WO2004087667A1 - Ester derivatives of (pyridinyloxy-phenyl)-methanol and process of preparation thereof - Google Patents

Ester derivatives of (pyridinyloxy-phenyl)-methanol and process of preparation thereof Download PDF

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WO2004087667A1
WO2004087667A1 PCT/IN2003/000114 IN0300114W WO2004087667A1 WO 2004087667 A1 WO2004087667 A1 WO 2004087667A1 IN 0300114 W IN0300114 W IN 0300114W WO 2004087667 A1 WO2004087667 A1 WO 2004087667A1
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pyridyloxy
compound
trichloro
benzene
tetrachloro
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PCT/IN2003/000114
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French (fr)
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Bommena Vittal Rao
Manjula Alla
Ramesh Chilukuri
Jyothsna Bandari
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Council Of Scientific And Industrial Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4

Definitions

  • the present invention relates to novel pyridinyloxy phenyl methanol derivatives, viz.,
  • the present invention also relates to a process for the preparation of new pyridinyloxy phenyl methanol esters specifically 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and/or 4-/3 -(2,3, 5,6- pyridinyl-4-oxy)phenylmethanol derivatives as potential crop protection chemicals.
  • Oshumi (T. Ohsumi, M. Hirano, N. Itaya, Y. Fujitha, Pestic. Sci., 12 (1981) 53) utilised pyrrole derivatives as alcohol moiety for synthesizing the novel pyrethroids.
  • Thomas P. Selby (ACS symposium series 355, synthesis and chemistry of agrochemicals: Page 162-172, ACS washington.DC.1987) reported the synthesis of heterocyclic pyrethroids by condensing methyl phenyl substituted pyrazoles with DV acid chloride and t ey were found to be more active than permethrin against musca domestica.
  • S. K. Malhotra S. K. Malhotra, J. C. VanHeertum, L.L. Larson & M. J. Ricks, J. Agric.
  • a new pyrethroid alcohol close congener and isomeric to the phenoxypyridinyl benzene methanol (Dowco-417) was prepared and utilised for the preparation of novel pyrethroid esters.
  • the new pyrethroid alcohols are 4-/3-(3,5,6- trichloropyridyl-2-oxy) phenylmethanol, 4-/3-(2,3,5,6-pyridinyl-4-oxy) phenylmethanol.
  • the main object of the invention is to provide novel pyridinyloxy phenyl methanol esters, viz., 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and 4-/3-(2,3,5,6-pyridinyl- 4-oxy)phenylmethanol esters useful as crop protection chemicals. It is another object of the invention to provide a process for the preparation of new pyridinyloxy phenyl methanol esters specifically 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and/or 4-/3-(2,3,5,6-pyridinyl-4-oxy)phenylmethanol esters which are useful as crop protection chemicals. Summary of the invention Accordingly, the present invention provides a pyridinyloxy phenyl methanol derivative of formula III
  • R is acid chloride residue, DV acid, ⁇ -isopropyl(4-chlorophenyl) acetic acid, ⁇ - isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl.
  • the compounds of the invention are selected from 4-(3,5,6-trichloro-2- pyridyloxy)benzaldehyde; 3-(3,5,6-trichloro-2-pyridyloxy)benzaldehyde; 4-(3,5,6-trichloro- 2-pridyloxy)phenyl methanol; - 3-(3,5,6-trichloro-2-pyridyloxy)phenyl methanol; l- ⁇ 3-[2- chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethylcyclopropylcarbonyloxy methyl ⁇ -4- (3,5,6-trichloro-2-pyridyloxy)benzene; l- ⁇ 3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2- dimethyl cyclopropylcarbonyloxymethyl ⁇ -3 -(3 , 5, 6-trichloro-2-pyri
  • X is selected from the group consisting of
  • the present invention also provides a process for the preparation of pyridinyloxy phenylmethanol esters of formula III
  • R is acid chloride residue, DV acid, ⁇ -isopropyl(4-chlorophenyl) acetic acid, ⁇ - isopropyl(4-dif ⁇ ouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by condensing hydroxy benzaldehyde followed by reduction.
  • the present invention also relates to a process for preparation of a compound of formula III
  • R is acid chloride residue, DV acid, ⁇ -isopropyl(4-chlorophenyl) acetic acid, ⁇ - isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by reacting hydroxy phenyl methanol directly with a halopyridine.
  • the present invention envisaged as a process for synthesis of a new molecule(s) involving 4-/3 -(3,5,6- trichloropyridyl-2-oxy) phenylmethanol and 4-/3-(2,3,5,6-pyridinyl-4-oxy)phenylmethanols, which in turn is reacted with acid chloride derived from a well established and commercially proven pyrethroid ester in a single step.
  • the final product, the hitherto unknown/ unreported novel pyrethroid esters is in the pure form, the critical criteria for considering it in biological screening program.
  • the pyridinyloxy phenyl methanol derivatives have been prepared according to the literature methods either by condensing hydroxy benzaldehyde followed by reduction or hydroxy phenyl methanol directly with halopyridines. (Gui-Dong Zhu, Verlyn Schaefer, Steven A. Boyd and Gregory F. Okasinki. J.Org.chem.67 (2002) 943). Synthesis of acid chloride was carried out according to the procedure of Farkas etal (Farkas, J.; Kourim. P.; Sorm. F. Chem.
  • the prehminary activities of the compounds synthesized have shown very good activity against Musca domestica (Insecticidal) and also anti bacterial activity.
  • Musca domestica Insecticidal
  • anti bacterial activity The various aspects of the present invention are illustrated in more detail in the following examples.
  • Example 2 Preparation of 3-(3,5,6-trichIoro-2-pyridyIoxy)benzaldehyde: A uniform mixture of 10.496 g (0.048 M) of 2,3,5,6- tetrachloropyridine, 2.0 g (0.016 M) of 3-hydroxy benzaldehyde, 1.32 g of potassium carbonate, 0.04 g of cupr ⁇ us 0.04g of 8-hydroxyquinoline and 20 ml of N-methyl pyrolidinone was taken in a round bottom flask and heated under reflux for 15 h under dry conditions. The progress of the reaction was monitored by TLC. Afterwards from the reaction mixture solvent was distilled off under vacuum and poured into water and extracted with chloroform.
  • Example 4 Preparation of 3-(3,5,6-trichloro-2-pridyloxy)phenyl methanol 3-(3,5,6-trichloro-2-pridyloxy)benzaldehyde 0.768 g (0.0025 M) was dissolved in a mixture of benzene (15 ml) and 1.5 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride). To this stirred mixture was added 0.153 g (0.0041 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC.
