WO2006067800A1 - Triorganoantimony compounds for pesticidal use - Google Patents

Triorganoantimony compounds for pesticidal use Download PDF

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WO2006067800A1
WO2006067800A1 PCT/IN2004/000407 IN2004000407W WO2006067800A1 WO 2006067800 A1 WO2006067800 A1 WO 2006067800A1 IN 2004000407 W IN2004000407 W IN 2004000407W WO 2006067800 A1 WO2006067800 A1 WO 2006067800A1
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antimony
compound
bis
flurophenyl
spp
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PCT/IN2004/000407
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French (fr)
Inventor
Krishnappa Chandrashekar
Hari Mohan Behl
Vishal Kumar
Om Prakash Sidhu
Palpu Pushpangadan
Chandana Venkateswara Rao
Sanjeev Kumar Shukla
Ashok Ranjan
Arvind Kumar Saxena
Ravi Kant
Kiran Singhal
Prem Raj
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Council Of Scientific And Industrial Research
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Priority to PCT/IN2004/000407 priority Critical patent/WO2006067800A1/en
Publication of WO2006067800A1 publication Critical patent/WO2006067800A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/90—Antimony compounds
    • C07F9/92—Aromatic compounds
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur

Definitions

  • the presenjt invention relates to a novel triorganoantimony compound.
  • the present invention particularly relates to a novel triorganoantimony compound Pentahalophenyl antimony (111) of general formula [(C 6 Xs) 2 Sb(R 1 )] wherein X is halogens such as chlorine, bromine, fluorine or iodine R 1 : is other organic group such as alkyl (Me, Et, iso- propyl, n-butyl) or / and (Ph, p- CH 3 C 6 H 4 , p- FC 6 H 4 m-F- C 6 H 4 , p- ClC 6 H 4 ) and to a processes for their preparation and to their use for controlling plant and animal pests, microbes and with cytotoxic properties.
  • Pentahalophenyl antimony 111 of general formula [(C 6 Xs) 2 Sb(R 1 )] wherein X is halogens such as chlorine, bromine, fluorine or iodine R 1 : is other organic group such as al
  • Antimony compounds are used for a variety of purposes including fillers or products related to insecticidal use, however most of the studies and patents are related to use of compounds with antimony as chemical resistant or as fillers and dilutants.
  • Cox et al in their patents have used antimony related compounds in developing Chemical resistant, water and dry particle impervious, flame resistant laminate antimony trioxide fire retardant additives.
  • these compounds invented or suggested by them as having insecticidal properties per se; neither they have recommended toxic role of the compounds that may suggest their use as insecticidal products.
  • Antimony trioxide has been suggested as filler employed for preparation of insecticidal pet collar by Hedde et al. (U.S patents. No: 6,543,389).
  • antimony pentachloride can be used as diluent in reaction process for synthesis of compounds.
  • Dyker et al (U. S patents. No: 6,127,364) where they have suggested use of antimony pentachloride in reaction process to eliminate water.
  • Antimony has been used in developing hydrolyzable compounds (U. S patents. No: 5,696,052) by Werle , et al. but there is no suggestion of insecticidal properties or molecules that have biocidal properties.
  • Antimony based molluscicides has been incorporated in the pest control composition by Sjogren (U.S patents. No: 4,732,762, and 4,971,796). But, not related to insecticidal and antimicrobial activity of antimony
  • Antimony oxide has been used as antifouling agents in Polymeric microparticles having pesticidal activity by Kanda , et al. as reported in U.S patents. No: 4,923,894. Antimony oxides have also been used as pigment partials only to impart opaque or translucent color insecticidal polymers by Farquharson , et al. (U.S patents. No: 4,888,174). But, not as pesticide
  • Fluorine compounds as insecticides Since, 1890 fluorine compounds have found use as insecticide. They are principally stomach poisons and to a limited extent contact poisons. Their insecticidal properties are related to the fluorine content and solubility in the digestive juices of the insect. Fluorides destroy gut epithelium of insects. However, this is not regarded as immediate cause of death.
  • Insects are known to live without food for long periods and even without gut for few days.
  • Fluorides form complexes and inhibit great number of metallo-enzymes (metal- containing enzymes) both in respiratory pathways and elsewhere.
  • the respiratory enzymes inhibited by fluorides are phosphoglucomutase, enolase, succine dehydrogenase and cytochrome oxidase.
  • While the non respiratory ones are phosphatases, peroxidases, catalases etc. thus fluorides excert leathal action any one of the key enzymes in respiratory and other metabolic pathways leading to death of insects. Fluorine poisoning produces spasms (excessive muscular contraction and sudden convulsive movement), regurgitation, flaccid paralysis and death.
  • insects fluoride with magnesium forms a complex magnesium fluoro phosphate and thus inhibits phosphate transfer in oxidative metabolism.
  • Fluorine compounds are known to cause phyto-toxicity; the phytotoxicity of such compounds is attributed to its higher water solubility. This is not a desirable trait.
  • the present invention relates to developing a safe compound that is free of this limitation.
  • NaF sodium fluoride
  • LD50 for rat oral 200. It is highly phytotoxic. It is not a safe product to use.
  • Sodium fluoaluminate sodium fluoride
  • Na 3 AlF 6 It is also known as sodium alumino fluoride or sodium aluminiumfluoride. Macrovitch and Stanley used it first as an insecticide in 1929 (6). It is found up to 98% in naturally occurring mineral cryolite. However, it can also be manufactured synthetically. It is useful for the control of chewing insects, the LD 50 for rat in oral application is 13.5. This is a highly toxic dose and is not recommended.
  • Organotins are the compounds of tin. Its example is Triphenyltin acetate which was the one of the earliest organotine that was used as an antifeedant. This compound acts as antifeedant against foliage feeding insects such as cotton leaf worm, Colorado potato beetle, caterpillars of Agrotis and grasshoppers (7). This is a banned product and is no more used. There is a need to develop safe and active compounds.
  • Triorganoantimony (III) derivatives are prepared using Grignard reaction; antimony (III) chloride and monohalocarbon compounds which are both aromatic and aliphatic in nature. But such compounds bears only one type of organic moieties attached to central metal atom ⁇ 1 ⁇ .
  • the main disadvantage of the above method is that the yields of Tribrganoantimony (III) are not high and only homopolymers could he made.
  • the normal or reverse addition of Grigard to organo antimony (III) halides varied the yields. More over, the yield of Grignard itself is dependent on the halocarbon used. In view of multivariables, studies are still needed to develop new process of synthesis ⁇ 1 ⁇ .
  • Tri-organo antimony (III) could also be prepared by trans metallation reactions involving di-organo thallium bromide and antimony, but the yield is low and the reaction involved is tedious ⁇ 2 ⁇ . 3. Another method involved in the reaction of organolithium derivatives in donor solvents like THF or ether ⁇ 3,4 ⁇ and antimony (III) halide ⁇ 3,4 ⁇ . In such cases homotriorgano derivatives can be prepared.
  • triorganoantimony (III) derivatives are also usually prepared by using sodium metal in high boiling hydrocarbon solvents and halocarbon ⁇ 4 ⁇ and antimony(III) halides. In such cases only homotriorgano derivatives could be prepared. Further the disposal of untreated sodium created a lot of risk and thus the handling is difficult.
  • the mixed organoderivatives are usually prepared in a very limited way using the organoantimony (III) halide ⁇ 3,5 ⁇ and organolithium solution in THF ⁇ 3,5 ⁇ .
  • the main objective of the present invention is to provide a novel triorganoantimony compound as insecticidal and its processing.
  • Another object of the present invention is to provide a compound of general formula R 2 SbR 1 wherein R 2 : is [(C 6 Xs) 2 ; where X are halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH 3 C 6 H 4 ,
  • Another object of the present invention is to prepare derivatives o with plurarity of uses as insecticidal, antifungal and cytotoxic agent.
