JPS631300B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides juvenile hormone (juvenil hormone)
The present invention relates to active hydroquinone ethers, and more particularly to hydroquinone ethers having at least one unsaturated aliphatic chain and a halogen-substituted end group, processes for their production and their application in pest control. Italian patent application filed by the applicant (No.
19332A/74; 28583A/74; 28116A/74) which exhibits juvenile hormone activity and which may be substituted with a dichlor- or trichlor-substituted end group, or with one end group consisting of a trichloromethyl group. Aliphatic compounds are described having the other end group consisting of a group. All of these compounds can be considered to have a terpenoid structure due to various unsaturations and methyl or ethyl side groups, and among them only those with trichloromethyl end groups are acaricidal. It showed that. Also, Geigy's German patent application (Publication No.
2312518), the following general formula (where R ₁ can be hydrogen, halogen, alkyl, vinyl, ethynyl, R ₂ is hydrogen, halogen, methyl or ethyl, R ₃ is hydrogen, halogen, methyl or alkoxy, R ₄ is hydrogen , halogen or methyl, R ₅ is hydrogen, or R ₃ and R ₅ form a carbon-carbon bond or an oxygen bridge, R ₆ is hydrogen or methyl, R ₇ is cyclohexyl or various substituted phenyl wherein Y can be a methylene or oxymethylene bridge and m and n can be 0 or 1. Such compounds have been endowed with juvenile hormone activity against Dysdercus fasciatus and Aedes aegypti. However, no activity against spider mites (Tetranychus urticae) in the larval or egg stages has been described. In addition, the applicant's Italian patent application (No.
No. 22349A/76) describes benzyl or phenyl ethers or thioethers with linear aliphatic chains (and therefore not terpenoid structures) with optionally substituted halogenated end groups. There is. Such compounds are endowed with juvenile hormonal and acaricidal activities, but they are not effective against the Tenebrio molitor.
It shows no activity against. Therefore, the object of the present invention is to provide a juvenile hormone that has at least one unsaturated and halogen-substituted terminal group, has effective juvenile hormone activity against the rice beetle, and is also effective against the rice beetle. The object of the present invention is to provide a new hydroquinone diether which also has activity in the following. Yet another object of the invention is to provide a method for controlling pest infestations. These and other purposes are based on the following general formula: (where Y ¹ and Y ² may be the same or different from each other and are Cl, F, or one of them together with X forms another carbon-carbon bond, ^{and _} or it is benzyl which may be substituted with CH ₃ or a halogen group, or it is phenyl which may be substituted with CH ₃ , OCH ₃ or a halogen group). Provided by: Said compound may have one mole of, for example, the following general formula: The alkenyl or alkynyl halide (wherein Y ¹ , Y ² and compound (where R has the meaning indicated for the formula)
It can be manufactured by processing with.
This manufacturing method is also an object of the present invention. Obviously, therefore, it is also possible to react the alkali salt of hydroquinone first with the R-halide and then with the intermediate of the general formula. If symmetrical diethers are to be obtained, 1 mol of the dialkali salt of hydroquinone is reacted with 2 mol of the halide of the general formula. A particularly advantageous method involves combining an alkali salt of hydroquinone or an alkali salt of a monosubstituted phenol R with the general formula (Here, Y ¹ and Y ² are Cl or F, but Y ³ is
Cl, Br, I) in a stoichiometric excess sufficient to form a double or triple bond by dehydrohalogenation between the first two carbon atoms of the end group. It has been found that the method consists of reacting in the presence of an alkali carbonate or hydroxide. This dehydrohalogenation is carried out between 50°C and 100°C, preferably at about 80°C, in dimethylformamide if double bonds are to be obtained or in dimethyl sulfoxide if triple bonds are to be obtained. carried out at a temperature of Thus, etherification and dehydrohalogenation can be carried out in one step. The compounds listed in the table below (among others) were prepared by the method described above.

