BE617109A - - Google Patents

Description

       

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  : "ALIPHATIC ETHERS OF DIARYL OXIDE HYDROXYMETHYLES" .-

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The present invention relates to novel aliphatic ethers of hydroxymethylated diaryl oxides and their production process.



   The novel compounds according to the present invention are aliphatic ethers of hydroxymethylated diaryl oxides of the general formula.
 EMI2.1
 (Rt7CH'2) - (ri-Ci-Az 'xn in which Ar represents an aromatic radical, this derivative of benzene is preferred, R represents an aliphatic radical having from 1 to 4 carbon atoms, R' is hydrogen, a halogen, an aryl radical, such as an ohenyl or naphthyl radical, or an alkyl or alkoxy radical, in particular radicals of this type which contain from 1 to 4 carbon atoms, m is an integer between 1 and 4 and n is an integer equal to 1 or 2.



   The manner in which the connection of the moiety formed by the aliphatic ether to the diaryl oxide is shown indicates that this aliphatic ether can be attached to either of the aromatic radicals. Usually, the fractions formed by the aliphatic ether of the polyfunctional compounds are distributed among the aromatic portions of the oxide, such that each aromatic radical of the compound has at least one fraction formed by the ali ether. - phatic and, when possible, an equal number of these fractions.



   Examples of the compounds of the invention are p-methoxymethyl diphenyl oxide, 4,4'-di- (methoxymethyl)
 EMI2.2
 diphenyl oxide, 4,4'-di- (ethoxymethyl} diphenyl oxide, 1,4? -di (butoxymethyl) diphenyl oxide, para-allyloxymethyl diphenyl oxide, para- (2-methylallyloxymethyl) diphenyl oxide,

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 EMI3.1
 ortho-allyloxymethyl di (para-chlorophenyl) oxy, z ,, 4'- di (allyloxymethyl} to {ortho-bromo? hény1) oxide, 24 '- d (al-lyloxymethyljdiphenyl oxide, 2,4 , 4r-tri (allyloxymethyl) di-phenyl oxide, 2,2r, 41-triiallyloacymétryl) dinhengl oxide, lu 4,4'di (allyloxymethyl) di (orthotolyl) oxide, 2,2Jdi (2 aethylallyloxymethyl) di (parabutylphenyl) ) oxide and 2,2T-di (2-aethylallyloxymethyl) di (para-butoxyphenyl) oxide.



   The new compounds of the invention can be
 EMI3.2
 easily formed by the Williamson-type reaction for the synthesis of ethers. In accordance with this reaction, a halogenomethylated diaryl oxide can be reacted with a suitable alcohol such as methanol, ethanol, propanol, butanol, allylic alcohol or 2-methallyl alcohol, in
 EMI3.3
 presence-demr alkali such as caustic soda or sodium carbonate, at high temperatures.



   The halogenomethylated diaryl oxides which can be used as starting materials in the process for the production of the new compounds according to the invention are generally known and correspond to the general formula:
 EMI3.4
 in which Ar is an aromatic radical, preferably derived from benzene, R is hydrogen, a halogen, an aryl radical such as a phenyl or naphthyl radical or an alkoxy or alkyl radical, in particular containing from 1 to 4 carbon atoms, X is a halogen such as chlorine or bromine, m is an integer between 1 and 4 and n is equal to 1 or 2.



   These compounds can be used in the form of a mixture of isomers or homologs or in the form of pure compounds. When a mixture is used, the novel compound of the present invention is a corresponding mixture of isomers and homologs of the compounds described, having the same or different number of aliphatic ether groups per molecule.

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   When preparing the compounds of the invention, an effective amount of an alkali hydroxide may be added to a mixture of the alcohol used and the halo-methylated diaryl oxide, or the latter may be added to a mixture of alcohol and alkali hydroxide. The resulting mixture is heated to an elevated temperature of at least about 60 ° C. under autogenous pressure or at atmospheric pressure. The most suitable reaction temperature is the reflux temperature of the mixture. Higher temperatures, for example up to about 300 ° C, can be used if care is taken to ensure adequate heat removal. exotherm of the reaction and if, when the mixture is above its boiling point, the reaction is carried out in a pressurized system.

   Care must be taken when adding the alkali or oxide because of the large amount of heat of reaction that can be given off.



   The amount of alkali used should preferably be at least one mole for each chemical equivalent of the halo-methyl moiety present in the diaryl oxide as a starting material. The upper limit amounts of alkali are not critical. They are imposed by economic and other practical conditions known to those skilled in the art. A preferred molecular ratio of the alkali to the organic halogen is about 1.05: 1.00.