  • object of the present invention is to provide a one pot Synthesis of Pentahalophenyl antimony (III) derivatives as general formula R 2 SbR 1 where in R 2 : is [(C 6 Xs) 2 ; where X are
  • halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH 3 C 6 H 4 , p- FC 6 H 4 m-F- C 6 H 4 , p- ClC 6 H 4 ), more preferably C 6 H 5i and its use as insecticidal, antimicrobial, antifungal and cytotoxic agent
  • R 2 SbR 1 wherein R 2 : is [(C 6 Xs) 2 ; where X are halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other 25 organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH 3 CgH 4 , p- FC 6 H 4 In- F- C 6 H 4 , p- ClC 6 H 4 ).
  • R 2 SbR 1 wherein formula of compound is R 2 SbR 1 where R 2 : is [(C 6 Xs) 2 ; where X is fluorine and R 1 is C 6 H 5 .
  • R 2 is [(C 6 Xs) 2 ; where X is fluorine and R 1 is C 6 H 5 .
  • insects belonging to Order Isopoda, Diplopoda, Chilopoda, Symphyla, Thysanura, Collembola, Orthoptera, Blattaria, Dermaptera, Isoptera, Phthiraptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and Class Arachnida.
  • the Median Lethal dose (LD 50 ) at 500-700 mg/kg body weight in animals such as rodents.
  • found safe at 25-75 mg/kg body weight in rodents and no significant change or adverse effect on the vital organs viz., liver, heart, kidney, stomach.
  • the present invention provides a one pot process for preparation of triorganoantimony of general formula (R) 2 SbR 1 wherein R: is (C 6 Xs) 2 R 1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH 3 C 6 H 4 , p- FC 6 H ⁇ m-F- C 6 H 4 , p- ClC 6 H 4 ) comprising. a. reacting aryl magnesium halide and antimaony halide at a refluxing temperature to obtain trisaryl antimony of formula (R) 3 Sb wherein R 3 is (C 6 Xs) 3 , b.
  • aryl magnesium halide is prepared by using aryl halide selected from group consisting of C 6 HsBr, CgCIsBr, p-fluro phenyl bromide, m- fluro phenyl bromide.
  • a process for preparation of triorgano antimony of general formula (R) 2 SbR 1 Grignard reagent used in step (iii) is selected from alkyl halide such as or aryl halide
  • a triorganoantimony wherein the representative compounds are as follows: i) Bis (pentaflurophenyl ) phenyl antimony ii) Bis (pentaflurophenyl ) methyl antimony iii) Bis (pentaflurophenyl ) ethyl antimony iv) Bis (pentaflurophenyl ) isopropyl antimony v) Bis (pentaflorophenyl ) p-methoxy phenyl antimony vi) Bis (pentachlorophenyl ) phenyl antimony vii) Bis (pentachlorophenyl ) methyl antimony viii) Bis (pentachlorophenyl
  • Present invention relates to the synthesise Pentahalophenyl antimony(l 11) derivatives as general formula R 2 SbR 1 where in where R 2 : is [(C 6 Xs) 2 ; where X are halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other organic group such as alkyl (Me, Et, iso-propyl , n- butyl) or / and (Ph, p- CH 3 C 6 H 4 , p- FC 6 H 4 ,m-F- C 5 H 4 , p- ClC 6 H 4 ), more preferably C 6 H 5 and there use thereof as insecticidal, antimicrobial, antifungal and, cytotoxic agents.
  • R 2 is [(C 6 Xs) 2 ; where X are halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other organic group such as alkyl (Me, Et, iso-
  • the present invention describes the procedure for the synthesis of R 2 SbR 1 : compound with insecticidal, antimicrobial, antifungal and cytotoxic activity.
  • the hydrocarbon and fluorocarbon based Grignard reagent (R-Mg-X) were prepared by conventional method (slow addition of organic halides to a stirred solution of metallic Mg). The resulting solution is known as Grignard reagent with general formula R-Mg-X.
  • the triorganoantimony (III) (both hydrocarbon and fluorocarbon based) resulting from former process was treated with antimony trihalide in presence or absence of solvent system for 4-5 hours; the resulting compound was R 2 SbX containing hydrocarbon and fluorocarbon based organic groups.
  • R 2 SbR 1 For the preparation of R 2 SbR 1 , freshly prepared and cooled R 1 -MgX reagent was added to R 2 SbX, dissolved in dry ether, slowly at -10 0 C with constant stirring. The resulting mixture was stirred for an additional hour at room temperature and subsequently refluxed for an hour more. The resulting mixture was then cooled to 0 0 C and treated with ice water containing NH 4 Cl followed by the addition of 4N. HCl (ImI) to the make solution acidic. The ether layer was separated and dried over Na 2 SO 4 and evaporated to give hydrocarbon and fluorocarbon based mixed triorganoantimony (III) (R 2 SbR 1 ) compound.
  • R 1 -MgX reagent was added to R 2 SbX, dissolved in dry ether, slowly at -10 0 C with constant stirring. The resulting mixture was stirred for an additional hour at room temperature and subsequently refluxed for an hour more. The resulting mixture was then cooled to
  • Ether/THF(tetrahedrofuran) Pe ⁇ tafluro magnesium bromide (Grignard) + antimony trichloride Tris penta flurophenyl antimony
  • Ether/THF Bispentaflurophenyl antimony + phenyl megnisiun bromide final compound
  • the active compound can be used for controlling pests, in particular insects and arachnids (mites) in agriculture, forestry, in the protection of stored products and of materials, and in the hygiene sector.
  • the compounds as in this invention may be preferably used as crop protection agents. They can be used against species and against all or some stages of development.
  • the potential pest species include: Order Isopoda. For example, Oniscus asellus, Armadillidium vulgqre and PorceUio scaber.
  • Order Thysanura For example, Lepisma saccharina.
  • Order Collembola For example, Onychiurus armatus.
  • Orthoptera For example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. and Schistocerca gregaria.
  • Order Blattaria For example, Blatta orientalis, Periplaneta americana, Leucophaea maderae and Blattella germanica.
  • Order Dermaptera For example, Forficula auricularia.
  • Order Isoptera For example, Reticulitermes spp.
  • Phthiraptera For example, Pediculus humanus corporis, Haematopinus spp.,
  • Thysanoptera For example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi and Frankliniella occidentalis.
  • Chilo spp. Pyrausta nubilalis, Ephestia kuehniella, Galleria mettonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema oryzae.
  • Hymenoptera For example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. Order of the Diptera, For example. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp:, Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., 5/ZHO hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Da
  • Siphonaptera For example, Xenopsylla cheopis and Ceratophyllus spp. Class of the Arachnida: For example, Scorpio maur ⁇ s, Latrodectus mactans, Acarus siro, Ar gas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.. Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus spp.
  • the compounds according to the invention also exhibit bactericidal and fungicidal properties.
  • An important aspects of this invention relates to these compounds that can be useful in treating microbial infections caused by Mycobacterium tuberculosis, Trypanosoma spp. Candida albicans, Aspergillus spp, Fusarium solani, Pseudomonas aeruginosa, Streptococcus aurens, Klebsiella pneumoniae, Streptococcus mutans and Crytococcus neoformans.
  • the invention relates to use of compound in appropriate concentration and formulation for treatment of plant diseases caused by fungi and bacteria both as preventive measure and curative for all kinds of plant diseases both in storage and field including glass houses and open fields. It can also be used for treatment of seeds cuttings, and plant propagates.
  • the invention also relates to use of compounds in appropriate form and dose for soil treatment for control/ sterilization of insects/mites and microbial infections.
  • Certain aspects of the invention relates to the methods of treating microbial infection casued by Mycobacterium tuberculosis, Trypanosoma spp. Streptococcus aurens, Klebsiella pneumoniae, Streptococcus mutans and Crytococcus neoformans, as well as plant pathogens such as Aspergillus spp, Fusarium solani, Pseudomonas aeruginosa,.
  • the method includes administering the compound in as amount effective for the treatment of microbial infection.
