WO1998051652A1 - Pesticide compounds, compositions and process for the preparation thereof - Google Patents

Pesticide compounds, compositions and process for the preparation thereof Download PDF

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Publication number
WO1998051652A1
WO1998051652A1 PCT/HU1998/000049 HU9800049W WO9851652A1 WO 1998051652 A1 WO1998051652 A1 WO 1998051652A1 HU 9800049 W HU9800049 W HU 9800049W WO 9851652 A1 WO9851652 A1 WO 9851652A1
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WO
WIPO (PCT)
Prior art keywords
optical isomer
compound
formula
derivatives
compounds
Prior art date
Application number
PCT/HU1998/000049
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English (en)
French (fr)
Inventor
Géza ÁRVAI
Ildikó BAKONYVÁRI
Béla BERTÓK
Zsuzsanna KURUCZNÉ RIBAI
László PAP
István Székely
Original Assignee
Chinoin Gyógyszer És Vegyészeti
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chinoin Gyógyszer És Vegyészeti filed Critical Chinoin Gyógyszer És Vegyészeti
Priority to AU74449/98A priority Critical patent/AU7444998A/en
Publication of WO1998051652A1 publication Critical patent/WO1998051652A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system

Definitions

  • Pesticide compounds, compositions and process for the preparation thereof are provided.
  • This invention relates to the (+) optically active isomer of the active ingredient of formula (I), to isomeric mixtures rich on the (+) optically active isomer, to pesticide compositions containing the (+) optically active isomer of the active ingredient of formula (I), to pesticide compositions containing the (+) optically active isomer of the active ingredient of formula (I) beside known pesticide synergists, to synergized pesticide compositions containing the (+) isomer of the pesticide synergist of formula (I) beside known pesticide active ingredients, furthermore to compositions containing the (+) isomer of the pesticide synergist of formula (I) beside known pesticide active ingredient and synergist, and to the process for the preparation thereof.
  • the racemic compound of formula I (MB-599) is described in WO 97/19040.
  • the compound of formula I has one center of asymmetry, thus it has two optical isomers.
  • the two isomers can be distinguished -among others, most easily, by their direction of optical rotation.
  • the above (+) optical isomer is the compound which, in its acetonic solution, rotates the plane of the linearly polarized light towards direction (+), i.e. to the right.
  • the two optical isomers are mirror-image pairs, their general physical characteristics (boiling point, refractivity, solidification temperature) are the same, but in optically active systems, thus in biological medium too, they behave differently. Consequently, their synergistic activities may differe, too.
  • synergists Compounds which are non-toxic, or only slightly toxic alone, but given together with a pesticide, in most cases with an arthropodicide agent, they enhance markedly the potency of the latter, are called synergists.
  • the synergistic potency is characterized by the so-called SR synergist ratio, which is given, for example in the case of insecticides, as follows:
  • the racemic compound of formula (I), known as MB-599, is an outstanding pesticide synergist, its optical isomers have not been previously prepared.
  • our invention we succeeded to prepare both the (+) isomer (MB- 755), and the (-) isomer (MB-754) and we subjected the compounds to a wide- range biological investigation.
  • the (+) optical isomer was biologically more active.
  • the difference between the activities of the isomers, as obtained for resistent species was much higher than expected and it showed one order of magnitude higher value (results are demonstrated in Table
  • the main criterium is that the amount of the synergists must be comparable with that of the active ingredient, the total amount of the synergists and the active ingredient must be as little as possible.
  • the significance of our invention lays in this point. It not only allows savings, which can cover the extra costs of the preparation of the optical isomers, but it is very important from the view of the environmental biology. The material can be applied in much smaller quantities, it is more selective and it is safer. The high difference in the activities of the isomers was observed for various types of active ingredients. With the compound according to our invention the effect of the following known arthropodicide active ingredients can favourably be synergized:
  • Acetamide derivatives e.g. oxamyl
  • Acetamidine derivatives e.g. acetamiprid
  • Benzoylurea compounds e.g. flucycloxuron, hexaflumuron, teflubenzuron, triflumuron, novaluron, lufenuron, chlorofluazuron;
  • Bicycloheptadien compounds e.g. heptenophos
  • Cross-bridged diphenyl compounds e.g. etofenprox, bromopropylate, methoxycholor, temephos, tetradifon;
  • Carbamates e.g. aminocarb, aldicarb, aldoxycarb, asulam, bendiocarb, benfuracarb, carbaryl, carbetamide, carbofuran, carbosulfan, diethofencarb, dioxacarb, ethiofencarb, fenobucarb, fenoxycarb, furathiocarb, isoprocarb, methomyl, oxamyl, pirimicarb (pirimor), propoxur, thiodicarb, thiofanox, xylylcarb;
  • Carbamoyloxime derivatives e.g. alanycarb, butocarboxim;
  • Cyclodienes e.g. aldrin, chlordane, endosulfan, heptachlor;