   The aliphatic alcohol is preferably used in an amount exceeding that required to react stoichiometrically with each halomethyl moiety available in the diaryl oxide as a starting material. Usually 2 to 10 moles of the alcohol per chemical equivalent of halomethyl fraction present gives very satisfactory results. Higher quantities can be used, but this is generally not economical

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In an improved embodiment of the above process, the halomethylated diaryl oxide is dissolved in a portion of the alcohol with which it is to react, and the resulting solution is added to the heated mixture of alcohol and alkali.

   In another embodiment, an unreactive organic solvent, for example dioxane, is used as the inert reaction medium. When the addition of the dialogenomethylated oxide to the reaction system is complete, the entire reaction mass is maintained at an elevated temperature, for example at the reflux temperature of the reaction mass, for a period of time. extended period of time.



   Although one can obtain an effective quantity
 EMI5.1
 of the desired product within a few minutes of contact with the reactants, it is usually desirable to apply the reaction conditions for several hours, in order to ensure the conversion of a substantial proportion of the reactants to the desired product. This is especially true if batch reaction techniques are used, but, as those skilled in the art will readily understand, with continuous processes in which unreacted ingredients are continually recovered and recycled into the streams sent to the stream. reaction zone, contact times can be relatively short for efficient operation.



   When a desired degree of conversion of the reactants to the desired product has been obtained, the reaction mass can be filtered to remove any alkali halides which may have formed during the reaction. Then, the filtrate is heated under reduced pressures to distill off unreacted alcohol or other volatiles which may be present. The product thus recovered comprises
 EMI5.2
 "-tt- t .l ',,. 4' .....: .....



  -. essentially the desired aliphatic ether of a hydroxymethylated diaryl oxide.
 EMI5.3
 



  The novel allyloxymethylated diaryl oxides of the present invention are useful as toxic constituents.

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 in compositions for combating insects and fungi. In such applications, the above products can be dispersed over finely divided inert solids and used as powdering agents. In other modes of use, the compositions can be dispersed in water using a wetting agent and the resulting aqueous suspension used as a spray.

   In still other operations, the compounds can be dissolved in suitable organic solvents and the resulting composition used directly or as a component of an oil-in-water or water-in-oil emulsion to obtain an oil-in-water or water-in-oil emulsion. a composition which can be used in the form of a spray or a slurry.



   EXAMPLE1
In a one liter flask fitted with a stirrer, a thermometer and a reflux condenser, about 250 em3 of methanol and about 40 g of caustic soda are introduced. The resulting composition is heated to approximately 65 ° C., then one begins to bring it to reflux. At this time, 133 g of para-chloromethyl diphenyl oxide are added dropwise, while stirring; then, the reaction mass is maintained at its reflux temperature for about 4 hours, then allowed to cool. The reaction product is filtered to remove sodium chloride, then the solid product is washed with toluene to remove any organic material that may be retained. A mixture of the initial filtrate and the toluene washed filtrate is washed three more times with water.

   The organic phase is then dried over anhydrous sodium sulfate and filtered. Distilled at about 100 ° C. and under pressure: the organic product thus recovered is reduced to remove the toluene and the residual alkanol therefrom. Finally, 116.5 g of product are obtained having an index of refraction n25 of 1.5638. This product is distilled and the fraction collected

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 binds at about 105 C and under a pressure of 0.25 mm d mercury weighs 105 g. The distillate has an index of refraction n25 of 1.5642. Part of the purified product is subjected to chemical analysis to determine the carbon and hydrogen contents. The infrared absorption spectrum of the purified product is also obtained.

   It is found that the purified product contains 78.45% of carbon and 6.66% of hydrogen, while the theoretical amounts are 78.48% for carbon and 6.69% for hydrogen, for monomethoxy diphenyl oxide. In addition, the infrared spectrum confirms that the structure of the resulting product is that of para-methoxymethyl diphenyl oxide.



   EXAMPLE 2
400 g of methanol and 198 g of 85% caustic potash are introduced into a 3-liter glass flask, fitted with a reflux condenser, a stirrer and a drop-by-drop funnel. . We heat the mixture
 EMI7.1
 d .- '3Jt.ant..j.1J..s.qu.'à,.' 3a. reflux temperature, and a solution of 401 g of 4,4t-di (chloromethyl-dipenyl oxide in 272 g of methanol) is added dropwise to the methanol-alkali solution. During the addition of the chloromethylated diaryl oxide, the reaction mass is maintained at its reflux temperature due to the exothermic nature of the reaction.