  • Some general aspects of the present invention are to use the synthesized compound as an 5 antimicrobial agent in many of the products such as in door paints, wall paints, plastic films, fibbers and articles. Accordingly, it can be used in hospitals, households, public institutions, ventilation systems, air cleaning, conditioning systems and waste disposal systems.
  • All plants and plant parts can be treated with the compounds as in the present invention. These plants include crop plants or ultivars, economically important plants, inclusive of the ] 0 transgenic plants.
  • the proposed compounds are particularly useful for plants with underground roots such as Chlorophytum, Acorus, gladiolus, sweet potato etc and other crop, medicinal and economically important plants.
  • the compounds are also useful for post harvest management where it produce (flowers, seeds, fruits, roots or parts thereof can be protected from fungal and bacterial infections as the 15 compounds have good anti-microbial properties.
  • the active compounds are recommended to be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
  • These 20 formulations are recommended to be used, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam-formers.
  • Antimony trichloride(2.28 gm, 10 m MoI) and Tris(Pentaflurophenyl)antimony(12.45 gm, 20 m MoI) were heated at 60- 7O 0 C in absence of solvent for about three hours. Cooling yielded white crystals which on recrystalisation from dichloromenthe gave the pure compound (yield 11.78 gm, 80%)
  • the compounds were applied by topical application method.
  • the compound was dissolved in acetone and different concentrations were prepared. 100 ⁇ l of each concentration was separately applied on the dorsal surface of each larva (5 ⁇ l/larvae). The larvae were provided with caster leaves as food. Larvae treated with acetone alone served as control.
  • Stomach toxicity was tested by leaf dip method. Compound was dissolved in acetone and different concentrations were prepared in water using 0.2% tween 20 as emulsifier. Leaf discs (25 cm 2 ) were prepared out of caster leaf and were dipped for 30 seconds in various concentrations of the test compound. Air-dried leaf discs were kept separately in Petriplates. Fourth instar larvae of S, litura were lease ion treated leaves @10 larvae/ replication and three replications were maintained for each concentration. Leaf discs dipped in known amount of acetone in distilled water containing 0.2% tween 20. Mortality was recorded after 48 h and mortality data was used for calculation of LC 50
  • Antifeedant activity of compound was tested against fourth instar larvae of S. litura using leaf dip method.
  • Compound was dissolved in acetone and different concentrations were prepared in water using 0.2% tween 20 as emulsifier.
  • Leaf discs (25 cm 2 ) were prepared out of caster ieaf and were dipped for 30 seconds in various concentrations of the test compound. Air dried to and offered for feeding.
  • Example.5. Acaricidal activity of "(C 6 Fs) 2 Sb(CeHs)" against spider mites Tetranychus sp. (AcarirTetranychidae)
  • Antibacterial activity was tested against three pathogenic strains of bacteria by disc diffusion method. Compound was dissolved in acetone and 1% solution was made in 10% DMSO and was tested for the activity against 3 strains of bacteria staphylococcus auervs, Klebsiella pneumoniae, Psuedomonas aeruginosas and using disc diffusion assay. 5 ⁇ l of solution was applied on 5 mm filter paper disc (Whatman No. 1) separately and air-dried. A 60 ⁇ l suspension of bacteria (10 6 CFU/ml) with reference to Mc Farland standard was spread on nutrient agar plates. The discs impregnated toxicant was placed on the inoculated media and incubated at 37 0 C for 24h. The zone of inhibition was measured using digital Vernier calliper.
  • Antifungal activity was tested against fungi Aspergillus flavus (MTCC: 2798) by tube Dilution technique, which determines the minimum inhibitory concentration (MIC) of an antifungal agent.
  • the MIC value defined as the smallest amount of an agent to inhibit the growth of microorganism.
  • Each tube contains a different concentration of the compound and inoculated with fixed amount of the organism being tested. After incubation, the amount of visible growth in the presence of the smallest concentration of the compound is observed. The tube completely inhibiting the growth of organism in the presence of the smallest concentration of the compound is expressed as the Minimum Inhibitory Concentration..
  • the antifungal assay of compound shows its antifungal activity against aflatoxin producing fungi A. flavus at the concentration of 125 ⁇ g/ inL (MIC).
  • A treated with (C 6 Fs) 2 Sb(C 6 H 5 );
  • B Control Fig.3. Inhibition of Strain Pseudomonas aeruginosa (MTCC: 741) by compound
  • R 2 is [(CgX 5 ) 2 ; where X are halogens such as chlorine, bromine, fluorine or iodine and R 1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH 3 C 6 H 4 , p- FC 6 H 4 m-F- C 6 H 4 , p- ClC 5 H 4 )]

Abstract

The invention concerns with synthesis of mixed triorganoantimony (III) compounds bearing halophenyl groups ('R2SbR1') , using metal turnings viz Lithium, Magnesium or Zinc in donor solvents with plurality of uses as microbiocides and insecticides for controlling undesirable micro organisms and pests in crop protection, protection of materials; household and veterinary pests apart from being cytotoxic.

Description

TRIORGANOANTIMONY COMPOUNDS FOR PERSTICIDAL USE
FIELD OF THE INVENTION
The presenjt invention relates to a novel triorganoantimony compound.
The present invention particularly relates to a novel triorganoantimony compound Pentahalophenyl antimony (111) of general formula [(C6Xs)2Sb(R1)] wherein X is halogens such as chlorine, bromine, fluorine or iodine R1: is other organic group such as alkyl (Me, Et, iso- propyl, n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H4 m-F- C6H4, p- ClC6H4) and to a processes for their preparation and to their use for controlling plant and animal pests, microbes and with cytotoxic properties. BACKGROUND OF THE INVENTION:
Antimony compounds are used for a variety of purposes including fillers or products related to insecticidal use, however most of the studies and patents are related to use of compounds with antimony as chemical resistant or as fillers and dilutants.
Several inventors, U.S patents. No: 6,716,881 Elbe, et al.; 6,319,940, Elbe, et al; 6,534,532, Elbe, et al.; 4,134,985, Gutman; 6,624,336, Sasaki, et al, have used compounds with antimony as catalysts for carrying out the respective reaction process but, however these inventors have not suggested any insecticide/biocidal activities of their compounds or products.
Cox et al in their patents (U.S patents. No: 6,713,411) have used antimony related compounds in developing Chemical resistant, water and dry particle impervious, flame resistant laminate antimony trioxide fire retardant additives.
There have been several inventions based on antimony oxide to dispense the insecticidal compounds (U.S patents. No: 6,710,045, Kraatz, et al ; 6,576,661, Brack , et al. ; 6,642,180,
Fischer, et al,; 6,653,343, Fischer , et al. , and 6,706,758, Fischer , et al.) or to reduce the concentration insecticidal compounds. However they have not suggested use of these compounds invented or suggested by them as having insecticidal properties per se; neither they have recommended toxic role of the compounds that may suggest their use as insecticidal products.
Antimony trioxide has been suggested as filler employed for preparation of insecticidal pet collar by Hedde et al. (U.S patents. No: 6,543,389).
Several other uses of antimony have been proposed. Heinemann , et al. as stated in their U.S patents. No: 6,031,107 that antimony pentachloride can be used as diluent in reaction process for synthesis of compounds. A similar use has been invented and advocated by Dyker , et al (U. S patents. No: 6,127,364) where they have suggested use of antimony pentachloride in reaction process to eliminate water.
Antimony has been used in developing hydrolyzable compounds (U. S patents. No: 5,696,052) by Werle , et al. but there is no suggestion of insecticidal properties or molecules that have biocidal properties.
U.S patents. No: 5,634,967 , Williams , et al. , incorporated antimony into the composition of cuprammonium compound and tebuconazole as compound that exhibit synergistic properties for preservation of wood . Antimony has been suggested as biologically-active compound by Lane , et al (U.S patents.