  • Example 5 Preparation of l- ⁇ 3-[2-chIoro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl cy opropyIcarbonylo_:ymethyl ⁇ -4-(3,5,!_-trichIoro-2-pyridylo_;y)benzene To a precooled solution of 4-(3,5,6-trichloro-2-pridyloxy)phenyl methanol 0.650 g
  • the crude product was purified by column chromatography on silica gel finer than 200 mesh using hexane as eluent.
  • the pure product was obtained as viscous oil in (0.780 g) 74 % yield.
  • the proton NMR spectrum of the ester shows
  • the crude product was purified by column chromatography on silica gel (finer than 200 mesh) using hexane as eluent.
  • the pure product was obtained as viscous oil in (0.70 g) 78.7 % yield.
  • the proton NMR spectrum of the ester shows following pattern.
  • Example 9 Preparation of l-[3-(2 9 2-dichlorovinyl)-2,2-dimethylcyclopropykarbonyIo_:y methyl]-4-(3,5,6-trich!oro-2-pyridyloxy)benzene
  • 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled.
  • a precooled solution of acid chloride 0.227 g (0.001 M) was added dropwise to this mixture while stirring, over a period of 15 min.
  • a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h.
  • the reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo.
  • the crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain (0.245 g), 50 % of the ester as an oil.
  • Example IS Preparation of 4-(2,3,5 5 6-trichloro-4-pridyloxy)phenyl methanol
  • Aldehyde 1.21 g (0.0035 M) was dissolved in a mixture of benzene (24 ml) and 2.4 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride).
  • To this stirred mixture was added 0.242 g (0.0065 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC.
  • the reaction mixture was then quenched by addition of water (50 ml) and neutralized to pH 7 by addition 5% HCl.
  • Example 17 Preparation of l- ⁇ 3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl eyclopropylcarbonyloxymethyl ⁇ -4-(2,3,5,6-tetrachIoro-4-pyridyloxy)benzene
  • Example 18 Preparation of l- ⁇ 3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl cyclopropylcarbony!oxymethyl ⁇ -3-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
  • Example 21 Preparation of l-[3-(2,2-dichIorovinyI)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
  • 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled.
  • a precooled solution of acid chloride 0.227 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min.
  • a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h.
  • the reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain 45 % of the ester.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

The present invention relates to novel pyridinyloxy phenyl methanol derivatives of the formula (III) with X=(a) or (b), obtained by the reaction of 4-/3-(3,5,6-pyridinyl-2-oxy)phenylmethanol and 4-/3-(2,3,5,6-pyridinyl-4-oxy)phenyl methanol with the acid chloride.

Description

ESTER DERIVATIVES OF (PYRIDINYLOXY-PHENYL ) -METHANOL AND PROCESS OF PREPARATION THEREOF
Field of the invention The present invention relates to novel pyridinyloxy phenyl methanol derivatives, viz.,
4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol derivatives and 4-/3-(2,3,5,6-pyridiιτyl- 4-oxy)phenylmethanol derivatives useful as crop protection chemicals. The present invention also relates to a process for the preparation of new pyridinyloxy phenyl methanol esters specifically 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and/or 4-/3 -(2,3, 5,6- pyridinyl-4-oxy)phenylmethanol derivatives as potential crop protection chemicals. Background of the invention
During the past decade or so the synthetic pyrethroids, (3-ρhenoxy methyl esters or (RS)-α-cyano-3-phenoxy benzyl esters) by the virtue of their high degree of insecticidal activity, rapid knock down properties and low mammalian toxicity, generated great excitement and have become the subject of much synthetic effort.
In recent past some of the pyrethroids having heterocycles as alcohol moiety have shown high degree of insecticidal activity with great degree of persistence in the field conditions. Earliest recorded nitrogen containing pyrethroid being tetrmethrin (T. Kato, K. Ueda and K. Fujimoto, Agri. Biol. Chem. 28 (1964) 914) wherein the alcohol compound is N- (3,4,5,6-tetrahydro-phthalimido) methyl alcohol. Masachika Hirano (M. Hirano, N. Itaya, T. Ohno, Y. Fujitha and Y.Hosioka, Pestic. Sci., 10 (1979) 291) reported pyrethroid type esters of substituted l-(3)-hydroxymethyl imidazolidin-2, 4-diones, which have knock down activity against insects.
Oshumi (T. Ohsumi, M. Hirano, N. Itaya, Y. Fujitha, Pestic. Sci., 12 (1981) 53) utilised pyrrole derivatives as alcohol moiety for synthesizing the novel pyrethroids. Of them 3 -benzyl pyrrol- 1-ylmethyl-cis, trans-3- (2,2-dichlorovinyl)-2, 2-dimethyl cyclopropane carboxylate, was found to be more active than permethrin against musca domestica.
Thomas P. Selby (ACS symposium series 355, synthesis and chemistry of agrochemicals: Page 162-172, ACS washington.DC.1987) reported the synthesis of heterocyclic pyrethroids by condensing methyl phenyl substituted pyrazoles with DV acid chloride and t ey were found to be more active than permethrin against musca domestica. S. K. Malhotra (S. K. Malhotra, J. C. VanHeertum, L.L. Larson & M. J. Ricks, J. Agric. Food Chem., 29 (1981) 1289) of Dow Chemical Company (USA) has come out with a new and extremely important generation of pyrethroid insecticides with low mammalian toxicity and other advantages over conventional insecticide by incorporating pyridoxy ring on to cyano-6- phenoxy-2-pyridinyl)methyl-3-(2,2-dichloroethenyl)-2,2-dimethyl cyclopropane carboxylate (Dowco-417). Dowco-417 is a highly active against important foliar pests especially sucking insects and because of its lower application rates, plants don't show any foliar injury, thus resulting in higher crop yields. Dowco-417, with it's rapid breakdown in the environment; has the little risk of environmental contamination. The efficacy of the compound with phenoxy pyridine as the new alcohol component prompted us to look for alternative isomeric congeners.
2-pyridinyloxy benzene derivatives (R. Hermann EP 24259 (1981), A. Mashiro, S. Junichi, Y. Kazuomi, K. Shinzo, K. Atsumi, Y. Naoko, EP 57,367 (1982)) have shown good herbicidal property and are the compounds of much synthetic effort in the last decade. 3,5,6- trichloropyridin-2-ol is the basic unit in the commercially important pesticide chlorpyriphos and trichlopyr. It is these points that prompted us to explore the biological potential of new pyridinyloxy phenylmethanol heterocyclic moiety by incorporating into known pyrethroid skeleton. The approach of imitating compounds with known biological activity has found major market outlet, is increasingly being used as a means of generating new products for crop protection. This has encouraged us to explore the potential of hitherto unreported pyridinyloxy phenyl methanol(s) as a new pyrethroid alcohol, as a close congener of meta- phenoxybenzyl alcohol, phenoxypyridinyl carbinol, by condensing with commercially well- established pyrethroid ester acid components like fenevalerate, flucythrinate, cypermethrin, lamda cyhalothrin, deltamethrin etc. 2,3,5,6-tetra chloropyridine (Perettie Donald' J, Dean Norman L,US patent 4281135(1981) is useful as herbicide.