【table】

Table: The compounds of the invention have very beneficial properties from the point of view of biological activity. In fact, these are
Although structurally very different from the typical insect growth regulators (dijuvenoids) of terpenoid structure, they exhibit considerable mormonic effects of the dijuvenyl type, as evidenced in particular for the pupa of the beetle beetle. The activity against other species varies depending on the compound tested, but in any case the effective action against Aedes in general must be noted. They also exhibit acaricidal activity against spider mite eggs and/or adults. See Example 7 and Table below for susceptibility data for the above species. The compounds of the invention can be formulated by methods of the prior art so that they can be absorbed into powders, for example in amounts of 0.5 to 50% or more. They can also be used as aqueous emulsions or suspensions with known surfactants. It can also be applied as a solution in a suitable solvent such as alcohol, acetone, etc. The compounds can also be applied as such or in formulations in amounts of at least 0.2 ppm to the pests to be controlled or to the habitat of the pests, or as food (nutrients) for the pests or their larvae or pupae. It can also be mixed with or sprinkled on eggs. The following examples are presented to further illustrate the invention, but are in no way limiting. Example 1 Production of 1,4-di(5-chloro-4-pentynyloxy)benzene (JH202) 5g in 100ml of DMF (dimethylformamide)
of hydroquinone and 4 g of NaOH were dissolved. The solution was then stirred for 1 hour at room temperature. 14 g of 1,5-dichloro-1-pentyne were then added dropwise to this solution and the mixture was then heated to 60° C. for 6 hours. After completion, the reaction mixture was cooled, poured into water and extracted with ethyl ether. The ether extract was then neutralized with dilute HCl, washed with water, and then
Dried over Na ₂ SO ₄ and finally concentrated. The residue was chromatographed on a silica gel column. Elution with a mixture of ether and petroleum ether (95:5) yielded 6 g of 1,4-di(5
-chloro-4-pentynyloxy)benzene was obtained. MP=62℃. ¹ HNMR spectrum (CDCl ₃ ) δ = 1.7−2.7 (8H, multiplet), 3.97 (4H, triplet),
6-8 (4H, singlet) Example 2 One-step preparation of 1,4-di(5-chloro-4-pentynyloxy)benzene (JH202) In 14 autoclaves, 6.5 of methyl sulfoxide, 0.5 Kg of hydroquinone and 1.3 Kg of NaOH beads were charged. The mixture was then heated at 80°C for 1 hour and then cooled to 30°C. Then under nitrogen atmosphere 2200
Kg of 1,1,1,5-tetrachloropentane was pumped with stirring. An exothermic reaction started and stabilized at 80°C. Once the exothermic reaction has stopped,
The temperature was maintained at 80°C for 4 hours. At the end of this period, the autoclave was opened at a temperature of 50° C. and the reaction mixture was washed with water, after which it was neutralized and extracted with CH ₂ Cl ₂ . The organic extracts were then dried and concentrated. The solid residue was dissolved again in hexane under heating,
It was then quickly passed through silica gel. By successive crystallization from the filtered hexane solution, 650 g of product having the properties described in Example 1 were obtained. Example 3 Production of 4-(5,5-dichloro-4-pentenyloxy)phenol 44g of hydroquinone and 80g of
Charged with NaOH. This mixture was then cooled and stirred for 1 hour. Then 345 g of 1,1,5-trichloro-1-pentene were added and the whole was heated at 60°C for 8 hours. At the end of this period the mixture was cooled, then poured into water, neutralized with HCl and extracted with ether. The extract was dried over Na ₂ SO ₄ and concentrated. After chromatography on a silica gel column, 250 g of 4-(5,5-dichloro-
