MX2007004631A - Insecticidal 3-(dihaloalkenyl) phenyl derivatives - Google Patents

Abstract

Certain novel 3-(dihaloalkenyl)phenyl derivatives have unexpected insecticidal activity. These compounds are represented by formula (I), where R through R5, a, b, D, E, G and U are fully described herein. In addition, compositions comprising an insecticidally effective amount of at least one compound of formula (I), and optionally, an effective amount of at least one of second compound, with at least one insecticidally compatible carrier ar also disclosed;along with methods of controlling insects comprising applying said compositions to a locus where insects are present or are expected to be present.

Description

DERIVATIVES OF INSECTICIDE 3- (DIHALOALQUENIL) PHENYLENE Field of the Invention The present invention relates to novel compounds and their use to control insects and acarids. In particular, it belongs to 3- (dihaloalkenyl) phenyl derivatives and agriculturally acceptable salts thereof, composition containing them and methods for their use to control insects and acarids.

BACKGROUND OF THE INVENTION It is well known that insects in general can cause significant damage, not only to crops in agriculture, but also, for example to structures and grass where damage is caused by insects from sweeping solids, such as termites. and white worms. These damages can result in the loss of millions of dollars of value associated with a given crop, lawn or structures. Insecticides and acaricides are useful for controlling insects and acarids which would otherwise cause significant damage to crops such as wheat, corn, soybeans, potatoes, and cotton to name a few. For the protection of the crops, insecticides and acaricides that can control insects and acarids without damaging the crops, and which do not have deleterious effects on mammals and other living organisms REF.3181386 are desired. US 5,922,880 discloses certain dihalopropene compounds which are used as insecticides and acaricides of the general formula: wherein Z is oxygen, sulfur, or NR4 (wherein R4 is hydrogen or Ci-C3 alkyl); And it's oxygen, sulfur, or NH; X's are independently chlorine or bromine; R2, R3 and R10 are independently halogen, C1-C3 alkyl, or Ci-C3 haloalkyl, t is an integer from 0 to 2; and R1 is A- (CR5R6) PCHR7- (Q1), AB- (CR5R6) PCHR7- (Q2), A- (CR11R12) SB- (CR5R6) P-CHR7- (Q3), A- C (R13) = C (R14) - (CR5R6) P-CHR7- (Q4), AB- (CRUR12) SC (R13) = C (R14) - (CR5R6) P-CHR7- (Q5), AB- (CRUR12) SC (= 0) -O- (CR5R6) P-CHR7- (Q6), or AC (R13) = C (R1) -C (= 0) -0- (CR5R6) p-CHR7- (Q7), where A is a optionally substituted heterocyclic ring; B is oxygen, S (0) q, NR9, C (= G1) G2 or G1C (= G2); q is an integer from 0 to 2; R9 is hydrogen, acetyl or C1-C3 alkyl; G1 and G2 are independently oxygen and sulfur; R5, R6, R7, R11 and R12 are independently selected from hydrogen, C1-C3 alkyl, or trifluoromethyl; R13 and R14 are independently selected from hydrogen, Ci-C3 alkyl, halogen or trifluoromethyl; p is an integer from 0 to 6; and s is an integer from 1 to 6. There is no disclosure or suggestion in the patent referred to above of the 3- (dihaloalkenyl) phenyl structures and the pesticidal activity of the compounds of the present invention.

Brief Description of the Invention In accordance with the present invention, it has been found that certain novel 3- (dihaloalkenyl) phenyl derivatives are surprisingly active for the control of insects and acarids when used in insecticidal and acaricidal compositions and methods of this. invention. The novel derivatives are represented by the following general formula I: I wherein R and R1 are independently selected from hydrogen, halogen, alkyl and cyano; R5 and R6 is independently selected from bromine and chlorine; a is an integer selected from 0 or 1; and when a is 1, D is -O-; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) 0-, where the asterisk denotes the D-junction; i, j, k, 1, m, n and o are integers independently selected from 0 and 1; when 1 is 1, Q is a 5- or 6-membered heterocyclic ring containing from 1 to 4 nitrogen atoms and 0 to 1 oxygen or sulfur atom; b is an integer selected from 0 to 1; and, when b is 1, G is selected from -O-, -CH20-, -CH = CH-, -S (0) h- / S (0) hCH2-, -S (0) hC2H4-, -HC = N-, -C (= 0), -0C (= 0) -, - C (= 0) 0-, -C (= 0) C2H4-, -C (= 0) 0CH2-, -C (= 0) NH-, -NR14-, -N (oxide) R14- and -NR14C (= 0) -, where h is an integer selected from 0, 1 and 2 and R 14 is selected from hydrogen, alkyl, alkoxyalkyl, arylalkyl alkenylalkyl, haloalkenylalkyl, dialkyl phosphonate, alkylcarbonyl, haloalkylcarbonyl, alkoxyalkylcarbonyl, arylcarbonyl and alkylsulfonyl; U is selected from the group consisting of: wherein: R7, R8, R10 and R11 are independently selected from hydrogen and halogen; R9 is selected from hydrogen, halogen and haloalkyl; R15 is alkoxycarbonyl; R16 is selected from alkyl and haloalkyl; R40 and R41 is independently selected from alkyl; provided that when (a) R, R1, R5 and R6 are chlorine; (b) a, i, j, k, n, and o are 0; (c) B1 is -CH-; (d) m is 1 and (e) U is the group X where R7 to R11 are hydrogen, when b is 1; and the agriculturally acceptable salts of these. The present invention also includes compositions containing an effective insecticidal amount of at least one compound of formula I, and optionally, an effective amount of at least one additional compound, with at least one vehicle compatible with the insecticide. The present invention also includes methods for controlling insects, in an area where control is desired, which comprises an effective insecticidal amount of the above composition at the location of the crops, or other areas where the insects present themselves or are expected to are present. The present invention also includes novel intermediate compounds that find utility in the synthesis of the compounds of formula I.

