Title of Invention	PYRIDINYLOXY PHENYL METHANOL ESTERS
Abstract	The present invention relates to novel pyndinyloxy phenyl methanol derivatives of the formula III, 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 and the process of preparation thereof

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PYRIDINYLOXY PHENYL METHANOL ESTERS Field of the invention The present invention relates to novel pyridinyloxy phenyl methanol esters, viz., 4-/3-(3,5,6-trichIoropyridyl-2-oxy) phenyl methanol derivatives and 4-/3-(2,3,5,6-pyridinyl-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-phenoxy methyl esters or (RS)-a-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. Fuji'moto, 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-l-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 they 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 picolinaldehydecyanohydrin, 3-phenyI-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-pyridinyI-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)phenyImethanol esters which are useful as crop protection chemicals. Summary of the invention Accordingly, the present invention provides a pyridinyloxy phenyl methanol esters of formula III wherein R is acid chloride residue, DV acid, α-isopropyl(4-chlorophenyl) acetic acid, a-isopropyI(4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-trifluoropropenyl)2,2-dimethyl cyclopropane carboxylic acid, 3-(2,2-dibrotnovinyl)-2,2-dimethyI cyclopropane carboxylic acid and X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl. (Formula Removed) The compounds of the invention are selected from 4-(3,5,6-trich]oro-2- pyridy!oxy)benzaldehyde; 3-(3,5,6-trichloro-2-pyridyloxy)benzaldehyde; 4-(3,5,6-trichloro-2- pridyloxy)phenyI methanol; 3-(3,5,6-trichforo-2-pyridyloxy)phenyl methanol; l-{3-[2-chloro-3,3,3- trifluoro-(Z)-l-propenyl]-2,2-dimethylcyclopropylcarbonyloxy methyi}-4-(3,5,6-trichloro-2- pyridyloxy)benzene; 1- {3- [2- chloro- 3, 3, 3- trifluoro - (Z) -1- propenyl ]- 2, 2- diniethylcyclopropylcarbonyloxy 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; l-[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)-lpropenyl]- 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; (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; 1 -[3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropylcarbonyloxy 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; 1 -[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 The present invention also provides a process for the preparation of pyridinyloxy phenylmethanol esters of formula III (Figure Removed) wherein R is acid chloride residue, DV acid, a-isopropyl(4-chlorophenyl) acetic acid, aisopropyl( 4-diflouromethoxyphenyl) acetic acid, 3-(2-chloro-3,3,3-tritluoropropenyl)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 Removed wherein R is acid chloride residue, DV acid, a-isopropyl(4-chlorophenyl) acetic acid, o> 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 hi 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: The preliminary 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 limiting the scope of the invention in any manner. Example 1: Preparation of 4- 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 ( Table Removed) 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 ' H NMR (200 MHz, CDC13): 7.2 (d, 2H); 7.8 (s, 1H); 8.0 (d, 2H); 10 (s, 1H); IR (KBr, on 1): 1420,1710; Mass (m/z) 303. Example 2: Preparation of 3-(3,5,6-trichloro-2-pyridyloxy)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 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 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 l H NMR (200 MHz, CDC13): 7.2-7.8 (m, 4H); 8.0 (s, 1H); 10 (s, 1H); IR (KBr, cm'l): 1410,1720; Mass (m/z) 303. Example 3: 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. stirringjavas* continued further for a period of 2 h, while monitoring the progress of the reaction by TEC. 