WO1982001003A1 - Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines - Google Patents

Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines Download PDF

Info

Publication number
WO1982001003A1
WO1982001003A1 PCT/US1980/001226 US8001226W WO8201003A1 WO 1982001003 A1 WO1982001003 A1 WO 1982001003A1 US 8001226 W US8001226 W US 8001226W WO 8201003 A1 WO8201003 A1 WO 8201003A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
pyridine
bis
methyl
chloro
Prior art date
Application number
PCT/US1980/001226
Other languages
French (fr)
Inventor
Chem Co Dow
Original Assignee
Malhotra S
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
Priority to BR8009109A priority Critical patent/BR8009109A/en
Priority to HU811893A priority patent/HU185165B/en
Priority to EP19810901356 priority patent/EP0060838A4/en
Priority to PCT/US1980/001226 priority patent/WO1982001003A1/en
Priority to AU71778/81A priority patent/AU531392B2/en
Priority to JP56501728A priority patent/JPS57501626A/ja
Application filed by Malhotra S filed Critical Malhotra S
Priority to CA000386035A priority patent/CA1170655A/en
Priority to BE0/205975A priority patent/BE890373A/en
Priority to IT49315/81A priority patent/IT1171535B/en
Priority to ES505583A priority patent/ES505583A0/en
Publication of WO1982001003A1 publication Critical patent/WO1982001003A1/en
Priority to DK224182A priority patent/DK224182A/en

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.

Abstract

Compounds are prepared corresponding to the formula (FORMULA) wherein Y represents chloro or R'; R represents (FORMULA) wherein X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio 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<un>u represents 3, 4-methylenedioxy and R' represents R with the proviso that R and R' can be the same or different. The compounds are useful as intermediates for the preparation of insecticidal substituted pyridine methyl esters of cyclopropane carboxylic acids.

Description

CERTAIN 6-CHLORO-2-DI- (SUBSTITUTED PHENOXY) METHYL PYRIDINES
Background of the Invention
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.
While the above procedure is efficient in the preparation of the desired compounds, the cost of the substituted phenoxy pyridine methanols used in that procedure has made the so prepared desired compounds very expensive and less attractive for exploitation.
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.
Summary of the Invention
The present invention is directed to compounds corresponding to the formula
Figure imgf000004_0001
wherein Y represents chloro or ' ; R represents
Figure imgf000004_0002
wherein 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 Xn 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.
Those compounds of the present invention wherein R and R' are the same can be prepared by the reaction of one mole of 2-chloro-6-(dichloromethyl)- pyridine with 3 moles of an alkali metal salt of the appropriate substituted phenol in the presence of a solvent. This reaction scheme is as follows:
Figure imgf000005_0001
Figure imgf000006_0001
wherein X and n are as hereinbefore defined and M is sodium, potassium, lithium or cesium.
In carrying out this reaction, 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. 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.
While the above procedure shows the use of an already prepared alkali metal salt of the phenol, this salt can be prepared in situ. In such a procedure, the pyridine reactant, an appropriate substituted ethoxy phenol and an alkali metal hydroxide are mixed together with the solvent and then heated as set forth hereinabove. The alkali metal hydroxide is employed in a molar amount equal to that employed for the phenol reactant.
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:
Figure imgf000007_0001
wherein X, n and M are as hereinbefore defined.
The 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:
Figure imgf000008_0001
wherein X, n and M are as hereinbefore defined.
The 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. In carrying out the hydrolysis step, one mole of the 6-(substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridine is mixed with an excess of 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. 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.
Description of Some Preferred Embodiments The following examples further illustrate the present invention.
Example I - 2-Chloro-6-(diphenoxymethyl)pyridine
Figure imgf000009_0001
A mixture of 25 grams (g) (0.13 mole ( ) ) of 2-chloro-6-(dichloromethyl)pyridine, 29.91 g (0.32 m) of phenol and 17.84 g (0.32 m) of potassium hydroxide in 100 milliliters (ml) of dimethylsulfoxide was heated, with stirring, for 6 hours at 70°C. The reaction mixture was cooled, diluted with water and extracted with 1,1,1-trichloroethane. The extract was washed with, water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to Kugelrohr distillation and 27.3 g of a yellow viscous liquid was recovered. This liquid was determined to be the desired 2-chloro-6-(diphenoxymethyl)pyridine by its nuclear magnectic resonance spectra and its elemental analysis- The product boiled at 150°C at 0.1 millimeter of mercury (mm) and had a refractive index of = 1.5991. The
Figure imgf000010_0001
elemental analysis showed the product to have carbon, hydrogen and nitrogen contents of 68.63, 4.40 and
4.49 percent, respectively, as compared with the theoretical contents of 69.34, 4.49 and 4.49 percent, respectively, as calculated for the above named compound.
By following the preparative procedure as outlined in the above example, the following co pounds set forth below in TABLE I can be prepared.
TABLE I
Figure imgf000011_0001
Figure imgf000011_0002
TABLE I (Continued)
Figure imgf000012_0001
TABLE I (Continued)
Figure imgf000013_0001
By following the preparative procedures as outlined above using ~one mole of the appropriate phenol or substituted phenol and one mole of the appropriate 2-chloro-6-(substituted phenoxy)pyridine, the following compounds can be prepared.
Figure imgf000014_0001
Figure imgf000015_0002
Example II - 2-[Bis-(4-methoxyphenoxy)methyl]-6-
-(4-methoxyphenox )pyridine
Figure imgf000015_0001
A mixture of 15.04 grams (g) (0.076 mole
(m) ) of 2-dichloromethyl-6-chloropyridine, 39.50 g (0.32 m) of £-methoxyphenol and 18.14 g (0.32 m) of potassium hydroxide in 100 illiliters (ml) of dimethylsul oxide was heated, with stirring, for 72 hours. The resulting mixture was cooled to 25°C, diluted with water and extracted with 1,1,1-trichloro- ethane. The extract was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to Kugelrohr distillation removing as impurities any material boiling up to 200°C at 0.05-1 millimeter of mercury (mm). 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.
By following the preparative procedure as outlined in the above example, the following compounds set forth below in Table II can be prepared.
TABLE II
Figure imgf000017_0001
Figure imgf000017_0002
TABLE II (Continued)
Figure imgf000018_0001
TABLE II (Continued)
Figure imgf000019_0001
Example III - 6-(3-Fluorophenoxy)picolinaldehyde
Figure imgf000020_0001
A solution of 2.5 g (0.0059 m) of 2-[bis- -(3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine and 20 ml of 80 percent acetic acid was heated, with stirring, at 150°C overnight. The reaction mixture was cooled, diluted with water and extracted with methylene chloride. The extract was washed with water and concentrated under reduced pressure. The desired 6-(3-fluorophenoxy)picolinaldehyde which melted at 42°-43°C.
Example IV - 6-(phenoxy)-picolinaldehyde
Figure imgf000020_0002
To a solution of 0.5 g of 2-[bis-(phenoxy)- methyl]-6-(phenoxy)pyridine in 15 ml of 1,4-dioxane was added dropwise, 5 percent sulfuric acid until the mixture just became turbid. The mixture was heated over a steam bath at 80°-90°C for about 10 minutes. The reaction mixture was poured into 20 ml of water, producing a yellowish emulsion and then extracted with 50 ml of ethyl ether. The extract was washed with 50 ml of a 5 percent aqueous sodium hydroxide solution and thrice with 50 ml portions of water and then with 50 ml of a saturated sodium chloride solution. 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 .
By following the preparative procedures as outlined in the above Examples, the following compounds can be prepared.
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000022_0001
Preparation of Starting Materials
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.