Detailed Description of the Invention The present invention relates to certain novel and useful insecticidal and acaricidal compounds, primarily 3- (dihaloalkenyl) phenyl derivatives (hereinafter referred to as "compounds of formula I") as shown in general formula I : I wherein R and R1 are independently selected from hydrogen, halogen, alkyl and cyano; R5 and R6 is independently selected from bromine and chlorine; a is an integer selected from 0 or 1; and when a is 1, D is -0-; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) 0-, where the asterisk denotes the D-junction; i, j, k, 1, m, n and o are integers independently selected from 0 and 1; and when 1 is 1, Q is a 5- or 6-membered heterocyclic ring containing from 1 to 4 nitrogen atoms and 0 to 1 oxygen or sulfur atom; b is an integer selected from 0 to 1; and, when b is 1, G is selected from -0-, -CH20-, -CH = CH-, -S (0) h-, -S (0) hCH2-, -S (0) hC2H4-, - HC = N-, -C (= 0), -0C (= 0) -, -C (= 0) 0-, C (= 0) C2H4-, -C (= 0) 0CH2-, -C (= 0) NH-, -NR14-, -N (oxide) R14- and -R14C (= 0) -, where h is an integer selected from 0, 1 and 2 and R14 is selected from hydrogen, alkyl, alkoxyalkyl, arylalkyl, alkenylalkyl, haloalkenylalkyl, dialkylphosphonate, alkylcarbonyl, haloalkylcarbonyl, alkoxyalkylcarbonyl, arylcarbonyl and alkylsulfonyl; U is selected from the group consisting of: wherein: R7, R8, R10 and R11 are independently selected from hydrogen and halogen; R9 is selected from hydrogen, halogen and haloalkyl; R15 is alkoxycarbonyl; R16 is selected from alkyl and haloalkyl; R40 and R41 is independently selected from alkyl; provided that when (a) R, R1, R5 and R6 are chlorine; (b) a, i, j, k, n, and o are 0; (c) B1 is -CH-; (d) m is 1 and (e) U is the group X where R7 to R11 are hydrogen, when b is 1; and the agriculturally acceptable salts of these. It is preferred that the 3- (dihaloalkenyl) phenyl derivatives of the group set forth above be those where Q is a cyclic radical of structure where, 1-, and 4- denotes the points of attachment to - (CH2) k- and to the sides - (CH2) m- of the bridging group E; B1 is -N- or -CH-; or a radical cyclic structure 1 E1 where E1 is selected from -CR34 = CR35-, -CR34 = N-, * -N = CR34-, -N = N-, * -C (= 0) CR34-, * -CR2 C (= 0 ) -, -CR3 R35CR36R37 -, * -C (= 0) NR34-, * -NR3 C (= 0) -, * -S (0) SCR3 R35-, * - S (0) sNR34-, * -OCR3 R35-, * -CR34R350- and -C (= 0) - where the asterisk denotes the union with the nitrogen designated as 1 in Q, s is a selected integer of 0, 1 or 2 and R34 to R37, inclusive, are selected independently of hydrogen, halogen, alkyl, alkoxy, alkoxyalkyl, haloalkyl, alkoxycarbonyl, nitro, cyano, amino, alkylamino, and aryl; and R34 to R37 at gem positions can be taken together to form 5, 6 or 7 spiro rings comprised of carbon, nitrogen and oxygen, or R34 to R37 at adjacent positions can be taken together to form rings of 5, 6 or 7 members comprised of carbon, nitrogen and oxygen or a ring fused with benzo; G1 is selected from O, S, N-J1, or C-J1 where J1 is cyano or nitro; The most preferred 3- (dihaloalkenyl) phenyl derivatives of the group set forth above are those wherein R and R 1 are independently selected from halogen; R5 and R6 each is chlorine; a and b are 0; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Q2- (CH2) m- (CH2) n- (CH2) o-, where the asterisk denotes the D-junction; i, j, k, m, n and o each is 0; when I is 1, Q is a cyclic radical of structure where, 1-, and 4- denotes the points of attachment to - (CH2) k- and to the sides - (CH2) m- of the bridging group E; B1 is -N-; and U is W and R9 is haloalkyl. Other preferred 3- (dihaloalkenyl) phenyl derivatives of the group set forth above are those wherein R and R 1 are independently selected from halogen; R5 and R6 each is chlorine; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) or-, where the asterisk denotes the D-junction; a, i, j, k, m, n and o each is 0; 1 is 1, and Q is a cyclic radical of structure * ~ 4 where, 1-, and 4- denotes the points of attachment to - (CH2) k- and to the sides - (CH2) m- of the bridging group E; B1 is -N-; b is 1, G is selected from -C (= 0) 0CH2-, -C (= 0) -, -C (= 0) CH2-, - C (= 0) C2H4- or -S02C2H4-; U is X; R9, R10 and R11 is hydrogen. Yet another preferred 3- (dihaloalkenyl) phenyl derivatives of the group set forth above are those wherein R and R 1 are independently selected from hydrogen and halogen; R5 and R6 each is chlorine; a and b each is 1 and G is -O-; E is a bridging group * - (CH2) i- (CH2) 3 · - (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) o-, where the asterisk denotes the union in D; 1 and o each one is 0, i, j, k each is 1, and m and n are selected from 0 or 1, and U is Z. Additional preferred 3- (dihaloalkenyl) phenyl derivatives of the group set forth above are those wherein R and R1 are independently selected from halogen; R5 and R6 each is chlorine; a and b each is 1 and G is -0-; E is a bridging group * - (CH2) i- (CH2) j- (CHsJk-Qj- (CH2) m- (CH2) n- (CH2) 0-, where the asterisk denotes the union at D; is 0, i, j and k each is 1, and m, n and o are independently selected from 0 or 1, and U is g X; R7, R8, R10 and R11 each is hydrogen and R9 is halogen 3- (dihaloalkenyl) derivatives ) further preferred phenyl of the group set forth above are those where R and R1 are independently selected from halogen, R5 and R6 each is chloro, E is a bridging group * - (CH2) i- (CH2) j - (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) o-, where the asterisk denotes the union in D; a, i, j, k, m, nyo each is 0; 1 is 1, and Q is a cyclic radical of the structure - -4 where? 1 is -CH-; b is 1 and G is -CH20-; u is W and R9 is haloalkyl. Additional preferred 3- (dihaloalkenyl) phenyl derivatives of the group discussed above are those where R and R1 are independently selected from halogen, R5 and R6 each s chlorine; a is 1; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) Q-, where the asterisk denotes the D-junction; i and j each is 1 and k, 1, m and o each is 0; b is 0; and U is Y. More preferred 3- (dihaloalkenyl) phenyl derivatives of the group set forth above are those wherein R and R1 are independently selected from halogen; R5 and R6 each is chlorine; a and b are 0; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) 0-, where the asterisk denotes the D-junction; i, j, k, m, n and o each is 0; I is 1, and Q is a cyclic radical of the structure where, 1-, and 4- denotes the points of attachment to - (CH2) k ~ and to the sides - (CH2) m- of the bridging group E; B1 is -N-; And U is X; R9, R10 and R11 is hydrogen and R9 is haloalkyl. In addition, in certain cases the compounds of the present invention may possess asymmetric centers, which may give rise to the optical enantiomorphs and diastereomers. The compounds can exist in two or more forms, i.e., eg, polymorphs, which are significantly different in physical and chemical properties. The compounds of the present invention may also exist as tautomers, wherein the migration of a hydrogen atom within the molecule results in two or more structures, which are in equilibrium. The compounds of the present invention also possess acidic or basic radicals, which may allow the formation of agriculturally acceptable or complex salts with agriculturally acceptable metals.

The invention includes the use of these enantiomorphs, polymorphs, tautomers, salts and metal complexes. Agriculturally acceptable salts and metal complexes include, without limitation, for example, ammonium salts, salts of organic and inorganic acids, such as hydrochloric acid, sulfonic acid, ethanesulfonic acid, pamoic acid, and other acid salts, and complexes with alkali metals and alkaline earth metals with, for example, sodium, potassium, lithium, magnesium, calcium and other metals. The methods of the present invention comprises causing an effective insecticidal amount of a compound of formula I to be administered to insects to kill or control the insects. The preferred effective insecticidal amounts are those that are sufficient to kill insects. It is within the scope of the present invention to cause a compound of formula I to be present within insects by contacting the insects with a derivative of this compound, this derivative being converted within the insect into a compound of formula I. This invention includes the use of these compounds, which are preferred as pro-insecticides. Another aspect of the present invention relates to compositions containing an effective insecticidal amount of at least one compound of formula I. Another aspect of the present invention relates to compositions containing an effective insecticidal amount of at least one compound of formula I, and an effective amount of at least one additional compound.

