JPH0226612B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to hydroxyneofyl chlorides and formula () {In formula (), R represents a lower acyl group} The acyloxyneophyl chloride represented by the formula () is hydrolyzed with acid in the presence or absence of an inert solvent to obtain the formula () The present invention relates to a method for producing hydroxyneofyl chloride represented by Hydroxyneofyl chloride represented by the formula () is a new compound, and is also a compound useful as an intermediate for pyrethroid insecticides. In recent years, synthetic pyrethroid insecticides have been in the spotlight as insecticides. This is because, along with its excellent insecticidal power, it is highly effective against pests resistant to organic phosphorus or carbamate agents, and is characterized by relatively low toxicity to humans and livestock. However, the disadvantage of this synthetic pyrethroid insecticide is that it is highly toxic to fish, which limits its range of use. Recently, the applicant has applied the general formula () {In formula (), R ¹ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an optionally substituted lower alkyl group, lower alkenyl group, lower alkoxy group, acyloxy group, lower alkylthio group, lower acyl group, Represents a methylenedioxy group. R ² and R ³ are the same or different hydrogen atoms,
represents a halogen atom, a lower alkyl group, or a lower alkoxy group} The 2-phenylpropyl ether derivative has extremely high insecticidal and acaricidal activity, and has excellent characteristics in terms of immediate effect and residual effect, The company applied for the patent after discovering that it has low toxicity not only to humans and livestock, but also to fish. (See Japanese Patent Application No. 55-148279 = JP-A No. 57-72928) In the above general formula (), a 2-phenylpropyl ether derivative in which R ¹ is substituted with an alkoxy group at the P position shows particularly excellent effects. It is an insecticide. Hydroxyneofyl chlorides are listed above ()
Although it is useful as an intermediate raw material for the 2-phenylpropyl ether derivative represented by the formula, it is a new compound that has never been synthesized before.
The reason for this is that hydroxyneofyl chlorides can be synthesized by, for example, chlorinating the side chain of t-butylphenol, but in this case, nuclear chlorination actually occurs on the benzene ring, which is the desired hydroxyneofyl chloride. It is presumed that this is because film chlorides cannot be obtained. As a result of various studies on the production method of hydroxyneofyl chloride, the present inventors found that by reacting acyloxy t-butylbenzene with chlorine under ultraviolet irradiation or in the presence of a radical initiator, We discovered that new compounds such as acyloxyneophyl chlorides can be isolated and obtained with high purity, and filed an application. Furthermore, they discovered that the corresponding hydroxyneofyl chlorides can be easily obtained with high purity by hydrolyzing this, and as a result of extensive study, they have completed the present invention. The hydroxyneofyl chloride that can be produced according to the present invention has the general formula () Specific examples include isomers of p-hydroxyneofyl chloride, m-hydroxyneofyl chloride, and o-hydroxyneofyl chloride. Furthermore, the acyloxyneofyl chloride used as a raw material in the method of the present invention has the general formula () These are acyloxyneofyl chlorides having an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivalyl group, etc., and specifically, the following compounds are mentioned. That is, p-acetoxyneofyl chloride, m
-Acetoxyneofyl chloride, o-acetoxyneofyl chloride, p-propionyloxyneofyl chloride, p-butyryloxyneofyl chloride, p-pivalyloxyneofyl chloride, etc., and these acyloxyneofyl chlorides can be obtained with good selectivity by reacting acyloxy t-butylbenzenes with chlorine under irradiation with ultraviolet light or in the presence of a radical initiator. Examples of acids used in the method of the present invention include mineral acids, organic acids, solid acids, and acidic polymer compounds, and specifically, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sulfamic acid, acid, acetic acid, p-toluenesulfonic acid, monochloroacetic acid,
