WO2018142423A1 - Nouveaux insecticides écologiques à base de composés de silicium et leur procédé de préparation - Google Patents

Nouveaux insecticides écologiques à base de composés de silicium et leur procédé de préparation Download PDF

Info

Publication number
WO2018142423A1
WO2018142423A1 PCT/IN2018/050050 IN2018050050W WO2018142423A1 WO 2018142423 A1 WO2018142423 A1 WO 2018142423A1 IN 2018050050 W IN2018050050 W IN 2018050050W WO 2018142423 A1 WO2018142423 A1 WO 2018142423A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
chlorobis
formula
silane
compounds
Prior art date
Application number
PCT/IN2018/050050
Other languages
English (en)
Inventor
Ganapati Dadasaheb Yadav
Godfree Pavalu Fernandes
Dhiraj Onkar KATOLE
Jagan Vipin AGARWAL
Original Assignee
Ganapati Dadasaheb Yadav
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 Ganapati Dadasaheb Yadav filed Critical Ganapati Dadasaheb Yadav
Publication of WO2018142423A1 publication Critical patent/WO2018142423A1/fr

Links

Classifications

    • 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 present invention relates to a novel biodegradable active insecticides. More particularly, the present invention provides novel insecticidal actives, silicon-based compounds or a salt thereof and process for preparation thereof. The present invention also provides the compositions comprising said novel biodegradable active insecticides and methods for the control and/or prevention of insect/pest using said compositions.
  • DDT 1, 1, 1- Trichloro-2,2-bis(4-chlorophenyl)ethane
  • the demerit of DDT is that it gets accumulated in the body of animal particularly predators, including human being. In addition to this, because of non-biodegradability nature, it gets trasported through the various food chains, and causes breast cancer, pancreatic cancer, reproductive disorder, etc.
  • the inventors of present invention developed an efficient and novel synthesis of eco-friendly silicon-based isosteres of DDT.
  • the said novel compounds are biodegradable and are effective as an insecticides as well as insect repellents.
  • the primary objective of the present invention aims to provide an eco-friendly insecticides.
  • One more objective of the present invention is to provide a novel silicon-based compounds possessing insecticidal and insect repellent properties.
  • One more objective of the present invention to provide a biodegradable and safe isostere of l, l, l-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT).
  • Another objective of the present invention is to provide an insecticidal compounds with a significant reduction in ecological and toxicological problems thereby overall making the compounds environment-friendly.
  • Another objective of the present invention is to provide a process for the synthesis of novel silicon-based compounds possessing insecticidal and insect repellent properties.
  • the present invention provides a novel silicon-based compounds or salt thereof with the general formula (I);
  • Rj represent halogen, hydrogen, alkyl, aikoxy or aryi group.
  • R.i and R2 represent chlorine, fluorine or metltoxy group.
  • R3 represents chlorine or hydroxy! group.
  • .R , R* and Rs represents chlorine or hydrogen a torsi
  • One more embodiment, of the present invention relate to processes for Synthesis of a compounds according to formula (I) comprising the following steps;
  • Step 1) Chloriiiaiion of compound of formula (H) to give mixture of chloromethyl trichlorosilane, dieh!oromethyl trichlorosilane and trichioromethyi triehiorositane compound, as represented by formula III, IV and V, respectively;
  • Step 2) Separation of chloromethyl trichlorosilane, . diehloromethyl trichlorosilane and tri chloromethyl trichlorosilane by distillation technique;