Another aspect of the present invention relates to methods of controlling insects by applying an effective insecticidal amount of a composition as set forth above in the location of crops such as, without limitation, cereals, cotton, vegetables and fruits, or other areas where the insects are present or are expected to be present. Another aspect of the present invention relates to novel intermediate compounds that find utility in the synthesis of compounds of formula I. The present invention also includes the use of the compounds and compositions set forth herein for the control of non-agricultural insect species. , for example, termites of dry wood, and subterranean termites; so also for its use as pharmaceutical agents. In the field of veterinary medicine, the compounds of the present invention are expected to be effective against certain endo- and ecto-parasites, such as insects and worms, which make victims on animals. Examples of these animal parasites include, without limitation, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis, and other species. As used in these specifications and unless otherwise indicated the substituent terms "alkyl" and "alkoxy" are used alone or as part of a larger radical, includes straight and branched chains of at least one or two carbon atoms. carbon, as suitable as a substituent, and preferably up to 12 carbon atoms, more preferably up to ten carbon atoms, more preferably up to seven carbon atoms. The term "alkenyl" and "alkynyl" used alone or as part of a larger radical, includes straight or branched chains of at least two carbon atoms containing at least one carbon-carbon triple or triple bond, and preferably up to 12 carbon atoms. carbon atoms, more preferably up to ten carbon atoms, more preferably up to seven carbon atoms. The term "aryl" refers to an aromatic ring structure, which includes fused rings, having six to ten carbon atoms, for example, phenyl or naphthyl. The term "heteroaryl" refers to an aromatic ring structure, which includes fused rings, wherein at least one of the atoms is different from carbon, for example, without limitation sulfur, oxygen, or nitrogen. The term "DMF" refers to N, N-dimethylformamide. The term "THF" refers to tetrahydrofuran. The term "DMPU" refers to 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone. The term "halogen" or "halo" refers to fluorine, bromine, iodine or chlorine. The term "room temperature" or "room temperature" is generally abbreviated "RT", for example, in reference to a temperature of the chemical reaction mixture, it refers to a temperature in the range of 20 ° C to 30 ° C. . The term "insecticide" or "acaricide", "insecticide" or "acaricide", refers to a compound of the present invention, either alone or in admixture with at least one of the additional compounds, or with at least one compatible carrier , which causes the destruction or inhibition of the action of insects or acarids. The term "independently selected from" as set forth above and in the claim section of the present claim refers to the possibility that the radicals, for example R5 and R6, may be the same or may be different without the group where makes the selection The 3- (dihaloalkenyl) phenyl derivatives of formula I can be synthesized by methods that are known to a person skilled in the art of available intermediates. Reaction Scheme 1 illustrates a general procedure for synthesizing 3 - (dihaloalkenyl) phenyl derivatives of formula I, inter alia, where a, b, i, j, k, m, n and i each is 0; 1 is 1 and Q is a cyclic radical of structure 1-, and 4- denotes the points of attachment to - (CH2) k- and to the side - (CH2) m- of the bridging group E; B1 is -N-; Reaction Scheme 1 where a, b, i, j, k, m, n and o each is 0 and where U is W and R9 is CF3 I is 1 Commercially available Commercially available 1) CH3CN / Reflux where R is bromine, R1 is (b) chlorine 2) Na t -butoxide / rac- [(C6H5) 2PCioH6] 2 / ((C6H5CH = CHCOCH = CHC6H5) 3 Pd2 / Toluene / 80 ° C 3) n-Bu4 + I "/ BCl3 / CH2Cl2 / dry ice-acetone at RT 4) K2C03 / DMF / 65 ° C As shown in Reaction Scheme 1, piperazine (Radical Q) was reacted with an appropriately substituted halo derivative, such as 2-chloro-5- (trifluoromethyl) pyridine (where U is W and R9 is CF3), producing the corresponding intermediate (a). The intermediate (a) in turn was reacted with an appropriate halo-substituted alkoxybenzene derivative, for example 2-bromo-1,3-dichloro-5-methoxybenzene (where R is bromine and R1 is chlorine), producing the intermediate (b) the intermediate (b), for example, 2-bromo-3-chloro-5-methoxy-1-. { 4- [5-trifluoromethyl) (2-pyridyl)] piperazinyl} benzene, then reduced with, for example, boron trichloride, producing the corresponding phenol, the intermediate compound (c). The intermediate (c) was then reacted under basic conditions with an appropriate haloalkene derivative (where R5 and R6 is chlorine), by means of which a compound of formula I is provided. Example 1, set forth below, provides a detailed method by means of which a compound of formula I of this type is made. Reaction Scheme 2 below illustrates a general procedure for synthesizing 3- (dihaloalkenyl) phenyl derivatives of formula I, inter alia, where 1, n and o each is O and i, j, k and m each is 1; U is the group Z where R40 and R41 each is methyl: Reaction Scheme 2 New compound ) K2C03 / DMF / 65 ° C ) NaOH / DMF / RT ) MDPU / 130 ° C 9) H2 / 10% Pd on carbon / EtOH Compound of formula 1 ) K2CO3 / DMF / 80 ° C As shown in Reaction Scheme 2, a properly substituted benzofuran-7-ol (where U is group W, R40 and R41 are CH3 and G is -0-), for example 7-hydrobenzofuran, was reacted with an acetate of haloalkyl of appropriate chain length (for example, where 1 is 0; a, b, i, j, k and m are 1; G is -0-), yielding the corresponding benzofuran-7-ylalkyl acetate, Intermediate (d) . The Intermediary (d) was reduced with the strong base, producing the corresponding alcohol, for example 4- (2,2-dimethyl-2,3-dihydrobenzo [2,3-dihydrobenzo [2,3-b] furan-7) iloxi) butan-l-ol, Intermediary (e). The Intermediate € was then converted to its sodium salt (f), which in turn reacted with an appropriate (arylalkyloxy) halobenzene, for example 1, 2, 3-trichloro-5- (phenylmethoxy) benzene (where R and R1 are chloro), providing the corresponding phenoxyalkylbenzofuran-7-yloxy derivative, Intermediate (g). The Intermediate (g) was then reduced under hydrogenation conditions, producing the corresponding phenol, intermediate (h), for example 3- [4- (2,2-dimethyl (2,3-dihydrobenzo [2,3] -furan] -7-yloxy)) butoxy] 4,5-dichlorophenol. The intermediate (h) was then reacted under basic conditions with an appropriate tetrahaloalkane derivative (where R5 and R6 are chlorine), by means of which a compound of formula I is provided. Example 2, set forth below, provides a detailed method by means of which a compound of formula I of this type is made. A person with experience, of course, will recognize that the formulation and form of application of a toxic can affect the activity of the material in a given application. Thus, for agricultural use the present insecticidal compounds can be formulated as a granule with relatively large particle size (eg, 8/16 or 4/8 US Mesh), as water soluble granules or dispersed in water, as powders, as powders that can be moistened, as concentrates that can be emulsified, as aqueous emulsions, as solutions, or as any other type of agriculturally useful formulations, depending on the desired mode of application. It will be understood that the quantities specified in this specification are intended to be approximations only, as if the word "approximately" were placed in front of the specified quantities. These insecticidal compositions can be applied either as sprinklers diluted in water, or powders, or granules to areas where the elimination of insects is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% as much as 95% or more by weight of the active ingredient. The powders are free flowing mixtures of active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shells and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxic; these finely divided solids have an average particle size of less than about 50 microns. A typical powder formulation useful herein is one that contains 1.0 parts or less of the insecticidal compound and 99.0 parts of talc. Moisturizing powders, also useful as insecticides, are in the form of finely divided particles that readily disperse in water or other dispersant. Moisturizing dust is applied lately at the location where the insect needs to be controlled either as a dry powder or as an emulsion in water or another liquid. Typical vehicles for moistening powders include Fuller's earth, kaolin clays, silicas and other highly absorbent inorganic diluents, already wet. Wettable powders are usually prepared to contain about 5-80% of the active ingredient, depending on the absorbency of the vehicle, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.0 parts of the insecticidal compound, 17.9 parts of Palmetto clay and 1.0 parts of sodium lignosulfonate and 0.3 parts of sulphonated aliphatic polyester. The additional wetting agent and / or oil is frequently It will be added to a tank mix to facilitate dispersion in the foliage of the plant. Other useful formulations for insecticidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions which can be dispersed in water, and can consist entirely of the insecticidal compound and a liquid or solid emulsifying agent, or they may contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvents. For insecticide application these concentrates are dispersed in water or other liquid vehicle and are normally applied as sprays to the area to be treated. The weight percentage of the essential active ingredient may vary according to the manner in which the composition is applied, but in general it comprises 0.5 to 95% of the active ingredient by weight for the insecticidal composition. Formulations that can flow are similar to ECs, except that the active ingredient is suspended in a liquid vehicle, usually water. Flowable formulations, such as ECs, may include a small amount of a surfactant, and will generally contain active ingredients in the range of 0.5 to 95%, often from 10 to 50%, by weight of the composition. For the application, formulations that can flow can be diluted in water or another vehicle, and are normally applied as a spray to the area to be treated. Typically the dispersing or emulsifying, wetting agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyester alcohols; highly sulphonated alcohols; polyethylene oxides; sulphonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and ethylene oxide addition products of these esters; and the product of addition of mercaptans. Many other types of useful surfactants are available in the trade. The surfactants, when used, typically comprise from 1 to 15% by weight of the composition. Other useful formulations include suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol or other suitable solvents. Still other formulations for insecticidal applications include simple solutions of the active ingredient in a solvent where it is completely soluble at a desired concentration, such as acetone, alkylated naphthalenes, xylenes, or other organic solvents. The granular formulations, where the toxic is carried out in relatively granular particles, are particularly useful for air distribution or for penetration into the canopy of the crop. Pressurized sprinklers, aerosols may also generally be used in which the active ingredient is dispersed in finely divided form as a result of vaporization of a solvent as a low boiling point dispersant vehicle. The water-soluble or water-dispersible granules flow freely, without dust, and easily miscible in water or water-soluble. In use by the farmer in the field, granular formulations, emulsifiable concentrates, flowable concentrates, aqueous emulsions, solutions, etc. may be diluted with water to give a concentration of the active ingredient in the range of 0.1% or 0.2% at 1.5 % or 2% The active insecticidal compounds of this invention can be formulated and / or applied with one or more additional compounds. These combinations can provide certain advantages, such as, without limitation, exhibit synergistic effects, for greater control of insect pests, reducing the application rates of the insecticide by means of this minimizing any impact to the environment and worker safety, controlling a broader spectrum of insect pests, safety of plant crops by phototoxicity, and improving tolerance to non-pest species, such as mammals and fish. Additional compounds include, without limitation, other pesticides, plant growth regulators, fertilizers, soil conditioners, or other agricultural chemicals. By applying an active compound of this invention, whether formulated alone or with other agricultural chemical compounds, an effective concentration and concentration of the active compound is of course employed; the amount may vary in the range of, eg, about 0.01 to about 3 kg / Ha, preferably about 0.03 to about 3 kg / Ha. For use in the field, where there are insecticide losses, larger proportions of insecticide may be employed (eg, four times the ratios mentioned above). When the active insecticidal compounds of the present invention are used in combination with a further compound, eg, with other pesticides such as herbicides, the herbicides include, without limitation, for example: N- (phosphonomethyl) glycine ("glyphosate"); aryloxyalkanoic acids such as (2,4-dichlorophenoxy) acetic acid ("2,4-D"), (4-chloro-2-methylphenoxy) acetic acid ("MCPA"), acid (+/-) -2- ( 4-chloro-2-methylphenoxy) propanoic ("MCPP"), ureas such as N, N-dimethyl-N '- [4- (1-methylethyl) phenyl] urea ("isoproturon"); imidazolines such as 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-imidazol-2-yl] -3-pyridinecarboxylic acid ("imazapyr"), a product of reaction comprising (+/-) -2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-imidazol-2-yl] -4-methylbenzoic acid and acid ( + / -) -2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-lH-imidazol-2-yl] -5-methylbenzoic acid ("imazametabenz"), acid (+/-) -2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-lH-imidazol-2-yl] -5-ethyl-3-pyrinocarboxylic acid ("imazatapyr"), acid (+/-) -2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lH-imidazol-2-yl] -3-quinolinecarboxylic acid ("imazaquin"); diphenyl ethers such as 5- [chloro-4- (trylfuoromethyl) phenoxy] -2-nitrobenzoic acid ("acifluorfen"), methyl 5- (2, 4-dichlorophenoxy) -2-nitrobenzoate ("bifenox"), and - [2-chloro-4- (trifluoromethyl) phenoxy] -N- (methylsulfonyl) -2-nitrobenzamide ("fomasafen"); hydroxybenzonitriles such as 4-hydroxy-3,5-diiodobenzonitrile ("ioxinyl") and 3,5-dibromo-4-hydroxybenzonitrile ("bromoxynil"); sulfonylureas such as 2- [[[[(4-chloro-6-methoxy-2-pyrimidyl) amino] carbonyl] amino] sufonyl] benzoic acid ("chlorauron"), 2-chloro-N- [[(4-methoxy -6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzensulfon-amide ("aclorsulfuron"), 2- [[[[[(4,6-dimethoxy-2-pyrimidinyl) amino] ] carbonyl] amino] hydroxide] methyl] benzoic acid ("bensulfuron"), 2- [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -1-methyl-1H-pyrazole -4-carboxylic acid ("pyrazosulfuron"), 3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] -2-triofencarbox acid lico ("tifensulfuron"), and 2- (2-chloroethoxy) -N- [[(4-methoxy-6-methyl-1,3,5-trizin-2-yl) amino] carbonyl] benzenesulfonamide ("triasulfuron" ); 2- (4-aryloxy-phenoxy) alkanoic acids such as (+/-) -2- [4- [(6-chloro-2-benzoxazolyl) oxy] phenoxy] -propanoic acid ("fenoxaprop"), acid (+ / -) -2- [4 [[5- (trifluoromethyl) -2- (trifluoromethyl) -2-pyridinyl] oxy] -phenoxy] scopanoic ("fluazifop"), acid (+/-) -2- [4- (6- (chloro-2-quinoxalinyl) oxy] -phenoxy] propane ("quizalofop"), and (+/-) -2- [(2,4-dichlorophenoxy) phenoxy] propanic acid ("diclofop"); benzothiadiazinones such as 3- (1-methylethyl) -1H-1,2,3-benzothiadiazin-4 (3H) -one-2,2-dioxide ("bentazone"); 2-chloroacetanilides such as N- (butoxymethyl) -2-chloro-N- (2,6-diethylphenyl) acetamide ("butachlor"), 2-chloro-N- (2-ethyl-6-methylphenyl) -N- ( 2-methoxy-l-methylethyl) acetamide ("metolachlor"), 2-chloro-N- (ethoxymethyl) -N- (2-ethyl-6-methylphenyl) acetamide ("acetochlor"), and (RS) -2- chloro-N- (2,4-dimethyl-3-thienyl) -N- (2-methoxy-1-methylethyl) acetamide ("dimethenamid"); arenocarboxylic acids such as 3,6-dichloro-2-methoxybenzoic acid ("dicamba"); pyridyloxyacetic acids such as [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl) oxy] acetic acid ("fluroxypyr") aryl triazolinones such as 1H-1,2,4-triazole-1-carboxamide ("amyarbazone"), 1, 2,4-triazole [4, 3-a] pyridin-3 (2H) -one ("azaphenidin"), N- (2,4-dichloro-5- [4- (difluoromethyl) ) -4,5-dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-l-yl] phenyl) methanesulfonamide ("sulfentrazone") and, 2-dichloro-5- [4- ( difluoromethyl) -4,5-dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-l-yl] -4-fluorobenzenepropanoate methyl ("carfentrazone-ethyl"); isoxazolidinones such as 2 [2-chlorophenyl) -4,4-dimethyl-3-isoxazoline ("clomazone"); and other herbicides. When the active insecticidal compounds of the present invention are used in combination with one or more of the second compound, eg, with other pesticides such as other insecticides, the insecticides include, for example: organophosphate insecticides, such as chlorpyrifos, diazinone , dimethoate, malathion, parathion-methyl, and terbufos; pyrethroid and non-pyrethroid insecticides, such as fenvalerate, deltamethrin, fenpropatrin, cyfluthrin, flucitrinate, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zefca-cypermethrin, bifenthrin, dissolved cyhalothrin, etofenprox, esfenvalerate, tralometrine, tefluthrin, cycloprotrin, betaciflutrin, silafluofen and acrinatrin; carbamate insecticides, such as hydroxide, carbaryl, carbofuran, and methomyl; organochloro insecticides, such as endosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides, such as diflubenuron, triflumuron, teflubenzuron, chlorfluazuron, flucycloxuron, hexaflumuron, noviflumuron, flufenoxuron, and lufenuron; and other insecticides such as, without limitation, amitraz, clofentezine, fenoximate, hexitiazox, cyhexatin, spinosad, imidacloprid, chlorfenaptr, hydramethyl, acequinocyl, fenbutatin oxide, methoxyfenozide, tebufenocide, halofenocide, indoxacarb, hydroxide, etiprole, ethoxazole, bifenazate, spirodiclofen, spiromesifen, methoprene, pyriproxyfen, phenoxycarb, pymetrozine, abamectin, emamectin, benzoate, milbemectin and other insecticides. When the active insecticidal compounds of the present invention are used in combination with one or more additional compounds, eg, with other pesticides such as with fungicides, the fungicides include, for example: benzimidazole fungicides, such as benomyl, carbendazim, thiabendazole and thiophanate methyl; 1,2,4-trizol fungicides, such as epoxiconazole, ciproconazole, flusilazole, flutriafol, propiconazole, tebuconazole, triadimefon, and triadimenol; substituted anilide fungicides, such as metalaxyl, oxadixyl, procymidone and vinclozolin; organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos, edifenfos, and tolclofos-methyl; morpholine fungicides, such as phenpropimorf, tridemorph, and dodemorf; other systemic fungicides, such as fenarimol, imazalil, prochloraz, tricyclazole, and triforino; dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb and ziram; non-systemic fungicides, such as chlorothalonil, diclofluanid, dithianon, iprodione, captan, dinocap, dodino, fluazinam, gluazatin, PCNB, pencicuron, quintozene, tricylamide, and validamicin; inorganic fungicides, such as copper and sulfur products, and other fungicides. When the active insecticidal compounds of the present invention are used in combination with one or more additional compounds, p. ex. , with other pesticides such as nematicides, the nematicides include, for example: carbofuran, carbosulfan, hydroxide, ethoprop, fenamphos, oxamyl, isazophos, cadusafos, and other nematicides. When the active insecticidal compounds of the present invention are used in combination with one or more additional compounds, e.g., with other materials such as plant growth regulators, plant growth regulators include, for example: hydrazole malefic acid, edema , giberelin, mepicuat, tidiazon, inabenfido, triafentenol, paclobutrazol, unconazole, DCPA, prohexadione, trinexapac-ethyl, and other plant growth regulators. The soil conditioners are materials that, when added to the soil, promote a variety of benefits for the effective growth of plants. Soil conditioners are used to reduce soil compaction, promote and increase the effectiveness of drainage, improve soil permeability, promote the optimum nutrient content of the plant in the soil, and promote better incorporation of the pesticide and fertilizer into the soil. floor. When the active insecticidal compounds of the present invention are used in combination with one or more additional compounds, e.g., with another material such as soil conditioner, soil conditioners include organic matter, such as humus, which promote retention of cationic nutrients from plants in the soil; mixtures of cationic nutrients, such as calcium, magnesium, potash, sodium and hydrogen complexes; or compositions of microorganisms that promote conditioning in the soil favorable for the growth of the plant. These compositions of microorganisms include, for example, bacillus, pseudomonas, azotobacter, azospirillum, rhizobium, and cyanobacteria bore the soil. Fertilizers are food supplements for plants, which commonly contain nitrogen, phosphorus and potassium. When the active insecticidal compounds of the present invention are used in combination with one or more additional compounds, e.g., with other materials such as fertilizers, the fertilizers include nitrogen fertilizers, such as ammonium sulfate, ammonium nitrate, and bone-meal; phosphate fertilizers, such as superphosphate, triple superphosphate, ammonium sulfate, and diammonium sulfate; and potassium fertilizers, such as muriate, potash, potassium sulfate, and potassium nitrate and other fertilizers. The following examples further illustrate the present invention, but, of course, should not be constructed in any way limiting the scope. The examples are organized with the current protocols for the synthesis of the compounds of formula I of the present invention, set forth a list of these synthesized species, and set forth certain biological data indicating the efficacy of these compounds.

