JPH0410469B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a novel carbamate (carbamate), a method for producing the same, and a pest control agent containing the carbamate as an active ingredient. The novel carbamate ester is represented by the following formula. In this formula, R ¹ represents a branched or straight-chain alkyl group having up to 4 carbon atoms, R ² represents a branched or straight-chain alkyl group having up to 6 carbon atoms, or R ¹ and R ² may be taken together with the enclosing molecular moiety to form a 5- to 7-membered heterocycle, n means a number of 1 or 2, and R ³ is up to 6 carbon atoms. or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁴ represents a methyl or methoxy group. The radical R ¹ is, for example, a methyl, ethyl, isopropyl or isobutyl group. Branched or straight-chain alkyl groups for R ² are, for example, methyl, ethyl, propyl, isopropyl and butyl. Preferred examples of the ring formed by R ¹ and R ² together with the molecular moiety containing them are a tetrahydrofuran ring and a tetrahydropyran ring. Branched or straight-chain alkyl groups for R ³ are, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl. The new carbamates are yellow to colorless oils or colorless solids, depending on the substituents, and are useful as insecticides or acaricides. It is particularly distinguished by its good action against sucking insects. The novel carbamate () can be converted from the corresponding salt of pyrazolinone () to the corresponding carbamate halide () as shown by the following reaction formula:
Obtained by reacting with In the formula, Z is a monovalent, preferably alkali metal cation or one equivalent of a polyvalent cation, and X is a halogen atom, especially a chlorine atom or a bromine atom. The reaction is suitably carried out in a solvent or diluent. An example is: Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, diglycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone,
Chlorinated aliphatic hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, aromatic hydrocarbons such as toluol, xylol, chlorobenzole, dimethylformamide, nitromethane, nitriles such as acetonitrile, Pionitrile. To carry out the process, chemical equivalents of each starting material are normally used. An excess of up to 200% of the generally inexpensive carbamoyl halide helps the reaction proceed. The reaction temperature can be varied within a wide range. It is generally operated up to 100°C, preferably between 30 and 90°C, the upper limit of this temperature being determined by the boiling point of the diluent. Kronen ether can be used as a catalyst. The salts of (hydroxy)-pyrazolinones used as starting materials, also called salts of pyrazolidinediones, can be prepared using a suitable condensing agent, e.g. In the presence of methylate, the corresponding disubstituted malonic acid dialkyl ester ()
can be produced by reacting with monosubstituted hydrazine (). The reaction is represented by the following formula, where R ⁵ and R ⁶ preferably represent a methyl group or an ethyl group. According to this method, pyrazolinone salts can be produced with good yield and purity. This salt can be used, for example, to remove the formed methanol from a solvent (e.g. toluene, xylol, cumol, etc.) after the end of the methylate addition.
chlorobenzole, cyclohexane) until pure solvent is removed. The crystalline salt obtained is separated from the solvent and dried. This salt, especially the sodium salt, can be used without further purification. The malon esters required for the preparation of the pyrazolinone salts can be prepared from the free acids by known methods (see Weigand Hilgetag, Organische Hemitsche Experimentier Kunst, 1970, 4th edition, pages 380-384). The free acid can be obtained from 2-alkylmalonic acid and chloromethyl-alkyl ether by the method described, for example, in Ar. 297(4), p. 219 et seq. (1964). Preparing certain free 2-alkylmalonic acids from chloromethyl ether is not the best method due to the known dangers of chloromethyl ether, which is said to be particularly carcinogenic. Particularly important malone esters with n=1 are therefore preferably prepared starting from 2-alkyl acrolein, formaldehyde and n-alkanol. This initially gives 2-hydroxymethylaldehyde in the presence of a tertiary amine, which can be oxidized, for example with nitric acid, to the corresponding malonic acid and then esterified. The reaction from to is below 150℃, e.g.
℃, preferably in an aqueous environment (i.e. using an aqueous formaldehyde solution) and under atmospheric pressure;
A slight excess of formaldehyde and an excess of alcohol (e.g. 4 to 1 mole of acrolein)
~6 mol) is preferred. Oxidation and esterification are carried out by known methods described for analogous substances. Example of manufacturing ethyl methoxymethylmalonic acid dimethyl ester: (a) Manufacturing 2-methoxymethyl-2-hydroxymethyl-butanal Triethylamine was added to a mixture of 1600 ml of methanol, 500 g of 30% formaldehyde solution and 328 g of 2-ethyl acrolein over 10 minutes. 41 g is added and the solution is then held at 78° C. for 7 hours. After distilling off the low-boiling components, 390 g (relative to 2-ethyl acrolein) of the above compound having a boiling point of 95-100°C at 3 mbar was obtained by vacuum distillation.