  • Step 3) The reaction of a compound of formula (III or IV or V) obtained in step 2) with a compound of formula (VI) i the presence of an organic solvent at a temperature range from 0 to 30 °G to form a compound of formula (I).
  • Step 4) Purification to obtain pure of -final product.
  • inventions of the present invention relate to processes for preparing a compound according to formula (I) as a free base, acid, or salts thereof. -Further, the embodiments relate to any synthetic intermediates, which are useful in the synthesis of a compound of formula (I) as a free base, acid, or salts thereof.
  • Figure 1 Illustrate ⁇ ⁇ -NMR spectra of Chlorobis(4-chlorophenyl) (trichloromethyl)silane synthesized in Example 1 (compound 1).
  • FIG. 1 Illustrate 13 C-NMR spectra of Chlorobis(4-chlorophenyl) (trichloromefhyl)silane synthesized in Example 1 (compound 1).
  • Figure 3 Illustrate IR spectra of Chlorobis(4-chlorophenyl) (trichloromethyl)silane synthesized in Example 1 (compound 1).
  • Figure 4 Illustrate MS spectra of C h 1 orob i s ( 4- eh 1 orophen y 1 ) (trichloromethyl)silane synthesized in Example 1 (compound 1).
  • Figure 5 Illustrate a bioefficacy of insecticide Chlorobis(4-chlorophcnyl) (trichloromethyl)silane (compound 1).
  • Figure 6 Illustrate a residual efficacy of insecticide Chlorobis(4-chlorophenyl) (trichloromethyl )silane (compound 1).
  • Figure 7 Illustrate a bioefficacy of Chloro(ehloromethyl)bis(4- ch 1 or opheny 1 )s i lan e (compound 3).
  • Figure 8 Illustrate a biodegradation studies for Chlorobis (4- chlor opheny 1) (trichloromethyl)silane (compound 1).
  • Figure 9 Illustrate a biodegradation studies for l, l, l-Trichloro-2,2-bis(4- chIorophenyl)ethane, [commercial available DDT] .
  • the term 'salt thereof is intended to mean salts formed by the addition. of an acids, such as organic or inorganic acids, any suitable bases or hydrates and alcoholates.
  • the organic acid may be, but is not lim ited to, acetic, formic, propanoic, methane sulfonic, benzene sulfonic, lactic, malic, citric, tartaric, succinic or maleic acid.
  • the inorganic acid may be, but is not limited to, hydrochloric, hydrobromic, sulfuric, nitric acid or phosphoric acid.
  • the base may be but is not. limited to, ammonia and hydroxides of alkali, or alkaline earth metals.
  • 'halogen' refers to fluorine, chlorine, bromine, and iodine.
  • the present invention provides a novel silicon>-based compounds or salt thereof with the general formula ( ⁇ ):
  • Ri and R2 independently represent the halogen, hydrogen, alkyl, aikoxy or aryl group.
  • Ri and 3 ⁇ 4> represent chlorine, fluorine or meihoxy group.
  • R4, Rs and « represents chlorine or hydrogen atom.
  • Compound 2 Chiorobis(4-ehlorophenyl)(dichloromethyl)silane
  • Compound 6 Chlorobis(4-fiuorophenyj.)(chlororaethyl)silatie;
  • Compound 7 Chlorobis(4-m.e ioxyphenyi)(triehloro5nethyl)silane;
  • Compound 8 -Chiorobis(4-methoxyphenylXdichlorometJiyl)siiaii-e;
  • Compound 12 Clilorobis ⁇ 4-metl ?xyphefiyi)(metliyl)silafte;
  • Compound 14 Chloro(dichloromelhyl)di-p-tolylsilane.
  • inventions .of the present -invention.. relate to processes tor synthesis, of a compounds having general formula (I) as a tree base, acid, or salts thereof. Further, additionally, embodiments relate to synthetic intermediates, which are useful in the synthesis of a compounds of formula (I) as a free base, acid, or salts thereof.
  • Rr and 'Ra eac independently represents any of chlorine,- fluorine arid methoxy group
  • 3 ⁇ 4 ' represents any of chlorine and hydroxy! group
  • the acceptable salts of the compounds of the present invention include, for example, salts with hydrochloric acid, sulfuric acid, phosphoric acid, tartaric acid, methanesulfonic acid and the like are included. These salts can be formed by the usual known methods.