Example 1 This Example illustrates a protocol for the preparation of 5- (3,3-dichloroprop-2-enyloxy) -2-bromo-3-chloro-1-. { 4- [5- (trifluoromethyl) (2-pyridyl)] piperazinyl} -benzene (Compound 19) Step A Synthesis of 2-bromo-l, 3-dichloro-5-methoxybenzene as an intermediate compound A solution of 5.0 grams (0.028 moles) of 1,3-dichloro-5-methoxybenzene (commercially available) in 35 ml of acetone was stirred and 5.0 grams (0.028 moles) of N-bromosuccinamide was added, then one ml of 10% aqueous hydrochloric acid was added. After the additions were complete, the reaction mixture was stirred at room temperature for a period of 30 minutes. After this time the reaction mixture was concentrated under reduced pressure to a residue. With the residue, a slurry was formed in 20 ml of hexane and an insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, yielding 4.8 grams composed of the objective. The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of [5- (trifluoromethyl) -2-pyridylpiperazine as an intermediate compound A stirred solution of 7.1 grams (0.083 moles) of piperazine (commercially available) and 5.0 grams (0.028 moles) of 2-chloro-5- (trifluoromethyl) ) pyridine (commercially available) in 75 ml of acetonitrile was heated to reflux for a period of two hours. After this time the reaction mixture was allowed to cool to room temperature, and then filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was dissolved in 75 ml of methylene chloride and washed with two 50 ml portions of water. The organic layer was dried with sodium sulfate, filtered and the filtrate was concentrated under reduced pressure to a residue. The residue was purified by column chromatography on silica gel using 100% methylene chloride, then 5% methanol in methylene chloride was used as eluents. The appropriate fractions were combined and concentrated under reduced pressure, yielding 4.5 grams of the objective compound. The MR spectrum was consistent with the proposed structure.

