JPS60252401A - Vermicidal compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pest control compounds, their manufacture, formulation into pest control compositions, and use against pests, particularly insects and mites.

The present invention provides compounds of formula (I): Ar (C
H)aA (CH)bQ (CH>.(CE=Ck'
) nCONR'R', (I) RI R is naphthyl optionally substituted with R3 and R6, where R6 is one or more hydrogen, alkyl,
alkenyl, alkynyl, alkoxy, amino, alkenoxy, acyloxy or acyl (all these groups may be optionally substituted) or methylenedioxy, cyano, nitro, 5OR8,5o2R8, SR
, 802NR10R1'', aryl, aryloxy or CO2R12, R8 to R1 are each independently alkyl, R7 is halo or optionally substituted alkyl, and or oxygen, sulfur, NH or N-alkyl; A is 10-
, -N(R")- (wherein R13 is hydrogen, alkyl or acyl), 5(0)d (where d is zero, 1 or 2) or a carbonyl group; a is zero to 6
b is from zero to 12; each H1 is each hydrogen, alkyl, fluoro, cyano or alkynyl; R and R3 are each independently selected from hydrogen, alkyl and halo; Q is -CH2- or oxygen; C is zero to 12; n is zero, 1 or 2; each E and E' is independently hydrogen or halo;
and R' and R5 are each independently hydrogen, alkyl, cycloalkyl, alkenyl or alkoxy (any of these groups may be optionally substituted with halo, alkenyl, alkyl, cycloalkyl, alkoxy, alkynyl or cyano) ), or NR' R5 forms a 5,6- or 7-membered heterocyclic group; a can represent zero only if Q is oxygen].

A particularly preferred group of compounds are compounds of the following formula (TA): where each substituent is as defined above.

Preferably the sum of b and C is at most 12, most preferably 6-7. When Q is a methylene group, b
The sum of and C is preferably an odd number, most preferably 6'8t or 5. When either one of R6 and R7 is substituted alkyl, this group is preferably trifluoromethyl. The above-mentioned “alkyl j
1 "Alkenyl" and similar groups are preferably 1-6
carbon atoms. When either R' or R5 is an alkenyl group, it is preferred that it is saturated in the alpha position. "Aryl" and "aryloxy" include phenyl and substituted phenyl. Optionally present substituents when R6 is alkyl and when R7 is alkyl and the like include alkyl, halo, aryl (preferably phenyl), nitro, alkenyl, alkynyl, alkoxy, acyl.

Preferably R' is a branched alkyl group such as isobutyl and R5 is hydrogen. It has been found that when an alkyl group is present at α to the nitrogen atom, the mite control activity is enhanced, and when placed on the other side, the insecticidal oiliness is enhanced. Conveniently, the configuration of the or each olefinic group bonded to the carbonyl group is E.

R6 is preferably an electron-withdrawing group such as halo or trifluoromethyl. Ar is preferably a phenyl group,
And R6 is preferably 11 or 2 trifluoromethyl groups. If only one CF'3 M is present, it is preferably in the meta position.

E is preferably hydrogen, most preferably E and E' are both hydrogen. However, if which is not hydrogen, preference is given to /, especially fluoro.

Compounds of formula (1) can be prepared in one of the following ways: a) by amidation of the corresponding acid or acid derivative; i.e. by reacting a compound of formula (II) with a compound of formula CI) (1) HNR'R5 (in each formula z''&i is hydroxyl, halo or phospho, and other variable symbols are as defined above).

b) by reacting a compound of formula (IV) with a compound of formula (V) or (V[): 1 (V) (Z'')3P=CF(CE=CE')qe(0
)NR'R5(Vl) (Z')2P=CE(CE=C
E')cLC(0)NR'R'↓ [in each formula 2' is alkyl, alkoxy (preferably ethoxy) or aryl (preferably pheny/I/) and p+q=n-1].

C) By reacting a compound of formula (Vll) with a compound of formula (■): (Vll) Ar(aH)aAI( 1 where z3 is a suitable leaving group such as -OH or halo) and the positions of - and z3- can be exchanged between the two compounds to produce an -A- bond in exactly the same reaction).

d) When Q is oxygen, the compound of formula (N) is converted to the compound of formula (
By reacting with compound X): 5 In this method also the positions of -OH and z3- can be reversed between each compound to produce a similar reaction.

e) by reacting a compound of formula CM) with a compound of formula (X[I): R''R''R' (Xll) Pc=c-(CB=cE')n-1-CO
NR'R' (Ha!l in each formula is a halogen atom).

f) by an elimination reaction involving a compound of formula (XI) =(
(wherein R14 is a suitable group such as lower alkyl),
.

g) by reacting a compound of formula (XIV) with a compound of formula (XV): (xv) &l-CCH=CH)m-xcONR'R5
(In each formula, Hal is a halide, such as bromo or iodo, M is a metal atom, such as anine, zirconium or aluminum, and Al is a metal-containing group, such as a bis-(cyclopentagenyl)zirconium chloride group. ).

The process is usually carried out in an aprotic solvent such as ether, dichloromethane or benzene, optionally in the presence of a quaternary amine such as triethylamine, but in the absence of water, at room temperature or below. .

Process (b) is carried out in an anhydrous inert solvent, e.g. an ether such as tetrahydrone, optionally in the presence of a base, preferably in the absence of oxygen, e.g. a nitrogen atmosphere, at low temperatures (-40 to 0° ). This Wittg type reagent can be obtained using lithium diynepropylamide.

When processes (C) and (a) involve the reaction of two alcohols, this is preferably done in a non-polar solvent at a temperature of about 80-110°C in the presence of a dehydrating agent such as concentrated sulfuric acid. Let's do it. It is preferred that one base is present when 2"' is halo. "Compendium Op Organic Synthesis Method", Harrinon and Hallin, Riley Interscience Methoda', Harrison
and Harrison, WileyTnter
Other standard methods for the formation of ethers and thioethers can be used, such as those described in Phys.