  • the compounds of the present inventio or its acceptable salts may form solvates (e.g., hydrates or the like) and/or crystal polymorphs.
  • the present invention encompasses those various solvates and crystal polymorphs.
  • “Solvates” may be those wherein any numbers of solvent molecules (e.g., water molecules or the like) are coordinated with the compounds of the present invention.
  • a generalize process steps for synthesis ' of novel silicon-based compounds having insectieidal properties as disclosed in present invention is exemplified below. Further, the technique of extraction, purification and/or crystallisation, which is performed in a normal experiment of organic chemistry may be conducted.
  • 'Ri' arid 'R 2 each independently represents any of chlorine, fluorine and methoxy group
  • 3 ⁇ 4' represents any of chlorine and hydroxy! group
  • Step 1) Chlormation of compound of formula (II) using of chlorine gas in the presence of UV light to give -mixture of ehloromethyl trichiorosilane, dichioromeihyl irichlorosilane. and Iriehloromethyl irichlorosiiane (Compounds of formula 111, T.V and V respectively).
  • Step 3 The reaction of specific chlorinated compound obtained in step 2, (compound of formula III, formula ' IV or form la V) with a Grignard reagent having general formula (VI) in the presence of an -organic solvent at a temperature range from 0 to 30 °C to obtain a compound of formula (I).
  • ⁇ R ' represents halogen, hydrogen, alky!. aikoxy or aryl group;
  • the Grignard reagent optionally he synthesized .in-sita lor this step, magnesium turning was taken in glass reactor and dry THF was added in it. To this refl xing suspension l-brotno-4-cWorobenzene was added with crystal of. -iodine. The reaction was stirred for 3 h.
  • Step 4) Purification by any suitable method.
  • the chlorinatio in step 1) is selected from any conventionally available method such as ehlorittaiion of methyl trichlorosilane using chlorine gas in the presence of UV light/visible light or addition of suitable chlorinating agents.
  • the reaction of step 1) is carried out for 0.5- 15 h between temperature range from 50 to 200 "C. i an. embodiment, of the process of the present invention, -the reaction of step 3 ⁇ is carried out for 0.5- 15 h.
  • a general method of the present invention i represented by the following representative scheme:
  • Step 3 Reaction with Grigna ' reagent
  • the present invention provides a compounds of general fommla (V) and. rocess of preparation thereof;
  • 3 ⁇ 4' represents chlorine or hydroxyl group.
  • the process for synthesis of compounds of general formula (V) comprising the following steps; Reaction of methyl trichlorosilane having formula (II) with Grignard reagent of formula (VI) in the presence of an organic solvent at a temperature range from 0 to 30 °C to form a compound of formula (V).
  • the general reaction is shown as follows.
  • the organic solvent is selected from any conventionally used organic solvent such as but not limiting to tetrahydrofuran, diethyl ether, dimethyl ether, isopropyl ether, toluene, and xylene.
  • the process for the preparation of the novel silicon- based compounds of formula (I) is carried out in a nitrogen or argon atmosphere.
  • the compounds of the present invention may be formulated as a powder, a granule, tablets, capsules, pills, a liquid and any suitable formulation thereof.
  • the effective doses of the present compounds may be mixed with excipients suitable for the dosage form, such as fillers, binders, disintegrators, and surfactants, as appropriate, to form stable preparations.
  • excipients suitable for the dosage form such as fillers, binders, disintegrators, and surfactants, as appropriate, to form stable preparations.