Step C synthesis of a mixture of 2-bromo-3-chloro-5-methoxy-1-. { 4- [5- (trifluoromethyl) (2-pyridyl)] piperazinyl} - benzene and 1,3-dichloro-5-methoxy-2-. { 4- [5- (trifluoromethyl) (2-pyridyl)] piperazinyl} benzene as intermediates A stirred mixture of 3.0 grams (0.012 moles) of 2-bromo-1,3-dichloro-5-methoxybenzene (Step A), 2.7 grams (0.012) of [5- (trifluoromethyl) -2-pyridylpiperazine ( Step B), 0.02 grams (0.00024 moles) of tris (hydroxyacetone ketone) dipalladium (0), 0.45 grams (0.00072 moles) of hydroxy-2, 2 'bis (diphenylphosphino) -1, 1'-hydrophile and 2.1 grams (0.022) moles) of sodium ter-butoxide in 150 ml of toluene was heated to 80 ° C where it was maintained for a period of 24 hours. After this time the reaction mixture was cooled and poured into 250 ml of water. The organic layer was separated, and the aqueous layer was extracted with two 75 ml portions of diethyl ether. The organic layer and the extracts were combined and washed with 50 ml of an aqueous solution saturated with sodium chloride. The combined extracts of the organic layers were dried with sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to a residue. The residue, which was a mixture of the products, was separated into its components by column chromatography on silica gel using as eluents: 50% hexane in methylene chloride, then 100% methylene chloride and finally 2% methanol. % in methylene chloride. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.17 grams of the objective compound. The NMR spectrum was consistent with the proposed structure.