No: 5,145,674), however, there is no suggestion of use as toxicant against insects or microbes. There have been several inventuions and studies suggesting use of Antimony as Antimony Trioxide Flame Retardant (U.S patents. No: 5,198,287, Samson , et al. , U.S patents. No 5,252,387 Samson et al.). U.S patents. No: 5,223,536, Cullen , et al., used antimony trifluoride in the reaction process for synthesis of methyl-2,3-difluromethylenedioxide benzene intermediate in the process of synthesis of l,4-diaryl-l-cyclopropyl-4-substituted butanes as insecticides and acaricides . but not related to antimony trifluoride as insecticide of antimicrobial agent.
Antimony based molluscicides has been incorporated in the pest control composition by Sjogren (U.S patents. No: 4,732,762, and 4,971,796). But, not related to insecticidal and antimicrobial activity of antimony
Antimony oxide has been used as antifouling agents in Polymeric microparticles having pesticidal activity by Kanda , et al. as reported in U.S patents. No: 4,923,894. Antimony oxides have also been used as pigment partials only to impart opaque or translucent color insecticidal polymers by Farquharson , et al. (U.S patents. No: 4,888,174). But, not as pesticide
Wheeler in U.S. patents. No: 4,423,064 mentions use of antimony pentafluoride for alkylation
2) Fluorine compounds as insecticides: Since, 1890 fluorine compounds have found use as insecticide. They are principally stomach poisons and to a limited extent contact poisons. Their insecticidal properties are related to the fluorine content and solubility in the digestive juices of the insect. Fluorides destroy gut epithelium of insects. However, this is not regarded as immediate cause of death.
Insects are known to live without food for long periods and even without gut for few days.
Fluorides form complexes and inhibit great number of metallo-enzymes (metal- containing enzymes) both in respiratory pathways and elsewhere. The respiratory enzymes inhibited by fluorides are phosphoglucomutase, enolase, succine dehydrogenase and cytochrome oxidase.
While the non respiratory ones are phosphatases, peroxidases, catalases etc. thus fluorides excert leathal action any one of the key enzymes in respiratory and other metabolic pathways leading to death of insects. Fluorine poisoning produces spasms (excessive muscular contraction and sudden convulsive movement), regurgitation, flaccid paralysis and death.
In insects fluoride with magnesium forms a complex magnesium fluoro phosphate and thus inhibits phosphate transfer in oxidative metabolism.
Fluorine compounds are known to cause phyto-toxicity; the phytotoxicity of such compounds is attributed to its higher water solubility. This is not a desirable trait. The present invention relates to developing a safe compound that is free of this limitation.
Examples of fluorine compounds that are toxic to insects
Sodium fluoride (NaF): NaF. It is used in baits for the control of cockroaches, earwigs, cutworms and grasshoppers and chewing lice on animals and poultry (6). LD50 for rat :oral 200. It is highly phytotoxic. It is not a safe product to use. Sodium fluoaluminate:
Na3AlF6: It is also known as sodium alumino fluoride or sodium aluminiumfluoride. Macrovitch and Stanley used it first as an insecticide in 1929 (6). It is found up to 98% in naturally occurring mineral cryolite. However, it can also be manufactured synthetically. It is useful for the control of chewing insects, the LD50 for rat in oral application is 13.5. This is a highly toxic dose and is not recommended.
Sodium fluosilicate : Na2SiF6 is phytotoxic, however, its soluble forms find use in mothproofing fabrics (6). LD50 for rabbit : oral is 150 to 200. 2) Organometal compounds as antifeedant:
Organotinsare the compounds of tin. Its example is Triphenyltin acetate which was the one of the earliest organotine that was used as an antifeedant. This compound acts as antifeedant against foliage feeding insects such as cotton leaf worm, Colorado potato beetle, caterpillars of Agrotis and grasshoppers (7). This is a banned product and is no more used. There is a need to develop safe and active compounds.
All above compounds are banned for usage due to their high mammalian toxicity Synthetic Organic Insecticidal Compounds Available (6) 1: Organometal Compounds
• Paris green (CH3COO)2CU-SCU(ASO2) 2: Phenolic Compounds
• Done (C7H6N2O5) • DNOCHP(Cl2H14N2O5)
• DINOCAP(CI8H24N2O5)
• Binapacryl (Ci5Hi8N2O6) 3: Thio-Cyano Compounds
4: Organochlorine Compounds • DDT (Ci4H9Cl5)
• Methoxychlor (Ci6H15O2Cl3)
• Dicofol (C14H9Cl5O)
• BHC (C6H6Cl6)
• Chlordane (C I0H6Ci8) • Heptachlor (C10H5Cl5)
• Aldrin (C22H8C16)
• Endrin (C12Hl8C16O)
• Endosulfan (C9H6C16O3S)
5: Organophosphorus Compounds • DDVP (C4H7O4CL2P)
• Mevinphos (C7Hi3O6P)
• Cortoxyphos (Ci4HIgO6P) • Phosphomedon (Ci0H19O5ClP)
• Monocrotophos(C7Hi4θ5NP)
• Docrotophos (C8Hi6O5NP)
• Parathion (Ci0Hι4NO5PS) • Fenitrothion (C I0Hi5O2PS2)
• Diazonon ( C]2 H2iN2O3PS)
• Chloropyriphos (C9HI ICI3NO3PS)
• Methyl demeton (CH3O)2PSO (CHz)2SC2H5
• Quinolphos (Ci2Hi5O3H2PS) • Malathion (CiOHi9O6PS2)
• Dimethoate (C5Hi2O4PS2N)
• Phorate (C7Hi7O2PS3) : Carbamates
• Isolan (CioHπ02N3) • Carbaryl (Ci2HuO2N)
• Carbofuran (Ci2Hi5NO3)
• Aldicorb (C7H14N2O2S) : Syntheticpyrethroids
• Allethrin • Cypermethrin
Fevalerate Permethrin Synthesis
1. The Triorganoantimony (III) derivatives are prepared using Grignard reaction; antimony (III) chloride and monohalocarbon compounds which are both aromatic and aliphatic in nature. But such compounds bears only one type of organic moieties attached to central metal atom {1}. The main disadvantage of the above method is that the yields of Tribrganoantimony (III) are not high and only homopolymers could he made. For preparing mixed triorganoantimony (III) derivatives the normal or reverse addition of Grigard to organo antimony (III) halides varied the yields. More over, the yield of Grignard itself is dependent on the halocarbon used. In view of multivariables, studies are still needed to develop new process of synthesis {1}.
2. Tri-organo antimony (III) could also be prepared by trans metallation reactions involving di-organo thallium bromide and antimony, but the yield is low and the reaction involved is tedious {2}. 3. Another method involved in the reaction of organolithium derivatives in donor solvents like THF or ether {3,4} and antimony (III) halide {3,4}. In such cases homotriorgano derivatives can be prepared.
The main disadvantage in this method is handling of organolithium reagent, which is very difficult due to its ignitious nature in the presence of air and moisture; which makes reaction very skilled and tricky.
Further disadvantage is that with antimony (III) chloride, only homoderivatives could be formed {1,4}.
Another disadvantage is that, this process could only be handled in laboratory scale being its susceptible nature to air and moisture {1,4}. 4. Further, the triorganoantimony (III) derivatives are also usually prepared by using sodium metal in high boiling hydrocarbon solvents and halocarbon {4} and antimony(III) halides. In such cases only homotriorgano derivatives could be prepared. Further the disposal of untreated sodium created a lot of risk and thus the handling is difficult.
The use of molten sodium is very risky due to its susceptibility towards moisture. Further disadvantage in the above method is that all reactants should be completely dry and reaction should be carried out under strict inert atmosphere.
Another disadvantage in the process to synthesize Sb derivatives is that the rate of addition of the reactants has to be controlled as the reaction is exothermic in nature hence, causes problems and is not convenient. There is a need to develop a process where this difficulty can be overcome. 5. The mixed organoderivatives are usually prepared in a very limited way using the organoantimony (III) halide {3,5} and organolithium solution in THF {3,5}.
6. Though some similar compounds have been synthesized, there use as pesticidal, cytotoxic and antimicrobial uses and applications have not been elaborated to use such 5 compounds for application to mitigate pest problems of plants and animals {6,7} .