These include trifluoromethanesulfonic acid, trichloromethanesulfonic acid, cation exchange resin, perfluorosulfonic acid, etc., and are used in an amount of 0.001 to 100 mol, preferably 0.01 to 50 mol, per mol of acyloxyneofyl chloride. If the amount used is less than this, the reaction rate will be very low and the yield will be poor. Furthermore, if the amount is more than this, the amount of by-products will increase or the reaction will be non-uniform, making stirring difficult in some cases. Although the use of a solvent is not necessarily essential in the method of the present invention, it is desirable to use a solvent in order to improve the yield. Examples of solvents include alcohols such as methanol, ethanol, i-propanol, and n-butanol, ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, and ethyl acetate. Esters, hydrocarbons such as toluene, xylene, benzene, n-hexane, chloroform, methylene chloride, carbon tetrachloride,
Examples include halogenated hydrocarbons such as chlorobenzene, aprotic polar organic solvents such as sulfolane, hexamethylphosphoramide, dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and water. These can be used alone or in combination of two or more. When a solvent is used, it is used in an amount of 0.1 to 50 parts, preferably 1.0 to 20 parts, per part of the acyloxyneophyl chloride. If the amount used is larger than this, the reaction rate will be reduced and productivity will be reduced. The general embodiments of the method of the present invention are as follows. Put the acyloxyneophyl chloride and an inert solvent into a flask and heat to 0°C to the boiling point, preferably 10°C to the boiling point (provided that the boiling point is 200°C).
If the temperature exceeds ℃, heating at 10 to 200℃ is preferable)
Add acid dropwise. Normally at the above specified temperature for a specified period of time
After stirring for 0.1 to 50 hours, the reaction mixture is drained into water, neutralized, and extracted with an organic solvent such as benzene or carbon tetrachloride. Wash the organic layer with water,
After dehydration and drying, the solvent is evaporated under reduced pressure to obtain a crude product. This product has high purity and can be used as it is as a raw material for pesticides such as insecticides and acaricides of the general formula () above, and especially
When R ¹ is an alkoxy group, the alkoxy group can be easily introduced using an alkylating agent without necessarily being isolated. If necessary, it is also possible to isolate and purify to a high degree of purity by column chromatography or distillation. This method can be carried out even if the order of addition of the acyloxyneophyl chlorides or acids is reversed. Next, the details of the present invention will be explained by referring to examples. Example 1 254 g of p-acetoxy t-butylbenzene, 500 g of carbon tetrachloride, and 2.5 g of benzoyl peroxide were placed in a flask and heated to 60°C while purging the system with nitrogen. Chlorine while stirring under high-pressure mercury lamp irradiation.
170g was blown at 60-83℃ for 7 hours. After cooling to room temperature, the mixture was poured into water and separated. The organic layer is 1
% sodium sulfite aqueous solution until neutral, and then washed with water. After drying with sodium sulfate,
The solvent was evaporated under reduced pressure to give 289 g of crude product as an oil.
I got it. As a result of analysis by gas chromatography, this product contained 44.7% unreacted p-acetoxy t-butylbenzene, 49.3% the desired p-acetoxyneofyl chloride, and 3.5% dichloride whose side chain was further chlorinated. , and nuclear chloride 0.7
It contained %. The selectivity of the target p-acetoxyneofyl chloride to the reacted raw materials was 89.1%. The crude product obtained here is purified by distillation under reduced pressure.
-105.0g of acetoxyneofyl chloride was obtained.
(bp127° to 131°C/1.7 to 1.8 mmHg.) The above purified p-acetoxyneofyl chloride
Put 4.0g and 40ml of methanol into a flask,
Heat to 45℃. Concentrated hydrochloric acid 0.4 while stirring at the same temperature.
Drop g. After stirring for another 2 hours, it was drained into water, extracted with benzene, and the extracted organic layer was washed with water.