Process (f) can be carried out with K at reflux in a suitable non-polar solvent such as benzene, toluene or xylene. Compounds of formula (XI) can be prepared, for example, by oxidation of the corresponding compounds with one 8R14 group using periodate. This latter compound can be prepared by reacting a compound of formula (XVD with a compound of formula (XvlI): The reaction is carried out in trifluoroacetic acid and trifluoroacetic acid, and then a metal compound of formula (XVI) is added at 0 to 20°C.

Intermediates of formulas (n) to α can be prepared by standard methods. For example, compounds of formulas (V) and (Vl) can be prepared by reaction of the phosphine, phosphonate or +2 phosphite with W-no-roamide. Expression (■)
The compounds can be prepared by hydrolysis of the ketal ring or oxidation of the alcohol.

Power/l/d? Vinyl-containing compounds (IY) can be prepared by oxidizing the corresponding alcohols using, for example, pyridinium chlorochromate or oxalyl chloride/DMSO. The acid function of formula (n) can be generated by hydrolysis of an ester, which can be formed by conventional Wittig or Wadsworth-Emmons reactions, e.g. The acid function of formula (II) can alternatively be prepared by hydrolysis of an ester of formula (II). Compounds of formula yx> can be produced by elimination reaction of a compound: In the formula (bean), z4 is as shown above, and A
One of A1, A2 and A3 is (CH<H)m, and the other one of A1, A'' and A3 is -CH2-, and one of the 6th examiners of A1, A2 and A3 is -CH2-. It'L
CH(OZ')-te, z5 is H or acyl such as acetyl, and the above -CH2- and CH(
OZ5)-groups (i are adjacent to each other. The reaction is carried out in an aromatic solvent, preferably in the presence of a mamolybdenum catalyst (e.g. molyzodenium hexypcarbonyl) and a base (e.g. bis-trimethylsilylacetamide). It is preferable to carry out this procedure.

Intermediates of formula (X[X) can be obtained by reacting a suitable aldehyde with a suitable sulfinyl compound followed by acylation.

The reaction is carried out using a base such as piperidine in a suitable solvent such as acetonitrile. Alcohols for producing compounds (■) and (■) can be synthesized by reacting the compound of formula (XX) with the compound of formula (bean): (In each formula, D' and f are independent hydroxyl or halo, and f may be a preserved hydroxyl group).

Process (g) is usually carried out, for example, in vinyl-bis-(cyclopentadiene/L/)zirconium chloride in tetrahydrofuran in the presence of palladium (O).

When d' is halo, the compound of formula (■) has the formula (X
It can be produced by the reaction of the compound of is Kroll). The reaction is allowed to proceed in a suitable inert solvent, for example an ether such as tetrahydrof2/.

Compound (XXI) can be prepared from an aryl I-lide (preferably iodo or zolomo).

The compounds of formula (I) can be used for the control of arthropods such as insects and acarid pests.

The compounds of formula (I) can be used as compounds themselves or in diluted form, as dipping liquids, sprays, lacquers, foams, dusts, powders, aqueous suspensions, pastes, dels, shampoos, greases, flammable solids, vaporizable mats, They can be used for the above purposes by application in known manners such as wettable powders, granules, aerosols, emulsifiable concentrates, oily suspensions, oily solutions, pressure packs, impregnated articles or pourable compositions. . The immersion concentrate is not applied as is, but is diluted with water and the neutralized animal is placed in a immersion bath containing this immersion solution. The spray is flowing or arched 1! Can be applied by J1' sprayer or by hand.

The animal can be saturated with the spray by still volume application, or can be surface covered with the spray by low volume or very low volume application.

Aqueous suspensions can be applied to animals in the same manner as sprays or dips. The dust can be distributed over the whole animal with a powder applicator or applied in a perforated bag attached to a tree or hanging pole.

Pastes, shampoos and greases can be applied by hand or distributed on the surface of an inert material with which the animal is rubbed,
This material can be applied by transferring it to the animal's skin. The pour composition is applied as a small unit liquid onto the back of the animal so that all or most of the liquid is retained on the animal.

A compound of formula (1) or an acid addition salt thereof can be formulated as a formulation that is ready for use in animals or as a formulation that requires dilution before application, both types of formulations containing a compound of formula (I). Contained in intimate admixture with one or more carriers or diluents. The carrier can be liquid, solid or gaseous or a mixture of such substances;
The compound of formula (I) weighs between 0.025 and 99 weights, depending on whether the formulation requires further dilution or not! It can be present at a concentration of -/capacity.

Dusts, powders and granules contain a compound of formula (I) in intimate admixture with a powdered solid inert carrier, such as suitable lye, kaolin, talc, mica, chalk, dibutham, vegetable carriers, starches and diatomaceous earth. .

Sprays of compounds of formula (1) can be used as emulsions in water (soak washes or spray wash solutions), or solutions in organic solvents (such as those listed below). Concentrates are preferably prepared with or without organic solvents.
Contains a mixture of active ingredients and one or more emulsifiers. The solvent can be present within wide limits, but
Preferably present in an amount of ~90 wt/vol.
It can be selected from kerosene, ketones, alcohols, xylenes, aromatic naphthas and other solvents known in the formulation art. Although the concentration of emulsifier can be varied within wide limits,
A range of 5 to 25 wt/'# is preferred, and the emulsifier is preferably a nonionic surfactant including polyoxyalkylene ethers of alkyl phenols and polyoxyethylene derivatives of anhydrous hexitol and sodium lauryl sulfate, fatty alcohol ether sulfur. Phates, anionic surfactants including Na and Ca salts of alkylaryl sulfonates and alkyl sulfosuccinates.

Wettable powders contain an inert solid carrier, one or more surfactants, and optionally stabilizers and/or antioxidants.

Emulsifiable concentrates contain emulsifiers and often organic solvents such as kerosene, ketones, alcohols, xylenes, aromatic naphthas, and other solvents known in the art.

Wettable powders and emulsifiable concentrates usually contain between 5 and 50% of the active ingredient.
95% by weight and diluted with water, for example, before use.

The two-pack contains a solution of host components in an organic solvent together with a resin and optionally a plasticizer.