In view of the above shortcomings and constraints, there was a need to develop a process, which could yield pure product of mixed triorganoantimony (III) derivatives in high yields and employing safer handling and which could be used as potent pesticide.
OBJECT OF THE INVENTION
[0 The main objective of the present invention is to provide a novel triorganoantimony compound as insecticidal and its processing.
Another object of the present invention is to provide a compound of general formula R2SbR1 wherein R2 : is [(C6Xs)2; where X are halogens such as chlorine, bromine, fluorine or iodine and R1: is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4,
15 p- FC6H4 m-F- C6H4, p- ClC6H4).
Another object of the present invention is to prepare derivatives o with plurarity of uses as insecticidal, antifungal and cytotoxic agent.
In one more object of the present invention is to provide a one pot Synthesis of Pentahalophenyl antimony (III) derivatives as general formula R2SbR1 where in R2 : is [(C6Xs)2; where X are
20 halogens such as chlorine, bromine, fluorine or iodine and R1: is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H4m-F- C6H4, p- ClC6H4), more preferably C6H5i and its use as insecticidal, antimicrobial, antifungal and cytotoxic agent
Accordingly the present invention provides a compound of general formula R2SbR1 wherein R2 : is [(C6Xs)2; where X are halogens such as chlorine, bromine, fluorine or iodine and R1: is other 25 organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3CgH4, p- FC6H4In- F- C6H4, p- ClC6H4).
In an embodiment of the present invention wherein formula of compound is R2SbR1 where R2 : is [(C6Xs)2; where X is fluorine and R1 is C6H5. In further embodiment of the present invention wherein used as dry or wettable powders, emmulsifable concentrates, or aerosol or semisolid or liquid/solid dosage forms.
In further embodiment of the present invention wherein used as insecticidal, antimicrobial, antifungal and cytotoxic agent. In another embodiment of the present invention wherein used for control of insects belonging to Order Isopoda, Diplopoda, Chilopoda, Symphyla, Thysanura, Collembola, Orthoptera, Blattaria, Dermaptera, Isoptera, Phthiraptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and Class Arachnida.
In further embodiment of the present invention wherein is useful for controlling insect pests of agricultural crops, vegetable crops, floriculture, and ornamental crops, medicinal and economic plants.
In further embodiment of the present invention wherein useful for controlling mite pests of agricultural crops, vegetable crops, floriculture, ornamental crops, medicinal, and economic plants. In one more embodiment of the present invention wherein useful for controlling pests such as lepidopteron caterpillars (leaf eating, fruit and shoot boring, leaf mining), aphids, leafhopper, plant hoppers, white flies, spider mites, tea mosquitoes, leaf minors, hemipteran bugs, storage pests, mosquitoes. In further embodiment of the present invention wherein useful as strong antifeedant against leaf, stem, flower, and fruit feeding insects.
In another embodiment of the present invention wherein useful as a systemic pesticide and is pesticidal when used in direct or indirect contact to eggs, larvae, pupa and adult insect and mite pests.
In one more embodiment of the present invention wherein useful as antibacterial agent against human pathogenic bacteria of the likes of Klebsiella pneumoniae, Staphylococcus aeureus, Pseudomonas aeruginosa.
In another embodiment of the present invention wherein useful as antifungal agent against parasitic fungi and aflatoxin producing fungi of the likes of Aspergillus flavus and A. parasiticus.
In one more embodiment of the present invention wherein the Median Lethal dose (LD50) at 500-700 mg/kg body weight in animals such as rodents. In further embodiment of the present invention wherein found safe at 25-75 mg/kg body weight in rodents and no significant change or adverse effect on the vital organs viz., liver, heart, kidney, stomach.
In one more embodiment of the present invention wherein the synthesis of (C6Xs)2Sb(R1) derivatives (as in Claim 1) as base material in high yields using Grignard reagent.
Accordingly the present invention provides a one pot process for preparation of triorganoantimony of general formula (R)2SbR1 wherein R: is (C6Xs)2 R1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H^m-F- C6H4, p- ClC6H4) comprising. a. reacting aryl magnesium halide and antimaony halide at a refluxing temperature to obtain trisaryl antimony of formula (R)3 Sb wherein R3 is (C6Xs)3 , b. reacting trisaryl antimony R3Sb obtained above with antimony halide optionally in presence of a solvent at a temperature ranging between 100-1500C for a period ranging between 3 to 5 hrs. to obtain bis (aryl) antimony halide, c. reacting bis (aryl) antimony halide obtained above in step (ii) with Grignard reagent of formula R1 -MgX wherein R1 is alkyl or aryl group to obtain tri organo antimony.
In another embodiment of the present invention a process for preparation of tri organo antimony of general formula (R)2SbR1 wherein aryl magnesium halide is prepared by using aryl halide selected from group consisting of C6HsBr, CgCIsBr, p-fluro phenyl bromide, m- fluro phenyl bromide.
In further embodiment of the present invention a process for preparation of triorgano antimony of general formula (R)2SbR1 Grignard reagent used in step (iii) is selected from alkyl halide such as or aryl halide In one more embodiment of the present invention a triorganoantimony, wherein the representative compounds are as follows: i) Bis (pentaflurophenyl ) phenyl antimony ii) Bis (pentaflurophenyl ) methyl antimony iii) Bis (pentaflurophenyl ) ethyl antimony iv) Bis (pentaflurophenyl ) isopropyl antimony v) Bis (pentaflorophenyl ) p-methoxy phenyl antimony vi) Bis (pentachlorophenyl ) phenyl antimony vii) Bis (pentachlorophenyl ) methyl antimony viii) Bis (pentachlorophenyl ) ethyl antimony ix) Bis (pentachlorophenyl ) isopropyl antimony x) Bis (pentachlorophenyl ) butane antimony xi) Bis (pentachlorophenyl ) p-methoxy phenyl antimony xii) Bis (p-flurophenyl ) phenyl antimony xiii) Bis (p -flurophenyl ) methyl antimony xiv) Bis (p -flurophenyl ) ethyl antimony xv) Bis (p -flurophenyl ) isopropyl antimony xvi) Bis (p -flurophenyl ) butyl antimony xvii) Bis (p -flurophenyl ) p-methyl phenyl antimony xviii)Bis (m-flurophenyl ) phenyl antimony xix) Bis (meta- flurophenyl ) methyl antimony xx) Bis (meta-flurophenyl ) ethyl antimony xxi) Bis (m-flurophenyl ) isopropyl antimony xxii) Bis (m-flurophenyl ) n-butyl antimony xxiii)Bis (m-flurophenyl ) p-methoxy phenyl antimony. SUMMARY OF THE INVENTION
Present invention relates to the synthesise Pentahalophenyl antimony(l 11) derivatives as general formula R2SbR1 where in where R2 : is [(C6Xs)2; where X are halogens such as chlorine, bromine, fluorine or iodine and R1: is other organic group such as alkyl (Me, Et, iso-propyl , n- butyl) or / and (Ph, p- CH3C6H4, p- FC6H4,m-F- C5H4, p- ClC6H4), more preferably C6H5 and there use thereof as insecticidal, antimicrobial, antifungal and, cytotoxic agents.
DETAILED DESCRIPTION OF THE INVENTION:
The present invention describes the procedure for the synthesis of R2SbR1: compound with insecticidal, antimicrobial, antifungal and cytotoxic activity. A. Synthesis of R2SbR1, both hydrocarbon and fluorocarbon based," comprises the following steps.
(01) Preparation of R-Mg-X:
The hydrocarbon and fluorocarbon based Grignard reagent (R-Mg-X) were prepared by conventional method (slow addition of organic halides to a stirred solution of metallic Mg). The resulting solution is known as Grignard reagent with general formula R-Mg-X.