Step E Synthesis of Compound 19 0.13 grams (0.003 moles) of 4-bromo-5-chloro-3- were placed in a bottle. { 4- [5-trifluoromethyl) (2-pyridyl)] piperazinyl) phenol, 0.09 grams (0.0006 moles) of 1, 1, 3-trichloropropene, 0.083 grams (0.006 moles) of potassium carbonate and 6 ml of DMF. The bottle was then sealed with stirring, heated to 65 ° C, where it was maintained for a period of 18 hours. After this time the bottle was cooled and the contents were drained in 25 ml of water. The mixture was extracted with two 15 ml portions of diethyl ether. The combined extracts were dried with sodium sulfate, filtered and the filtrate was concentrated under reduced pressure to a residue. The residue was purified by column chromatography on silica gel using 50% hexane in methylene chloride as eluent. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.12 grams of Compound 19. The NMR spectrum was consistent with the proposed structure.

Example 2 This example illustrates a protocol for the preparation of 7-. { 4- [5- (#, 3-dichloroprop-2-enyloxy) -2, 3-dichlorophenoxy] butoxy} -2, 2-dimethyl-2, 3-dihydro-benzo [b] furan Compound 2 Step A Synthesis of 4- (2, 2-dimethyl-2, 3-dihydrobenzo [2,3-b] furan-7-yloxy) butyl ester an intermediate Under a nitrogen atmosphere a solution of 5.0 grams ( 0.030 mole) of 7-hydroxybenzofuran (known compound), 6.5 grams (0.033 mole) of 4-bromobutyl acetate and 6.2 grams (0.045 mole) of potassium carbonate in 75 ml of DMF was stirred at room temperature for a period of five days. The reaction mixture was then stirred with 75 ml of water and saturated with solid sodium chloride. The mixture was extracted with three 50 ml portions of diethyl ether, and the combined extracts were washed with a 50 ml portion of water. The organic layer was then dried with sodium sulfate, filtered and the filtrate was concentrated under reduced pressure, yielding 8.0 grams of the objective compound. The MR spectrum was consistent with the proposed structure.

Step B: Synthesis of 4- (2,2-dimethyl-2,3-dihydrobenzo [2, 3-b] furan-7-yloxy) butan-1-ol as an intermediate With stirring, to a solution of 2.24 grams (0.056) moles) of sodium hydroxide in 125 ml of methanol was added 8.0 grams (0.028 mole) of 4- (2,2-dimethyl-2,3-dihydrobenzo [2,3-b] furan-7-yloxy) butyl acetate . After the addition was complete, the reaction mixture was stirred at room temperature for a period of three hours. After this time 150 ml of water were added to the reaction mixture, and the mixture was acidified to a pH of 6 with concentrated hydrochloric acid. The mixture was extracted with four 50 ml portions of diethyl ether. The combined extracts were washed with a 50 ml portion of water, dried with sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, yielding 5. 6 grams of the objective compound. The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 1, 2, 3-trichloro-5 - (phenylmethoxy) benzene as an intermediate A stirred solution of 5. 8 grams (0. 029 moles) of 3, 4, 5-trichlorophenol (commercially available) and 3. 8 ml (0.032 moles) of benzyl bromide and 4. 45 grams (0.032 moles) of potassium carbonate in 75 ml of DMF was heated to 80 ° C where it was maintained for a period of two hours. After this time the reaction mixture was allowed to cool to room temperature and then 150 ml of water was added. The mixture was extracted with three 50 ml portions of diethyl ether and the combined extracts were washed with a 50 ml portion of water. The organic layer was dried with sodium sulfate, filtered and the filtrate was concentrated under reduced pressure, yielding 7. 1 grams of the objective compound. The NMR spectrum was consistent with the proposed structure.

Step D Synthesis of 7-. { 4- [2,3-dichloro-5- (phenylmethoxy) phenoxy] } -2, 2-dimethyl-2, 3-dihydrobenzo [b] furan as an intermediate Under a nitrogen atmosphere, a solution of 0.32 grams (0.008 moles) 60% sodium hydride (in mineral oil) in 2 ml of THF was stirred and a solution of 1.65 grams (0.007 moles) of 4- (2,2-dimethyl-2,3-dihydrobenzo [2,3-b] furan-7-yloxy) butan-1-ol was added dropwise. (Step B) in 10 ml of THF. After the addition was complete, the reaction mixture was heated to 40 ° C where it was stirred for a period of 15 minutes. After this, the reaction mixture was allowed to cool to room temperature and then concentrated under reduced pressure to a residue. To the residue was added a solution of 1.00 grams (0.0035 moles) of 1,2,3-trichloro-5- (phenylmethoxy) benzene (Step C) in 35 ml of 1,3-dimethyl-3, 4, 5, 6- tetrahydro-2 (1H) -pyrimidinone. After the addition was complete, the reaction mixture was heated to 130 ° C where it was stirred for a period of 18 hours. After this time the reaction mixture was cooled and stirred with 50 ml of an aqueous solution saturated with sodium chloride, then extracted with three portions of 25 ml of diethyl ether. The combined extracts were washed with a 25 ml portion of water, dried with sodium sulfate, filtered and the filtrate was concentrated under reduced pressure to a residue. The residue was purified by column chromatography on silica gel using 25% methylene chloride in hexane and 50% methylene chloride in hexane as eluents. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.54 grams of the target Compound. The NMR spectrum was consistent with the proposed structure.

Step E Synthesis of 3- [4- (2, 2-dimethyl (2,3-dihydrobenzo [2, 3-b] furan-7-yloxy)) butoxy] 4,5-dichlorophenol as an intermediate A mixture of 0.5 grams (0.001 moles) of 7-. { 4- [2,3-dichloro-5- (phenylmethoxy) phenoxy] } -2, 2-dimethyl-2, 3-dihydrobenzo- [b] furan and 0.1 gram (Catalyst) of 10% palladium on carbon in 75 ml of ethanol was placed in a Parr hydrogenation bottle and hydrogenated using a hydrogenation Parr. Once the theoretical content of the hydrogen gas had been exhausted, the reaction mixture was filtered to remove the catalyst, and the filtrate was concentrated under reduced pressure to a residue. The residue was purified by column chromatography on silica gel using 100% methylene chloride as eluent followed by 5% methanol in methylene chloride. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.17 grams of the objective compound. The NMR spectrum was consistent with the proposed structure.

Step F: Synthesis of Compound 2 A stirred solution of 0.17 grams (0.00043 mole) of 3- [4- (2, 2-dimethyl (2,3-dihydrobenzo [2,3-b] furan-7-yloxy)) butoxy] -4, 5-dichlorophenol, 0.12 grams (0.00064 moles) of 1,1,1,3-tetrachloropropane and 0.12 grams (0.00086 moles) of potassium carbonate in 20 ml of DMF was heated to 80 ° C where it was kept for a period of 18 hour period. After this time the reaction mixture was allowed to cool to room temperature and then 25 ml of saturated aqueous solution was added with sodium chloride. The mixture was then extracted with two 25 ml portions of diethyl ether. The combined extracts were washed with a 25 ml portion of water, dried over sodium sulfate, filtered and the filtrate was concentrated under reduced pressure to a residue, yielding 0.23 grams of Compound 2. The NMR spectrum was consistent with the proposed structure. The following tables set forth some compounds of formula I: Table 1 Derivatives of 3- (dihaloalkenyl) phenyl insecticide where R5 and R6 are chloro; and a and b each is 1; G is -0-; E is the bridging group * - (CH2) i- (CH2) j- (CH2) k-Qi- (CH2) m- (CH2) n- (CH2) o-, where i,, k each is 1, ymyn is 0; U is Z.