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: l H NMR (200 MHz, CDC13): 4.7 (s, 2H); 7.0-7.2 (d, 2H); 7.3-7.5 (d, 2H); 7.8 (s, 1H); IR (KBr, cml): 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 l H NMR (200 MHvCDCl3): 4.7 (2H, s); 7.0-7.6 (m, 4H); 7.8 (s, 1H); IR (KBr, on 1): 3200, 1410; Mass (m/z) 305. Example 5: Preparation of l-{3-[2-chloro-3^^-trifluoro-(Z)-l-propenyl]-2,2-dimethyl cyclopropyIcarbonyloxymethyl}-4-(3,5,6-trichIoro-2-pyridyloxy)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, 1H); 2.2 (t, 1H); 5.1 (s, 2H); 6.8-7.0 (d, 1H); 7.0-7.2 (d, 2H); 7.3-7.5 (d, 2H); 7.8 (s, 1H); IR (KBr, cm'l): 3090, 2990, 1720, 1400, 1280,1190, 980, 810; Mass (m/z) 493. Example 6: Preparation of l-{3-[2-chloro-3^5^-trifluoro-(Z)-l-propenyl]-2^-dimethyl cyclopropylcarbonyloxymethyI}-3-(3,5,6-trichloro-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. ! H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, 1H); 2.2 (t, 1H); 5.1 (s, 2H); 6.9 (d, 1H); 7.0-7.4 (m, 4H); 7.8 (s, 1H); IR (KBr, crnl): 3090, 2995, 1720,1550,1290,1190, 950, 870; Mass (m/z) 493. Example 7: Preparation of 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-chlorophenyl)-3- metbylbutanoate 0.8715g (0.0028 M) of 4-(3,5,6-trichloro-2-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 0.577 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-pyridyloxy)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, 1H); 3.2 (d, 1H); 5.1 (q, 2H); 7.2 (d, 2H); 7.4 (d, 4H); 7.8 (s, 1H); IR (KBr, cm"- 1):1715,1410; Mass (m/z) 500. Example 8: Preparation of 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-diflouromethoxyphenyl)-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 organiclayers 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, CDCU): 0.7 (d, 3H); 1.0 (d, 3H); 2.3 (m, 1H); 3.0 (q, 1H); 4.6 (s, 1H); 5.1 (q, 2H); 7.2 (d, 4H); 7.4 (d, 4H); 7.8 (s, 1H); IR (KBr, cm'l): 1715,1410; Mass (m/z) 531. Example 9: Preparation of l-[3-(2,2-dichlorovinyl)-24-dimethylcyclopropylcarbonyk>xy raethyl]-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 0.227 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. 1H NMR (200 MHz, CDC13): 8 1.3 (s, 6H); 1.9 (d, 1H); 2.1 (t, 1H); 5.1 (s, 2H); 6.2 (d, 1H); 7.2 (d, 2H); 7.4 (d, 2H); 7.8 (s, 1H); IR (KBr, cm'l): 3090, 1720, 1400; Mass (m/z) 496. Example 10: Preparation of l-[3-(2,2-dichlorovinyI)-2,2- dimethylcyclopropylcarbonyloxy methyl]-3-(3,5,6-trichIoro-2-pyridyIoxy)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. 1H NMR (200 MHz, CDC13): 6 1.3 (s, 3H); 1.9 (d, 1H); 2.1 (t, 1H); 5.1 (s, 2H); 6.2 (d, 1H); 7.2 -7.4 (m, 4H); 7.8 (s, 1H); IR (KBr, on 1):3090, 1710, 1410; Mass (m/z) 496. Example 11: Preparation of l-[3-(2,2-dibroinovinyl)-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 nil 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 .xontaining 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. 1H NMR (200 MHz, CDC13): 8 1.3 (s, 6H); 1.9 (d, 1H); 2.1 (t, 1H); 5.1 (s, 2H); 6.2 (d, 1H); 7.2 (d, 2H); 7.4 (d, 2H); 7.8 (s, 1H); IR (KBr, cm'l): 1720,1400; Mass (m/z) 585 . Example 12: Preparation of l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl] -3-(3,S,6-trichloro-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 0.316 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. 