(02) Preparation of hydrocarbon and fluorocarbon based triorganoantimony (III) compounds:
The resulting Grignard solution formed by the above method was cooled upto -10 0C and antimony (III) halide (3.78g, 0.016 mol) was dissolved in dry ether added slowly with constant stilting. This resulting mixture was stirred for an addiiional hour at room temperature and subsequently refluxed for one more hour. The resulting mixture was then cooled up to 0 0C and treated with ice water containing NH4Cl. 4N HCl (ImI) was added and stirred to make the solution acidic. The ether layer was separated and dried over Na2SO4 and evaporated to give triorganoantimony(III) compound for both hydrocarbon and flurocarbon groups.
(03) Preparation Of R2SbX
The triorganoantimony (III) (both hydrocarbon and fluorocarbon based) resulting from former process was treated with antimony trihalide in presence or absence of solvent system for 4-5 hours; the resulting compound was R2SbX containing hydrocarbon and fluorocarbon based organic groups.
(04) Preparation Of R2SbR1:
For the preparation of R2SbR1, freshly prepared and cooled R1 -MgX reagent was added to R2SbX, dissolved in dry ether, slowly at -10 0C with constant stirring. The resulting mixture was stirred for an additional hour at room temperature and subsequently refluxed for an hour more. The resulting mixture was then cooled to 0 0C and treated with ice water containing NH4Cl followed by the addition of 4N. HCl (ImI) to the make solution acidic. The ether layer was separated and dried over Na2SO4 and evaporated to give hydrocarbon and fluorocarbon based mixed triorganoantimony (III) (R2SbR1) compound.
Sequence of reactions -1O0 C (1) 3C6F5MgBr+SbCl3 (C6F5)3Sb+3MgBrCI
Ether/THF(tetrahedrofuran) (Peπtafluro magnesium bromide (Grignard) + antimony trichloride Tris penta flurophenyl antimony)
Neat
(2) 2(C5Fs)3Sb + SbCl3 3(C6Fs)2SbCl
60-70 ° C (Tris penta flurophenyl antimony + antimony trichloride Bispentaflurophenyl antimony)
-1O0 C
(3) (C6Fs)2SbCl+ C6H5MgBr- (C6Fs)2Sb(C6H5) + Mg(Br)Cl
Ether/THF (Bispentaflurophenyl antimony + phenyl megnisiun bromide final compound)
B. Use of compounds R2SbR1 as pesticide (05) The active compound can be used for controlling pests, in particular insects and arachnids (mites) in agriculture, forestry, in the protection of stored products and of materials, and in the hygiene sector. The compounds as in this invention may be preferably used as crop protection agents. They can be used against species and against all or some stages of development. The potential pest species include: Order Isopoda. For example, Oniscus asellus, Armadillidium vulgqre and PorceUio scaber.
Order Diplopoda. For example, Blaniulus guttulatus.
Order Chilopoda. For example, Geophilus carpophagus and Scutigera spp.
Order Symphyla. For example, Scutigerella immaculata.
Order Thysanura. For example, Lepisma saccharina. Order Collembola. For example, Onychiurus armatus.
Order Orthoptera. For example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. and Schistocerca gregaria.
Order Blattaria. For example, Blatta orientalis, Periplaneta americana, Leucophaea maderae and Blattella germanica. Order Dermaptera. For example, Forficula auricularia. Order Isoptera. For example, Reticulitermes spp.
Order Phthiraptera. For example, Pediculus humanus corporis, Haematopinus spp.,
Linognathus spp., Trichodectes spp. and Damalinia spp.
Order Thysanoptera. For example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi and Frankliniella occidentalis.
Order Heteroptera. For example, Eurygaster spp., Dysdercus intermedins, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
Order Homoptera. For example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vapor ariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseitdococcus spp. and Psylla spp. Order Lepidoptera. For example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, LithocoUetis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp.. Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mettonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema oryzae.
Order of the Coleoptera For example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,
Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstiϊiάlϊs, Costelytra ∑eaϊandica and Lissorhoptrus oryzophilus.
Order of the Hymenoptera. For example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. Order of the Diptera, For example. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp:, Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., 5/ZHO hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and Liriomyza spp.
Order of the Siphonaptera: For example, Xenopsylla cheopis and Ceratophyllus spp. Class of the Arachnida: For example, Scorpio maurυs, Latrodectus mactans, Acarus siro, Ar gas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.. Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp. and Brevipalpus spp.
(06) At appropriate application rates, the compounds according to the invention also exhibit bactericidal and fungicidal properties.
An important aspects of this invention relates to these compounds that can be useful in treating microbial infections caused by Mycobacterium tuberculosis, Trypanosoma spp. Candida albicans, Aspergillus spp, Fusarium solani, Pseudomonas aeruginosa, Streptococcus aurens, Klebsiella pneumoniae, Streptococcus mutans and Crytococcus neoformans.
The invention relates to use of compound in appropriate concentration and formulation for treatment of plant diseases caused by fungi and bacteria both as preventive measure and curative for all kinds of plant diseases both in storage and field including glass houses and open fields. It can also be used for treatment of seeds cuttings, and plant propagates.
The invention also relates to use of compounds in appropriate form and dose for soil treatment for control/ sterilization of insects/mites and microbial infections.
Certain aspects of the invention relates to the methods of treating microbial infection casued by Mycobacterium tuberculosis, Trypanosoma spp. Streptococcus aurens, Klebsiella pneumoniae, Streptococcus mutans and Crytococcus neoformans, as well as plant pathogens such as Aspergillus spp, Fusarium solani, Pseudomonas aeruginosa,. The method includes administering the compound in as amount effective for the treatment of microbial infection.
Some general aspects of the present invention are to use the synthesized compound as an 5 antimicrobial agent in many of the products such as in door paints, wall paints, plastic films, fibbers and articles. Accordingly, it can be used in hospitals, households, public institutions, ventilation systems, air cleaning, conditioning systems and waste disposal systems. (08) All plants and plant parts can be treated with the compounds as in the present invention. These plants include crop plants or ultivars, economically important plants, inclusive of the ] 0 transgenic plants. The proposed compounds are particularly useful for plants with underground roots such as Chlorophytum, Acorus, gladiolus, sweet potato etc and other crop, medicinal and economically important plants.
The compounds are also useful for post harvest management where it produce (flowers, seeds, fruits, roots or parts thereof can be protected from fungal and bacterial infections as the 15 compounds have good anti-microbial properties.
(09) The active compounds are recommended to be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances. These 20 formulations are recommended to be used, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam-formers.
Following examples are given by way of illustration and should not construed the scope of the invention.
25 Examples. 1
1. Tris( Pentaflurophenyl) antimony
CeF5Br (12.35 gm, 0.05 mol) dissolved in dry ether, was added drop wise to Mg (1.2 gm, 0.05 mol) turnings at 0°C. The resulting Grignard solution was cooled to -1O0C and (3.78 gm, 0.0165 mol) SbCl3 dissolved in dry ether slowly added with constant stirring. This mixture was stirred
30 for an additional hour at room temperature and subsequently refluxed for one hour more. The mixture was then cooled to 0°C and treated with ice water containing NH4Cl and subsequently followed by the addition of 4 N HCl (1 ml) and stirred to make the solution acidic. The ether layer was separated and dried over Na2SO4 and evaporated to give (C6Fs)3Sb. Yield 3.11 gm, 30 %, m.p. 74°C (found C; 34.5: Sb; 19.32) (calculated for Ci8Fi5Sb: C; 34.7: Sb; 19.54) The brownish layer was extracted with CHCl3 and after working up it in usual manner give another crop of (C6F5)3Sb. Yield 3.63 gm, 35 %, m.p. 74°C (found C; 34.49:Sb ; 19.34) ( calculated for Ci8Fi5Sb: C; 34.7: Sb; 19.54)
2. Bis ( pentaflorophenyl)antimony (III) chloride.
Antimony trichloride(2.28 gm, 10 m MoI) and Tris(Pentaflurophenyl)antimony(12.45 gm, 20 m MoI) were heated at 60- 7O0C in absence of solvent for about three hours. Cooling yielded white crystals which on recrystalisation from dichloromenthe gave the pure compound (yield 11.78 gm, 80%)
3. Bis(Pentaflourophenyl)phenylantiraony(III)
Bromobenzene(31.4 gm, 0.2 mol) dissolved in dry ether was added drop- wise to Mg(5 gm, 0.21 mol)turning at 0°C. The resulting Grignard solution was cooled to -10°C and (9.8 gm, 0.2 mol) Bis(Pentaflorophenyl)antimonychloride dissolved in dry ether was added to it slowly. This mixture was stirred for an additional hour at room temperature and after completion of the reaction was treated with a saturated NH4Cl solution. The ether layer was separated and dried over Na2SO4. The solvent was then evaporated from the solution in vacuum and residue recrystallised from ethanol. All operations were undertaken in protective under N2 atmosphere to avoid moisture. (Yield 6.39 gm, 60 %). Examples.2. Test for Contact toxicity of "(C6Fs)2Sb(C6H5)" against Spodoptera litura
The compounds were applied by topical application method. The compound was dissolved in acetone and different concentrations were prepared. 100 μl of each concentration was separately applied on the dorsal surface of each larva (5μl/larvae). The larvae were provided with caster leaves as food. Larvae treated with acetone alone served as control.
