CA1170655A - 6-(chloro or substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridines - Google Patents
6-(chloro or substituted phenoxy)-2-di-(substituted phenoxy)methyl pyridinesInfo
- Publication number
- CA1170655A CA1170655A CA000386035A CA386035A CA1170655A CA 1170655 A CA1170655 A CA 1170655A CA 000386035 A CA000386035 A CA 000386035A CA 386035 A CA386035 A CA 386035A CA 1170655 A CA1170655 A CA 1170655A
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- Prior art keywords
- chloro
- carbon atoms
- pyridine
- alkyl
- methyl
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds are prepared corresponding to the formula wherein Y represents chloro or R'; R represents
Compounds are prepared corresponding to the formula wherein Y represents chloro or R'; R represents
Description
6-(CHLORO OR SUBSTITUTED PHENOXY)-2--DI-(SUBSTITUTED PHENOXY)METHYL PYRIDINES
Substituted phenoxy pyridine methyl esters of cyclopropane carboxylic acids are taught in U.S.
Patent 4,163,787 issued August 7, 1979. These com-pounds are useful in the kill and control of various insect pest. These compounds are prepared by the reaction of an appropriate substituted phenoxy pyridine methanol with an appropriate 2,2-dimethyl-3-(2,2-dihalo-ethenyl)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 desired compounds very expensive : and less attractive for exploitation.
The present invention is directed to compounds corresponding to the formula y~ CH(R)2 . wherein Y represents chloro or R'; R represents 28,863-F -1-~ ,.
_O _~Xn wherein X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkyl-thio of l 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 making 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 prepare additional intermediate compounds for conversion into the corresponding picolinaldehydes. The picolinalde-hydes can in turn be converted to substituted phenoxy pyridine methanols. These latter compounds can then ; 20 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 insec-ticidal substituted pyridine methyl esters of cyclo-propane carboxylic acids.
~`
The 6-(chloro or substituted phenoxy)-2-di--(substituted phenoxy)methyl pyridines of the present invention are either solids or liguids which are only slightly soluble in water and usually are moderately to highly soluble in common organic solvents.
28,863-F -2-g~ r~
The compounds of the present invention can be ~repared by the reaction of one mole of 2-chloro-6--(dichloromethyl)pyridine with from l to 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 whereir. ~ and "~' 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:
Cl ~ C~(C1~2 + M0 - ~ ~ So1vent >
( $ n) + MCl H H
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 100 to 200C and stirred for from 2 to 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, 28,363-F -3-j ~ J~
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 ~L ~ y~iuine reactant to 3 molar eguivalents of the phenol reactant. However, 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 proce-dure, the pyridine reactant, an appropriate substituted methoxy 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 sulfoxide, 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:
28,863-F -4-i s l:~
Cl--~CH(c1)2 + MO~ n S~
Cl~L ( H
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 phenoxy)methyl)pyridine with one mole of an alkali metal salt of the appropxiate substituted phenol in the presence of a solvent. This reaction scheme is : as follows:
Cl~ ~ ~ )2 ~
~ CE~- ~0~ ) + MCl 28,863-F -5-J 3 ~
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 phenoxy)-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 60 to 150C for from 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.
- The following examples further illustrate the present invention.
28,863-F -6-~ ~ ,'3fi~5 Example 1 - 2-Chloro-6-(diphenoxymethyl)pyridlne Cl ~ CH- ( O - ~ ) A mixture of 25 g (0.13 mole ) of 2-chloro--6-(dichloromethyl)pyridine, 29.91 g (0.32 mole) of phenol and 17.84 g (0.32 mole) of potassium hydroxide in 100 ml of dimethylsulfoxide was heated, with stirring, for 6 hours at 70C. The reaction mixture was cooled, 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 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 mm of mercury and had a refractive index of n25 = 1.59~1. The elemental analysis showed the product to have carbon, hydrogen and nitrogen con-tents 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 compounds set forth below in TABLE I can be prepared.
28,863-F -7-~ 1 706~5 V
~ O ~ O D O
o~ ~ t` U~
o ~ ~ o~ ,i t~
u~ o U~
. ~n . .
~1 ~
.. t~ 11 11 11 11 11 !J
~ Nla ~la ~ ~la ~la ~la .~ Z I ~ , O
~C I
~ m o ~
H \~
OD
~ l ~ ~ ~ ~ ~ ~
~:1 V ,U~ V ' d' Is') I ~ u~
<~Z ,~ ~ 0 ~;
V ~:1 t` O ~1 ~ ~
V ~` ~O O
D ~ ~ O
U~
X~
~1 V S~
V 0 ~4 V V
l l l l l l d~ ~ ~ ~ ~r) ~) 28, 863-F -8-- ~ ~ 7`~5 *
h ~U~ ~o Oo ~,1o~
hr--d' ~ O
In ~U~
d V1111. Il ~1 Nl~ ~1~ ~la NIÇ:~
rC C C C
O
0 0 U~ U~
d' $ I ~
H
~ ~~ ~1 -rl tn o .. . ~
.~ ~ ~ o v ~n ~DLn ~ ~ td ~1 h 3 ~o ~ ~ o ~ ~~ ~ ~1~
o C
P:~ ~0 Ln P~
~) ~~D O CO
o N ~d' O ~
O o 11 ~ ~4 H ~: C~
:~ - O
I
a: ~ v~o I
E~ ~ d'~ ~
28, 863-F -9-I :1 7~655 Example 2 - 2-[Bis-(4-methoxyphenoxy)methyl]-6--(4-methoxYphenoxy)pyridine C~3O ~ O ~ C~- (o ~ OcH3)2 A mixture of 15.04 g (0.076 mola3 of 2--dichloromethyl-6-chloropyridine, 39.50 g (0.32 mole) of p-methoxyphenol and 18.14 g (0.32 mole) of potas-sium hydroxide in 100 ml of dimethylsulfoxide was heated, with stirring, for 72 hours. The resulting mixture was cooled to 25C, diluted with water and extracted with l,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, removing as impurities any material boiling up to 200C
at 0.05 to 1 mm of mercury. The 2-[bis-(4-methoxy-phenoxy)methyl]-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 com-pound.
By following the preparative procedure as outlined in the above example, the following com-pounds set forth below in Table II can be prepared.
28,863-F -10-t ~
o ~a O
In rl ~
. ~, ,, O OD ~I Ln o aD ~ ~ ' ~ ~
I ~ o ~ o o a) Ln ~ . ..
~1 r~ ~n a -I ~ O
. ~ Z ~
N
O ~
H O 1~
C~ ~ ~ O
~n c~
I ~1 ~ O t~
~Z ~ r~
Z I
O I ~
oo ~ ~ ~ a ~1 ~ ~ ~D O
~c ~ ~
: ~ 10 ~ ~
~DO rl t`
,~ h m v v m I
28, 863-F -11-r~
*
s~
rl o U~
~o ~ 11 ,i o U~ U~ I U
Nla .~a P
~ ~ N ~D
t`~ ~
oD OD
a~ .
~ ~ . ~
,~ r~ ~ . o U~
P`~
td .~ ~ ~
N a . ~D
d ~
:~ ' ~ P:
~ O ~ .
~ . . r~
o ~ 0 11 H ~ V
-O *
. ~
1~4 d' E~ .
28, 863-F -12-1 ~ S1 ~ 6 ~
Example 3 - 6-(3-Fluorophenoxy)picolinaldehyde F ~ o ~ C=o A solution of 2.5 g (0.0059 mole) of 2-[bis--(3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine and 20 ml of 80 percent acetic acid was ..eated, with stirring, at 150C overnight. The reaction mixture was COolêd, 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 to 43C.
