JPS6234022B2 - - Google Patents

Description

[Detailed description of the invention] The present invention is based on the general formula

[Formula] (wherein, (representing an integer up to 5). Halogenated alkyl phenyl ethers are useful as intermediates for agricultural chemicals. However, conventional methods for producing ether compounds include (1) a method using a polar solvent (for example, Tetsuji Kametani, Organic Synthetic Chemistry, Reaction Edition 1, pp. 35-54, Nankodo Publishing); (2) quaternary ammonium Methods using phase transfer catalysts such as salts, quaternary phosphonium salts (e.g., W.P. Weber, G.W.
Gokel, Phase Transfer Catalysis in Organic Synthesis (WPWeber, GWGokel, Phase Transfer
Catalysis in Organic Synsesis) 73-84
Page) and other methods are known. However, when these methods are used for the purposes of the present invention, the general formula

[Formula] (wherein n, R and m have the same meanings as above) are produced in large quantities and the yield is low. In addition, since method (1) uses an expensive solvent, it is necessary to recover the solvent.
Furthermore, in method (2), it was necessary to recover the catalyst, and the operations were complicated in both cases. The present inventors conducted various studies to obtain a method that does not have these drawbacks, and as a result, a method was developed in which a dihalogenated alkane and a substituted phenol were reacted in the presence of an alkali by adding a nonionic surfactant. It was discovered that the reaction was rapid and that halogenated alkyl phenyl ethers could be obtained in high yields.
The present invention has now been completed. That is, the present invention provides a compound having the general formula X(CH ₂ )nX' (wherein X and
and X′ may be the same or different. n
represents an integer of 2 or more. ) and the general formula

[Formula] (wherein, R represents a hydrogen atom, an alkyl group, a halogen atom, a nitro group, a trifluoromethyl group, or a methylthio group, and m represents an integer from 0 to 5) was reacted in the presence of an alkali and a nonionic surfactant to form the general formula

This is a method for producing a halogenated alkyl phenyl ether represented by the formula: (wherein X, n, R and m have the same meanings as above). Hereinafter, to specifically explain the present invention, general formula X (CH ₂ ) used in the method of the present invention
The dihalogenated alkane represented by nX′ is
X and X' are halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and
X' may be the same or different, and n is preferably an integer of 2 or more, preferably an integer of 2 to 6; for example, 1・2-dichloroethane, 1,2-dibromoethane, 1-chloro-2
-bromoethane, 1-chloro-2-iodoethane, 1,3-dichloropropane, 1,3-dibromopropane, 1-chloro-3-bromopropane,
1-chloro-3-iodopropane, 1-fluoro-3-chloropropane, 1,4-dichlorobutane, 1-chloro-4-bromobutane, 1,5-dichloropentane, 1-chloro-5-bromopentane, 1. 6-dichlorohexane, 1-chloro-6
- Bromohexane, etc., but are not limited to these. Also general formula