  • Diazoles e.g. fipronil
  • Diphenyl ethers e.g. diophenolan
  • Hydrazides RH 5992, RH 5849, CGA 215'944;
  • Nereistoxin analogues e.g. bensultap, cartap; Chloronicotinyl analogues: e.g. imidacloprid;
  • Nitroethylen and nitromethylen analogues e.g. nitenpiram;
  • Organophosphor compounds e.g. quinalphos, diazinon, phosalone, dimethoate, azinphos-methyl,
  • Organotin compounds e.g. azocyclotin, cyhexatin, fenbutatin oxide; Oxadiazin carboxylates: e.g. DPX-MP062, DPX-JW062;
  • Phenoxy compounds e.g. diafenthiuron, diophenolan
  • Pyrazoles e.g. pyrazophos
  • Pyrethroides e.g. allethrin, bioallethrin (esbiol), acrinathrin, deltametrin, halphenprox, flumetrin, f ⁇ nvalerate, empenthrin, prallethrin, resmethrin, MTI-800, flufenprox, permethrin, tetramethrin, ZX-8901, cypermethrin, and their isomers and isomer-combinations, such as ⁇ -cypermethrin, theta- cypermethrin;
  • Pyridazinones e.g. pyridaben, NC-196;
  • Pyridine derivatives e.g. chlorpyriphos
  • Pyrimidine derivatives e.g. pyrimiphos-ethyl, pyrimiphos-methyl
  • Pyrroles e.g. AC 303, 630 (chlorphenapyr);
  • Terpenoid derivatives e.g. methoprene
  • Tetrazines e.g. clofentezine, SzI-121 (flufenzin); Thiadiazines: e.g. buprofezin;
  • Thiazolidin e.g. hexythiazox, ethoxazol
  • Triazoles e.g. isazophos, RH 7988;
  • Chlorinated hydrocarbons e.g. lindane
  • Macrocyclic lactones e.g. ivermecrin/avermectin, doramectin, noxidectin, emamectin, milbemicin; Tebuphenpyrade;
  • Pheny proxy mate Pheny proxy mate
  • Insecticides of plant ridge e.g. azadiractin, naphthoquinones, pyretrides and their derivatives, plant-extracts.
  • azadiractin e.g. azadiractin, naphthoquinones, pyretrides and their derivatives, plant-extracts.
  • the above known active ingredients are described in the 8th and 10th Edition of the Pesticide Manual, A.G.Chem.New Compound Review Vol. 11(1993) and ACS Symposium Series 504 p. 272., and the European Patent Application No. 0635499 (SZI-121), respectively.
  • Compounds of formula I can be prepared by stereoselective substitution, by reacting the compounds of general formula II and III, where X and Y mean groups suitable for ether formation.
  • X and Y mean groups suitable for ether formation.
  • the compound according to the present invention is not known from the literature.
  • the compound of formula I can be formulated as independent composition or in admixture with other known pesticide (s), preferably arthropodicide active ingredients, and according to the application goal known carriers and other auxiliary materials may be used.
  • pesticide preferably arthropodicide active ingredients
  • auxiliary materials may be used.
  • emulsion concentrates, microemulsions, ULVs, microsuspensions, suspensions, dusters, aerosols, vaporators and smokers may be prepared. [Rhone Poulenc-Geronazzo: Surfactant and Specialities for Plant Protection, Application Manual (1994), ICI: Surfactants, Application Manual (1992)].
  • compositions containing the compound of the present invention and the compositions containing the known active ingredient(s) can be used consecutively, or by making a tank-mixture of them.
  • Synergistic activities of compound MB-755 of the present invention and of reference compound MB-599 have been determined for various active ingredients on house fly (Musca domestica) and on L2 phase larvae of cotton bollworm (Helicoverpa armigera) using the method of treatments described in biological Example 3.
  • active ingredients ISO common names are given (see: Pesticide Manual 1994). The obtained synergist ratios are shown below: Table 4
  • Treatment was performed as described in Example 3, using Hamilton MicroLab P microdispenser.
  • 10 female, 2-3 day old flies were treated on the ventral side of their thorax with 0.2 ⁇ l test solution.
  • Selection and counting of the flies were performed under the action of C0 2 .
  • After treatment the flies were kept in plastic cups covered with tulle. After 24 hours mortality % was recorded. Depending on the results the experiments were performed in 2-4 replica. Results are demonstrated in the table below.
  • the resulting product was grained in an alpine- 100 typ mill. Average particle size was 1-2 ⁇ m. This composition may be used to prepare microsupensions.
  • the material thus obtained may be preferably used for the preparation of microemulsions.
  • the mixture of 0.02-0.02 parts by mass of the active ingredient and of the synergist is dissolved in 10 parts by mass of propanol, to the resulting solution 99.96 parts by mass of odourless petroleum are added and the mixture is stirred until a homogenous solution is obtained.
  • the resulting oily dispersible preparation can directly be used in ULV applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/HU1998/000049 1997-05-14 1998-05-11 Pesticide compounds, compositions and process for the preparation thereof WO1998051652A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74449/98A AU7444998A (en) 1997-05-14 1998-05-11 Pesticide compounds, compositions and process for the preparation thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU9700893A HU223972B1 (hu) 1997-05-14 1997-05-14 Arthropodicid hatású (+/-)-1-(1-/but-2-inil-oxi/-etil)-3,4-dimetoxi-benzol (+) optikai izomerje, előállítása, hatóanyagként a vegyületet tartalmazó készítmény és alkalmazása
HUP9700893 1997-05-14