After dehydration and drying over sodium sulfate, the solvent was evaporated under reduced pressure to obtain 3.2 g of an oil. This material crystallized when allowed to cool. Recrystallization from n-hexane gave colorless needle-like crystals. mp65.5~67.5℃. Elemental analysis value (%): C64.84, H7.24, Cl19.43 Calculated value as C ₁₀ H ₁₃ OCl (%): C65.04 H7.10, Cl19.20 IR: νmax 3200, 2960, 1605, 1450, 1370,
1240, 1185, 830, 750, 730 cm ^-1 NMR: δ ^CDCl3 1.4 (S, 6H, CH ₃ ), 3.56 (S,
2H, CH ₂ ), 6.7~7.2 (4H, H of φ)
ppm This confirmed that the needle-like crystals were p-hydroxyneofyl chloride. In order to demonstrate the usefulness of the compounds of the present invention, below are reference examples and reference test examples of the synthesis and insecticidal effects of 2-(alkoxyphenyl)propyl ether derivatives produced using the compounds of the present invention as raw materials. Shown as Reference Example 7g of p-hydroxyneofyl chloride, 40g of diethyl sulfate, 20g of potassium carbonate and N,N-
Put 200ml of dimethylformamide into the flask,
The mixture was heated to 50°C while stirring in a nitrogen stream. After stirring at the same temperature for 2 hours, 4.0 g of potassium carbonate was added. After stirring for another 1.5 hours at the same temperature,
Added 20 g of diethyl sulfate and stirred for 2.5 hours.
After cooling to room temperature, it was poured into water. After acidifying with hydrochloric acid, the mixture was extracted with benzene. After washing the extract layer with water,
After dehydrating and drying the organic layer with sodium sulfate, the solvent was distilled off under reduced pressure to obtain 9 g of a crude product.
As a result of gas chromatography analysis, this product contained 74.2% p-ethoxyneofyl chloride.
It contained. Yield 82.7%. This product was purified by silica gel column chromatography (developing agent: benzene) to obtain pure p-ethoxyneofyl chloride. Next, 8.93 g (0.042 mol) of p-ethoxyneofyl chloride obtained as above, 8.0 g (0.04 mol) of 3-phenoxybenzyl alcohol, 45%
3.9g of NaOH and 50ml of dimethyl sulfoxide
The mixture was heated and stirred at 140°C for 3 hours. 1.8 g of 45% NaOH was added and the reaction was continued for another 4 hours at the same temperature. The reaction solution was discharged into 500 ml of water, extracted with benzene, the benzene extract was washed with water, and then dried with Glauber's salt. Benzene was distilled off under reduced pressure, and the resulting crude ether was subjected to column chromatography on 250 g of silica gel (developing solvent: toluene/n-hexane).
Separated and purified by 3-phenoxybenzyl 2-
7.5 g (yield 50%) of (4-ethoxyphenyl)-2-methylpropyl ether was obtained. mp35.4～36.2℃ NMR δ CDCl ₃ 1.25 (6H, s) 1.30 (3H,
t) 3.35 (2H, s) 3.92 (2H, q) 4.20 (2H, s) 6.6 to 7.4 (13H, m) ppm Reference test example Compound of reference example {3-phenoxybenzyl 2-(4-ethoxy phenyl)-2-methylpropyl ether}, 20 parts of Solpol SM-100 (registered trade name of Toho Chemical), and 60 parts of xylol were stirred and mixed to form an emulsion. Dilute the prepared emulsion with water and
Prepare to 100 and 200 ppm concentrations. Sweet potato leaves were immersed in each chemical solution for 10 seconds, air-dried, placed in a plastic cup with a diameter of 10 cm, and 2nd instar larvae of Spodoptera were released and left in a constant temperature room at 25°C. After 48 hours of treatment, the number of live and dead insects was investigated and the mortality rate was calculated. The results are shown as the average value of three consecutive results. (A) was similarly tested as a control compound.

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Claims (1)

[Claims] 1 Formula () Hydroxyneofyl chloride represented by 2. The compound according to claim 1, wherein the compound of formula () is p-hydroxyneofyl chloride. 3 formula () It is characterized by hydrolyzing an acyloxyneofyl chloride represented by the formula (in which R represents a lower acyl group) with an acid in the presence or absence of an inert solvent. A method for producing hydroxyneofyl chloride represented by