  When the addition of the ether is complete, the reaction mixture is maintained at its reflux temperature for about 3 hours, to ensure substantially complete conversion of the reactants to the desired product. The reaction mixture is then cooled and filtered to remove the potassium chloride. The filtrate is heated in vacuo to remove unreacted methanol, and the residual product is distilled in a vacuum. 15.24 cm Vigreaux column, under reduced pressure. The fraction obtained boils at about 143 ° C. under an absolute pressure of 0.3 mm of mercury.

   With respect to matter

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 EMI8.1
 the starting yield of 4,4'-di (methoxymethyljdiphenyl oxide thus obtained is 62.5%. This product is a colorless liquid having a refractive index n25 of 1.5543 '.
In a manner similar to that described above, other compositions in accordance with the present invention are prepared by replacing methanol with other alcohols, such as ethanol, propanol and butanol. , for
 EMI8.2
 form them, - 1. ' di (alkoYVm '<; "' 'I ..' \ ... 3'1ph. 'corresponding oxides. The refractive index and the boiling point under reduced pressure of these products are given in Table I below. - below.



   TABLE I
 EMI8.3
 
<tb> Composition <SEP> Index <SEP> of <SEP> Point <SEP> Rende-
<tb>
 
 EMI8.4
 prepared fraction at eb. is lying
 EMI8.5
 
<tb> 25 & <SEP> C <SEP> Pressure <SEP>%
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> absolute <SEP> ¯¯¯¯¯
<tb>
 
 EMI8.6
 4 4'dz (ethoxymethpl
 EMI8.7
 
<tb> dlphenyl <SEP> oxide <SEP> le, 5405 <SEP> 166 C <SEP> 72
<tb>
<tb>
<tb>
<tb>
<tb> 0.1 <SEP> mm <SEP> Hg
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 4,4t-di (propoxymethyl) ,, <SEP> ...

   <SEP> 1.5321 <SEP> 186 C <SEP> 67
<tb>
<tb>
<tb>
<tb> diphenyl <SEP> oxide <SEP> 0.2 <SEP> mm <SEP> Hg
<tb>
 
 EMI8.8
 4,4r-di (butoxymethyl) 1.5265 lg3 C 51
 EMI8.9
 
<tb> diphenyl <SEP> oxide <SEP> 0.3 <SEP> mm <SEP> Hg
<tb>
 
EXAMPLE 3
The mixed reaction products obtained by chic romethylation of diphenyl oxide are etherified with methanol, ethanol, propanol and butanol in the presence of an alkali, in accordance with the process used in Example 2. The compositions of Mixed chloromethylated diaryl oxide which are used are given in Table II below. A convenient way to. to designate a particular reaction mixture is to give the weight of chlorine in that mixture.
 EMI8.10
 



  ,. .;, t. '"' 'he

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 TABLE II Compositions of methylated diaryl oxide classified according to their chlorine content
 EMI9.1
 17.6% Cl bzz Cl 25.2% Cl 3 0 7% Cl
 EMI9.2
 
<tb> (CMDPO-17 <SEP> (CMDPO-23) <SEP> (CMDPO-25) <SEP> (CMDPO-32)
<tb>
<tb>
<tb>
<tb> Constituent <SEP> Moles <SEP>
<tb>
<tb>
<tb>
<tb> Diphenyl <SEP> oxide
<tb>
<tb>
<tb> (DPO) <SEP> 17.3 <SEP> 0.0 <SEP> 0.0 <SEP> 0.0
<tb>
<tb>
<tb>
<tb> o-monochlorome-
<tb>
<tb>
<tb> thyl <SEP> DPO <SEP> 5.3 <SEP> 0.5 <SEP> 0.25 <SEP> 0.0
<tb>
<tb>
<tb>
<tb> p-monochlorome-
<tb>
<tb>
<tb> thyl <SEP> DPO <SEP> 42.9 <SEP> 4.7 <SEP> 2.35 <SEP> 0.04
<tb>
 
 EMI9.3
 o, p1-dichloromethyl DPO 10.8 35t + 17.7 1.9 p, pt-dichloromethyl DPO 20.6 37.7 69.5 8.6 rich7.oromethyl.
 EMI9.4
 
<tb>



  DPO <SEP> 2.3 <SEP> 21.1 <SEP> 10.5 <SEP> 89.0
<tb>
 
 EMI9.5
 Tetrachlorome-
 EMI9.6
 
<tb> thyl <SEP> DPO <SEP> 0.5-1.0 <SEP> 0.5-1.0 <SEP> 0.5 <SEP> -
<tb>
 
 EMI9.7
 Note; OEMPO - diphenyl oxyio chloromethyl DPO = diphenyl oxide
 EMI9.8
 The mixed aikoxymethyl products thus obtained are shown in Table III below at the same time as their refractive index, their density and their color.