The immersion washing liquid can be prepared not only from emulsifying concentrates, but also from formula (I
) in intimate admixture with a dispersant and one or more surfactants, aqueous suspensions, wettable powders and soap-based dips.

Aqueous suspensions of a compound of formula (I) can include suspensions in water with the accompanying suspending agents, stabilizers or other auxiliaries.

Aqueous solutions can also be formed from acid addition salts of compounds of formula (I). Suspensions or solutions can be applied neat or in diluted form in known manner.

Greases (or ointments) can be made from vegetable oils, esters of synthetic fatty acids or mutton fat using an inert base such as soft paraffin. The compound of formula (1) is preferably uniformly dispersed throughout the mixture in the form of a solution or suspension. Greases can also be made from emulsifiable concentrates, which are then diluted with an ointment base.

Pastes and shampoos are also semi-solid formulations in which the compound of formula (1) may be present as a homogeneous dispersion in a suitable base such as soft or liquid paraffin, or glycerin, gum paste or It can also be made from a non-greasy base using a suitable soap. When greases, shampoos and pastes are normally used without further dilution, they should contain the compound of formula (I) in therapeutic amounts.

Aerosol sprays can be prepared as a simple solution of the active ingredient in an aerosol propellant, a co-solvent such as a halogenated alkane, and the solvents listed above. Pour formulations can be prepared as solutions or suspensions containing the compound of formula (1) in a liquid medium that also contains a viscous oil to minimize spreading of the formulation on the animal's surface. Avian or mammalian hosts can also be protected against infestation by acarine ectoparasites by carrying a suitably shaped plastic article impregnated with a compound of formula (I). Such articles include impregnated collars, tags, straps, sheets and strips that can be placed on the body.

The concentration of the compound of formula (1) applied to the animal will vary depending on the compound chosen, the interval between treatments, the nature of the formulation, and the potential for penetration, but will generally range from 0.001 to 20.0 weight/volume of the compound. Preferably between 0.0 and 10 times should be present in the application formulation. The amount of compound deposited on the animal will vary depending on the method of application, the size of the animal, the concentration of the compound in the application formulation, the dilution factor of the formulation, and the nature of the formulation.
Generally, except for non-diluted formulations such as pour-on formulations, 0.00
0.01% to 0.5%, and for non-diluted formulations such as pourable formulations 0.1 to 20.0%, preferably 0.1%.
Deposited at concentrations ranging from ~10%.

Dust, grease, paste and aerosol formulations can generally be applied in a variety of ways as described above, and concentrations of 0.001 to 2 oi/volume of the compound of formula (I) can be used in the application formulations.

Insect pests include Coleoptera (Coleoptera).
) [For example, Anobium, Tribolium, Cythophilus (
Sitophilus), Ant, ho
nomus) or Anthrenu
s species], Lepidoptera (e.g. Ephestia, Heliothis), Spodoptera (5po
aoptQra ) or Tineola
) species], Diptera (e.g. Musca, *eaes, Cu1ex, Glossin
a), Bt, omoxys, Haematobls, Tabanus
anus), Baitorotaea (H7drOtae & )
, Lucilia, Chr.
ysomia), calitroq,
a), Dermatobia (Hypoderma) and Thulenobsis (
MelOph, aquS) species], Phth
iraptera) [Malophaqa force
), such as Damarina sp.
lura), for example Linognathus (LinogΩ
athus) and Haematobinus ("Haemato")
pinus ) species], Hemiptera ( Hem1ptera )
[For example, Aphis or Clmex 1m E, Orthoptera
era) (for example, cyst cell force (5 chiato
cerca) or Acheta (grin)],
Dictyoptera (e.g. 131attela, Perj, planeta or Bl
atta ) species], Hymenoptera
) (for example, 5olenopsis
) or monomolyrum (MOnOmOrium) t
A], Isoptera (T80pter & ) (e.g. Reticuli, termes)
81phonaptera (e.g. ctenocephalides), Hymenoptera (81phonaptera) (e.g.
es ) or Pu1ex species], Thysanura (e.g. L.
episma ) species], Hymenoptera (Dermaptera)
) (e.g. Forficula species) and Pscoptera (e.g. Peripsocus jl
Including the - member of l[).

Examples of mite pests include Boophilus
philus), Rhipicephalus
pha-1us), Amp., Rio-? (Ambl
yomma) genus,/...
Tic and Tetranychus species, such as the genus Ma), the genus Ixodea, the genus Haemaphysalis, the genus Dermocentor and the genus Anocentor 14;
Psoroptes spp., Psorergates spp., Coryogutes (C
horioptes) species and demodex (Dem
odex ) species such as mites and man r species.

The compounds of the invention exhibit killing and/or combating activity against arthropod pests and can be used to control juvenile and adult pests.

The compounds of the invention may contain one or more additional active ingredients (
For example, it can be combined with oleoids, carbamates and organic phosphorus) and/or a rusting agent. Furthermore, the activity of the compounds of the invention may be inhibited by a synergist or enhancer, such as a synergist of the oxidase inhibitor type such as piperonyl butoxide or NA16688; a second compound of the invention; or a pyrethroid pest control agent. It can be enhanced by adding compounds. When an oxidase inhibitor synergist is present in the formulation of the invention, the ratio of synergist to acid (I) compound ranges from 25:1 to 1:25, for example about 10:1.

Stabilizers to prevent any chemical degradation that may occur with the compounds of the invention include, for example, antioxidants (e.g. tocophenol, butylated hydroxyanisole and butylated hydroxytoluene) and scavengers (e.g. epichlorohydrin). include.

It is understood that the matter claimed by the present invention includes the following matters: ←) Compound of formula (D): (b) Process for producing a compound of formula (1); (C) Formula (1)
(d) A method for producing a pest control composition such as (d)
e) a method for controlling insect or acarid pests comprising applying a compound of formula (■) to the pest or its environment; (f) a synergistic agent-containing pest control composition comprising a compound of formula (1); and @ Fortified or non-fortified mixtures of compounds of formula (I) with 51 pest control compounds: (6) Novel intermediate compounds in the production of compounds of formula (I).