Most commercially valuable products generally related to esters derived from meta phenoxybenzyl alcohol, or some close congener their of, with that of acid chloride residue derived from either DV acidchloride and p- substituted phenyl isovaleric acid such as cypermethrin (M. Eliott, A. W. Farnaham, N. F. Janes, P. H. Needham, D. A. Pulman, Nature, 248(1974) 710), cyhalothrin, fenvalerate, (NL Ohno, K. Fujimoto, Y. okuno, T. Mizutani, ϊvI.Hirano, N.Itaya, T. Honda & H.yoshioka, Pest. Sci., 7 (1976) 241, flucythrinate, deltamethrin (M. Elliott & N. F. Janes, Chem Soc. Reviews, 7 (1978) 437; Pest. Sci. 11(1980) 119), phenothrin, (K. Fujimoto, N. Itaya, Y. Okuno, T. Yamanguchi, Agri. Biol. Chem, 28 (1964) 914), permethrin (M. EUiott, A. W. Farnham, N. F. Janes, P. H. Needham, D. A. Pulman, J. H. Stevenson 246, (1974) 710) etc.
Of late, many compounds have been prepared and patented which are derived from other than usual m-phenoxy benzylalcohol etc., but from other structurally similar analogues with a view to enhance the bio-efficacy and stability of the novel pyrethroids generated. 6- Phenoxy picolinaldehydecyanohydrin, 3-phenyl-2-methyl benzyl alcohol, methyl phenyl substituted pyrazole methanol, are some of the new alcoholic moieties used to generate the novel pyrethroid esters and prepared so, were shown to possess high degree of insecticidal activity. Encouraged by these developments, a new pyrethroid alcohol, close congener and isomeric to the phenoxypyridinyl benzene methanol (Dowco-417) was prepared and utilised for the preparation of novel pyrethroid esters. The new pyrethroid alcohols are 4-/3-(3,5,6- trichloropyridyl-2-oxy) phenylmethanol, 4-/3-(2,3,5,6-pyridinyl-4-oxy) phenylmethanol. As a major goal of our research for the discovery and development of potent and biologically active agents, the new pyridinyloxy phenyl methanol derivatives (pyrethroid esters) could possibly provide a new alternative source for protection of plants, animals and human beings. Objects of the invention
The main object of the invention is to provide novel pyridinyloxy phenyl methanol esters, viz., 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and 4-/3-(2,3,5,6-pyridinyl- 4-oxy)phenylmethanol esters useful as crop protection chemicals. It is another object of the invention to provide a process for the preparation of new pyridinyloxy phenyl methanol esters specifically 4-/3-(3,5,6-trichloropyridyl-2-oxy) phenyl methanol and/or 4-/3-(2,3,5,6-pyridinyl-4-oxy)phenylmethanol esters which are useful as crop protection chemicals. Summary of the invention Accordingly, the present invention provides a pyridinyloxy phenyl methanol derivative of formula III
Figure imgf000004_0001
wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α- isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl.
The compounds of the invention are selected from 4-(3,5,6-trichloro-2- pyridyloxy)benzaldehyde; 3-(3,5,6-trichloro-2-pyridyloxy)benzaldehyde; 4-(3,5,6-trichloro- 2-pridyloxy)phenyl methanol; - 3-(3,5,6-trichloro-2-pyridyloxy)phenyl methanol; l-{3-[2- chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethylcyclopropylcarbonyloxy methyl}-4- (3,5,6-trichloro-2-pyridyloxy)benzene; l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2- dimethyl cyclopropylcarbonyloxymethyl} -3 -(3 , 5, 6-trichloro-2-pyridyloxy)benzene; 4-(3 , 5 , 6- trichloro-2-pyridyloxy)benzyl 2-(4-chlorophenyl)-3 -methylbutanoate; 1 -[3 -(2,2- dichlorovinyl)-2, 2-dimethyl cyclopropylcarbonyloxymethyl] -4-(3 , 5, 6-trichloro-2- pyridyloxy)benzene; l-[3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl] - 3 -(3 , 5, 6-trichloro-2-pyridyloxy)benzene; 1 -[3 -(2,2-dibromovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl] -4-(3,5,6-trichloro-2-pyridyloxy)benzene; l-[3-(2,2- dibromovinyl)-2,2-dimethylcyclopropylcarbonyloxy methyl] -3-(3,5,6-trichloro-2- pyridyloxy)benzene; 4-(2,3,5,6-tetrachloro-4-pyridyloxy) benzaldehyde; 3-(2,3,5,6- tetrachloro-4-pyridyloxy) benzaldehyde; 4-(2,3,5,6-trichloro-4-pyridyloxy)phenyl methanol; 3-(2,3,5,6-trichloro-4-pyridyloxy)phenyl methanol; l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l- propenyl]-2,2-dimethylcyclopropylcarbonyloxymethyl}-4-(2,3,5,6-tetrachloro-4-pyridyloxy) benzene; l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2- dimethylcyclopropylcarbonyloxymethyl } -3 -(2,3 , 5 , 6-tetrachloro-4-pyridyloxy) benzene; 4- (2,3,5,6-tetrachloro-4-pyridyloxy)benzyl 2-(4-chlorophenyl)-3-methylbutanoate; 4-(2,3,5,6- tetrachloro-4-pyridyloxy)benzyl-2-(4-diflouromethyl phenyl)-3 -methylbutanoate; l-[3-(2,2- dichlorovinyl)-2, 2-dimethylcy clopropylcarbonyloxy methyl] -4-(2, 3 , 5 , 6-tetrachloro-4- pyridyloxy)benzene; l-[3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropylcarbonyloxymethyl]- 4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene; l-[3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene; l-[3-(2,2- dibromovinyl)-2,2-dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4- pyridyloxy)benzene; 4-(3 , 5, 6-trichloro-2-pyridyloxy)benzyl 2-(4-diflouromethylphenyl)-3 - methylbutanoate.
In one embodiment of the invention, X is selected from the group consisting of
Figure imgf000005_0001
The present invention also provides a process for the preparation of pyridinyloxy phenylmethanol esters of formula III
Figure imgf000006_0001
III wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α- isopropyl(4-difϊouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by condensing hydroxy benzaldehyde followed by reduction.
