistic expression.

[0080]

Table 9 Table 8B Metaruhijiumu-Anisopuriae - nitroglycerin ^{guanidine% 0 10 5 10 7 0 9} 9 6 0.0001 9 5 0.001 9 0.01 8 ○ in MADA strain / g of soil / grade soaking solution Example 9 showing strong synergism Metalhidium anisopriae (Metarhizi)
um anisopliae) two different strains--
MADA strain (CBS No. 326) and BIO
(DSM No. 3884) and Conidiobols
Coronatus (Conidiobolus cornat)
us) was used to repeat the procedure of Example 8. However, the filter paper disks were soaked with distilled water or a 0.001% solution of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine.
The results observed over 10 days are reported in Table 9.

[0081]

[Table 10]

Example 10 Metalhidium anisopriae (Metarhizi)
um anisogliae) (MADA strain, CBS
No. 326) and the amounts of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine shown in Table 10 were used to repeat the procedure of Example 8.
The results observed after 5 days are reported in Table 10, using the same scale as described in Example 8.

As the results shown in Examples 9 and 10 corroborate, spores were prepared by adding a low strength 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine diet. Concentrations can be reduced to 10 4 independent of fungal species or strains, and a more effective termite control is still obtained than is obtained with soil treated with water soaked bait only. Let's do it.

[0084]

[Table 11]

Example 11 Fungus Actinomucors
p. ), Paecilomyces farinosus (Paecilo)
myces farinosus, and Beuveria bassiana
a) and the bacterium Serratia s
p. ) Was used to repeat the procedure of Example 5. Discs of filter paper were soaked in distilled water or 0.001% solution of 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine. The results observed over the 7 day period are reported in Table 11.

In Table 11, the grade systems used and reported in the left column of each box were as follows: Normal: No change compared to untreated control + Minor: Surface termites or baits. Food intake or tunnel formation is somewhat affected ++ Moderate: Multiple surface termites, food intake or tunnel formation are substantially reduced; symptoms of poisoning (inactivity, ataxia).

+++ Severe: All termites are superficial, no food intake and no tunneling; increased symptoms of poisoning. ++++ Lethal: 95-100% of termites are dead or dying.

The numbers reported in the right column of each box in Table 11 are% mortality.

[0089]

[Table 12]

[0090]

[Table 13]

Example 12 The procedure of Example 5 was repeated using discs of filter paper and two types of soil soaked in solutions of several different nitromethylene compounds of varying concentrations. One type of soil was unsterilized soil taken from the field. The second type of soil was autoclaved. The concentration of each nitromethylene and the results observed after 4 days are reported in Table 12.

The nitromethylenes used in this example are as follows:

[0093]

[Chemical 11]

[0094]

[Chemical formula 12]

[0095]

[Chemical 13]

The degree of poisoning is reported in Table 12 using the same grade system used in Table 11.

[0097]

[Table 14]

Although the present invention has been described in detail above for purposes of illustration, such details are for purposes of illustration only and those skilled in the art will be within the spirit and scope of the invention, except as limited by the claims. It should be understood that change is possible without doing so.

The main features and aspects of the present invention are as follows.

1. At a site where termites are observed or suspected to be present, at least one selected from the group consisting of (a) nitroguanidines, nitromethylenes, pyrazolines and pyrethroids in an effective amount. A method of eradicating termites characterized by the presence of a chemical and (b) an entomopathogenic fungus or bacterium.

2. The method according to item 1 above, wherein the chemical substance is nitromethylene.

3. The method according to claim 1, wherein the chemical substance is 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine.

4. The fungus is Actinomucor sp.
ctinomucor sp. ) A method according to item 3 above, which is a genus.

5. The method according to the above item 3, wherein the fungus is a species of Paecilomyces farinosus.

6. The method according to the above-mentioned item 3, wherein the fungus is Conidiobolus cornatus species.

7. The fungus is Metarhizium anisopriae
The method according to claim 3 which is a seed.

8. The fungus is Actinomucor sp.
ctinomucor sp. ) The method according to item 1 above.

9. The method according to the above item 2, wherein the fungus is Paecilomyces farinosus.

10. The method according to the above item 2, wherein the fungus is Conidiobolus cornatus.

11. The fungus is Metarhizium anisopria.
The method according to the above item 2 which is e).

12. The method according to the above-mentioned item 1, wherein the fungus is Actinomucor sp.

13. The method according to the above 1, wherein the fungus is Paecilomyces farinosus.

14. The method according to the above-mentioned item 1, wherein the fungus is Conidiobolus cornatus.

15. The fungus is Metarhizium anisopria.
The method according to claim 1, which is e).

16. An effective amount of at least one chemical termite selected from the group consisting of (a) nitroguanidines, nitromethylenes, pyrazolines and pyrethroids and (b) an entomopathogenic fungus or A composition for controlling termites, which comprises bacteria.