The following is a non-limiting illustration of preferred embodiments of the invention.

Example 1 N-isobuty/I/1l-(3'-trifluoromethylbenzyloxy)-(2, 4 g)-undecadienamide a) Sodium metal (0,54,9,23,6 mmol) at 1 ,7-hebutanediol (9.5 g, 70.5 mmol) in anhydrous toluene (130 m) at 100°C. 6-Dolifluoromethylpenzyl chloride (5 g, 25.27 mmol) is added at room temperature and the mixture is heated to reflux for 1 hour. The cooled reaction mixture is filtered and the organic phase is dried. The crude product obtained by removing the solvent was purified by column Chromadog 2F (silica; 1:1 ether/
7-(3'-trifluoromethyl-benzyloxy)-hebutan-1-o)
L/7.18 g (969 b of theory) is obtained.

b) Dimethyl sulfoxide (2,1
3d; 27.6 mmol) is added. The product of step (a) (IF; 13.8 mmol) is added at -78[deg.]G.

After 60 minutes at this temperature, triethylamine (9.7 mg
) is added and the reaction mixture is allowed to come to room temperature. water,
washed with 2N hydrochloric acid, sodium bicarbonate and syline;
After drying and removal of the solvent, 6 g of 17-(5'-trifluoromethylbenzyloxy)-hebutan-1-al are then obtained (theoretical amount of 76 fb).

(C) Triethyl-4-phosphonocrotonate (2,611; 10.45 mmol) in tetrahydrofuran
Lithium diisoptetraviramide in anhydrous tetrahydro-72in (7.5 m) [This compound was composed of n-zotyllithium (10 mmol) and diynnorobylamine (10 mmol).
, 45 mmol)] under a groin atmosphere at -70°C. The solution is warmed to 0°C, recooled to -40°C, treated with the product of step (b) (6,9; 10,45 mmol) and then left at room temperature for 18 hours.

After standard work-up, the crude product obtained was purified by column chromatography (silica; 300 ether:hexane) to give ethyl l-(3'-trifluoromethylbenzyloxy)-(2B,4Iii)- Unde casino et 1.75. ! i' is obtained (theoretical quantity of 44 chi).

(d) the product of step (C) (1,74 &; 4.5
Milimo/l/) was mixed with water (20 m/l) and ethanol (6 m/l/).
Hydrolyzed with potassium hydroxide (0,88,!i') in 0d) for 18 hours at room temperature to give 1l-(3'
−)! j fluoromethylbenzyloxy)-(2E, 4
K)-undecadienoic acid i,oIi is obtained (theoretical amount of 6
6%).

(e) The product of step (d) (1 g; 2.8 mmol) was dissolved in phenyl N-phenylphosphoroamide chloridate (1 g; 3.8 mmol) in anhydrous chloromethane.
and triethylamine (0.66+d; 4.8 mmol) for 60 minutes at Konn-Ton under a groin atmosphere.

Isobutylamine (0.66 mA; 6.6 mmol) and triethylamine (0.66d; 4.8 mmol) are added and after 24 hours the reaction mixture is subjected to standard work-up. The crude product was subjected to column chromatography (
1:1 hexane:ether; silica).
-isobutyl 1l-(3'-trifluoromethylbenzyloxy)-(2g.

4E)-undecacyenamide 0.5719 is obtained (50% of theory); melting point: 48-5000° Nuclear magnetic resonance vector (NMR): 7.52.4H1m, aromatic; 7.2.1H, dN of m J3.2=16, a 3
z6.05.2H, m, H4,5; 5.7B, IH, a
.

J2.3=16, H2J 5.74.11E(,m,
NH; 4.55.2H16, benzyl CHa z
3.53.2Hz tzHl 1 ; 3.16.2H
, d1isozotyl of a; 2.16.2H,m, H6s
1.48.9 Hs mN isobutyl, H7,8,9
, 10; 0.93.6■, d1 inbutyl.

Using essentially the same synthetic sequence with the following differences, the following compounds are prepared: Example 2 N-isobuty/L'9-(5'-trifluoromethylbenzyloxy)-(2) , 4E)-Nonadienamide In step (a), 1,5-bentanediol is used in place of 1,7-hebutanediol.

Example 6 N-2-methyl-butyl 9-<3'-trifluoromethylbenzyloxy)-(2g, 41-nonadienamide step (c)), converting 1,5-bentanediol to 1,7-
Hebutanediol is used in place of hebutanediol, and in step (e) 2-methyl-butylamine is used in place of isobutylamine.

Example 4 N-isobutyl 1l-(3',5'-bis-trifluoromethylbenzyloxy)-(2g,4E)-undecadienamide step (with 6,5-bis-trifluoromethylbenzylbromide is used in place of 6'-trifluoromethylbensyl tetrahydride.

Example 5 N-isobutyl 11-(pentafluorobenzyloxy)-(2B, 41-undecadienamide In step (a), pentafluorobenzyl bromide is
- used in place of trifluoromethylbenzyl chloride.

Example 6 N-Inbutyltupendyloxy-(2E.

In the 41-hebutadienamide step (a), benzyl chloride and 1,6-zogastric pandiol are used as the main raw materials.

Example 7 N-isobutyl 1l-(2,4-dichlorobenzyloxy)-(2E#4E)-undecadienamide In step (a), 2,4-dichlorobenzyl chloride was
'-Trifluoromethylbenzyl chloride.

Example 8 N-isobutyl 10-(benzyloxy)-(2ET4
In the 1-decadienamide step (c)), benzyl chloride and 1,6-hexanediol are used as main raw materials.