67%) separated. (b) Production of methoxymethylethylmalonic acid First, add 400 ml of 66% nitric acid (d ²⁰ = 1.40).
100 mg of MnCl ₂ .H ₂ O are added and then 140 g of 2-methoxymethyl-2-hydroxymethylbutanal are added over a period of 45 minutes at 40°C. Cool to 0℃,
Separate the precipitated acid and dry. Yield: 105g
(62% relative to aldol), melting point: 72-75°C with decarboxylation. (c) Production of malon ester Add 225 g of anhydrous potassium carbonate and 144 g of ethylmethoxymethylmalonic acid to 500 ml of acetone. Furthermore, 206 g of dimethyl sulfate was added dropwise, and the mixture was stirred under reflux for 5 hours. Then, when it is cold, it is suctioned and filtered.
The concentrated solution is transferred into chloroform, washed with water and aqueous sodium bicarbonate solution, and dried.
When concentrated and then distilled, the boiling point is 48-57℃/0.1
141.3 g of malon ester with mmHg is obtained. Production example of tetrahydropyran-3,3-dicarboxylic acid methyl ester: To 74 g of methanol, add tetrahydropyran-3,
Add 57.5g of 3-dicarboxylic acid and heat at 10-20℃.
Introduce HCl gas until saturation. Still at room temperature 4
After stirring for an hour, 130 ml of toluene is added.
The toluene phase is separated, dried, evaporated and then distilled, yielding 41.6 g of the above ester having a boiling point of 85-90°C/0.01 mmHg. Example 1 2-Methyl-4-ethyl-4-methoxymethyl-5-dimethylcarbamoyloxypyrazolinone-(3) 348 g of ethyl-methoxymethylmalonic acid dimethyl ester are dissolved in 1.7 g of xylol and 87 g of methylhydrazine and 307 g of 30% sodium methylate solution are added dropwise thereto. The methanol is then distilled while adding xylol until pure xylol is transferred. The sodium salt of pyrazolidone produced is filtered off by suction, washed with ether, and then dried. Yield: 317g. 208 g of it is dissolved in 800 ml of acetone, 0.1 g of 15-krone-5 is added, and 130 g of dimethylcarbamoyl chloride are added dropwise under reflux. 3 more
After refluxing for an hour, it is filtered with suction while cold and concentrated by evaporation. Filter the crystals with strong suction and wash with hexane. Yield 147.1g, melting point 80-83℃. Elemental analysis C H N Calculated value (%) 51.35 7.44 16.33 Actual value (%) 51.2 7.5 16.4 Example 2 7-oxa-2,3-diaza-2-methyl-spiro[4,5]decen-3-one- 1-yl-
4-N,N-dimethylcarbamate ester (a) Production of 3,3-biscarboxy-tetrahydropyran 600 g of nitric acid (d ²⁰ = 1.40) and 0.1 g of MnCl ₂ H ₂ O
3-formyl-3-hydroxymethyl-tetrahydropyran for 90 minutes at 30-35°C.
Add 45g. The excess of nitric acid is then destroyed by addition of a stoichiometric amount of formaldehyde solution. After distilling off the water, the residue is transferred into a small amount of diisopropyl ketone and cooled to precipitate crystals. Yield: 58g (40% relative to aldol),
Melting point: 140℃ with decarboxylation. (b) 41.4 g of tetrahydropyran-3,3-dicarboxylic acid methyl ester is dissolved in 200 ml of xylol and 10.4 g of methylhydrazine is added dropwise. This is then added with 30% sodium methylate solution 37.2
The bath temperature is gradually raised to 170° C., and xylol is added dropwise depending on the extent to which methanol is distilled off. It is then precipitated by adding 50 ml of ether at room temperature. This is separated, washed with ether and dried to give 35.8 g of the sodium salt. Add 12.4g of this sodium salt to 70ml of acetone and
Prepared with 20 mg of 15-krone-5, 7.1 g of dimethylcarbamic acid chloride was added dropwise under reflux,
Keep at boiling for 4 hours. The acetone phase that was filtered off with suction is then concentrated by evaporation and stirred with hexane. Yield: 4.2g, melting point: 51-53°C. Elemental analysis C H N Calculated value (%) 51.76 6.71 16.46 Actual value (%) 51.7 6.7 16.5 By making slight changes corresponding to the above examples, the following compounds having the following melting points or indicated as oily substances were obtained. can get. