EP0060838A1 - Certaines 6-chloro-2-bi-(phynoxy substitue) methyle pyridines - Google Patents

Certaines 6-chloro-2-bi-(phynoxy substitue) methyle pyridines

Info

Publication number
EP0060838A1
EP0060838A1 EP81901356A EP81901356A EP0060838A1 EP 0060838 A1 EP0060838 A1 EP 0060838A1 EP 81901356 A EP81901356 A EP 81901356A EP 81901356 A EP81901356 A EP 81901356A EP 0060838 A1 EP0060838 A1 EP 0060838A1
Authority
EP
European Patent Office
Prior art keywords
compound
pyridine
bis
methyl
chloro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP81901356A
Other languages
German (de)
English (en)
Other versions
EP0060838A4 (fr
Inventor
Sudarshan K. Malhotra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0060838A1 publication Critical patent/EP0060838A1/fr
Publication of EP0060838A4 publication Critical patent/EP0060838A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07D213/643—2-Phenoxypyridines; 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
    • C07D213/61—Halogen atoms or nitro radicals

Definitions

  • Substituted phenoxy pyridine methyl esters of cyclopropane carboxylic acids are taught in U.S. Patent 4,163,787 issued August 7, 1979. These compounds are taught to be useful in the kill and control of various insect pest. These compounds are taught as being prepared by the reaction of an appropriate substituted phenoxy pyridine methanol with an appropriate2,2-dimethyl-3-(2, -dihaloethenyl)cyclopropane carboxylic acid halide.
  • the substituted phenoxy pyridine methanols are prepared from the corresponding picolinaldehyde which in turn is made from the corresponding methyl picolinate. It is the cost of the above aldehyde and picolinate intermediates which makes the cost of the methanols so high. New processes for preparing these materials are being sought.
  • the present invention is directed to compounds corresponding to the formula
  • X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkyl- thio of 1 to 4 carbon atoms, alkyl sulfonyl of 1 to 4 carbon atoms, trifluoromethyl, chloro, fluoro or bromo; n represents an integer of 0 to 2 or X n represents 3,4-methylenedioxy and R' represents R with the proviso that R and R' can be the same or different; and to a method for malting such compounds.
  • the present invention is also directed to the conversion of the above intermediate compounds to the corresponding picolinaldehydes, or in the use of those compounds wherein R' is chloro to as intermediates prepare additional intermediate compounds for conversion into the corresponding picolinaldehydes .
  • the so prepared picolinaldehydes can in turn be converted to substituted phenoxy pyridine methanols .
  • These latter compounds can then be reacted with an appropriate 2,2-dimethyl-3-(2,2-dihaloethenyl)- cyclopropane carboxylic acid halide, as taught in U.S. Patent 4,163,787, to prepare insecticidal substituted pyridine methyl esters of cyclopropane carboxylic acids .
  • the 6-(chloro or substituted phenoxy)-2-di-(sub- stituted phenoxy)methyl pyridines of the present invention are either solids or liquids which are only slightly soluble in water and usually are moderately to highly soluble in common organic solvents .
  • the compounds of the present invention can be prepared by the reaction of one mole of 2-chloro-6- -(dichloromethyl)pyridine with from about 1 to about 3 moles of an alkali metal salt of at least one substituted phenol in the presence of a solvent.
  • X and n are as hereinbefore defined and M is sodium, potassium, lithium or cesium.
  • the pyridine reactant and the salt of the phenol are mixed together in the presence of a solvent and heated to a temperature of from about 100 to about 200°C and stirred for from about 2 to about 24 hours. Thereafter, the reaction product is cooled, diluted with water and extracted with a solvent such as for example, 1,1,1-trichloroethane, methylene chloride, chloroform, ethyl acetate or ethyl ether.
  • a solvent such as for example, 1,1,1-trichloroethane, methylene chloride, chloroform, ethyl acetate or ethyl ether.
  • the solvent extract is water washed, dried and concentrated under reduced pressure and if desired, purified by distillation or other conventional methods.
  • the reaction consumes the reactants in stoichiometric proportions, i.e. one molar equivalent of the pyridine reactant to 3 molar equivalents of the phenol reactant. However, due to the nature of the reaction, it is preferred that a 5 to 25 percent excess of the phenol reactant be employed.
  • Representative solvents for use in carrying out this reaction include dimethyl sul oxide, dimethyl formamide, N-methyl-2-pyrrolidone, toluene and xylene.
  • Those compounds of the present invention wherein R' is chloro can be prepared by the reaction of one mole of 2-chloro-6-(dichloromethyl)pyridine with 2 moles of an alkali metal salt of the appropriate substituted phenol in the presence of a solvent.
  • This reaction scheme is as follows:
  • reaction and the separation of the desired product can be carried out as set forth above for those compounds wherein R and R' are the same.
  • Those compounds of the present invention wherein R and R' are different can be prepared by the reaction of one mole of a 2-chloro-6-((disubstituted phenox )methyl)pyridine, prepared as above, with one mole of an alkali metal salt of the appropriate substituted phenol in the presence of a solvent- This reaction scheme is as follows:
  • reaction and the separation of the desired product can be carried out as set forth above for those compounds wherein R and R' are the same or wherein R' is chloro..
  • the 6-(substituted phenox )-2-di-(substituted phenoxy)methyl pyridine product can be hydrolyzed to the corresponding 6-(substituted phenoxy)picolinaldehyde by acid hydrolysis with an inorganic or organic acid and, if desired, in the presence of a solvent.
  • an inorganic or organic acid such as, for example, sulfuric acid, dilute hydrochloric acid or acetic acid.
  • the reaction can be conducted, if desired, in the presence of a solvent or reaction medium such as, for example, 1,4-dioxane, monoglyme or water.
  • a solvent or reaction medium such as, for example, 1,4-dioxane, monoglyme or water.
  • the mixture is heated to a temperature of from about 60° to about 150°C for from about 10 minutes to 12 hours or more.
  • the reaction product is cooled, diluted with water and extracted with a solvent such as, for example ethyl ether, methylene chloride or chloroform.
  • the desired product can be recovered from the solvent extract by conventional recovery techniques which include, for example, water washing, washing with diluted sodium hydroxide and a saturated salt solution, drying and solvent removal under reduced pressure.
  • This liquid was determined to be the desired 2-chloro-6-(diphenoxymethyl)pyridine by its nuclear magnectic resonance spectra and its elemental analysis-
  • the elemental analysis showed the product to have carbon, hydrogen and nitrogen contents of 68.63, 4.40 and
  • the 2-[bis-(4-methoxyphenoxy) ethyl]-6-(4-methoxyphenoxy)pyridine product was removed as the residue of the distillation and was a brown thick oil.
  • the product was obtained in a yield of 25.3 g and upon analysis, was found to have carbon, hydrogen and nitrogen contents of 70.80, 5.37 and 3.09 percent, respectively, as compared with the theoretical contents of 70.59, 5.45 and 3.05 percent, respectively, as calculated for the above named compound.
  • the extract was then dried over sodium sulfate and the solvent removed by evaporation under reduced pressure.
  • the residue was a yellow-orange oil which solidified partially on cooling to yield 0.25 g of the desired product.
  • the product was confirmed by Infrared and Nuclear Magnetic resonance analysis .
  • the 2-(chloro-6-(dichloromethyl)pyridines employed as starting materials in the present invention are known compounds which can be prepared as taught in U.S. Patent 3,687,827.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Preparation de composes ayant la formule: (FORMULE) ou Y represente chloro ou R'; R represente (FORMULE) ou X represente independamment un alkyle de 1 a 4 atomes de carbone, un alkoxy de 1 a 4 atomes de carbone, un alkylthio de 1 a 4 atomes de carbone, un alkyle sulfonyle de 1 a 4 atomes de carbone, un trifluoromethyle, un chloro, un fluoro ou un bromo; n represente un nombre entier de 0 a 2 ou Xn represente le 3,4-dioxymethylene et R' represente R avec la condition que R et R' puissent etre identiques ou differents. Les composes sont utiles comme intermediaires pour la preparation d'esters methyliques de pyridine substitues insecticides d'acides cyclopropane.
EP19810901356 1980-09-18 1980-09-18 Certaines 6-chloro-2-bi-(phynoxy substitue) methyle pyridines. Withdrawn EP0060838A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1980/001226 WO1982001003A1 (fr) 1980-09-18 1980-09-18 Certaines 6-chloro-2-bi- (phenoxy substitue) methyle pyridines