Claims

WHAT IS CLAIMED IS;
A compound corresponding to the formula
Figure imgf000023_0001
wherein Y represents chloro or R' ; R represents
Figure imgf000023_0002
wherein X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio 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 Xn represents 3, -methylenedioxy and R' represents R with the proviso that R and R' can be the same or different.
2. The compound of Claim 1 in which Y is chloro.
3. The compound of Claim 2 which is 2-chloro- -6-(diphenoxymethyl)pyridine.
4. The compound of Claim 2 which is 2-chloro- -6-(bis(4-chlorophenoxy)methyl)pyridine.
5. The compound of Claim 2 which is 2-chloro- -6-(bis(3-fluorophenoxy)methyl)pyridine.
6. The compound of Claim 2 which is 2-chloro- -6-(bis(4-fluorophenoxy)methyl)pyridine.
7. The compound of Claim 1 in which Y is R' and R' represents R.
8. The compound of Claim 1 in which R and R' are different.
9. The compound of Claim 1 in which R and R' are the same.
10. The compound of Claim 9 which is 2-[bis-(phenoxy)methyl]-6-(phenox )pyridine.
11. The compound of Claim 9 which is 2-[bis- -4-meth lphenox )methyl]-6-(4-methylphenoxy)pyridine.
12. The compound of Claim 9 which is 2-[bis- -3-chlorophenoxy)methyl]-6-(3-chlorophenox )pyridine.
13. The compound of Claim 9 which is 2-[bis- -4-chlorophenox ) ethyl]-6-(4-chlorophenoxy)pyridine.
14. The compound of Claim 9 which is 2- [bis-3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine.
15. The compound of Claim 9 which is 2-[bis-4- luorophenox ) ethyl]-6-(4-fluorophenox )pyridine.
16. A process for the preparation of compounds corresponding to the formula
Figure imgf000025_0002
wherein Y represents chloro or R' ; R represents
Figure imgf000025_0001
wherein X independently represents alk l of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkyl sulfonyl of 1 to 4 carbon atoms, trifluoromethyl, chloro, fluoro or bro o; n represents an integer of 0 to 2 or Xn represents 3,4-methylenedioxy and R' represents R with the proviso that R and R' can be the same or different, which comprises reactihg one mole of 2-chloro-δ-(dichloromethyl)pyridine with from about 1 to about 3 moles of an alkali metal salt of at least one substituted phenol which corresponds to the formula
Figure imgf000026_0001
wherein M represents sodium, potassium, lithium or cesium at a temperature of from about 100 to about 200°C and in the presence of a solvent and recovering the desired product therefrom.
17. The process as defined in Claim 16 wherein Y is chloro.
18. The process as defined in Claim 17 wherein one mole of 2-chloro-6-(dichloromethyl)pyridine is reacted with about one mole of the alkali metal salt of the substituted- phenol.
19. The process as defined in Claim 18 wherein a 5 to 25 percent excess of the phenol reactant is employed.
20. The process of Claim 19 wherein the compound prepared is 2-chloro-6-(diphenoxymethyl)- pyridine.
21. The process of Claim 19 wherein the compound prepared is 2-chloro-6-(bis(4-chlorophenoxy)- methyl)pyridine.
22. The process of Claim 19 wherein the compound prepared is 2-chloro-6-(bis(3-fluorophenox )- methyl)pyridine.
23. The process of Claim 19 wherein the compound prepared is 2-chloro-6-(bis(4-fluorophenoxy)- methyl)pyridine.
24. The process as defined in Claim 16 wherein Y is R' and R' represents R and R and R' are different.
25. The process as defined in Claim 24 wherein 2-chloro-6-((disubstituted phenoxy)methyl)- pyridine is first prepared and one mole of this material is reacted with about one mole of the alkali metal salt of the substituted phenol.
26. The process as defined in Claim 16 wherein Y is R' and R' represents R and R and R' are the same.
27. The process as defined in Claim 16 wherein one mole of 2-chloro-6-(dichloromethyl)- pyridine is reacted with about 3 moles of the alkali metal salt of the substituted phenol.
28. The process as defined in Claim 27 wherein a 5 to 25 percent excess of the phenol reactant is employed.