Compound R R1 m n R10 No. 1 H H 0 0 Cl 2 Cl Cl 1 0 H 3 H H 1 0 Cl 4 Cl Cl 1 1 H 5 Cl H 0 0 Cl 1-1 where R 5 and R 6 are chloro; and a and b each is 1; G is -O-; E is the bridging group * - (CH2) i- (CH2) j- (CH2) k-Q2- (CHa) m- (CH2) n- (CH2) 0-, where i, j and k are 1; m, n and o are 0 or 1; U is X; R7, R8, R10 and R11 are hydrogen: 1-2 Compound R R m n Rio No. Cl Cl 1"or" o ~ c Cl Cl 0 0 or Cl Cl 1 1 or Cl Cl Cl 1 1 Cl where R5 and R6 are chloro; a is 0 and b is 0 or 1; E is the bridging group * - (CH2) i- (CH2) j - (CH2) ic-Qj- (CH2) m- (CH2) n- (CH2) o-, where i, j, k, m , nyo are 0; 1 is 1; Q is the cyclic radical where B1 is -N-; U is X; R8, R10 and R11 are hydrogen: 1-3 Compound R R1 b G R7 R9 No. 10 Cl Cl 1 C (= 0) H CF3 11 Cl Cl 1 C (= 0) OCH2 Cl H 12 Cl Cl 1 C (= 0) C2H4 H H 13 Cl Cl 0 - H CF3 14 Cl Cl 1 C (= 0) CH2 H H Cl Cl 1 C (= 0) CH2 H Cl 16 Cl Cl 1 S02C2H4 H Cl where R5 and R6 are chloro; a is 0; b is 0 or 1; E is the bridge-forming group * _ (CH2) i- (CH2) j- (CH2) * - Q- (CH2) m- (CH2) n- (CH2) 0-, where i, j, k, m , nyo are 0; 1 is 1; Q is the cyclic radical where B1 is -N-; U is W: 1-4 Compound R R1 B1 b G R9 NO. 17 Cl Cl N 0 - CF3 18 Br Cl CH 1 CH20 CF3 19 Br Cl N 0 - CF3 where R5 and R6 are chlorine; a is 1; b is 0; E is the bridging group * - (CH2) i- (CH2) j- (CH2) k -Qi- (CH2) m- (CH2) n- (CH2) 0-, where i and j are 1; k, 1, m, n and o are 0; : U is Y: where R5 and R6 are chloro; a is 1; b is 0; E is the bridging group * - (CH2) i- (CH2) j- (CH2) k-Qj- (CH2) m- (CH2) n- (CH2) or-, where i, j and k are 1; m, n and o are 0; 1 is 1; Q is the cyclic radical they are hydrogen 1-6 Compound R R1 Q R8 R9 Do not . 21 Cl Cl Cl H where R5 and R6 are chloro; a is 0 and b is 0 or 1; E is the bridging group * - (CH2) i- (CH2) j - (CH2) k-Qi- (CK2) m- (CH2) n- (CH2) 0-, where i, j, k, m , nyo are 0; 1 is 1; Q is the cyclic radical where B1 is -N-; U is T: 1-7 Compound R R1 B1 b G R9 No. 24 Cl Cl N 0 - CF3 Br Cl CH 1 CH20 CF3 26 Br Cl N 0 - CF3 27 Cl Cl N 0 - CH3 28 Br Cl CH 1 CH20 CH3 29 Br Cl N 0 - CH3 Cl Cl N 0 - C (CH3) 3 21 Br Cl CH 1 CH 20 C (CH 3) 3 32 Br Cl N 0 - C (CH 3) 3 where R 5 and R 6 are chloro; a and b each is 1; G is -0-; E is the bridging group * - (CH2) i- (CH2) j- (CH2) k-Q2- (CH2) m- (CH2) n- (CH2) 0-, where i, j and k are 1; m is 0 or 1; n and o are 0; 1 is 0; U is T: 1-8 Compound R R1 m R9 No. 33 Cl Cl 0 CF3 34 Cl Cl 0 CH3 35 Cl Cl 0 C (CH 3) 3 36 Cl Cl 1 CF 3 37 Cl Cl 1 CH 3 38 Cl Cl 1 C (CH 3) 3 The following table sets forth the data on the physical characteristics of certain compounds of formula I of the present invention. The test compounds of formula I are identified by the numbers corresponding to those in Table 1: Table 2 Data Characterizing Derivatives of the Insecticide 3 - (Dihaloalkenyl) phenyl Compound No Empirical Formulas Physical State (PF ° C) 1 C22H23CI3O4 Solid 2 C23H24C I4O4 Liquid 3 C23H25C1304 Solid 4 C24H26CI4O4 Liquid 5 C22H22CI4O4 Oil 6 CigHi7Cl503 Solid 7 C18H15C I 5O3 Oil 8 C20H19CI 5O3 Solid 9 C2iH2iCl503 Solid 10 C2iHi7Cl4F3 202 Liquid 11 C21H19CI5N2O3 Liquid 12 C22H22C I4 2O2 Liquid 13 C20Hi7Cl4F3N2O 98-101 14 C21H20CI4N2O2 Solid 15 C21H19CI5N2O2 Solid 16 C2iH2iCl5N203S Solid 17 Ci9H16Cl4F3N30 93 - 96 18 C2iHi9BrCl3F3N202 Oil 19 Ci9Hi6BrCl3F3N30 Solid 20 C2iH27Cl4N04 Liquid The activity of the candidate insecticides against the cotton bollworm (Heliothis virescens [Fabricius]) was evaluated on a surface treated with the diet of proof . In this test with a pipette, an artificial dietary diet based on wheat germ at (65-70 ° C) was placed in each well of a four-by-six multiple well plate (24 wells) (ID # 430345- 15-5 mm diam X 17.6 mm depth; Corning Costar Corp., One Alewife Center, Cambridge, MA 02140). The diet was allowed to cool to room temperature before treatment with the candidate insecticide. For a determination of the insecticidal activity, candidate insecticide solutions were prepared by testing using a Packard 204DT Multiprobe® Robotic System (Packard Instrument Company, 800 Research Parkway, Meriden, CT 06450), where the robot first dilutes a standard solution of DMSO 50 millimolar of the candidate insecticide with a 1: 1 solution of water / acetone (V / V) in a stock solution of 1: 7 water / acetone ratio 1: 7. The robot then pipettes 40 microliters of the solution prepared on the surface of the diet into each of the three wells in the 24-well multiple plate. The process was repeated with solutions of seven other candidate insecticides. Once treated, the contents of the multiple well plate were allowed to dry, leaving 0. 25 millimoles of the candidate insecticide on the surface of the diet, or a concentration of 0. 25 millimolar. Controls without appropriate treatment contain only DMSO on the surface of the diet were also included in this test.

For evaluations of the insecticidal activity of a candidate insecticide with different application rates, the test was established as described above using submultiples of the standard 50 millimolar DMSO solution of the candidate insecticide. For example, the standard solution of 50 millimolar was diluted by means of the robot with DMSO to give 5, 0. fifty . 25, 0. 05, 0. 005, 0 0005 millimolar, or more diluted solutions of the candidate insecticide. In these evaluations there were six replications of each proportion of the application placed on the surface of the diet in the plate of 24 multiple wells, for a total of four application rates of the candidate insecticide in each plate. In each well of the test plate was placed a second newborn larva of the cotton bollworm, each weighing approximately five milligrams. After the larvae were placed in each well, the square was sealed with clear multi-layer adhesive tape. The tape on each well was drilled to ensure an adequate supply of air. The plates were then kept in a growth chamber at 25 ° C and 60% relative humidity for five days (light of 14 hours / day). After the five-day exposure period the insecticidal activity was evaluated for each proportion of the application of the candidate insecticide as percentage of insect weight inhibition relative to the weight of control insects without treatment. The data of the insecticidal activity with the selected proportions of this test are given in Table 3. The test compounds of formula I were identified by means of numbers corresponding to those in Table 1.