Example 4 - 6-(Phenoxy)PicolinaldehYde ~ 0 ~ C=0 To a solution of 0.5 g (0.0025 mole) of
Substituted phenoxy pyridine methyl esters of cyclopropane carboxylic acids are taught in U.S.
Patent 4,163,787 issued August 7, 1979. These com-pounds are useful in the kill and control of various insect pest. These compounds are prepared by the reaction of an appropriate substituted phenoxy pyridine methanol with an appropriate 2,2-dimethyl-3-(2,2-dihalo-ethenyl)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 desired compounds very expensive : and less attractive for exploitation.
The present invention is directed to compounds corresponding to the formula y~ CH(R)2 . wherein Y represents chloro or R'; R represents 28,863-F -1-~ ,.
_O _~Xn wherein X independently represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkyl-thio of l 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 making 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 prepare additional intermediate compounds for conversion into the corresponding picolinaldehydes. The picolinalde-hydes can in turn be converted to substituted phenoxy pyridine methanols. These latter compounds can then ; 20 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 insec-ticidal substituted pyridine methyl esters of cyclo-propane carboxylic acids.
~`
The 6-(chloro or substituted phenoxy)-2-di--(substituted phenoxy)methyl pyridines of the present invention are either solids or liguids which are only slightly soluble in water and usually are moderately to highly soluble in common organic solvents.
28,863-F -2-g~ r~
The compounds of the present invention can be ~repared by the reaction of one mole of 2-chloro-6--(dichloromethyl)pyridine with from l to 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 whereir. ~ and "~' 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:
Cl ~ C~(C1~2 + M0 - ~ ~ So1vent >
( $ n) + MCl H H
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 100 to 200C and stirred for from 2 to 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, 28,363-F -3-j ~ J~
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 ~L ~ y~iuine reactant to 3 molar eguivalents of the phenol reactant. However, 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 proce-dure, the pyridine reactant, an appropriate substituted methoxy 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 sulfoxide, 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:
28,863-F -4-i s l:~
Cl--~CH(c1)2 + MO~ n S~
Cl~L ( H
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 phenoxy)methyl)pyridine with one mole of an alkali metal salt of the appropxiate substituted phenol in the presence of a solvent. This reaction scheme is : as follows:
Cl~ ~ ~ )2 ~
~ CE~- ~0~ ) + MCl 28,863-F -5-J 3 ~
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 phenoxy)-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 60 to 150C for from 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.
- The following examples further illustrate the present invention.
28,863-F -6-~ ~ ,'3fi~5 Example 1 - 2-Chloro-6-(diphenoxymethyl)pyridlne Cl ~ CH- ( O - ~ ) A mixture of 25 g (0.13 mole ) of 2-chloro--6-(dichloromethyl)pyridine, 29.91 g (0.32 mole) of phenol and 17.84 g (0.32 mole) of potassium hydroxide in 100 ml of dimethylsulfoxide was heated, with stirring, for 6 hours at 70C. The reaction mixture was cooled, 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 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 mm of mercury and had a refractive index of n25 = 1.59~1. The elemental analysis showed the product to have carbon, hydrogen and nitrogen con-tents 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 compounds set forth below in TABLE I can be prepared.
28,863-F -7-~ 1 706~5 V
~ O ~ O D O
o~ ~ t` U~
o ~ ~ o~ ,i t~
u~ o U~
. ~n . .