29. The process of Claim 28 wherein the compound prepared is 2-[bis-(phenoxy)methyl]-6-
-(phenoxy)pyridine.
30. The process of Claim 28 wherein the compound prepared is 2- [bis-4-methylphenoxy)methyl]-6-(4-methylphenoxy)pyridine.
31. The process of Claim 28 wherein the compound prepared is 2-[bis-3-chlorophenoxy)methyl]-6-(3-chlorophenoxy)pyridine.
32. The process of Claim 28 wherein the compound prepared is 2-[bis-4-chlorophenoxy)methyl]-6-(4-chlorophenoxy)pyridine.
33. The process of Claim 28 wherein the compound prepared is 2-[bis-3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine.
34. The process of Claim 28 wherein the compound prepared is 2-[bis-4-fluorophenoxy)methyl]-6-(4-fluorophenoxy)pyridine.
35. A process for the preparation of compounds corresponding to the formula
Figure imgf000028_0001
wherein R' represents R; R represents
Figure imgf000028_0002
and wherein X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio 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 represents 3, 4-methylenedioxy with the proviso that
R and R' can be the same or different, which comprises, heating to a temperature of from about 60 to about
150°C a compound of the formula
Figure imgf000029_0001
and an inorganic or organic acid in the presence of a solvent for a period of time sufficient to convert the starting compound to the. desired product and separating the desired product therefrom.
36. The process as defined in Claim 35 wherein the compound heated is 2-[bis-(phenoxy)methyl]-6-(phenoxy)pyridine and the recovered compound is 6-(phenoxy)picolinaldehyde.
37. The process as defined in Claim 35 wherein the compound heated is 2-[bis-(4-methylphenoxy)' methyl]-6-(4-methylphenoxy)pyridine and the recovered compound is 6-(4-methylphenoxy)picolinaldehyde.
38. The process as defined in Claim 35 wherein the compound heated is 2-[bis-(3-chlorophenoxy)methyl]-6-(3-chlorophenoxy)pyridine and the recovered compound is 6-(3-chlorophenoxy)picolinaldehyde.
39. The process as defined in Claim 35 wherein the compound heated is 2-[bis-(4-chlorophenoxy) ethyl]-6-(4-chlorophenoxy)pyridine and the recovered compound is 6-(4-chlorophenoxy)picolinaldehyde.
40. The process as defined in Claim 35 wherein the compound heated is 2- [bis-(3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine and the recovered compound is 6-(3-fluorophenoxy)picolinaldehyde.
41. The process as defined in Claim 35 wherein the compound heated is 2-[bis-(4-fluorophenoxy)methyl]-6-(4-fluorophenoxy)pyridine and the recovered' compound is 6-(4-fluorophenoxy)picolinaldehyde.
PCT/US1980/001226 1980-09-18 1980-09-18 Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines WO1982001003A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
HU811893A HU185165B (en) 1980-09-18 1980-09-18 Process for preparing 6-/substituted phenoxy/-piolinaldehyde derivatives
EP19810901356 EP0060838A4 (en) 1980-09-18 1980-09-18 Certain 6-chloro-2-di-(substituted phenoxy) methyl pyridines.
PCT/US1980/001226 WO1982001003A1 (en) 1980-09-18 1980-09-18 Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines
AU71778/81A AU531392B2 (en) 1980-09-18 1980-09-18 6-(chloro or substituted phenoxy)-2-di-(substituted phenoxy) methyl pyridine
JP56501728A JPS57501626A (en) 1980-09-18 1980-09-18
BR8009109A BR8009109A (en) 1980-09-18 1980-09-18 6- (CHLORINE OR PHENOXY-REPLACED) -2-DI (PHENOXY-REPLACED) METHYL PYRIDINE
CA000386035A CA1170655A (en) 1980-09-18 1981-09-16 6-(chloro or substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridines
BE0/205975A BE890373A (en) 1980-09-18 1981-09-16 6- (CHLORO OR PHENOXY SUBSTITUE) -2-DI- (PHENOXY SUBSTITUE) METHYL PYRIDINES
IT49315/81A IT1171535B (en) 1980-09-18 1981-09-17 6- (CHLORINE OR PHENOXY REPLACED) -2-DI- (PHENOXY-REPLACED) METHYLPYRIDINE AND RELATED PRODUCTION PROCESS
ES505583A ES505583A0 (en) 1980-09-18 1981-09-17 A PROCEDURE FOR THE PREPARATION OF NEW PIRIDINE DERIVATIVES.
DK224182A DK224182A (en) 1980-09-18 1982-05-18 CERTAIN 6-CHLOR-2-DI- (SUBSTITUTED PHENOXY) METHYLPYRIDINES

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOUS80/01226800918 1980-09-18
PCT/US1980/001226 WO1982001003A1 (en) 1980-09-18 1980-09-18 Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines

Publications (1)

Publication Number Publication Date
WO1982001003A1 true WO1982001003A1 (en) 1982-04-01

Family

ID=22154555

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1980/001226 WO1982001003A1 (en) 1980-09-18 1980-09-18 Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines

Country Status (11)

Country Link
EP (1) EP0060838A4 (en)
JP (1) JPS57501626A (en)
AU (1) AU531392B2 (en)
BE (1) BE890373A (en)
BR (1) BR8009109A (en)
CA (1) CA1170655A (en)
DK (1) DK224182A (en)
ES (1) ES505583A0 (en)
HU (1) HU185165B (en)
IT (1) IT1171535B (en)
WO (1) WO1982001003A1 (en)

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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4262000A (en) * 1979-03-09 1981-04-14 Bayer Aktiengesellschaft Combating fungi with 3-substituted pyridine derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4262000A (en) * 1979-03-09 1981-04-14 Bayer Aktiengesellschaft Combating fungi with 3-substituted pyridine derivatives

Also Published As

Publication number Publication date
HU185165B (en) 1984-12-28
AU531392B2 (en) 1983-08-18
EP0060838A4 (en) 1983-03-23
EP0060838A1 (en) 1982-09-29
IT8149315A0 (en) 1981-09-17
JPS57501626A (en) 1982-09-09
AU7177881A (en) 1982-04-14
CA1170655A (en) 1984-07-10
ES8306723A1 (en) 1983-06-01
BE890373A (en) 1982-03-16
IT1171535B (en) 1987-06-10
ES505583A0 (en) 1983-06-01
DK224182A (en) 1982-05-18
BR8009109A (en) 1982-08-10

Similar Documents

Publication Publication Date Title
KR940001774B1 (en) Pyridine-2,3-dicarboxylate esters
EP0057473A2 (en) A process for preparing trifluoromethylpyridyl (oxy/thio) phenoxypropionic compounds being especially active as herbicides
TW201029975A (en) Process for manufacturing substituted 3-pyridylmethyl ammonium bromides
US6015905A (en) Process for the preparation of 2-(6-substituted pyrid-2-yloxymethyl) phenylacetate
US4351943A (en) Production of 6-(chloro or substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridines
US4260766A (en) Preparation of (dichloromethyl) pyridines by reductive dechlorination
US4324896A (en) 6-(Substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridines
JP3963499B2 (en) Improved process for the preparation of 5- (alkoxymethyl) pyridine-2,3-dicarboxylate
WO1982001003A1 (en) Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines
JP3287845B2 (en) Method for improving the synthesis of 2,6-dichloro-5-fluoronicotinic acid and 2,6-dichloro-5-fluoronicotinoyl chloride
US4358594A (en) Process for preparing certain 6-phenoxy-2-pyridinecarboxaldehydes
JPS63156753A (en) Production of alkyltrifuloroacetoacetate
US4349680A (en) 6-(Chloro or substituted phenoxy)-2-di-(substituted phenoxy) methyl pyridines
US4267336A (en) Process for producing 4-(pyridyl-2-oxy)-phenoxyalkanecarboxylic acid or its derivatives
KR100567197B1 (en) Chemical process for preparing 2-hydroxy-6-trifluoromethylpyridine
CA1217192A (en) Method of preparing esters of aryloxyphenoxy propanoic acid
US5017705A (en) Production of 3,5,6-trichloropyridin-2 ol and novel intermediates thereof
JPH0770037A (en) Production of cyanoacylcyclopropane compound and 2-cyanoacyl-4-butanolide compound used therefor
JP2002524447A5 (en)
US4127582A (en) Method of preparing alkyl halopyridinyloxyalkanoates
JP3293676B2 (en) Process for producing halomaleic acid and halofumarate esters
JPH06199798A (en) Preparation of 2,3-pyridine-dicarboxylic acid from 3-(2-imidazolin-2-yl)-picolinic acid
US6066734A (en) Chloropyrimidine process
JPH0234932B2 (en) ARIIRUOKISHUDOTAINOGOSEIHOHO
JPS632954B2 (en)

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): AU BR DK GB HU JP SU US

AL Designated countries for regional patents

Designated state(s): AT CH DE FR LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1981901356

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1981901356

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1981901356

Country of ref document: EP