Examples 9-66 and 72-116 Compounds of Table 1 are prepared in a similar manner; where Ar is phenyl, a is 1, n is 2, R4 is hydrogen, and Q is -CH2-: Table 1 9H2 Isobutyl IQ H41-Methylnorobyl 11 5-CFa 2 Isobutyl 12 2.6-dicJ, 5 Isobutyl 13 3.4-
Methylenedioxy 6 Isobutyl 15 3.4-Methylenedioxy 6 Cyclohexyl 16 3-Br 3
Cyclonorovir methyl 17 3-Br 6 2-methoxypropyl 18H5 1-methylpropyl 19 5-CF3 2 2-methoxypropyl 20 2
．． 3-C1g 5 2-methylpropyl 21 216-
R125 cyclopropylmethyl 22 3-aF3 2
Cyclopropylmethyl 26H6 1-Methylprogyl 24 3.4-methylenedioxy 4 Isobutyl 25
3.4-Methylenedioxy 5 Inbutyl 26 3
-C13isobutyl27 3-C132-methoxyzorobyl28 5-C1
5 cyclopropylmethyl 29 H5 isobutyl 60 H6 isobutyl 61 3 + 5- C1251-methylnorovir 52
3.5-CI2 5 Isobutyl Table 1 (continued) 33, 2+4-R126 Isobutyl 54 3-ON
3 Isobutyl 55 3-CN 5 2-Methylbutyl 56 3-CN
3 2-methoxypropyl 57 5-CN 5 2-
Methoxypropyl 3B 3-CN 5 Isobutyl 39 3-ON 5 Cyclopropylmethyl 40 3.
5-C123 Isobutyl 41 6-F 3 Isobutyl 42 3-F 5 Isobutyl 43 6-CF54 Isobutyl 44 3-CF3 4 2-Methoxyzorobyl 45 3
-CFs 3 2-methoxypropyl 46 3-CF3
5 1-Methylpropyl 47 2 * 5-012 5
Isobutyl 48 5-CFa 4 Isobutyl 49 3.5-dimethyl, 6 Inbutyl 50 2.
6-Dichlor A/ 5 Isobutyl Table 1 (continued) 51 3.4-Dichlor 6 Isobutyl 52 6-c
p,, 6 5-methylbutyl 53 6-CF, 3
2-Methylzorobyl-2-enyl 54 6-aF, 6 1+2-dimethylprosh 55 5
-CF3 3 Isopropyl 56 3.5 (CFi)a 3 Isobutyl 57 3r
5-(CF3)2 3 2-Methylzolo f-2-Kokaku 5
8 4-6th zotyl 6 isobutyl 59 2=5-C
125 Isobutyl 60 5 p 5-012 3 2-Methylpropyl 6
1 3.5(C:F3)2 3 2-Methoxypropyl 62 3-CFa 3 2-Chlorzolovir 63 3-
F 3 1,2-dimethylatrovir 72 515-F
z 5 Isobutyl 73 6.5-F23 Inbutyl 75 3-CF3, 3 Table 1 (Continued) 76 3.4J, :lz 5 1.2-DimethyIo Bisilev 7 216-C'2 5 1.2-Dimethylpropyl 78 3.4-012 5 Inbutyl 79 216
-012 5 Isobutyl 8LJ 3-8O2NEtz
6 Isobutyl 3i 3-8O2NEt2 5 Isobutyl 82 5-OCI (+CF33 Isobutyl 53
4-OCF5 3 Isobutyl 84 3-ocH2cF, 3 1.2-dimethylpropyl 85 4-ocF3 3 1,2-dimethylpropyl 86 3NOz 3 Isobutyl 87 2.4-F2 5 Isobutyl 88 2.4-12 3 1,2 -dimethylzorovir 8
9 6-CF3 3 Isoprogyloxy90 6-C
Fr<3 2,2-dimethylzorobyl91 3-CF
3 3 1.1-dimethylpropyl y5 4-al 3
Isozo flV Table 1 (continued) 94 3-CF, 3 1-ethylpropyl 95 H7
Isobutyl 96 H6 Inbutyl 97 4-owt6 Isobutyl 9B 2-C1,4-F 5 Isobutyl 99 3.5
-(CF3)2 5 1 t2-dimethyAriProvir 1
00 3.5(CFs)z 5 1-methylpropyl 1
01 H5α-methylbenzyl 102 3-oph 6 C2-dimethylpropyl ID
3 3-OPh 3 Isobutyl 104 2-C13 Inbutyl 105 4-CF3 3 Isobutyl 106 4-CF3 6 1.2-Dimethylzorobyl 1
07 3-F 4 3-methylbutyl 11Q 5-8E
t 5 1,2-dimethylpropyl, Table 1 (Continued) Example number R' b + c R5 1113-8(0)Et 3 1,2-dimethyzo and t robicile 112 2-F, 5-al 6 Inbutyl 11
3 2-. 5-F 5 Isobutyl 114 4Ph 5
Isobutyl 115 3-F2CF36 Inbutyl 116 6-F
2CFs 6 1.2-Dimethylzolobyl Examples 64-71 The following compounds are prepared in a similar manner: 64 N-isobutyl 8- (2-(6'-trifluoromethylbenzyloxy)-ethoxyocta-2B, 4=-dienamide 65 N-isobuty/1/8-[:1-(3
-trifluoromethylphenyl)-ethoxyocta-2E + 4 E-dienamide 66 N-isobuty/'9-C2-C5'#5'-dichlorophenoxy)-ethoxyocta-2, 4 B-
Dienamide 67N-2-methoxypropyl 9-(2-thenylmethoxy)-nona-2ET4E-dienamide 68N-isobutyl 9-(2-thenylmethoxy)-nona-21,4-dienamide 69 N-isobutyl 1
l-(2-chenylmethoxy)-undeca-2, 4F
-Dienamide 70 N-isobuty/I/9-(2-furfurylmethoxy)-nona-2E 14E-dienamide 71 N-isobutyN9-benzylthiooxytuna-2K, 4E-
Dienamide Examples 117-162 The following compounds are prepared in a similar manner: 117 N-isobutyl 11-(α-ethynylpencyloxy)undeca-2B,4E-dienamide 118 N-isobutyl 9-(2-naphthylmethoxy)-
nona-2g+4B-dienamide 119N-isobutyl 1l-(2-furfuryloxy)-undeca-2BC,
4 to 1 dienamide 120 N-isobutyl 11- (3-thenylmethoxy)-undeca-2E 14 E-dienamide 121 N-isobutyl 9-(6-chenylmethoxy)-
nona-2E,jl;-dienamide 122N-isobutyl 1l-(3-trifluoromethylphenyl)-10-
Oxo-undeca-2E 14 K-dienamide 126N-isobutyl 10-benzthioxy-deca-2
E, 4B-dienamide 124N-inbutyl 9- <5-furfuryloxy)
-nona-2E 14E-dienamide 125N-isozothi#1l-(3-fur7lyloxy)-undeca-2E
, 4B-dienamide 126N-isodecyl N'-methyl-N'-benzyl-
9-aminoundeca-2, 4B-dienamide 127N-isobutyl 8-(1-(S', 5'-dichlorophenoxy)-methoxy)-octa2mt4E-dienamide 128N-isobutyl 10-(1-(5', 5 '
-di11o)vphenoxy)-methoxytudeca-2E
, 4B-dienamide 129N-isobutyl [8-(octa-2E.