~1 ~
.. t~ 11 11 11 11 11 !J
~ Nla ~la ~ ~la ~la ~la .~ Z I ~ , O
~C I
~ m o ~
H \~
OD
~ l ~ ~ ~ ~ ~ ~
~:1 V ,U~ V ' d' Is') I ~ u~
<~Z ,~ ~ 0 ~;
V ~:1 t` O ~1 ~ ~
V ~` ~O O
D ~ ~ O
U~
X~
~1 V S~
V 0 ~4 V V
l l l l l l d~ ~ ~ ~ ~r) ~) 28, 863-F -8-- ~ ~ 7`~5 *
h ~U~ ~o Oo ~,1o~
hr--d' ~ O
In ~U~
d V1111. Il ~1 Nl~ ~1~ ~la NIÇ:~
rC C C C
O
0 0 U~ U~
d' $ I ~
H
~ ~~ ~1 -rl tn o .. . ~
.~ ~ ~ o v ~n ~DLn ~ ~ td ~1 h 3 ~o ~ ~ o ~ ~~ ~ ~1~
o C
P:~ ~0 Ln P~
~) ~~D O CO
o N ~d' O ~
O o 11 ~ ~4 H ~: C~
:~ - O
I
a: ~ v~o I
E~ ~ d'~ ~
28, 863-F -9-I :1 7~655 Example 2 - 2-[Bis-(4-methoxyphenoxy)methyl]-6--(4-methoxYphenoxy)pyridine C~3O ~ O ~ C~- (o ~ OcH3)2 A mixture of 15.04 g (0.076 mola3 of 2--dichloromethyl-6-chloropyridine, 39.50 g (0.32 mole) of p-methoxyphenol and 18.14 g (0.32 mole) of potas-sium hydroxide in 100 ml of dimethylsulfoxide was heated, with stirring, for 72 hours. The resulting mixture was cooled to 25C, diluted with water and extracted with l,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, removing as impurities any material boiling up to 200C
at 0.05 to 1 mm of mercury. The 2-[bis-(4-methoxy-phenoxy)methyl]-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 com-pound.
By following the preparative procedure as outlined in the above example, the following com-pounds set forth below in Table II can be prepared.
28,863-F -10-t ~
o ~a O
In rl ~
. ~, ,, O OD ~I Ln o aD ~ ~ ' ~ ~
I ~ o ~ o o a) Ln ~ . ..
~1 r~ ~n a -I ~ O
. ~ Z ~
N
O ~
H O 1~
C~ ~ ~ O
~n c~
I ~1 ~ O t~
~Z ~ r~
Z I
O I ~
oo ~ ~ ~ a ~1 ~ ~ ~D O
~c ~ ~
: ~ 10 ~ ~
~DO rl t`
,~ h m v v m I
28, 863-F -11-r~
*
s~
rl o U~
~o ~ 11 ,i o U~ U~ I U
Nla .~a P
~ ~ N ~D
t`~ ~
oD OD
a~ .
~ ~ . ~
,~ r~ ~ . o U~
P`~
td .~ ~ ~
N a . ~D
d ~
:~ ' ~ P:
~ O ~ .
~ . . r~
o ~ 0 11 H ~ V
-O *
. ~
1~4 d' E~ .
28, 863-F -12-1 ~ S1 ~ 6 ~
Example 3 - 6-(3-Fluorophenoxy)picolinaldehyde F ~ o ~ C=o A solution of 2.5 g (0.0059 mole) of 2-[bis--(3-fluorophenoxy)methyl]-6-(3-fluorophenoxy)pyridine and 20 ml of 80 percent acetic acid was ..eated, with stirring, at 150C overnight. The reaction mixture was COolêd, 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 to 43C.
Example 4 - 6-(Phenoxy)PicolinaldehYde ~ 0 ~ C=0 To a solution of 0.5 g (0.0025 mole) of
2-[bis-(phenoxy)methyl]-6-(phenoxy)pyxidine in 15 ml of 1,4-dioxane was added dropwise, 5 percent sulfuric acid until the mixture just became turbid. The mix-ture was heated over a steam bath at 80-90C 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 por-tions of water and then with 50 ml of a saturated sodium chloride solution. The extract was then dried 28,863-F -13-fi ~ r~
over sodium sulfate and the solvent removed by evapora-tion 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.
28,863-F -14-
over sodium sulfate and the solvent removed by evapora-tion 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.
28,863-F -14-
Claims (8)
1. A compound corresponding to the formula wherein Y represents chloro or R'; R represents 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 repre-sents 3,4-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.
28,863-F -15-
28,863-F -15-
4. The compound of Claim 1 which is 2-[bis-(phenoxy)methyl]-6-(phenoxy)pyridine.
5. A process for the preparation of com-pounds corresponding to the formula wherein Y represents chloro or R'; R represents 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 repre-sents 3,4-methylenedioxy and R' represents R, with the proviso that R and R' can be the same or differ-ent, which comprises reacting one mole of 2-chloro--6-(dichloromethyl)pyridine with from 1 to 3 moles of an alkali metal salt of at least one substituted phenol which corresponds to the formula 28,863-F -16-wherein M represents sodium, potassium, lithium or cesium at a temperature of from 100° to 200°C and in the presence of a solvent and recovering the desired product therefrom.
6. The process of Claim 5 wherein Y is chloro.
7. The process of Claim 6 wherein one mole of 2-chloro-6-(dichloro-methyl)pyridine is reacted with about two moles of the alkali metal salt of the substituted phenol to produce a 2-chloro-6-((disubstituted phenoxy)methyl) pyridine.
8. The process of Claim 7 wherein one mole of 2-chloro-6-((disubsti-tuted phenoxy)methyl)pyridine is reacted with about one mole of the alkali metal salt of the substituted phenol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1980/001226 WO1982001003A1 (en) | 1980-09-18 | 1980-09-18 | Certain 6-chloro-2-di-(substituted phenoxy)methyl pyridines |
| US80/01226 | 1980-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170655A true CA1170655A (en) | 1984-07-10 |
Family
ID=22154555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000386035A Expired CA1170655A (en) | 1980-09-18 | 1981-09-16 | 6-(chloro or substituted phenoxy)-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)
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2909287A1 (en) * | 1979-03-09 | 1980-09-18 | Bayer Ag | 3-SUBSTITUTED PYRIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
-
1980
- 1980-09-18 BR BR8009109A patent/BR8009109A/en unknown
- 1980-09-18 EP EP19810901356 patent/EP0060838A4/en not_active Withdrawn
- 1980-09-18 WO PCT/US1980/001226 patent/WO1982001003A1/en not_active Ceased
- 1980-09-18 HU HU811893A patent/HU185165B/en unknown
- 1980-09-18 JP JP56501728A patent/JPS57501626A/ja active Pending
- 1980-09-18 AU AU71778/81A patent/AU531392B2/en not_active Withdrawn - After Issue
-
1981
- 1981-09-16 BE BE0/205975A patent/BE890373A/en not_active IP Right Cessation
- 1981-09-16 CA CA000386035A patent/CA1170655A/en not_active Expired
- 1981-09-17 IT IT49315/81A patent/IT1171535B/en active
- 1981-09-17 ES ES505583A patent/ES505583A0/en active Granted
-
1982
- 1982-05-18 DK DK224182A patent/DK224182A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| IT8149315A0 (en) | 1981-09-17 |
| AU7177881A (en) | 1982-04-14 |
| IT1171535B (en) | 1987-06-10 |
| WO1982001003A1 (en) | 1982-04-01 |
| JPS57501626A (en) | 1982-09-09 |
| EP0060838A1 (en) | 1982-09-29 |
| AU531392B2 (en) | 1983-08-18 |
| HU185165B (en) | 1984-12-28 |
| DK224182A (en) | 1982-05-18 |
| BE890373A (en) | 1982-03-16 |
| ES8306723A1 (en) | 1983-06-01 |
| BR8009109A (en) | 1982-08-10 |
| ES505583A0 (en) | 1983-06-01 |
| EP0060838A4 (en) | 1983-03-23 |
| IT8149315A1 (en) | 1983-03-17 |
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