1H NMR (200 MHz, CDC13): 5 1.3 (s, 3H); 1.9 (d, 1H); 2.1 (t, 1H); 5.1 (s, 2H); 6.2 (d, 1H); 7.2 -7.4 (m, 4H); 7.8 (s, 1H); IR (KBr, crnl):1710, 1420; Mass (m/z) 585. Example 13: Preparation of 4-(2^,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 MHzvCDCl3): 6.9-7.1 (d, 2H); 7.8-8.0 (d, 2H); 10 (s, 1H); IR (KBr, cnr-1): 1710, 1410; Mass (m/z) 337. Example 14: Preparation of 3-(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 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, 1H); IR (KBr, cm 1): 1710, 1400; Mass (m/z) 337. Example IS: Preparation of 4-(2,3,5,6-trichloro-4-pridyIoxy)phenyI 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% 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 (1.04 g) 86 % yields. The product has melting point 110 °C. The data for the alcohol is l 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% HC1. 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 l H NMR (200 MHz, CDC13): 4.7 (2H, s); 7.0-7.6 Or. 4H); 7.8 (s, 1H); 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 cvclopropylcarbonyloxyniethyI}-4-{2,3,5,6-tetrachloro-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 1 H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, 1H); 2.2 (t, 1H); 5.1 (s, 2H); 6.6-6.8 (d, 1H); 6.8-7.0 (d, 2H); 7.3-7.5 (d, 2H); IR (KBr, crnl): 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 cyclopropylcarbonyloxymethyl}-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. The proton NMR spectrum of the ester shows 1 H NMR (200 MHz, CDC13): 1.3 (s, 6H); 2.0 (d, 1H); 2.2 (t, 1H); 5.1 (s, 2H); 6.9 (d, 1H); 7.0-7.4 (m, 4H); IR (KBr, crnl): 3070, 2910, 1720, 1400, 1290 1190,1010, 790; Mass (m/z) 527 . Example 19: Preparation of 4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzyl 2-(4- chlorophenyl)-3-methyIbutanoate 0.38 g (0.001 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 precooled solution of the 3-(4-chlorophenyl)-4-methylpentanoyl chloride 0.29 g (0.0012 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-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, 1H); 3.1 (q, 1H); 5.1 (q, 2H); 6.8 (d, 2H); 7.2 -7.5 (m, 6H); IR(KBr, crn 1):1715, 1410; Mass (m/z) 533. Example 20: Preparation of 4-(2,3A6-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 wa&, dissolved in dry dichloroethane and cooled in ice. To this cooled solution was added a precooled 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: 1H NMR (200 MHz, CDC13): 0.7 (d, 3H); 1.0 (d, 3H); 2.2 (m, 1H); 3.1 (d, 1H); 4.3 (s, 1H); 5.1 (q, 2H); 6.7 (d, 2H); 7.1 -7.3 (m, 6H); IR (KBr, crn 1): 1715, 1410; Mass (m/z) 565. Example 21: Preparation of l-[3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2r3,5,6-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. 1H NMR (200 MHz, CDC13): 6 1.3 (s, 6H); 1.9 (d, 1H); 2.3 (t, 1H); 5.0 (d, 1H); 6.2 (d, 1H); 7.2 (d, 4H); 7.4 (d, 4H); IR (KBr, cm'l): 3070, 1720,1510; Mass (m/z) 530. Example 22: Preparation of l-[3-(2,2-dichlorovinyI)-2^- dimethylcyclopropylcarbonyloxy methyl]-3-(2^,5,6-tetrachloro-4-pyridyloxy)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 0.227 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 Erlenmeyet; 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. 1H NMR (200 MHz, CDC13): 8 1.3 (s, 6H); 1.9 (d, 1H); 2.1 (t, 1H); 5.0 (s, 2H); 6.2 (d, 1H); 6.6-6.8 (d, 1H); 6.9 (s, 1H); 7.0-7.2 (d, 1H); 7.4 (m, 1H); IR (KBr, cm'l):3020, 1720, 1400; Mass (m/z) 530. Example 23: Preparation of l-[3-(2,2-dibromovinyl)-2,2- dimethylcyclopropylcarbonyloxy methyl]-4-(2^,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. 