The present invention also relates to a process for preparation of a compound of formula III
Figure imgf000006_0002
wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α- isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by reacting hydroxy phenyl methanol directly with a halopyridine. Detailed description of the invention
In view of the growing importance for new molecules which could potentially provide new alternate protective agents, a synthetic strategy has been designed wherein a new molecule are synthesized and are evaluated for their bio-efficacy. The present invention envisaged as a process for synthesis of a new molecule(s) involving 4-/3 -(3,5,6- trichloropyridyl-2-oxy) phenylmethanol and 4-/3-(2,3,5,6-pyridinyl-4-oxy)phenylmethanols, which in turn is reacted with acid chloride derived from a well established and commercially proven pyrethroid ester in a single step.
The final product, the hitherto unknown/ unreported novel pyrethroid esters is in the pure form, the critical criteria for considering it in biological screening program. The pyridinyloxy phenyl methanol derivatives have been prepared according to the literature methods either by condensing hydroxy benzaldehyde followed by reduction or hydroxy phenyl methanol directly with halopyridines. (Gui-Dong Zhu, Verlyn Schaefer, Steven A. Boyd and Gregory F. Okasinki. J.Org.chem.67 (2002) 943). Synthesis of acid chloride was carried out according to the procedure of Farkas etal (Farkas, J.; Kourim. P.; Sorm. F. Chem. Listy 52(1958), 699.The relative and absolute sterochemistry about the cyclopropane ring influences both the level and spectrum of activity exhibited by these compounds. It is very well known that cis diasteromers are more active than the trans and the component of the racemate of R configuration at the carboxyl stereo centre is the more active. Accordingly DV acid chloride used was a single resolved isomer (IR-Cis -Acid) and as a consequence the corresponding esters are single isomers only and in case of esterification with fluorinated acid, only one isomer was obtained and no trace of other diastereomer. The reaction mechanism of the process of the invention is given below:
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000008_0001
Figure imgf000008_0002
The prehminary activities of the compounds synthesized have shown very good activity against Musca domestica (Insecticidal) and also anti bacterial activity. The various aspects of the present invention are illustrated in more detail in the following examples.
These examples should not be construed as hmiting the scope of the invention in any manner.
Example 1: Preparation of 4-(3,5,6-trichloro-2-pyridyIoxy)benzaldehyde:
A uniform mixture of 10.496 g (0.048 M) of 2,3,5,6- tetrachloropyridine, 2.0 g (0.016 M) of 4-hydroxy benzaldehyde, 1.32 g of potassium carbonate, 0.04 g of cuprous chloride, 0.04g of 8-hydroxyquinoline and 20 ml of N-methyl pyrolidinone was taken in a round bottom flask and heated under reflux for 15 h under dry conditions. The progress of the reaction was monitored by TLC. Afterwards the reaction mixture was extracted, poured into water and extracted with chloroform. The combined extracts were washed with water and dried over sodium sulfate (anhydrous). The organic layer was then concentrated under vacuum and crude product was chromatographed (silica gel, hexane) to get the pure product (2.6 g) 54 % yield. Solid product has melting point 123.7 °C. The spectral data for the compound is 2 H NMR (200 MHz, CDC13): 7.2 (d, 2H); 7.8 (s, IH); 8.0 (d, 2H); 10 (s, 1H); _R (KBr, cm'l): 1420,1710; Mass (m/z) 303.
Example 2: Preparation of 3-(3,5,6-trichIoro-2-pyridyIoxy)benzaldehyde: A uniform mixture of 10.496 g (0.048 M) of 2,3,5,6- tetrachloropyridine, 2.0 g (0.016 M) of 3-hydroxy benzaldehyde, 1.32 g of potassium carbonate, 0.04 g of cuprσus 0.04g of 8-hydroxyquinoline and 20 ml of N-methyl pyrolidinone was taken in a round bottom flask and heated under reflux for 15 h under dry conditions. The progress of the reaction was monitored by TLC. Afterwards from the reaction mixture solvent was distilled off under vacuum and poured into water and extracted with chloroform. The combined extracts were washed with water and dried over anhydrous sodium sulfate. The organic layer was then concentrated under vacuum and crude product was chromatographed (silica gel, hexane) to get the pure product (4.0 g) 83 % yield. Solid product has melting point 141.8 °C. The spectral data for the compound is * H NMR (200 MHz, CDC13): 7.2-7.8 (m, 4H); 8.0 (s, IH); 10 (s, IH); IR (KBr, cm"l): 1410, 1720; Mass (m/z) 303.
Example s: Preparation of 4-(3,5,6-trichloro-2-pridyloxy)phenyl methanol
4-(3,5,6-trichloro-2-pridyloxy)benzaldehyde 0.913 g (0.0030 M) was dissolved in a mixture of benzene (20 ml) and 2 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride). To this stirred mixture was added 0.182 g (0.0048 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC. The reaction mixture was then quenched by addition of water (50 ml) and then neutralized to pH 7 by addition 5% aq. HC1. The layers were separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The pure phenyl methanol was obtained in (0.724 g) 81 % yield. The product has melting point 122.8 °C. The spectral data for the alcohol is: 1 H NMR (200 MHz, CDC13): 4.7 (s, 2H); 7.0-7.2 (d, 2H); 7.3-7.5 (d, 2H); 7.8 (s, IH); IR (KBr, cm"l): 3200, 1420; Mass (m/z) 305. . Example 4: Preparation of 3-(3,5,6-trichloro-2-pridyloxy)phenyl methanol 3-(3,5,6-trichloro-2-pridyloxy)benzaldehyde 0.768 g (0.0025 M) was dissolved in a mixture of benzene (15 ml) and 1.5 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride). To this stirred mixture was added 0.153 g (0.0041 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC. The reaction mixture was then quenched by addition of water (50 ml) and neutralized to pH 7 by addition aq. 5% HC1. The layers were separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The pure product was obtained in (0.616 g) 79.6 % yield. Crystallisine solid product has melting point 108.3 °C The data for the alcohol is ! H δ NMR (200 MHz, CDC13): 4.7 (2H, s); 7.0-7.6 (m, 4H); 7.8 (s, IH); IR (KBr, cml): 3200,
1410; Mass (m/z) 305.