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    TABLE III
 EMI10.1
 
<tb> Experienced <SEP> Compound <SEP> Precursor <SEP> 20 <SEP> 20 <SEP> Color
<tb>
<tb>
<tb> ce <SEP> alkoxym- <SEP> PDO <SEP> chloro- <SEP> nD <SEP> d20
<tb>
<tb>
<tb> n <SEP> thyl <SEP> DPO <SEP> methylated
<tb>
<tb>
<tb> mixed-
<tb>
<tb>
<tb> 1 <SEP> Methoxymethyl
<tb>
<tb> DPO <SEP> CMPDO-17 <SEP> --- <SEP> --- <SEP> ---
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> Ethoxymethyl <SEP> DPO <SEP> "<SEP> 1.5586 <SEP> 1.073 <SEP> yellow
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> Propoxvmethyl <SEP> 1.5515 <SEP> 1.059 <SEP> yellow
<tb>
<tb>
<tb> DPO <SEP> "<SEP> dark
<tb>
<tb>
<tb>
<tb> 4 <SEP> Butoxymethyl <SEP> 1.5452 <SEP> 1.042 <SEP> yellow
<tb>
<tb>
<tb> DPO
<tb>
<tb>
<tb>
<tb>
<tb> 5 <SEP> Methoxymethyl <SEP> CMDPO-23 <SEP> 1.5611 <SEP> 1,

  117 <SEP> yellow
<tb>
<tb>
<tb> DPO <SEP> clear
<tb>
 
 EMI10.2
 6 Ethoxymethyl n 1.5t67 l'0'7 yellow DPO clear 7 Propôxymethyl n 115381 1.054 yellow
 EMI10.3
 
<tb> DPO
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 8 <SEP> Butoxymethyl <SEP> "<SEP> 1.5300 <SEP> 1.033 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO <SEP> medium
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 9 <SEP> Methoxymethyl <SEP> CMPDO-25 <SEP> 1.5589 <SEP> 1.110 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO <SEP> very
<tb>
<tb>
<tb> clear
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 10 <SEP>.

   <SEP> Ethoxymethyl <SEP> "<SEP> 1.5442 <SEP> 1.069 <SEP> yellow
<tb>
<tb>
<tb> DPO <SEP> very
<tb>
<tb>
<tb>
<tb> clear
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 11 <SEP> Propoxymethyl <SEP> "<SEP> 1.5355 <SEP> 1.046 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO '
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 12 <SEP> Butoxymethyl <SEP> n <SEP> 1.5209 <SEP> 1.020 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 13 <SEP> Methoxymethyl <SEP> CMDPO-32 <SEP> 1.5540 <SEP> 1.112 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO <SEP> clear
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 14 <SEP> Ethoxymethyl <SEP> "<SEP> 1.5375 <SEP> 1.064 <SEP> yellow
<tb>
<tb>
<tb>
<tb> DPO <SEP> medium
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 15 <SEP> Propoxymethyl <SEP> "<SEP> 1.5277 <SEP> 1,

  040 <SEP> amber
<tb>
<tb>
<tb>
<tb> DPO <SEP> trouble
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 16 <SEP> Butoxymethyl <SEP> "<SEP> 1.5210 <SEP> 1.010 <SEP> yellow
<tb>
<tb>
<tb> DPO <SEP> dark
<tb>
 Note: DPO = diphenyl oxide
CMPDO = chloromethylated diphenyl oxide

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   EXAMPLE 4
In a representative operation, we introduce.



  580 g of allyl alcohol and 200 g of caustic soda, 670
 EMI11.1
 of 4,4'-dichloromethyl diphenvi oxide set 500 g of dioxane in a three-liter flask fitted with a reflux condenser, a stirrer and a dropwise introduction funnel.



  The resulting mixture is heated to its reflux temperature and the reaction is continued for about 2 hours. The reaction mixture was then cooled, and the precipitated sodium chloride was separated therefrom by filtration. Residual dioxane and allyl alcohol are removed from the filtrate by heating it to about 100 ° C. under a reduced pressure of about 100 mm Hg. The filtrate is further purified by distilling it in a molecular distillation apparatus of the modified Hickman type. The boiled fraction between 80 and 90 C under an absolute pressure of between 1 and 5 microns of mercury weighs 371 g. It is in the form of a clear liquid with an index of refraction n25 of 1.551. The pro-
 EMI11.2
 product thus obtained is - ± 'A 4,4-di (allyloxymethyl) diphenyl oxy- de.