lt-dienamido)yl-benzyl sulfoxide 130 N-1-methylzolopyl 9-(2-(3'.

5'-dichlorophenoxy)-ethoxytsuononor-2B
, 4F, -dienamide 161N-isozothi #9-
(α-methylbenzyloxy)-nona-2B, 4B-
Dienamide 162N-Isobutyl 9-(α-cyanobenzyloxy)-nona-2,E l 4 'E-Dienamide A, lethal activity against house flies Musca domestica
a) The activity of the compounds of the invention against (WRL g ) is determined by applying a solution of the pseudoline compound in Cellosolve to test insects, with and without synergistic agent auxiliary treatment. This was proven by K. The test compound was a synergist [6 μg piperonyl butoxide (P
B)/insects]. Mortality was assessed after 48 hours. The results are shown in Figure 2. In this Table 2, = represents about, 1.5< means a value greater than 11.5, and 0.9 < 3 means a value between 0.9 and 6.0.

Table 2 1 = u, 6 χ6 2 0.2 ”6 4 0.025 0.12 8 5ku16 21.8 6< 14 0.18<0.6 1.8<6 25 1.8<6 Evening 10 26 0.18<0.6 1.8<6 27 Yu1.8 28 1.8<6 61 0.11 χ1.5 64 6ku41 Yu0.9 46 Taro45 Sa1.8 10( 470 ,18<0.6 1.8<6 49 3<5 Table 2 (continued) 52 1.8<6 55 0.18<(J, 6 54 Ll, 18<0.6 58 N1.8 62 21 .8 64 Sa10 65 0.18<0.6 χ10 66 0.06<0.18 1.8<667 6<10 70 6(10 720,5<0.9 74 Evening5 76 α0.6 6< 10 80 310 82 0.6<1.8 6<10 83 0.6(1,8 861,8<6 88 0.18(0,6 895〈 Table 2 (continued 90 0.3<0.9 91 0.9<3 92 0.3<0.9 95 N5 96 3(5 971,8<6 99 Sahada02 106 α0,9 104 Σ0.5 105 0.9<3 108 0.09 109 0 .09 117 Sa 1.8 118 0.9 (5 1221,5 < 125 6 < 10 124 1.8 < 6 126 20 ( 1270,9 (3 1300,09 < 0.5 B, activity against mosquitoes This invention The overthrowing activity of the compound was evaluated as follows:
Cu1ex quinquefasciatus)
K, odorless petroleum distillate (OPD)/dichloromethane (80,
/20) Ejaculate the test compound solution skin 2- in a wind tunnel,
The number of knockdowns was evaluated at 1 minute intervals for 10 minutes. Insects were transferred to holding cups and maintained on sugar/water for 24 hours.

The number of deaths in 24 hours was evaluated. The results are shown in Table 6.

Table 6 2 0.5 (1,5) 1.2 100 710.03
(0,15) 8.6564 26 0.3(1,5) < 1 100 800.0
3(0,15) 3.2652141 0.1(0,5
) 35 65 0.1 (0,5) 1゜71005666 0,
Ho, 5) 1.29640C1 Activity against house flies Mixed male and female Musca domestica (Musca dome)
77.77 Kearn
(S and March) chamber and sprayed with 0.2 - of a solution of the test compound in OPD/dichloromethane. The number of knockdowns was evaluated at 1 minute intervals for 10 minutes. The results are shown in Table 4.

Table 4 2 0.1 6.186 26 0.3(1,5) 2.510041 0.3(
1,5) 2.6100660.6(1,5) 2.3
100 66 0.1 (0,5) 5.196 53 0.1 (0,5) 6.2100 The activity of the compounds of the present invention against dhalein beetles was determined by
narius) were exposed to a 1:5 ratio of the test compound and a synergist (piperonyl butoxide) on the grain by trapping. Mortality was assessed after 6 days. The results are shown in Table 5 below.

Table 5 2 20 (100) 84 4 50 (500) 10L] E. Activity against cockroaches (Cockroaches)
The activity of the compounds of the invention against P. rmanica ) K was demonstrated by exposing insects to a 1:1 ratio of test compound and synergist (piperonyl butoxide) on glass deposits for 1 hour. The number of defeats was assessed after 10 and 60 minutes, and the number of deaths after 1 and 6 days. The results are shown in Table 6 below.

Table 6 2 1400 (1400) 5050 4 700 (700) 5232 F, Activity against Mosquito Larvae The activity of the compounds of the present invention against mosquito larvae was determined when the sixth stage larvae of Aedes aeqypti were treated with the test compound and synergistically. Agent (piperonyl butoxide)
This is evidenced by exposure to an aqueous suspension containing a 1:51 ratio of K. The results are shown in Table 7 below.

Table 7 2 2.5 (12,5) 100 G, Activity against cattle tick (a) Injection of test compound at 507V in DMSO:acetone (1M)
/7 Prepared as a solution. Compound administration is 0.2μ of solution
It is carried out using a micro applicator that dispenses cedar. A female Boophilus micropulus (female Boophilus m1cr), an infectious species, has absorbed enough of the compound in the solution.
opus) at a rate of 10 μg/tic at a site immediately adjacent to the mouthparts. Reduce the dose by reducing the concentration.

After injection, the ticks are kept at 24°C and 85% RE for 14 days. At this point the ticks are tested for the presence of viable eggs and the % Reproductive Prevention (IR%) is obtained. The number of dead tics was also recorded and the results are shown in Table 8.

Table 8 31 10 1060 0 3 1070 10 1 1040 0 54 10 10100 20 3 1090 50 1 1040 10 63 10 10100 5 85 10 10100 50 (b) Immersion test compound in Easo 200/wetting agent 11001
Prepare as R/,, e solution. Dilute with water to achieve desired concentration. A group of 20 fully-fed females of infectious species B
, m1croplus are placed in a mesh basket and the basket is immersed in the test dilution for 10 minutes. After soaking, the tic is removed, dried and fixed to a double-sided adhesive tape, and the tape itself is fixed to a white plastic plate. The ticks held on the plate are kept at 24° C. and 85% RH for 14 days.

Each egg mass is scored on a 0-40 scale for quality and quantity to obtain an overall score for each group. This measure was corrected for water control eggs and graphed on log-propit paper, with 50% and 90% inhibitory concentrations (IR5Q and IR5Q and IR5Q and 1R
99) is determined.

Similarly, determine the 50% and 9096 lethal concentrations.

The results are shown in Table 9.

Table 9 Compound example number lR501R99LC50LC905
40,0010,0190,04>0.046g, -r
Stard Beetle (Mustard Beetle) (
Phaedon Coc Realiae
Second stage larvae are used in all tests and the compound is applied topically to the dorsal abdominal surface using a micro applicator. From 10 to 66 larvae are used for the chemical compound taniiso degree. Analar acetone and butanone are used as solvents.

In the first test, 1 drop of 50μ is applied to each larva, after which as the larvae become unaffected by the solvent,
This suitable dimension increases to 1 μe.

After treatment, all larvae tested at one time (usually 20) are collected together on a turnip leaf. Place the larvae on the moist filter paper in a Petri dish and cover with a second layer of filter paper on the lid of the dish.

The Petri dish is kept in an incubator at 20° C. and 16 hours photoperiod. Turnip leaves are replaced when they are eaten by larvae.

Larvae are evaluated at intervals from 1 hour to 216 hours after treatment. The following evaluation criteria were used to classify larvae: 1. Healthy larvae that eat and move around the plate; 2. Paralysis: larvae that writhe or show slight dislocation movements; 6. Dead: larvae that do not move; Larva begins to shrink.

Compounds of Formulation Example 1 and Emulsifiable Concentrate Example 4 10. aO Echira y K, EO (mt, hylan) 20.00
Xylene 67,50 Butylated hydroxyanisole 2.50100.00 2. Compound of wettable powder example 4 25.0 Attapulgide 69,50 Butylated hydroxytoluene 2.50100.00 Compound of dust example 4 0.50 Butylated Hydroxyanisole 0.10 Talc 99
．． 40 100, mouth 0 4, compound of feed example 4 40.25 icing sugar 99.65 butylated hydroxytoluene o, i.

100.00 5. Compound of lacquer example 4 2.5 Resin 5.0 Butylated hydroxyanine 0.5 Highly aromatic petroleum distillate 92.0 100.0 6. Compound of aerosol example 4 0.60 Butylated hydroxy Anisole 0.101.1.1-
Trichloroethane 4. OO odorless kerosene 15.60 7, compound of spray example 4 0.1 butylated hydroxyanine 0.1 xylene 10
．． 0 Odorless Kerosene 89.8 1 DO, D.

8. Compound of Reinforcing Spray Example 4 0.1 Permethrin 0.1 Butylated Hydroxyanisole 0.1 Xylene 10.1 Odorless Kerosene 89.8 100 DO Agent Akira Asamura Procedural Amendment (Showa 60) May 1st, 2016 Mr. Ushihi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 69880 of 19852, Title of the invention: Pest control compound3, Relationship with the person making the amendment, Address of the patent applicant5, Date of amendment order: Showa year, month, day 8, content of amendment: Engraving of the specification as attached (no change in content)

Claims (1)