Example 5: Preparation of l-{3-[2-chIoro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl cy opropyIcarbonylo_:ymethyl}-4-(3,5,!_-trichIoro-2-pyridylo_;y)benzene To a precooled solution of 4-(3,5,6-trichloro-2-pridyloxy)phenyl methanol 0.650 g
(0.0021M) in benzene taken in a round bottom flask fitted with guard tube and condenser, 0.497 g (0.0019 M) of precooled solution of the acid chloride in dry benzene (2 ml) was added to the reaction mixture over a period of 15 min. Subsequently 3 drops of pyridine was added and the reaction mixture was allowed to warm up to 15-20 °C and maintained at that temperature for 18h. At the end of that period the reaction mixture was quenched by addition of water, after the layer separation aqueous layer extracted with benzene. The combined organic layers were washed with 5% sodium bicarbonate, water, dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography on silica gel finer than 200 mesh using hexane as eluent. The pure product was obtained as viscous oil in (0.780 g) 74 % yield. The proton NMR spectrum of the ester shows
1 H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, IH); 2.2 (t, IH); 5.1 (s, 2H); 6.8-7.0 (d, IH); 7.0-7.2 (d, 2H); 7.3-7.5 (d, 2H); 7.8 (s, IH); IR (KBr, cm l): 3090, 2990, 1720, 1400, 1280, 1190, 980, 810; Mass (m/z) 493. Example 6: Preparation of l-{3-[2-chIoro-3,3,3-trifluoro-(Z)-l-propenyI]-2,2-dimethyl cyclopropyIcarbonyloxymethyl}-3-(3,5,6-trichIoro-2-pyridyloxy)benzene
To a precooled solution of 3-(3,5,6-trichloro-2-pyridyloxy)phenyl methanol 0.550 g (0.0018 M) taken in a round bottom flask fitted with guard tube and condenser; 0.420 g (0.0016 M) of precooled solution of the acid chloride in dry benzene was added to the reaction mixture over a period of 15 min. Next 3 drops of pyridine was added and the reaction mixture was allowed to warm up to 15-20 °C and maintained at that temperature for 18h. The reaction mixture was quenched by addition of water, layers separated and then extracted with benzene. The combined organic layers were washed with 5% sodium bicarbonate, water, dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography on silica gel (finer than 200 mesh) using hexane as eluent. The pure product was obtained as viscous oil in (0.70 g) 78.7 % yield. The proton NMR spectrum of the ester shows following pattern. x H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, IH); 2.2 (t, IH); 5.1 (s, 2H); 6.9 (d, IH); 7.0-7.4 (m, 4H); 7.8 (s, IH); IR (KBr, cml): 3090, 2995, 1720, 1550, 1290, 1190, 950, 870; Mass (m/z) 493. Example 7: Preparation of 4-(3,5,6-trichloro-2-pyridyIoxy)benzyl 2-(4-chIorophenyl)-3- methylbutanoate
0.8715g (0.0028 M) of 4-(3,5,6-trichloro-2-ρyridyloxy)phenyl methanol was dissolved in dry dichloroethane and cooled in ice. To this cooled solution was added a precooled solution of the 3-(4-chlorophenyl)-4-methylρentanoyl chloride 0.577 g (0.0025 M) in dichloroethane, dropwise over a period of 15 min., followed by the addition of 3 -drops of pyridine. The reaction mixture was allowed to warm-up to room temperature and maintained at that temperature for 18h. The reaction mixture was quenched with water. After the layer separation the aqueous layer was extracted with dichloroethane and the combined organic layers were washed with 5% sodium bicarbonate, followed by water and dried over anhydrous sodium sulfate. The solvent removed under reduced pressure to get crude ester, which was purified by column chromatography. The 4-(3,5,6-trichloro-2-ρyridyloxy)benzyl 2-(4-chlorophenyl)-3-methylbutanoate was obtained in 47.5% yield (0.688 g). The proton NMR data for the compound is: ! H NMR (200 MHz, CDC13): 0.7 (d, 3H); 1.0 (d, 3H); 2.4 (m, IH); 3.2 (d, IH); 5.1 (q, 2H); 7.2 (d, 2H); 7.4 (d, 4H); 7.8 (s, IH); IR (KBr, cm" 1):1715,1410; Mass (m/z) 500.
Example 8: Preparation of 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-diflouromethoxy phenyl)-3-methylbutanoate
0.58 g (0.0019 M) of 4-(3,5,6-trichloro-2-pyridyloxy)phenyl methanol was dissolved in dry dichloroethane and cooled in ice. A pre-cooled solution of the 3-(4- diflouromethylphenyl)-4-methylpentanoyl chloride 0.54 g (0.002 M) in dichloroethane was added dropwise over a period of 15 min., followed by the addition of 3 drops of pyridine. The reaction mixture was allowed to warm-up to room temperature and maintained at that temperature for 18h. The reaction mixture was quenched with water. After the layer separation the aqueous layer was extracted with dichloroethane and the combined organic layers were washed with 5% sodium bicarbonate, followed by water and dried over anhydrous sodium sulfate. The solvent removed under reduced pressure to get crude ester, which was purified by column chromatography. The 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-diflouromethoxyphenyl)-3-methylbutanoate was obtained in 52 % yield as an yellowish viscous liquid. NMR data for the compound is given below: l H NMR (200 MHz, CDC13): 0.7 (d, 3H); 1.0 (d, 3H); 2.3 (m, IH); 3.0 (q, IH); 4.6 (s, IH); 5.1 (q, 2H); 7.2 (d, 4H); 7.4 (d, 4H); 7.8 (s, IH); IR(KBr, cml): 1715, 1410; Mass (m/z) 531.
Example 9: Preparation of l-[3-(292-dichlorovinyl)-2,2-dimethylcyclopropykarbonyIo_:y methyl]-4-(3,5,6-trich!oro-2-pyridyloxy)benzene In a two-necked round bottomed flask 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.227 g (0.001 M) was added dropwise to this mixture while stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain (0.245 g), 50 % of the ester as an oil. ' H NMR (200 MHz, CDC13): δ 1.3 (s, 6H); 1.9 (d, IH); 2.1 (t, IH); 5.1 (s, 2H); 6.2 (d, IH); 7.2 (d, 2H); 7.4 (d, 2H); 7.8 (s, IH); IR (KBr, cml): 3090, 1720, 1400; Mass (m/z) 496. Example 10: Preparation of l-[3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-3-(3,5,6-trich!oro-2-pyridyloxy)benzene
In a two-necked round bottomed flask 0.152 mg (0.0005 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.227 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain 0.120 g (48 %) of the ester as an oil. 1 H NMR (200 MHz, CDC13): δ 1.3 (s, 3H); 1.9 (d, IH); 2.1 (t, IH); 5.1 (s, 2H); 6.2 (d, IH); 7.2 -7.4 (m, 4H); 7.8 (s, IH); IR (KBr, cml):3090, 1710, 1410; Mass (m/z) 496.