  • the novel silicon-based compounds of formula (I) also used in a method to treat or prevent pest or insect.
  • the formulation comprising any selected compound having general formula (I) and additives selected from any of the conventionally used additives, but not limiting to fillers, binders, disintegrators, and surfactants, pH modifying agents, thickening agents, viscosity modifying agents, surfactants and mixture thereof.
  • the compounds of the present invention can be used in combination with other agents/active agents or the like (hereinafter referred to as combination formulation) to increase the activity of the compounds, reduce the dose of the compounds, or the like.
  • Step 1 Chlorination: Chlorination reaction assembly was completely dried and flushed using nitrogen gas. 25 g of methyl trichlorosilane (formula II) was taken in a glass reactor. Chlorination of methyl trichlorosilane was conducted at temperature between 70 °C to 155 °C in the presence of ultraviolet/visible light by passing chlorine gas (40 ml min) which was dried by passing through sulphuric acid. The unreacted chlorine gas and generated hydrochloric acid gas were passed into empty scrubber and further neutralized in sodium hydroxide solution and then in water. The reaction was conducted for 3 to 15 h under reflux condition.
  • reaction mass consist of a mixture of chloromethyl trichlorosilane, dichloromethyl trichlorosilane and trichloromethyl trichlorosilane.
  • reaction temperature The effect of reaction temperature on the selectivity for chlorinated compounds shown in table 1.
  • the selectivity of the products were studies using HPLC analysis.
  • Step 2 Separation of chlorinated compounds: Separation of chloromethyl trichlorosilane, dichloromethyl trichlorosilane and trichloromethyl trichlorosilane from reaction mass was done by distillation at different temperatures. The fractions of distillate were collected in three moisture-free conical flasks in series which were cooled in an ice bath.
  • First collection was at 60 to 80 °C of unreacted methyl trichlorosilane, second collection was at 100-120 °C of chloromethyl trichlorosilane, third collection was at 140-155 °C of dichloromethyl trichlorosilane and remaining in the round bottom flask was white waxy solid of trichloromethyl trichlorosilane.
  • Step 3 Reaction assembly was completely dried and flushed using nitrogen to remove moisture. Schlenk technique was used for the moisture free reaction. Freshly dried tetrahydrofuran was placed in glass reactor and added chlorinated product (chloromethyl trichlorosilane, dichloromethyl trichlorosilane or trichloromethyl trichlorosilane).
  • chlorinated product chloromethyl trichlorosilane, dichloromethyl trichlorosilane or trichloromethyl trichlorosilane.
  • Grignard reagent was added drop wise via cannula through the addition funnel at temperature 0 °C under constant stirring. The molar ratio of chlorinated compound to Grignard reagent was 1 :2. After complete addition of Grignard reagent, the temperature of reaction mass was slowly increased up to 30 °C and kept constant for 0.5-15 h.
  • Step 4 Purification of the product: Ethyl acetate was added to the reaction mixture. White precipitate of magnesium salt was formed and separated by centrifuge. Ethyl acetate and THF was evaporated on a rotary evaporator. Yield and purity of different final products are given in table 2. The characterization data of final products is given in table 3.
  • Step 1 Reaction assembly was completely dried and flushed using nitrogen to remove moisture. Schlenk technique was used for the moisture free reaction. Freshly dried tetrahydrofuran was placed in glass reactor and added Methyltrichlorosilane. To this, 4-chlorophenyl magnesium bromide was added drop wise via cannula through the addition funnel at temperature 0 °C under constant stirring. The molar ratio of Methyltrichlorosilane to 4-chlorophenyl magnesium bromide was 1:2. After complete addition of 4-chlorophenyl magnesium bromide, the temperature of reaction mass was slowly increased up to 30 °C and kept constant for 0.5-15 h.
  • Step 2 Purification of the product: Ethyl acetate was added to the reaction mixture and solid magnesium salt was separated by centrifuge. Ethyl acetate was evaporated on a rotary evaporator. Yield-84 % and Purity-92 %.
  • IR 3024.76, 2961.47 and 2904.16 cm “1 (Aromatic C-H), 1643.76, 1578.93 and 1484.29 (Si-Ph), 1078.62 and 1015.04 cm “1 (Si-CH3), 785.56 cm “1 (Aliphatic C-Cl stretching), 651.98 cm “1 (Si-Cl).
  • WHO cone bioassay method The test solutions of different concentration were prepared in THF (0.05 % w/w, 0.10 % w/w and 0.20 % w/w) and sprayed on the surface (Cement surface) and air dried.
  • Two mosquitoes species namely A nopheles stephensi and Anopheles Culicifacies, (laboratory bread susceptible, nonblood feed) of aged 2-5 days old were introduced into WHO plastic cone ( 12 cm diameter) placed surface treated with active agent (10 mosquitoes for each bioassay/cone).
  • Mosquitoes were exposed for 30 min on the every treated surfaces and observed knockdown at 5 minutes interval up to 30 minutes.
  • the mosquitoes were transferred to 150 ml plastic cup having 10 % sugar/sucrose solution. The plastic cup was placed in room maintained at standard temperature 27 °C ⁇ 2 °C and relative humidity of 80 % ⁇ 10 % RH. Percent mortality were calculated after 24 h.
  • a) % Mortality The results are depicted in figure 7. It shows that 20 % mortality was found for 0.05 % w/w of the test compound after 24 h. When 0.10 % w/w compound was sprayed, then up to 30 min mortality was 20 % and up to 24 h mortality was 50 %. For 0.20 % w/w of the test compound, mortality at 20 min, 25 min, 30 min and 24 h was 10 %, 30 %, 60 % and
  • Example 4 Evaluation and comparison for decomposition rate of synthesized compound chlorobis(4-chlorophenyl)(trichloromethyl)silane (silicon isosteres of DDT) as per present invention and l,l,l-Trichloro-2,2-bis(4- chlorophenyl)ethane (DDT).
  • Soil treatment The red lateritic soil was taken from Institute of Chemical Technology, Mumbai, India, garden and dried it in the oven at 100 °C. Then dry soil was sieved through the mesh having size 710 nm for soil uniformity. The organic impurities (if any) were removed by washing 500 g soil with 700 ml acetone (first wash), again washing the soil with 150 ml acetone (second wash) and dried in an oven at 55 °C. Then this soil was washed with 1 L distilled water, dried it and finally washed with a 0. 1 M acetate buffer solution of pH 4.6 and dried at 55 °C and measuring the pH 7.8 which was earlier 8.5. Sieve the soil through 710 nm sieve.
  • This soil was used for degradation study of DDT and silicon isostere of DDT.
  • ii) Preparation of contaminated soil and enzyme loading Initially, the soil was autoclaved for 1 h in an autoclave and then used for the study. In the volumetric flask, the test compound (0.5 g) was dissolved in 100 ml acetone. For each study, 10 ml test compound solution was used from the volumetric flask. 100 g of soil was taken in the conical flask from prepared autoclaved soil and contaminated it with 10 ml test compound solution, mixed it properly and air dried 3h to evaporate acetone from the soil.
  • Sample name i) Control isostere biodegradation (CIB), ii) Enzymatic isostere biodegradation (EID), iii) Control DDT biodegradation (CDB) and iv) Enzymatic DDT biodegradation (EDB).
  • Pesticide Amount (g) 0.05 0.05 0.05 0.05 0.05 0.05