Publications (1)

Publication Number Publication Date
WO1998051652A1 true WO1998051652A1 (en) 1998-11-19

Family

ID=89995128

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/HU1998/000049 WO1998051652A1 (en) 1997-05-14 1998-05-11 Pesticide compounds, compositions and process for the preparation thereof

Country Status (7)

Country Link
AR (1) AR015663A1 (es)
AU (1) AU7444998A (es)
HR (1) HRP980249A2 (es)
HU (1) HU223972B1 (es)
PA (1) PA8451501A1 (es)
WO (1) WO1998051652A1 (es)
ZA (1) ZA983924B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8097603B2 (en) 2003-05-08 2012-01-17 Bayer Animal Health Gmbh Compositions for controlling parasites on animals

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019040A2 (en) * 1995-11-21 1997-05-29 Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. Pesticide compounds, compositions and process for the preparation thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997019040A2 (en) * 1995-11-21 1997-05-29 Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. Pesticide compounds, compositions and process for the preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
I. SZÉKELY ET AL: "MB-599, a new synergist in pest control", BRIGHTON CROP PROTECTION CONFERENCE - PESTS & DISEASES, vol. 2, 1996, pages 473 - 479, XP000671522 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8097603B2 (en) 2003-05-08 2012-01-17 Bayer Animal Health Gmbh Compositions for controlling parasites on animals

Also Published As

Publication number Publication date
AU7444998A (en) 1998-12-08
HUP9700893A3 (en) 1999-12-28
HRP980249A2 (en) 1999-02-28
ZA983924B (en) 1998-11-09
HU9700893D0 (en) 1997-07-28
HU223972B1 (hu) 2005-03-29
AR015663A1 (es) 2001-05-16
HUP9700893A2 (hu) 1999-05-28
PA8451501A1 (es) 2000-05-24

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