Example 11: Preparation of l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl] -4-(3,5,6-trichloro-2-pyridyloxy)benzene
In a two-necked round bottomed flask 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.316 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain (0.245 g) 50 % of the ester. 1 H NMR (200 MHz, CDC13): δ 1.3 (s, 6H); 1.9 (d, IH); 2.1 (t, IH); 5.1 (s, 2H); 6.2 (d, IH); 7.2 (d, 2H); 7.4 (d, 2H); 7.8 (s, IH); IR (KBr, cml): 1720,1400; Mass (m/z) 585 . Example 12: Preparation of l-[3-(2,2-dibroniovinyl)-2,2- diniethylcyclopropylcarbonyϊoxy methyl] -3-(3,5,β-trichloro-2-pyridylo_ )hen_;ene
In a two-necked round bottomed flask 0.152 mg (0.0005 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.316 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain 0.120 g (48 %) of the ester.
1 H NMR (200 MHz, CDC13): δ 1.3 (s, 3H); 1.9 (d, IH); 2.1 (t, IH); 5.1 (s, 2H); 6.2 (d, IH); 7.2 -7.4 (m, 4H); 7.8 (s, IH); IR (KBr, cml): 1710, 1420; Mass (m/z) 585. Example 13: Preparation of 4-(2,3,5,6-tetrachloro-4-pyridyloxy) benzaldehyde A uniform mixture of 12.072 g (0.048 M) of 2,3,4,5,6- pentachloropyridine, 2.0 g
(0.016 M) of 4-hydroxy benzaldehyde, 1.32 g of potassium carbonate, 0.04 g of cuprous chloride , 0.04g of 8-hydroxyquinoline and 20 ml of N-methyl pyrolidinone was taken in a round bottom flask and heated under reflux for 15 h under dry conditions the progress of the reaction was monitored by TLC. Afterwards the reaction mixture was poured into water and extracted with chloroform the combined extracts were washed with water and dried over sodium sulfate anhydrous. The organic layer was then concentrated under vacuum and crude was chromatographed (silica gel, hexane) to get the pure product 4.04 g (75 %) yield. The product has melting point 140.3 °C. The spectral data for the compound is ! H NMR (200 MHz, CDC13): 6.9-7.1 (d, 2H); 7.8-8.0 (d, 2H); 10 (s, IH); IR (KBr, cm-1): 1710, 1410; Mass (m/z) 337.
Example 14: Preparation of 3-(2,3,5,6-tetrachIoro-4-pyridyIoxy) benzaldehyde:
A uniform mixture of 12.072 g (0.048 M) of 2,3,4,5,6- pentachloropyridine, 2.0 g (0.016 M) of 3-hydroxy benzaldehyde, 1.32 g of potassium carbonate, 0.04 g of cuprous chloride, 0.04g of 8-hydroxyquinoline and 20 ml of N-methyl pyrolidinone was taken in a round bottom flask and heated under reflux for 15 h under dry conditions the progress of the reaction was monitored by TLC. Afterwards the reaction mixture was steam distilled and poured into water and extracted with chloroform. The combined extracts were washed with water and dried over anhydrous sodium sulfate. The organic layer was then concentrated under vacuum and crude product was chromatographed (silica gel, hexane) to get the pure product 3.88 g (72 %) yield. The product has melting point 140.1 °C. The spectral data for the compound is H NMR (200 MHz, CDC13): 7.0-7.8 (m, 4H); 10 (s, IH); IR (KBr, cml): 1710, 1400; Mass (m/z) 337. Example IS: Preparation of 4-(2,3,556-trichloro-4-pridyloxy)phenyl methanol Aldehyde 1.21 g (0.0035 M) was dissolved in a mixture of benzene (24 ml) and 2.4 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride). To this stirred mixture was added 0.242 g (0.0065 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC. The reaction mixture was then quenched by addition of water (50 ml) and neutralized to pH 7 by addition 5% HCl. The layers were separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The pure phenyl methanol was obtained in (1.04 g) 86 % yields. The product has melting point 110 °C. The data for the alcohol is * H NMR (200 MHz, CDC13): 4.7 (2H, s); 6.7-6.9 (d, 2H); 7.2-7.3 (d, 2H); IR (KBr, cml): 3200, 1410, Mass (m/z) 339 . Example 16: Preparation of 3-(2,3,5,6-trichloro-4-pridyloxy)phenyI methanol
3-(2,3,5,6-trichloro-4-pridyloxy)benzaldehyde 1.2 g (0.0035 M) was dissolved in a mixture of benzene (24 ml) and 2.4 ml of methanol taken in a 2- necked round bottom flask fitted with condenser and guard tube (calcium chloride). To this stirred mixture was added 0.240 g (0.0065 M) of sodium borohydride in portions over a period of 15 min. stirring was continued further for a period of 2 h, while monitoring the progress of the reaction by TLC. The reaction mixture was then quenched by addition of water (50 ml) and neutralized to pH 7 by addition 5% HCl. After the layer separation and the aqueous layer was extracted with dichloromethane. The combined organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The pure phenyl methanol was obtained in (0.704 g), 79.9 % yield. Solid product has melting point 143.5 °C. The data for the alcohol is ! H NMR (200 MHz, CDC13): 4.7 (2H, s); 7.0-7.6 (m, 4H); 7.8 (s, IH); IR (KBr, cml): 3200, 1410; Mass (m/z) 339.