Publications (2)

Publication Number Publication Date
EP0060838A1 true EP0060838A1 (fr) 1982-09-29
EP0060838A4 EP0060838A4 (fr) 1983-03-23

Family

ID=22154555

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810901356 Withdrawn EP0060838A4 (fr) 1980-09-18 1980-09-18 Certaines 6-chloro-2-bi-(phynoxy substitue) methyle pyridines.

Country Status (11)

Country Link
EP (1) EP0060838A4 (fr)
JP (1) JPS57501626A (fr)
AU (1) AU531392B2 (fr)
BE (1) BE890373A (fr)
BR (1) BR8009109A (fr)
CA (1) CA1170655A (fr)
DK (1) DK224182A (fr)
ES (1) ES8306723A1 (fr)
HU (1) HU185165B (fr)
IT (1) IT1171535B (fr)
WO (1) WO1982001003A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933239B1 (en) * 2013-07-16 2015-01-13 Dow Global Technologies Llc Bis(aryl)acetal compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909287A1 (de) * 1979-03-09 1980-09-18 Bayer Ag 3-substituierte pyridin-derivate, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8201003A1 *

Also Published As

Publication number Publication date
DK224182A (da) 1982-05-18
ES505583A0 (es) 1983-06-01
CA1170655A (fr) 1984-07-10
WO1982001003A1 (fr) 1982-04-01
BR8009109A (pt) 1982-08-10
BE890373A (fr) 1982-03-16
AU7177881A (en) 1982-04-14
EP0060838A4 (fr) 1983-03-23
IT1171535B (it) 1987-06-10
JPS57501626A (fr) 1982-09-09
HU185165B (en) 1984-12-28
IT8149315A0 (it) 1981-09-17
ES8306723A1 (es) 1983-06-01
AU531392B2 (en) 1983-08-18

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19820517

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Designated state(s): CH DE FR LI LU NL

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Effective date: 19840912

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Inventor name: MALHOTRA, SUDARSHAN K.