   In a manner identical to that described
 EMI11.3
 above, 4,4I- * di (2-methylallyloxymethyl) di-phenyl oxide is prepared by replacing the allyl alcohol used above with 2-ethylallyl alcohol. The 4,4'-di- (2-methyl-allyloxymethyl) diphenyl oxide thus oreparated boils at 110-115 C under absolute pressures of 1 to 10 microns of mercury.



  The refractive index n25 of the compound is 1.5451.



   EXAMPLE 5
In a representative operation ,; spraying an aqueous dispersion containing 600 parts per million of 4.4'-
 EMI11.4
 di (2-methylallyloxymethyl) diphenyl oxide on young tomato plants until the leaves are fully impregnated. The spray impregnated plants are then allowed to dry and then inoculated with a suspension.

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 aqueous spores of the organism Alternaria solani. For comparison, the fungus was also inoculated into control plants which had not been treated with the above fungicidal composition. After inoculation, the plants are incubated for about 24 hours at about 23 ° C and 100% relative humidity.

   The plants are then maintained under normal growing conditions until the disease has fully developed in the inoculated control plants. A comparison of the control plants with the plants which were initially treated with the fungicidal composition of the invention shows that the malody was controlled at about 65%.



   In another operation, the application to young bean plants of an aqueous dispersion containing 4,4'- di (allyloxymethyl) diphenyl oxide as the only toxic ingredient at a concentration of 0.12 part per 100 parts of water. , provides 70% protection of bean plants against the larvae of Mexican bean weevils, of the species "Epilachana varivestis". The experiment was carried out by immersing the young bean plants for a while in the above insecticidal dispersion and on the dry plants, 10 Mexican bean weevil larvae per plant. Mortality checks are carried out after 5 days, the plants having been maintained at about 21 ° C.

   By way of comparison, a control group of bean plants is identically infested with the larvae, except that they are not treated with the compound object of the present invention. In this group, the weevil larvae continue to live without reducing the number of live larvae.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

CLAIMS 1.- New compound consisting of an aliphatic ether of a hydroxymethylated diaryl oxide, characterized in that it is represented by the general formula: <Desc / Clms Page number 13> EMI13.1 in which Ar is an aromatic radical, preferably derived from benzene, R is an aliphatic radical having 1 to 4 carbon atoms, Rt is hydrogen, halogen, an aryl radical such as a radical phenyl or naphthyl or an alkyl or alkoxy radical, preferably containing from 1 to 4 carbon atoms, m is an integer between 1 and 4, n is an integer equal to 1 or 2. 2. - Compound consisting of a mixture of isomers and homologues of the compound corresponding to the above formula, this mixture containing an identical or different number of aliphatic ether groups per molecule. 3. A process for the production of new compounds according to claim 1 or claim 2, characterized in that it consists in reacting a diaryl oxide of formula EMI13.2 (X-CH2 m --.- Ar-C-Ar --- Rn in..laqelle -8t an aromatic radical, preferably derived from benzene, R is hydrogen, a halogen, an aryl radical such as that a phenyl or naphthyl radical, or an alkyl or alkoxy radical, in particular comprising from 1 to 4 carbon atoms, X is a halogen such as chlorine or bromine, m is an integer between 1 and 4 and n is equal to 1 or 2, with an alcohol: aliphatic having 1 to 4 carbon atoms and in the presence of an alkali, at elevated temperatures. 4. A process according to claim 3, characterized in that the amount of aliphatic alcohol used is greater than that required for a stoichiometric reaction with each halo-methylated moiety available in the diaryl oxide constituting the material of the mixture. departure. 5. A process according to claim 4, characterized in that the aliphatic alcohol is used in an amount of 2 to 10 moles per chemical equivalent of the halogen fraction. <Desc / Clms Page number 14> no-methylated, available in the diaryl oxide constituting the starting material. 6. A process according to any one of claims 3 to 5, characterized in that the reaction is carried out at a temperature of at least 60 C. 7. A process according to any one of claims 3 to 6, characterized in that the alkali is used in an amount of at least 1 mole per chemical equivalent of halogenomethylated fraction present in the diaryl oxide. 8. A process for the production of an aliphatic ether of a hydroxymethylated diaryl oxide by reacting a halomethylated diaryloxide with an aliphatic alcohol in the presence of an alkali at elevated temperature, in substance as described above. 9.- Aliphatic ether of a hydroxymethylated diaryloxide when produced by the process according to claims 3 to 8. 10. - New compound consisting of an aliphatic ether of a hydroxymethylated diaryloxide substantially as described above, with reference to the examples *