In the substituted phenol represented by the formula, R is a hydrogen atom and the number of carbon atoms is 1.
The above, preferably C ₁ to ₈ , straight chain, finely divided,
Any one may be used, for example, a methyl group, an ethyl group, a normal-propyl group, an iso-propyl group,
normal-butyl group, secondary butyl group, tert-butyl group, pentyl group, hexyl group,
These include alkyl groups such as an octyl group, halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a nitro group, a trifluoromethyl group, a methylthio group, and m represents an integer from 0 to 5. , preferably an integer from 0 to 3, such as phenol, O-cresol, m-cresol, P-cresol, 2,3-dimethylphenol, 3,4-
Dimethylphenol, 4,5-dimethylphenol, 4-ethylphenol, 2-iso-propylphenol, 4-tert-butylphenol, 2-secondary butylphenol, 4-secondary pentylphenol, 3-methyl-6
-iso-propylphenol, 5-methyl-4-
Iso-propylphenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-fluorophenol, 4-bromophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,4,6- Trichlorophenol, 4-chloro-5-methylphenol, 2
-Methyl-4-chlorophenol, 4-nitrophenol, 2,4-dinitrophenol, 2-nitro-4-methylphenol, 5-trifluoromethylphenol, 4-methylthiophenol, 4-methylthio-m-cresol, etc. Examples include, but are not limited to. Further, examples of the alkali include alkali metals, alkaline earth metals, hydroxides and carbonates thereof, and the like. The nonionic surfactants used in the reaction of the present invention are listed (brand names in brackets), for example, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monostearate (Tween 60). , Polyoxyethylene Sorbitan Monooleate (Tween 80), Polyoxyethylene Sorbitan Monooleate (Tween 81), Polyoxyethylene Sorbitan Trioleate (Tween 85) Sorbitan Monooleate (Span 80), Polyoxyethylene Alkylamine ( Amit 105), polyethylene glycol-600, polyoxyethylene lauryl ether (Emulgen 105), polyoxyethylene oleyl ether (Emulgen 404), polyoxyethylene alkyl phenyl ether (Liponox NCA), fluorosurfactant (Ftardient 200) ), dimethyl laurylamine (Furmin 20D), dimethyl coconut oil alkylamine (Furmin DMC), and the like, but are not limited to these. Used in the method of the invention. The appropriate amount of the dihalogenated alkane to be used is at least equimolar, preferably 2 to 10 times the molar amount of the substituted phenol. The amount of alkali to be used is equal to or more, preferably 1.1 to 3 times the mole of the substituted phenol, and it is preferably used as an aqueous solution. Furthermore, the amount of nonionic surfactant to be used varies somewhat depending on the individual compound, but preferably 0.0005 to 5 wt%, preferably 0.005 to 1 wt%, based on the substituted phenol.
% is appropriate. Further, the reaction temperature in the present invention can be carried out at 0°C or higher, preferably 30 to 130°C, and if necessary, the reaction may be carried out under pressure (in an autoclave). As described above, in the present invention, when reacting a halogenated alkane and a substituted phenol, the reaction is carried out in the presence of an alkali and a nonionic surfactant. phenyl ethers (In the formula, n, R and m represent the same meanings as above.) It is possible to suppress the by-product of This is a highly effective manufacturing method. The present invention will be explained more clearly by Examples and Comparative Examples below, but these are not intended to limit the present invention. Example 1 18.8 g (0.2 mol) of phenol, 76.2 g (0.6 mol) of 1,4-dichlorobutane, and firmin
0.19g of DMC (1.0wt% based on phenol) was placed in a 300ml 4-diameter glass flask equipped with a cooler, thermometer, dropping funnel, and stirrer, and the reactor was heated externally while maintaining the liquid temperature at 100℃. , 35 g of 48% potassium hydroxide was added from the dropping funnel. After dropping, the reaction was carried out at reflux temperature for 3 hours.
32.2 g of 4-chlorobutylphenyl ether was obtained. The yield was 87.2% (based on phenol). Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that Furmin DMC was not used, and 25.8 g of 4-chlorobutylphenyl ether was obtained. The yield was 69.9% (based on phenol). Comparative Example 2 Phenol 18.8g (0.2mol), potassium hydroxide
96% flakes, 16.1g, 500ml dimethylformamide (DMF) and 1,4-dichlorobutane
Add 76.2 g (0.6 mol) to a 14-diameter glass flask equipped with a cooler thermometer and a stirrer, and
The reaction was carried out at ℃ for 3 hours. Pour the reaction solution into water, separate the organic layer, and distill it to 122-123℃/7mmHg.
22.1g of fraction was obtained. The yield of 4-chlorobutyl phenyl ether was 59.9% (based on phenol). Comparative Example 3 2.27g (5 mol%) of triethylbenzylammonium chloride instead of Firmin DMC
Using the same method as in Example 1, 4
-25.0 g of chlorobutyl phenyl ether was obtained.
The yield was 67.8% (based on phenol). Example 2 The amount of 1,4-dichlorobutane used was 127.0g
(1 mol) and the same procedure as in Example 1 was repeated except that 36.4 g of 4-chlorobutylphenyl ether was obtained. The yield was 98.6% (based on phenol). Example 3 The same procedure as in Example 2 was carried out except that 13.5 g of a 30% aqueous potassium carbonate solution was used, and 33.3 g of 4-chlorobutylphenyl ether was obtained. The yield was 90.2% (based on phenol). Examples 4 to 44 The same procedure as in Example 2 was conducted except that the substituted phenol, dihalogenated alkane, surfactant, etc. were used differently. The results are shown in the table below.

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula X(CH ₂ ) _o X' (wherein, X and X' represent a halogen atom,
X and X' may be the same or different. n represents an integer of 2 or more. )
A dihalogenated alkane represented by the general formula (In the formula, R represents a hydrogen atom, an alkyl group, a halogen atom, a nitro group, a trifluoromethyl group, or a methylthio group, and m represents an integer from 0 to 5.) It is characterized by being reacted in the presence of a nonionic surfactant. general formula A method for producing a halogenated alkyl phenyl ether represented by the formula (wherein, X, n, R and m have the same meanings as above).