Example 17: Preparation of l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl eyclopropylcarbonyloxymethyl}-4-(2,3,5,6-tetrachIoro-4-pyridyloxy)benzene
To a precooled solution of phenyl methanol 0.550 g (0.0016 M) taken in a round bottom flask fitted with guard tube and condenser; 0.420 g (0.0016 M) of precooled solution of the acid chloride in dry benzene was added to the reaction mixture over a period of 15 min. Subsequently 3 drops of pyridine was added and the reaction mixture was allowed to warm up to 15-20 (C and maintained at that temperature for 18h. Then the reaction mixture was quenched by addition of water, layers separated and then extracted with benzene. The combined organic layers were washed with 5% sodium bicarbonate, water, dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography on silica gel finer than 200 mesh using hexane as eluent. The pure product was obtained as viscous oil in (0.855 g) 83.6 % yield. The proton NMR spectrum of the ester shows * H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, IH); 2.2 (t, IH); 5.1 (s, 2H); 6.6-6.8 (d, IH); 6.8-7.0 (d, 2H); 7.3-7.5 (d, 2H); IR (KBr, cml): 3070, 2950, 1720, 1510, 1350, 1150, 805; Mass (m/z) 527. Example 18: Preparation of l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2-dimethyl cyclopropylcarbony!oxymethyl}-3-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
To a precooled solution of phenyl methanol 0.650 g (0.0019 M) taken in a round bottom flask fitted with guard tube and condenser; 0.446 g (0.0017 M) of precooled solution of the acid chloride in dry benzene was added to the reaction mixture over a period of 15 min. Next 3 drops of pyridine was added and the reaction mixture was allowed to warm up to 15- 20 °C and maintained at that temperature for 18h. At the end of that period the reaction mixture was quenched by addition of water layers separated and then extracted with benzene. The combined organic layers were washed with 5% sodium bicarbonate, water, dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography (silica gel, finer than 200 mesh) using hexane as eluent. The pure product was obtained as viscous oil in (0.707 g) 70 % yield. Proton NMR spectrum of ester shows l H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, IH); 2.2 (t, IH); 5.1 (s, 2H); 6.9 (d, IH); 7.0- 7.4 (m, 4H); IR (KBr, cml): 3070, 2910, 1720, 1400, 1290 1190, 1010, 790; Mass (m/z) 527. Example 19: Preparation of 4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzyI 2-(4- chIorophenyl)-3-methylbutanoate
0.38g (0.001M) of 4-(2,3,5,6-tetrachloro-4-pyridyloxy)phenyl methanol was dissolved in dry dichloroethane and cooled in ice. To this cooled solution was added a precooled solution of the 3-(4-chlorophenyl)-4-methylpentanoyl chloride 0.29g (0.0012M) in dichloroethane was added dropwise over a period of 15 minutes followed by the addition of 3 drops of pyridine. The reaction mixture was allowed to warm-up to room temperature and maintained at that temperature for 18h. The reaction mixture was quenched with water. After the layer separation the aqueous layer was extracted with dichloroethane and the combined organic layers were washed with 5% Sodium bicarbonate, followed by water and dried over anhydrous sodium sulfate. The solvent removed under reduced pressure to get crude ester, which was purified by column chromatography. The 4-(2,3,5,6-tetrachloro-4- pyridyloxy)benzyl 2-(4-chlorophenyl)-3-methylbutanoate was obtained in 49.5% yield. The spectral data of the sample: l H NMR (200 MHz, CDC13): 0.7 (d, 3H); 1.0 (d, 3H); 2.31 (m, IH); 3.1 (q, IH); 5.1 (q, 2H); 6.8 (d, 2H); 7.2 -7.5 (m, 6H); IR (KBr, cml):1715, 1410; Mass (m/z) 533.
Example 20: Preparation of 4-(2,3?5,6-tetrachloro-4-pyridyloxy)benzyl-2-(4- diflouromethoxy phenyl)-3-methylbutanoate
0.22 g (0.00064 M) of 4-(2,3,5,6-tetrachloro-4-pyridyloxy)phenyl methanol was dissolved in dry dichloroethane and cooled in ice. To this cooled solution was added a pre- cooled solution of the 3-(4-diflouromethoxyphenyl)-4-methylpentanoyl chloride 0.184 g (0.00071 M) in dichloroethane was added dropwise over a period of 15 min., followed by the addition of 3 -drops of pyridine. The reaction mixture was allowed to warm-up to room temperature and maintained at that temperature for 18h. The reaction mixture was quenched with water. After the layer separation the aqueous layer was extracted with dichloroethane and the combined organic layers were washed with 5% Sodium bicarbonate, followed by water and dried over anhydrous sodium sulfate. The solvent removed under reduced pressure to get crude ester, which was purified by column chromatography. The 4-(2, 3,5,6- tetrachloro-4-pyridyloxy)benzyl 2-(4-diflouromethyl phenyl)-3 -methylbutanoate was obtained in 52% yield as a yellow viscous oil. The NMR spectrum of the compound shows the following chemical shifts:
1 H NMR (200 MHz, CDC13): 0.7 (d, 3H); 1.0 (d, 3H); 2.2 (m, IH); 3.1 (d, IH); 4.3 (s, IH); 5.1 (q, 2H); 6.7 (d, 2H); 7.1 -7.3 (m, 6H); IR (KBr, cml): 1715, 1410; Mass (m/z) 565. Example 21: Preparation of l-[3-(2,2-dichIorovinyI)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene In a two-necked round bottomed flask 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.227 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain 45 % of the ester. l H NMR (200 MHz, CDC13): 6 1.3 (s, 6H); 1.9 (d, IH); 2.3 (t, IH); 5.0 (d, IH); 6.2 (d, IH); 7.2 (d, 4H); 7.4 (d, 4H); IR (KBr, cml): 3070, 1720, 1510; Mass (m/z) 530. Example 22: Preparation of l-[3-(2,2-dichlo_ovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-3-(2,3,5,6-tetrachloro-4-pyridyloxy)bensene
In a two-necked round bottomed flask 0.339 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.227 g (0.002 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was purified by column (containing finer than 200 mesh silica gel) chromatography (hexane as eluent) to obtain 49 % of the ester. 1 H NMR (200 MHz, CDC13): δ 1.3 (s, 6H); 1.9 (d, IH); 2.1 (t, IH); 5.0 (s, 2H); 6.2 (d, IH); 6.6-6.8 (d, IH); 6.9 (s, IH); 7.0-7.2 (d, IH); 7.4 (m, IH); IR (KBr, cml):3020, 1720, 1400; Mass (m/z) 530.
Example 23: Preparation of l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
In a two-necked round bottomed flask 0.304 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.316 g (0.001 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was fed into a column containing finer than 200 mesh silica gel and chromatographed (hexane as eluent) to obtain 48 % of the ester. 1 H NMR (200 MHz, CDC13): δ 1.3 (s, 6H); 1.9 (d, IH); 2.3 (t, IH); 5.0 (d, IH); 6.2 (d, IH); 7.2 (d, 4H); 7.4 (d, 4H); IR (KBr, cml):3070, 1710, 1510; mass (m/z) 619. Example 24: Preparation of l-[3-(2,2-dibromovinyI)-2,2- dimethylcyclopropylcarbonyloxy methyl]-3-(2,3,5,6-tetrachloro-4-pyridy!oxy)benzene
In a two-necked round bottomed flask 0.339 g (0.001 M) of the alcohol dissolved in 4 ml of dry hexane and cooled. A precooled solution of acid chloride 0.0.316 g (0.002 M) was added dropwise to this mixture while maintaining constant stirring, over a period of 15 min. To this a drop of pyridine is added and the ice bath is removed and the reaction maintained at room temperature for 48 h. The reaction mixture was poured into Erlenmeyer flask containing 50 ml water and extracted with benzene. The organic layers were washed with 5% sodium bicarbonate and the organic layer is dried over anhydrous sodium sulfate and then evaporated under vacuo. The crude mixture was purified by column (containing finer than 200 mesh silica gel) chromatography (hexane as eluent) to obtain 50 % yield of the ester. 1 H NMR (200 MHz, CDC13): δ 1.3 (s, 6H); 1.9 (d, IH); 2.1 (t, IH); 5.0 (s, 2H); 6.2 (d, IH); 6.6-6.8 (d, IH); 6.9 (s, IH); 7.0-7.2 (d, IH); 7.4 (m, IH); IR (KBr, cml): 3020, 1710, 1400; Mass (m/z) 619. Example 25: Preparation of the aryl pyridyl ethers via alternate route:
A) To a solution of 4-hydroxy benzaldehyde (0.213 g, 0.0023 M) and 2,3,5,6- tetrachloropyridine (0.493 g , 0.0023 M) in DMF (8 ml) was added cesium carbonate (0.740 g, 0.0023 M) at room temperature. The reaction mixture was stirred at 70 °C for 4-6 h. The solvent was removed from reaction mixture under vacum and crude mixture was taken into chloroform and washed with water, dried over sodium sulfate and concentrated. The pure product was obtained by column chromatography in 80% yield.