Table 3 Insecticidal activity of Certain Derivatives of 3- (dihaloalkenyl) phenyl When Applied to the Surface of the Diet of the Cotton Bellworm (Heliotis virescens [Fabricius]) 9 11 10 48 11 100 12 61 13 3 14 99 15 8 16 81 17 100 18 17 19 100 20 98 Concentration of the candidate insecticide on the surface of the diet is 0.25 millimolar As set forth in Table 3, the tested compounds provide growth inhibition of the cotton bollworm. Compounds 2, 4, 7, 11, 17 and 19 provided 100% growth inhibition when compared to the growth of the cotton bollworm in untreated controls. While this invention has been described with an emphasis on preferred embodiments, it will be understood by those of ordinary skill in the art that variations of the preferred embodiments may be used and that this intends that the invention may be practiced otherwise than as specifically described. at the moment. Accordingly, this invention includes all embodiments encompassed within the scope and scope of the invention as defined by the following claims. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (2)

Rei indications Having described the invention as above, the content of the following claims is claimed as property: 1. Compound of formula I: I characterized in that R and R1 are independently selected from hydrogen, halogen, alkyl and cyano; R5 and R6 is independently selected from bromine and chlorine; a is an integer selected from 0 or 1; and when a is 1, D is -0-; E is a bridging group * - (CH2) i- (CH2) j- (CH2) k-Q! - (CH2) m- (CH2) n- (CH2) 0-, where the asterisk denotes the union at D; i, j, k, I, m, n and o are integers independently selected from 0 and 1; and when 1 is 1, Q is a 5- or 6-membered heterocyclic ring containing from 1 to 4 nitrogen atoms and 0 to 1 oxygen or sulfur atom; b is an integer selected from 0 or 1; and, when b is 1, G is selected from -0-, -CH20-, -CH = CH-, -S (0) h-, -S (0) hCH2-, -S (0) hC2H4-, - HC = N-, -C (= 0), -0C (= 0) -, -C (= 0) 0-, C (= 0) C2H4-, -C (= 0) 0CH2-, -C (= 0) H-, -NR14-, -N (oxide) R14- and -NR14C (= 0) -, where h is an integer selected from 0, 1 and 2 and R14 is selected from hydrogen, alkyl, alkoxyalkyl, arylalkyl, alkenylalkyl, haloalkenylalkyl, dialkylphosphonate, alkylcarbonyl, haloalkylcarbonyl, alkoxyalkylcarbonyl, arylcarbonyl and alkylsulfonyl; U is selected from the group consisting of: wherein: R7, R8, R10 and R11 are independently selected from hydrogen and halogen; R9 is selected from hydrogen, halogen and haloalkyl; R15 is alkoxycarbonyl; R16 is selected from alkyl and haloalkyl; R40 and R41 is independently selected from alkyl; provided that when (a) R, R1, R5 and R6 are chlorine; (b) a, 1, j, k, n, and o are 0; (c) B1 is -CH-; (d) m is 1 and (e) U is the group X where R7 to R11 are hydrogen, when b is 1; and the agriculturally acceptable salts of these. Compound according to claim 1, characterized in that Q is a cyclic radical of structure where, |- 1-, and 4- denotes the points of attachment to - (CH2) k- and to the sides - (CH2) m- of the bridging group E; B1 is -N- or -CH-; or Q is a cyclic radical of structure where E1 is selected from -CR34 = CR35-, -CR3 = N-, * -N = CR34-, -N = N-, * -C (= 0) CR34-, * -CR24C (= 0) -, -CR34R35CR36R37-, * -C (= 0) NR34-, * -NR3C (= 0) -, * -S (0) sCR34R35-, * -S (0) sNR34-, * -OCR34R35-, * - CR34R350- and -C (= 0) - where the asterisk denotes the union with the nitrogen designated 1 in Q, s is a selected integer of 0, 1 or 2 and R34 to R37, inclusive, are independently selected from hydrogen, halogen, alkyl , alkoxy, alkoxyalkyl, haloalkyl, alkoxycarbonyl, nitro, cyano, amino, alkylamino, and aryl; and R34 to R37 at gem positions can be taken together to form 5, 6 or 7 spiro rings comprised of carbon, nitrogen and oxygen, or R34 to R37 at adjacent positions can be taken together to form rings of 5, 6 or 7 members comprised of carbon, nitrogen and oxygen or a ring fused with benzo; G1 is selected from 0, S, N-J1, or C-J1 where J1 is cyano or nitro; 3. Compound according to claim 1, characterized in that when 2 is 1; Q is a cyclic radical of structure where, 1-, and 4- denotes the points of attachment to - (CH2) k- and to the sides - (CH2) m- of the bridging group E; B1 is -N- OR -CH-; or Q is a cyclic radical of structure 1 E where E1 is selected from * -CR34 = N-, * -N = CR34-, -N = N-, where the asterisk denotes the junction with the nitrogen designated as 1 in Q, and R34 are independently selected from hydrogen, halogen, alkyl, alkoxy, alkoxyalkyl, haloalkyl, alkoxycarbonyl, nitro, cyano, amino, alkylamino, and aryl; b is an integer selected from 0 or 1; and, when b is 1, G is selected from O, -CH20-, -S (0) 2C2H4-, -C (= 0), - C (= 0) OCH2-, -C (= 0) CH2- and -C (= 0) C2H4-. 4. Compound according to claim characterized in that R and R1 are independently selected from halogen; a, i, j, k, m, n, and o each is 0; 1 is 1; Q is a cyclic radical of structure

1 -I ^! ¾ '4 where, B1 is -N-; and U is W and R9 is halogen. 5. Compound according to claim 3, characterized in that R and R1 are independently selected from halogen; a, i, j, k, m, n, and o each is 0; 1 is 1; Q is a cyclic radical of structure where, B1 is -N-; b is 1; G is selected from -C (= 0) 0CH

2-, -C (= 0), -C (= 0) CH2-, -C (= 0) C2H4- and -S02C2H4-; and U is X; R8, R10 and R11 is hydrogen. 6. Compound according to claim 3, characterized in that R and R1 are independently selected from hydrogen or halogen; a and b each is 1 and G is -0-; 1 and o each one is 0; i, j, k each is 1; m and n are independently selected from 0 and 1; and U is Z. 7. Compound according to claim 3, characterized in that R and R1 are independently selected from halogen; a and b each is 1 and G is -0-; 1 is 0; i, j and k each is 1; m, n and o are independently selected from 0 and 1; and U is X; R7, R8, R10 and R11 are hydrogen and R9 is halogen. 8. Compound according to claim 3, characterized in that R and R1 are independently selected from halogen; a, i, j, k, m, n and o each is 0; 1 is 1; Q is a cyclic radical of the structure where B1 is -CH-; b is 1 and G is -CH20-; U is W and R9 is haloalkyl. 9. Compound according to claim 3, characterized in that R and R1 are independently selected from halogen; a is 1; i and j each is l and k, 1, m, n and o are 0; b is O; and U is Y. Compound according to claim characterized in that R and R are independently selected from halogen; a, b, i, j, k, m, n and o each is 0; 2 is 1; Q is a cyclic radical of the structure where B1 is -N-; and U is X; R, R8, R10 and R11 are hydrogen and R9 is haloalkyl. 11. Composition comprising an effective insecticidal amount, characterized in that it is of a compound according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 in admixture with at least one extender or adjuvant agriculturally acceptable. 12. Insecticidal composition according to claim 11, characterized in that it also comprises one or more additional compounds selected from the group consisting of pesticides, plant growth regulators, fertilizers and soil conditioners. Method for controlling insects, characterized in that it comprises applying an effective insecticidal amount of a composition according to claim 11 to a locality where insects are present or are expected to be present. 14. Method of insect control, characterized in that it comprises applying an effective insecticidal amount of a composition according to claim 12 to a locality where the insects are present or are expected to be present.