4-pentenyloxy)phenol was obtained. This material was an oil with the following ¹ H NMR characteristics (CDCl ₃ ). δ=1.6−2.6 (4H, multiplet),
3.95 (2H, triple line), 6.2 (1H, single line), 6.8 (4H,
single line). Example 4 Preparation of 1-(5,5-dichloro-4-pentenyloxy)-4-(p-methylbenzyloxy)benzene (JH217) 4 ml of the phenol from Example 3 in 40 ml of DMF and 1 g
of KOH was dissolved. The solution was stirred at room temperature for 1 hour, after which 2.3 g of p-methylbenzyl chloride was added dropwise. Then while stirring this mixture
Heated at 40-50°C for 6 hours. After normal treatment with water, extraction with ethyl ether and chromatography of the distillate on a silica gel column (eluent: petroleum ether/ether (95:5)), 5.2 g
1-(5,5-dichloro-4-pentenyloxy)-4-(p-methylbenzyloxy)benzene was obtained. MP=66℃. Example 5 1-(5,5-dichloro-4-pentenyloxy)-4-phenyloxybenzene (JH385)
Preparation of 2 g of 4-phenoxyphenol was dissolved in 25 ml of DMF, and 0.7 g of KOH was added thereto. The whole mixture was then kept stirring for 1 hour at room temperature,
Thereafter, 1.86 g of 1.1.5-trichloro-1-pentene was added dropwise to this mixture. After 6 hours the mixture was poured into water and then extracted with ethyl ether. The residue obtained by concentrating the ether phase was purified on a chromatographic column. This gave 3 g of product exhibiting the following properties. ¹ HNMR (CDCl ₃ ) δ=1.6−2.6 (4H, multiplet), 3.9 (2H, triplet),
5.9 (1H, triplet), 6.6-7.5 (9H, multiplet), Example 6 1-(5-chloro-4-pentynyloxy)-4
- Preparation of phenyloxybenzene (JH386) Following exactly the same method as in Example 5, 2 g of 4-phenoxyphenol, 0.7 g of KOH, 25 ml of DMF,
1.5 g of 1,5-dichloro-1-pentyne was used. This gave 2.1 g of a compound exhibiting the following properties. ¹ HNMR (CDCl ₃ ) δ=1.7−2.6 (4H, multiplet), 3.97 (2H, triplet),
6.7-7.5 (9H, multiplet) Example 7 Biological Activity Tests were carried out in a controlled environment against pests of the following species and genera: Tenebrio
molitor), Aedes aegipty,
Spider mite (Tetranychus urticae) (adults and eggs). The conditions under which the tests were conducted and the criteria for evaluation are listed below for each genus. (1) Pupae aged 0 to 24 hours were treated by topically applying an acetone solution of the compound to the third or final caudal ventral plate. The results were evaluated approximately 9 days later when the insects in the control group hatched. As an index of activity, the percentage ratio of the number of dead, malformed and abnormal individuals to the number of treated individuals was used according to the following formula: Activity = (death + malformation + number of abnormal individuals) / number of treated individuals (2) Egyptian Aedes 3 ml of an acetone solution of the compound is mixed with 297 c.c. of drinking water, which is supplied with appropriate nutrients and Twenty-five 4-day-old larvae were transferred. The results show that it takes 2 to 3 days until the larvae in the control group hatch.
Inspected daily. Activity was then determined in the same manner as for the rice beetle. (3) Spider mite eggs Lay spider mite eggs on semicircular specimens of bean leaves.
It was then treated by spraying with an aqueous solution having a test compound concentration of 0.1‰. The % mortality was evaluated as 0 for semicircular samples of untreated leaves. Adult mites Semicircular samples of bean leaves were infested with adult mites and subsequently treated in an aqueous dispersion with a test compound concentration of 0.1‰. Mortality rate % was evaluated as 0 for untreated samples. The results obtained are summarized in the table.