B) To a solution of 4-hydroxy benzyl alcohol (0.218 mg, 0.0023 mmol) and 2,3,5,6- tetrachloropyridine (0.493 mg, 0.0023mmol) in DMF (8 ml) was added cesium carbonate (0.740 mg, 0.0023 mmol) at room temperature. The reaction mixture was heated at 70 ° C for 6-8 h. At the end of the reaction the solvent was distilled off and the residue was taken up into chloroform and washed with water, dried over sodium sulfate and concentrated. The pure product was obtained by column chromatography in almost 85 % yield.

Claims

We claim:
1. A pyridinyloxy phenyl methanol derivative of formula III wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α-isopropyl(4- diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2-dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl.
Figure imgf000019_0001
2. The compound of claim 1, which is 4-(3,5,6-trichloro-2-pyridyloxy)benzaldehyde
3. The compound of claim 1, which is 3-(3,5,6-trichloro-2-pyridyloxy)benzaldehyde
4. The compound of claim 1, which is 4-(3,5,6-trichloro-2-pridyloxy)phenyl methanol 5. The compound of the claim 1, which is 3-(3,
5,6-trichloro-2-pyridyloxy)phenyl methanol
6. The compound of the claim 1, which is l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]- 2,2-dimethylcyclopropylcarbonyloxy methyl}-4-(3,5,6-trichloro-2-pyridyloxy)benzene
7. The compound of the claim 1, which is l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]- 2,2-dimethyl cyclopropylcarbonyloxymethyl} -3 -(3 , 5 ,6-trichloro-2-pyridyloxy)benzene
8. The compound of the claim 1, which is 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4- chlorophenyl)-3 -methylbutanoate
9. The compound of claim 1, which is l-[3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropylcarbonyloxymethyl]-4-(3,5,6-trichloro-2-pyridyloxy)benzene
10. The compound of the claim 1, which is l-[3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl]-3-(3, 5, 6-trichloro-2-pyridyloxy)benzene
11. The compound of the claim 1 which is l-[3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl] -4-(3,5,6-trichloro-2-pyridyloxy)benzene
12. The compound of claim 1, which is l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl] -3 -(3 , 5, 6-trichloro-2-pyridyloxy)benzene
13. The compound of claim 1, which is 4-(2,3,5,6-tetrachloro-4-pyridyloxy) benzaldehyde
14. The compound of claim 1, which is 3-(2,3,5,6-tetrachloro-4-pyridyloxy) benzaldehyde
15. The compound of claim 1, which is 4-(2,3,5,6-trichloro-4-pyridyloxy)phenyl methanol
16. The compound of claim 1, which is 3-(2,3,5,6-trichloro-4-pyridyloxy)phenyl methanol
17. The compound of claim 1, which is l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2- dimethylcyclopropylcarbonyloxymethyl}-4-(2,3,5,6-tetrachloro-4-pyridyloxy) benzene
18. The compound of claim 1, which is l-{3-[2-chloro-3,3,3-trifluoro-(Z)-l-propenyl]-2,2- dimethylcyclopropylcarbonyloxymethyl} -3 -(2,3 , 5, 6-tetrachloro-4-pyridyloxy) benzene
19. The compound of claim 1, which is 4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzyl 2-(4- chlorophenyl)-3 -methylbutanoate
20. The compound of claim 1, which is 4-(2,3,5,6-tetraehloro-4-pyridyloxy)benzyl-2-(4- diflouromethyl phenyl)-3 -methylbutanoate
21. The compound of claim 1, which is l-[3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
22. The compound of claim 1, which is l-[3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropylcarbonyloxymethyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
23. The compound of claim 1, which is l-[3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
24. The compound of claim 1, which is l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzene
25. The compound of claim 1, which is 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4- diflouromethylphenyl)-3-methylbutanoate
26. A process for the preparation of pyridinyloxy phenylmethanol derivatives of formula III wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α- isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by condensing hydroxy benzaldehyde followed by reduction.
Figure imgf000020_0001
27. A process for the preparation of a compound of formula III
Figure imgf000020_0002
III wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, α- isopropyl(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2- dimethyl cyclopropane carboxylic acid, 3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl by reacting hydroxy phenyl methanol directly with a halopyridine.
PCT/IN2003/000114 2003-03-31 2003-03-31 Ester derivatives of (pyridinyloxy-phenyl)-methanol and process of preparation thereof WO2004087667A1 (en)

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EP0000508A1 (en) * 1977-07-20 1979-02-07 Ciba-Geigy Ag Phenyl acetates of 2-oxypyridyl, process for their preparation and their use as pesticides
EP0023891A1 (en) * 1979-08-07 1981-02-11 Ciba-Geigy Ag Pyridyl-2-oxy-phenyloxime ethers and esters, their preparation and their use as herbicides
JPS59227861A (en) * 1983-06-10 1984-12-21 Mitsui Toatsu Chem Inc 2-arylethyl ether derivative, thioether derivative, its preparation, insecticidal and acaricidal composition
EP0317265A2 (en) * 1987-11-17 1989-05-24 Zeneca Inc. Novel imidate insecticides
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EP0023891A1 (en) * 1979-08-07 1981-02-11 Ciba-Geigy Ag Pyridyl-2-oxy-phenyloxime ethers and esters, their preparation and their use as herbicides
JPS59227861A (en) * 1983-06-10 1984-12-21 Mitsui Toatsu Chem Inc 2-arylethyl ether derivative, thioether derivative, its preparation, insecticidal and acaricidal composition
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