[Claims] (1) According to formula (1), R6 is naphthyl which may be substituted with #, where R6 is 1 or μ is 12 or more hydrogens, halo, alkyl, alkenyl, alkynyl, alkoxy, amino, alkeneoxy, acyloxy or acyl (these groups may be optionally substituted), or methylenedioxy, cyano, nitro, 802R", 5OIR"
, SR9,5o2NR"°H1m, aryl, aryloxy or C□,,BIW, R8~H12
are each alkyl, and R7 is halo or optionally substituted alkyl;
and X is oxygen, sulfur, NH or N-alkyl 36FA is -o-, -N(R'')- (where B13 is hydrogen, alkyl or acyl), 5(0), (
where d is zero, 1-): or 2) or a carbonyl group; a is zero to 6; b is zero to 12; each R1 is hydrogen, alkyl, fluoro, cyano or alkynyl, respectively; R and R are each independently selected from hydrogen, alkyl and halo; Q is -CH2- or oxygen; C is from zero to 12;
6 is zero, 1 or 2; E and E' are each independently hydrogen or halo; and R4 and R5
are each independently hydrogen, alkyl, cycloalkyl,
is an alkenyl or alkoxy group, any of which groups may be optionally substituted by halo, alkenyl, alkyl, 7-chloroalkyl, alkoxy, arginyl or cyan, or NR' R5 is 5.
forming a 6- or 7-membered heterocyclic group; provided that a can represent zero only when Q is oxygen]. (2) A compound according to claim 1 which is a compound of formula (IA) in which each substituent is as defined in claim 1. (3) A compound according to claim 1 or 2, in which the sum of b and C is not greater than 12. (4) The compound according to claim 6, wherein the sum of b and C is 6 to 7. (6) The compound according to any one of claims 1 to 4, wherein 51R' has an alkyl group α to nitrogen, and R5 is hydrogen. The compound according to any one of claims 1 to 5, wherein the configuration of one or each bonded olefinic group is E. (7) The compound according to claim 1, wherein Ar is a phenyl group. The compound according to any one of Items 1 to 6. (8) N-isodityl 1l-(3'-)lifluoromethylbenzyloxy)-(2E T 4 F )-undecadienamide; or N- Inbutyl 1l-(3'
, 5'-historif/I/olmethylbenzyloxy)-(2,4E)-undecadienamide. (9) Naphthyl optionally substituted with R6 according to formula (I), where R6 is one or more hydrogen, halo, alkyl,
Alkenyl, alkynyl, alkoxy, amino, alkenoxy, acyloxy, acyl (these groups may be optionally substituted, methylenedioxy, cyano, nitro, 5o2R8,80RB, SR', BO,
NR1OR”, aryl, aryloxy or C0
2R1i1, R8 to RL are each alkyl, R7 is halo or optionally substituted alkyl, and X is oxygen, sulfur, NH or N-alkyl; is 10-, -N
(R13)- (wherein R13 is hydrogen, alkyl or acyl), 5(0)d (where d is zero, 1 or 2) or a carbonyl group; a is zero to 6; b is from zero to 12; each R1 is each hydrogen, alkyl, fluoro, cyano or alkynyl; R
″′ and R3 are each independently selected from hydrogen, alkyl, and halo; Q is -CH2- or #element; C is zero to 12; n is zero, 1, or 2; each E and E' is each independently hydrogen or halo; and R' and R5 are each independently hydrogen,
is alkyl, cycloalkyl, alkenyl or alkoxy (any of which groups may be optionally substituted by halo, alkenyl, alkyl, cycloalkyl, alkoxy, alkynyl or cyano) or NR'R' is 5. forming a 6- or 7-membered heterocyclic group; provided that a can represent zero only when Q is oxygen. Reacting the compound with a compound of formula (1): (1) HNR4R5 (in each formula z'' is hydroxyl, halo or phospho: and the other groups are as defined above),
or b) reacting a compound of formula (ff) with a compound of formula (v) or <VD: (V) (z')r5p=cg(cg=cg')qe(
o) NR4R5(Vl) (Z”)2P=CB(CF=
CBC') C(0)NR'R'〇- (2 in each formula is alkyl, alkoxy or aryl, and p+q=Ω-1, or C) formula (V
React a compound of lυ with a compound of formula (Vlll): (in each formula z3 is a suitable leaving group such as -OH or halo, and the -super and z3- positions or d) reacting a compound of formula (■) with a compound of formula (X) in the production of a compound which is C1'-oxygen; (X) Z3-(O
H) (cg=cr)ncoNR'n'c 3 (the positions of -OH and z3- groups in each formula may be reversed between the two compounds), or e) React with a compound of formula (■): (Xll)EC-C-(CE=CE')n, -coN
R'n5 (Hal & 1 in each formula is a rodene atom),
or f) by an elimination reaction involving a compound of formula (XI[), in which R14 is a suitable group such as lower alkyl, or g) a compound of formula (XIV) and a compound of formula (XV). React with: (X V ) Hal-(L H=(-H)m-IC
ON R' R5 (in each formula, Hal is a halide, and M is a metal atom or a metal group) E. A method for producing a compound of the above formula (1), characterized in that: (10) is optionally substituted naphthyl, where R6
is one or more hydrogen, halo, alkyl, alkenyl, alkynyl, alkoxy, amino, alkeneoxy, acyloxy or acyl (all of which may be optionally substituted), or methylenedioxy, cyano, Nitro, 5OR8, 5o2R8, SR',
5o2NR10Ri, aryl, aryloxy or CO2H12, R8 to R12 are all each alkyl, R7 is . . . or an optionally directly substituted alkyl, and or oxygen, sulfur, NH or N-alkyl: A is -0-, -N(
R,'')- (where p, 15 is hydrogen, alkyl or acyl), 5(O)d (where d is zero, 1 or 2) or a carbonyl group; a is zero to 6; : b is zero to 12; each R1 is independently hydrogen, alkyl, fluoro, cyano, or alkynyl; B2 and R3 are each independently selected from hydrogen, alkyl, and no; Q is 10; H2- or oxygen; C is zero to 12; D is zero, 1 or 2
and R4 and R5 are each hydrogen, alkyl, cycloalkyl, alkenyl or alkoxy (
Any of these groups may be optionally substituted with halo, alkenyl, alkyl, cycloalkyl, alkoxy, alkynyl or cyano), or NR4''R5 is a 5.6- or 7-membered ring system. forming a group; a can represent zero only if Q is isthmus; zl is a hydroxyl, no-touch or phosphoroimidate ester group, p is zero or 1: R1' is lower alkyl; and M is a metal atom or a metal-containing group. and R6 is one or more hydrogen, alkyl, alkenyl, alkynyl, alkoxy, amino, alkeneoxy, acyloxy, or acyl/I/ (all of these groups may be optionally substituted) , or methylenedioxy, cyano, nitro, 5O2R8,5OR
8, SR', 5o2NR1'R11, aryl, aryloxy or Co2R12'R8~R1''
are each alkyl, R7 is alkyl or optionally substituted, and X is oxygen, sulfur, NH or N-alkyl; A
is -o-, -NCR"')- (where R13 is hydrogen, alkyl or acyl), 5(0)d (where d is zero, 1 or 2 or a carbonyl group; a is zero ~6; b is zero to 12; each R1 is each hydrogen, alkyl, fluoro, cyano or alkynyl; R2 and R3 are each independently selected from hydrogen, alkyl and ); Q is 10H2- or oxygen: C is zero to 12; n is zero, 1 or 2; E and E' are each independently hydrogen or halo; and R' and R5 are each independently is a hydrogen, alkyl, cycloalkyl, alkenyl or alkoxy group, any of which groups may be optionally substituted by halo, alkenyl, alkyl, cycloalkyl, alkoxy, alkynyl or cyano, or NR 'R6 forms a 5.6- or 7-membered heterozygote group; however, only when Q is oxygen, a can represent a 4-membered compound. Pest control composition comprising a carrier or a dispensing agent.0 Claim 11 further comprising a synergistic agent.
composition of the term. 0. The composition of claim 11 or 12, further comprising a second pest control compound.