Fourth instar larvae of S. litura (30 larvae for each concentration) were used for experimentation. Mortality was recorded after 48 h and treatment mortality was corrected with control mortality using Abbot' s_formula. Corrected mortality = (T-C)/ (100-C) X 100.
Where:
T= Treatment mortality. C= Control mortality. . Mortality data was used for calculation of LC50
Table.l. Contact toxicity of "(C6Fs)2Sb(C6H5)" against Spodoptera litura
Figure imgf000018_0001
Example.3. Test for Stomach toxicity of "(C6Fs)2Sb(C6H5)" against Spodoptera litura
Stomach toxicity was tested by leaf dip method. Compound was dissolved in acetone and different concentrations were prepared in water using 0.2% tween 20 as emulsifier. Leaf discs (25 cm2) were prepared out of caster leaf and were dipped for 30 seconds in various concentrations of the test compound. Air-dried leaf discs were kept separately in Petriplates. Fourth instar larvae of S, litura were lease ion treated leaves @10 larvae/ replication and three replications were maintained for each concentration. Leaf discs dipped in known amount of acetone in distilled water containing 0.2% tween 20. Mortality was recorded after 48 h and mortality data was used for calculation of LC50
Table.2. Stomach toxicity of "(C6Fs)2Sb(C6H5)" against Spodoptera litura
Figure imgf000018_0002
Example.4. Antifeedant activity of "(C6Fs)2Sb(C6H5)" against S. litura.
Antifeedant activity of compound was tested against fourth instar larvae of S. litura using leaf dip method.
Compound was dissolved in acetone and different concentrations were prepared in water using 0.2% tween 20 as emulsifier. Leaf discs (25 cm2) were prepared out of caster ieaf and were dipped for 30 seconds in various concentrations of the test compound. Air dried to and offered for feeding. Leaf discs dipped in known amount of acetone in distilled water containing 0.2% tween 20 used as control.
Insects were allowed to feed for 48 h and after 48 h leaf area left uneaten was measured using leaf area meter. Difference between leaf area provided and leaf area left over is taken as amount of leaf area consumed. Antifeedant activity (%) = (C-T)/(C+T)*100, where C= leaf area consumed in control, T= leaf area consumed in Treatment. Data was used for calculation of EC50 antifeedant activity. Table.3. Antifeedant activity of "(C6Fs)2Sb(C6H5)" against S. litura.
Figure imgf000019_0001
Example.5. Acaricidal activity of "(C6Fs)2Sb(CeHs)" against spider mites Tetranychus sp. (AcarirTetranychidae)
Compound was dissolved in acetone and different concentrations were prepared in water using 0.2% tween 20 as emulsifier. Leaf discs of mulberry (5cm2 diameter) where dipped in different concentrations for 30 seconds air dried and placed over wet cotton in Petriplates. Adult female mites where released on treated leaf discs and mortality were recorded 48 h after treatment. Mites released on leaf discs treated with water containing 0.2 % tween 20 served as control. Mortality data was used for calculation of LC50 Table.4. Toxicity of (C6Fg)2Sb(C6H5)" to S. litura and TetranycU s|>.^" 04
Figure imgf000020_0001
Example. 6. Antibacterial activity Of(C6Fs)2Sb(C6H5)"
Antibacterial activity was tested against three pathogenic strains of bacteria by disc diffusion method. Compound was dissolved in acetone and 1% solution was made in 10% DMSO and was tested for the activity against 3 strains of bacteria staphylococcus auervs, Klebsiella pneumoniae, Psuedomonas aeruginosas and using disc diffusion assay. 5μιl of solution was applied on 5 mm filter paper disc (Whatman No. 1) separately and air-dried. A 60μl suspension of bacteria (106 CFU/ml) with reference to Mc Farland standard was spread on nutrient agar plates. The discs impregnated toxicant was placed on the inoculated media and incubated at 37 0C for 24h. The zone of inhibition was measured using digital Vernier calliper.
Table. 5. Antimicrobial activity of (C6Fs)2Sb(C6H5)"
Figure imgf000020_0002
SbCl3: Intial compund; (C6Fs)2Sb(C6H5): Final compund: Ampicillin: Known compound. The above result shows that final compound (C6F5)ZSb(CeH5) is having very promising activities than initial starting material SbCl3 and known compound ampicillin. Example.7. Testing for antifungal activity Of (C6Fs)2Sb(C6H5)"
Antifungal activity was tested against fungi Aspergillus flavus (MTCC: 2798) by tube Dilution technique, which determines the minimum inhibitory concentration (MIC) of an antifungal agent.
The MIC value defined as the smallest amount of an agent to inhibit the growth of microorganism. Each tube contains a different concentration of the compound and inoculated with fixed amount of the organism being tested. After incubation, the amount of visible growth in the presence of the smallest concentration of the compound is observed. The tube completely inhibiting the growth of organism in the presence of the smallest concentration of the compound is expressed as the Minimum Inhibitory Concentration..
The antifungal assay of compound shows its antifungal activity against aflatoxin producing fungi A. flavus at the concentration of 125μg/ inL (MIC).
Fig.l. Inhibition of Strain Klebsiella pneumoniae (MTCC: 109) by compound
Figure imgf000021_0001
A: treated with (C6Fs)2Sb(C6H5); B: Control Fig.2. Inhibition of Strain Staphylococcus aeureus (MTCC: 96) by compound
Figure imgf000021_0002
A: treated with (C6Fs)2Sb(C6H5); B: Control Fig.3. Inhibition of Strain Pseudomonas aeruginosa (MTCC: 741) by compound
Figure imgf000022_0001
l Example. 6 Structure of (CnFO? Sb(QHV) The IR spectra of (C6Fs)2PhSb was recorded in the range 4000-200 cm -1and the absorption characteristic of C-F and C-H stretching along with mass sensitive vibrational modes of diagnostics -value have been identified The values are in close proximity with those reported for (C6Fs)3Sb and (CoHs)3Sb The characteristic Sb-C stretching frequency occur at 445 cm"1 (Sb- CβFs) and 460 cm"1 (Sb-Ph) corresponding to 'Y' mode, vibrational mode, V sym(Sb-C) corresponding to 't' mode appear at 279 and 268 cm"1 assignable to Sb-C6F5 and Sb- C6H5
Stretching mode respectively These assignments have been made on the basis of approximate normal coordinate calculations carried out on R3Sb compounds assuming the 'R' groups to be single atoms It may be noted that on the basis of Raman spectra tertiary stibmes have been reported to possess expected trigonal pyramidal C3v symmetry structure. Assuming organic group R and R; to be single atoms tπaryl stibines could have skeleton of C3v symmetry showing the expected pyramidal structure with the lone pair presumably occupying the 4th coordination position round the antimony
The UV spectra of (C6Fs)2(C6Hs)Sb exhibit an intense absorption at 252 mμ suggesting the interaction of non bonded electrons of antimony atom with π orbitals of the aromatic ring. 19F NMR spectra of the compound was recorded in CDCl3 using CF3COOH as reference at 85.26 MHz. The characterstic signals of F2 6, F3 5 and F4 were observed at -120.34 ppm, -160.36 ppm and -142.30 ppm respectively. The peak of F4 was easily recognized due to its half intensity compared to F2j6 and F3 5 peaks. F4 signals appear at triplet of triplet due to spin- spin coupling. 1H NMR spectra showed a multiplet due to aromatic protons in the range δ 7.20- 7.90 ppm. The value are in good proximity shown by phenyl stibines.