1H NMR (200 MHz, CDC13): 6 1.3 (s, 6H); 1.9 (d, 1H); 2.3 (t, 1H); 5.0 (d, 1H); 6.2 (d, 1H); 7.2 (d, 4H); 7.4 (d, 4H); IR (KBr, cm'l):3070, 1710,1510; mass (m/z) 619. Example 24: Preparation of l-[3-(2,2-dibromovinyl)-2»2-? dimethylcyclopropylcarbonyloxymethyll-3-(2,3,5,6-tetrachloro-4-pyridyloxy)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 flaskcontaining 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. 1H NMR (200 MHz, CDC13): 8 1.3 (s, 6H); 1.9 (d, 1H); 2.1 (t, 1H); 5.0 (s, 2H); 6.2 (d, IHJf 6.6-6.8 (d, 1H); 6.9 (s, 1H); 7.0-7.2 (d, 1H); 7.4 (m, 1H); IR (KBr, cnfl): 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 ° Cfor 6-8 h. At the end of the reaction the solvent was distilled off and the residue wastakenup into chloroform and washed with water, dried over sodium sulfate and concentrated. The pure product was obtained by column chromatography in almost 85 % yield. We claim: 1. A pyridinyloxy phenyl methanol esters 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. (Formula Removed) 2. A compound of the claim 1, which is 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-chlorophenyl)-3 -methylbutanoate. 3. A compound of claim 1, which is 4-(2,3,5,6-tetrachloro-4-pyridyloxy)benzyl-2-(4-diflouromethylphenyl)-3-methylbutanoate. 4. A compound of claim 1, which is 4-(3,5,6-trichloro-2-pyridyloxy)benzyl 2-(4-diflouromethylphenyl)-3-methylbutanoate. 5. A process for the preparation of pryidinyloxyphenyl methanol esters of general formula (III) as possible crop protection agents by reacting pyridinyloxyphenyl methanol "derivatives represented by I and acid chloride represented by II, wherein X represents 3,5,6-trichloropyridyl or 2,3,5,6-tetra chloropyridyl group, R represents acid chloride residues from (2,2-dichlororvinyl)-2,2-dimethyl cyclopropyl, (2,2-dibromovinyl)-2,2- dimethylcyclopropyl,α-isopropyl(4-chlorophenyl),a-isopropyl(4- ,3-(2-chloro-3,3,3-trifluoropropenyl)2,2-dimethylcyclopropyl,3- (2,2-dibromovinyl)-2,2-dimethy cyclopropyl group in presence of a base as a promoter wherein the mole ratio of pyridinyloxyphenyl methanol derivatives represented by I and acid chloride represented by II ranges from 0.9: 1.0 to about 1:1.2 at a temperature of 0- 100°C for a period of 2-24 hrs. (Formula Removed) 6. A process as claimed in claims 5 wherein the said process is conducted in presence of polyhalohydrocarbon, solvent selected from the group of dichloromethane, dicloroethane, hexane,but preferably in the solvent dry hexane, or dry benzene. 7. A process as claimed in claims 5-6 wherein the said process is carried out in the presence of a base as promoter, both organic and inorganic alkylamine,heterocyclic bases, alkali hydroxides etc. preferably triethyl amine and/or pyridine. 8. A process as claimed in claims 5-7 wherein the reaction is effected for a period, preferably 18hrs. 9. A process as claimed in claims 5 -8 wherein the said process is conducted under agitation and at temperature, preferably in the range of 0-15 °C. 10. A pyridinyloxy phenyl methanol esters substantially as herein describe with reference to examples accompanying this specification.

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240-DEL-2003-Abstract-(16-03-2009).pdf

240-del-2003-abstract.pdf

240-DEL-2003-Claims-(16-03-2009).pdf

240-DEL-2003-Claims-(20-04-2009).pdf

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240-DEL-2003-Description (Complete)-(16-03-2009).pdf

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240-DEL-2003-Form-1-(16-03-2009).pdf

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240-DEL-2003-Form-3-(16-03-2009).pdf

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240-DEL-2003-Petition-137-(16-03-2009).pdf