17. The composition according to the above item 16, wherein the chemical substance is nitromethylene.

18. The composition according to the above-mentioned item 17, wherein the fungus is Conidiobolus cornatus.

19. The fungus is Metarhizium anisopria.
The composition of claim 17 which is e).

20, the fungus is Actinomucor sp.
The composition according to the item.

21. The composition according to the above item 17, wherein the fungus is Paecilomyces farinosus.

22, an effective amount of (a) at least one formula

[0122]

[Chemical 14]

In the formula, R is hydrogen, an acyl group, a substituted acyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocycle group, or a substituted heterocycle group, and A is (1) hydrogen, Acyl group, alkyl group,
A monofunctional group selected from an aryl group, a substituted acyl group, a substituted alkyl group and a substituted aryl, or (2) a bifunctional group connected to Z, E is an electron-removing group, and X is N or CH, and Z is (1) hydrogen, an acyl group, a substituted acyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocycle group, a substituted heterocycle group, a group OR, NR ₂ , A compound represented by a monofunctional group selected from SR or (2) a bifunctional group linked to A or X, and (b) a termite consisting of an entomopathogenic fungus or bacterium. Inhibiting composition.

23, in the compound of formula I, Z is NH, CH or NR'R ", wherein each of R'and R" is hydrogen or an alkyl group,
At least one of R ′ and R ″ is an alkyl group,
A is an alkyl group, E is CN or NO ₂ ,
23. The composition according to claim 22, wherein X is N or CH and R is a 5 or 6 membered heterocycle ring optionally substituted with halogen or an alkyl group.

24, in the compounds of formula I, A and Z are together a nitrogen-containing 5- or 6-membered ring optionally substituted with thioalkyl or a thioalkyl or sulfur-containing 5 or 6-membered ring. , E is CN or NO ₂ , X is N or CH, and R is a 5- or 6-membered heterocycle ring optionally substituted with halogen or an alkyl group,
The composition according to the above item 22.

25. The composition according to the above item 22, wherein (b) is a fungus.

26. The composition according to the above item 25, wherein the fungus is Paecilomyces farinosus.

27. The composition according to the above item 25, wherein the fungus is Paecilomyces farinosus.

28, (b) is the above-mentioned second which is a bacterium
The composition according to item 2.

29, an effective amount of (a) at least one formula

[0131]

[Chemical 15]

In the formula, A is (1) a monofunctional group selected from hydrogen, an acyl group, an alkyl group, an aryl group, a substituted acyl group, a substituted alkyl group and a substituted aryl, or (2) Z Is a connected bifunctional group, E is an electron withdrawing group, X is N or CH, and Z is (1)
Is it a monofunctional group selected from hydrogen, acyl group, substituted acyl group, alkyl group, substituted alkyl group, aryl group, substituted aryl group, heterocycle group, substituted heterocycle group, group OR, NR ₂ and SR Or (2) a bifunctional group connected to A or X, Y is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, 1 to 4 carbons An alkylthio group having an atom, a haloalkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, an amino group, an alkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, an alkylsulfonyl group or an arylsulfonyl group, And n is 1 or 2, and (b) a termite consisting of an entomopathogenic fungus or bacterium. Inhibiting composition.

30. The composition according to above item 29, wherein (b) is an entomopathogenic fungus.

31, the fungus is Actinomucor sp. Sp.
The composition according to item 0.

32. The composition according to the above item 30, wherein the fungus is Paecilomyces farinosus.

33, (b) is the above-mentioned second which is a bacterium
Item 9. The composition according to Item 9.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area A01N 43:78) (A01N 63/04 47:40) (A01N 63/04 43:50) (A01N 63/00 51:00) (A01N 63/00 43:78) (A01N 63/00 47:40) (A01N 63/00 43:50) (72) Inventor David A. Price 32960 Bellovich, Florida, USA・ Cirtain 9th Avenue 1446

Claims (2)

[Claims] 1. An effective amount of at least one selected from the group consisting of (a) nitroguanidines, nitromethylenes, pyrazolines and pyrethroids at a site where termites are observed or suspected to be present. A method of eradicating termites characterized by the presence of a chemical and (b) an entomopathogenic fungus or bacterium. 2. An effective amount of at least one chemical termiticide selected from the group consisting of (a) nitroguanidines, nitromethylenes, pyrazolines and pyrethroids and (b) an entomopathogenic fungus or A composition for controlling termites comprising a bacterium.