Landscapes

  • 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)

Abstract

La présente invention concerne de nouveaux composés à base de silicium ou un sel de ceux-ci de formule générale (I), dans laquelle R1 et R2 représentent l'atome d'halogène, d'hydrogène, le groupe alkyle, alcoxy ou aryle et R3, R4, R5 et R6 représentent l'atome de chlore ou d'hydrogène ou un groupe hydroxyle. Lesdits composés sont des insecticides actifs biodégradables. L'invention concerne également un procédé de fabrication desdits composés, et des compositions pharmaceutiques les contenant et leur utilisation.
PCT/IN2018/050050 2017-02-02 2018-02-01 Nouveaux insecticides écologiques à base de composés de silicium et leur procédé de préparation WO2018142423A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201721003943 2017-02-02
IN201721003943 2017-02-02

Publications (1)

Publication Number Publication Date
WO2018142423A1 true WO2018142423A1 (fr) 2018-08-09

Family

ID=63039423

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2018/050050 WO2018142423A1 (fr) 2017-02-02 2018-02-01 Nouveaux insecticides écologiques à base de composés de silicium et leur procédé de préparation

Country Status (1)

Country Link
WO (1) WO2018142423A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2561178A (en) * 1949-07-28 1951-07-17 Gen Electric Organopolysiloxanes
GB1002129A (en) * 1961-03-20 1965-08-25 Ici Ltd Organosilicon compounds containing phosphorous
US4921976A (en) * 1987-11-18 1990-05-01 Toshiba Silicone Co., Ltd. Vinyl-containing unsaturated organosilicon compound and process for preparing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2561178A (en) * 1949-07-28 1951-07-17 Gen Electric Organopolysiloxanes
GB1002129A (en) * 1961-03-20 1965-08-25 Ici Ltd Organosilicon compounds containing phosphorous
US4921976A (en) * 1987-11-18 1990-05-01 Toshiba Silicone Co., Ltd. Vinyl-containing unsaturated organosilicon compound and process for preparing the same

Similar Documents

Publication Publication Date Title
KR930007992B1 (ko) 치환된 실릴기를 갖는 신규 에테르 화합물의 제조방법
PL112140B1 (en) Insecticide
CZ124894A3 (en) Phenylhydrazine derivatives, a pesticidal agent containing such compounds and method of controlling undesired insects
CN104693035B (zh) 水杨酸类反‑(β)‑法尼烯类似物及其应用
CN112457288B (zh) 一种胡椒酸衍生物及其应用
CN107474021B (zh) 噁二嗪衍生物及其制备方法和应用
WO2018142423A1 (fr) Nouveaux insecticides écologiques à base de composés de silicium et leur procédé de préparation
CN102134195A (zh) 可用于杀虫的酯化合物
AU657214B2 (en) New derivatives of 7-ethynyl alpha-(methoxymethylene) 1-naphthalene acetic acid, their preparation process and their use as pesticides
CN108250156A (zh) 一种肉桂酸噁二嗪衍生物及其制备方法和应用
JPH07103079B2 (ja) パラアリールオキシアラルキルアミン誘導体および殺虫・殺ダニ剤
JPH05271170A (ja) アミド化合物並びにそれを用いた害虫忌避剤及び害虫駆除剤
USRE22597E (en) Parasiticida
CN114478667B (zh) 4”,23-氧醚基取代的阿维菌素B2a/B2b衍生物及其制备方法和应用
KR20090024394A (ko) 새로운 불소함유 페닐포름아미딘 유도체 및 살충제로서 이의 용도
JPS58121246A (ja) 置換ベンジルエステル及びこれを有効成分とする殺虫剤
US3433826A (en) Alkoxyphenyl-n-methyl carbamic acid ester
TW382623B (en) Pesticide compounds, compositions and the preparation
JP2023099930A (ja) アザレアコナカイガラムシ及びカイガラムシ類の寄生蜂の誘引物質
Whittaker AN INVESTIGATION OF REACTIONS DIRECTED TOWARDS"': fHE SYNTHESIS OF 2-METHYL-2-(METHYLTHIO) PROPANAL OXIME
JPS58154592A (ja) 有機リン酸エステル誘導体及びそれを含む殺虫、殺ダニ剤
JPH0239481B2 (fr)
JPS5967210A (ja) 線虫防除剤
CN108003054A (zh) 一种含二苯醚的菊酰胺化合物及其制备方法与应用
NO115321B (fr)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18747664

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18747664

Country of ref document: EP

Kind code of ref document: A1