Mass spectra of (C6Fs)2 Sb(C6H5) showed the dominance of (C6F5)M+ apart from (C6F5)2 M+ by loss of phenyl group, spectra also showed the formation of SbF2 +, SbF and Sb+. Similar transitions have been reported for (C6 Fs)3Sb {5} .
X-ray diffraction studies carried on R3M, R2MX, compounds ( R=an organic group, X=halide; M=As, Sb, and Bi) confirm their pyramidal structure with the valance bond approximately ±394 {8}.
A similar structure seems to be more plausible for (C6Fs)2SbPh with certain deviations. Single X- ray crystal study along with normal coordinate analysis is in progress {9}. Structure of the compound shown below
f*"T Lone pair electron
Figure imgf000023_0001
Structure of "(C6Fg)2Sb(C6H5)"
The IR (Infra red) Data for supporting the said structure of the compound. Table1 IR assignment (Cm-I) of the X-sensitive modes for phenyl -Sb and F5C6-Sb in mixed triarylstibine (C6Fs)2(C6H5)Sb
Figure imgf000023_0002
* = Below 200 List of the compounds with general structure R2SbR1
[(where in where R2 : is [(CgX5)2; where X are halogens such as chlorine, bromine, fluorine or iodine and R1: is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H4 m-F- C6H4, p- ClC5H4)]
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001

Claims

We claim:
1. A triorganoantimony compound of general formula R2SbR1 where in R2 : is [(C6Xs)2; where X are halogens such as chlorine, bromine, fluorine or iodine and R1: is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H4,m-F- C6H4, p- ClC6H4).
2. A triorganoantimony as claimed in claim 1 wherein the representative compounds are as follows: i) Bis (pentafiurophenyl ) phenyl antimony ii) Bis (pentafiurophenyl ) methyl antimony iii) Bis (pentafiurophenyl ) ethyl antimony iv) Bis (pentafiurophenyl ) isopropyl antimony v) Bis (pentaflorophenyl ) p-methoxy phenyl antimony vi) Bis (pentachlorophenyl ) phenyl antimony vii) Bis (pentachlorophenyl ) methyl antimony viii) Bis (pentachlorophenyl ) ethyl antimony ix) Bis (pentachlorophenyl ) isopropyl antimony x) Bis (pentachlorophenyl ) butane antimony xi) Bis (pentachlorophenyl ) p-methoxy phenyl antimony xii) Bis (p-flurophenyl ) phenyl antimony xiii) Bis (p -flurophenyl ) methyl antimony xiv) Bis (p -flurophenyl ) ethyl antimony xv) Bis (p -flurophenyl ) isopropyl antimony xvi) Bis (p -flurophenyl ) butyl antimony xvii) Bis (p -flurophenyl ) p-methyl phenyl antimony xviii)Bis (m-flurophenyl ) phenyl antimony xix) Bis (meta-fiurophenyl ) methyl antimony xx) Bis (meta-fiurophenyl ) ethyl antimony xxi) Bis (m-flurophenyl ) isopropyl antimony xxii) Bis (m-flurophenyl ) n-butyl antimony xxiii)Bis (m-flurophenyl ) p-methoxy phenyl antimony.
3. A compound as claimed in claim 1 wherein formula of compound is R2SbR1 where R2 : is [(COXS)2; where X is fluorine and R1 is C6H5.
4. A compound as claimed in claim 3 wherein the said compound is used as dry or wettable powders, emmulsifable concentrates, or aerosol or semisolid or liquid/solid dosage forms.
5. A compound as claimed in claim 3 wherein the said compound is used as insecticidal, antimicrobial, antifungal and cytotoxic agent.
6. A compound as claimed in claim 3 wherein the said compound is used for control of insects belonging to Order Isopoda, Diplopoda, Chilopoda, Symphyla, Thysanura, Collembola, Orthoptera, Blattaria, Dermaptera, Isoptera, Phthiraptera, Thysanoptera,
Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and Class Arachnida.
7. A compound as claimed in claim 3 wherein the said compound is useful for controlling insect pests of agricultural crops, vegetable crops, floriculture, and ornamental crops, medicinal and economic plants.
8. A compound as claimed in claim 3 wherein the said compound is useful for controlling mite pests of agricultural crops, vegetable crops, floriculture, ornamental crops, medicinal, and economic plants.
9. A compound as claimed in claim 3 wherein the said compound is useful for controlling pests such as lepidopteron caterpillars (leaf eating, fruit and shoot boring, leaf mining), aphids, leafhopper, plant hoppers, white flies, spider mites, tea mosquitoes, leaf minors, hemipteran bugs, storage pests, mosquitoes.
10. A compound as claimed in claim 3 wherein the said compound is useful as strong antifeedant against leaf, stem, flower, and fruit feeding insects. 11. A compound as claimed in claim 3 wherein the said compound is useful as a systemic pesticide and is pesticidal when used in direct or indirect contact to eggs, larvae, pupa and adult insect and mite pests.
12. A compound as claimed in claim 3 wherein the said compound is useful as antibacterial agent against human pathogenic bacteria of the likes of Klebsiella pneumoniae, Staphylococcus aeureus, Pseudomonas aeruginosa. 13. A compound as claimed in claim 3 wherein the said compound is useful as antifungal agent against parasitic fungi and aflatoxin producing fungi of the likes of Aspergillus flavus and A. parasiticus.
14. A compound as claimed in claim 3 wherein the said compound has the Median Lethal dose (LD50) at 500-700 mg/kg body weight in animals such as rodents.
15. A compound as claimed in claim 3 wherein the said compound was found safe at 25-75 mg/kg body weight in rodents and no significant change or adverse effect on the vital organs viz., liver, heart, kidney, stomach.
16. A one pot process for preparation of triorganoantimony of general formula (R)2SbR1 wherein R: is (C6Xs)2 R1 : is other organic group such as alkyl (Me, Et, iso-propyl , n-butyl) or / and (Ph, p- CH3C6H4, p- FC6H4m-F- C6H4, p- ClC6H4) comprising. a. reacting aryl magnesium halide and antimaony halide at a refluxing temperature to obtain trisaryl antimony of formula (R)3 Sb wherein R3 is (C6Xs)3 , b. reacting trisaryl antimony R3Sb obtained above with antimony halide optionally in presence of a solvent at a temperature ranging between 100-1500C for a period ranging between 3 to 5 hrs. to obtain bis (aryl) antimony halide, c. reacting bis (aryl) antimony halide obtained above in step (ii) with Grignard reagent of formula R1 -MgX wherein R1 is alkyl or aryl group to obtain tri organo antimony. 19. A process for preparation of triorganoantimony of general formula (R)2SbR1 wherein aryl magnesium halide is prepared by using aryl halide selected from group consisting of C6H5Br, C6Cl5Br, p-fluro phenyl bromide, m- fluro phenyl bromide.
20. A process for preparation of triorganoantimony of general formula (R)2SbR1 wherein Grignard reagent used in step (iii) is prepared by using alkyl halide or aryl halide 21. A process as claimed in claim 1 wherein the reaction process is carried out under N2 atmosphere.
22. A process as claimed in claim 1 wherein said synthesized compound is partially water- soluble.
23. A process for the synthesis Of (C6Xs)2Sb(R1) compound as synthesised in high yields using Grignard reagent.
PCT/IN2004/000407 2004-12-24 2004-12-24 Triorganoantimony compounds for pesticidal use WO2006067800A1 (en)

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