【table】

Claims (1)

[Claims] First-order general formula [Here, Y ¹ and Y ² may be the same or different from each other and are Cl or F, or one of them together with X forms another carbon-carbon bond. and X is H or together with Y ¹ or Y ² forms one further carbon-carbon bond, and R is (wherein Y ¹ _, Y ² and hydroquinone diether. 2 R is the following formula Claim 1 characterized in that it is based on
Hydroquinone diether as described in Section. cubic formula The hydroquinone diether according to claim 1, wherein the group ClC≡C-( _CH2 ) _3- . 4. The hydroquinone diether according to claim 1, wherein R is a benzyl group optionally substituted with a _CH3 group. 5. The hydroquinone diether according to claim 1, wherein R is phenyl. 6. The compound according to claim 2, which is 1,4-di(5,5-dichloro-4-pentenyloxy)benzene. 7 1,4-di(5-chloro-5-fluoro-4
-pentenyloxy)benzene. 8. The compound according to claim 2, which is 1,4-di(5,5-difluoro-4-pentenyloxy)benzene. 9. The compound according to claim 3, which is 1,4-di(5-chloro-4-pentynyloxy)benzene. 10 The compound according to claim 4, which is 1-(5,5-dichloro-4-pentenyloxy)-4-benzyloxybenzene. 11 Claim 4, characterized in that it is 1-(5,5-dichloro-4-pentenyloxy)-4-(p-methylbenzyloxy)benzene.
Compounds described in Section. 12 1-(5-chloro-4-pentynyloxy)
The compound according to claim 4, which is -4-(p-methylbenzyloxy)benzene. 13 The compound according to claim 5, which is 1-(5,5-dichloro-4-pentenyloxy)-4-phenyloxybenzene. 14 1-(5-chloro-4-pentynyloxy)
The compound according to claim 5, which is -4-phenyloxybenzene. 15 The following general formula [Here, Y ¹ and Y ² may be the same or different from each other and are Cl or F, or one of them together with X forms another carbon-carbon bond. and X is H or together with Y ¹ or Y ² forms one further carbon-carbon bond, and R is (wherein Y ¹ _, Y ² and A method for producing a hydroquinone diether having the following general formula: (where R has the same meaning as given above) and the following general formula: (wherein Y ¹ , Y ² and X have the same meaning as given above and halogen is a Cl, Br or I atom) Manufacturing method. 16 The following general formula' [Here, Y ¹ and Y ² may be the same or different from each other, and are Cl, F, or one of them can be combined with X to form another carbon-carbon bond. and X is H or together with Y ¹ or Y ² forms one further carbon-carbon bond, and R is (wherein Y ¹ , Y ² and (wherein Y ¹ , Y ² , X and halogen have the same meanings as shown above). 17 The following general formula'' [Here, Y ¹ and Y ² may be the same or different from each other and are Cl or F, and R is the following formula (wherein Y ¹ and Y ² are as described above) A method for producing a hydroquinone diether of (Here, Y ¹ and Y ² have the same meaning as above, Y ³
is Cl, Br or I) in dimethylformamide at 50-100°C in the presence of a stoichiometric amount of alkali hydroxide or carbonate to form a double bond between the terminal carbon atoms. A method for producing a compound of the formula I″, which is characterized by forming a bond. 18 The following general formula [Here, Y ¹ is Cl or F, and R' is a group of the following formula Y ¹ -C≡C-(CH ₂ ) ₃ - (where Y ¹ is as described above)] A method for producing an ether, comprising a dialkali salt of hydroquinone and the following general formula: (Here, Y ¹ and Y ² may be the same or different from each other and are Cl or F, and Y ³ is Cl, Br or I.) Formula I, characterized in that a triple bond is formed between the terminal carbon atoms by reacting in dimethyl sulfoxide at 50-100° C. in the presence of carbonate or carbonate.
A method for producing the compound. 19 The following general formula [Here, Y ¹ and Y ² may be the same or different from each other and are Cl or F, or one of them together with X forms another carbon-carbon bond. , X is H or together with Y ¹ or Y ² forms one further carbon-carbon bond, R is (wherein Y ¹ _, Y ² and A composition for controlling invasion or infestation of pests, characterized by containing a hydroquinone diether as an active ingredient.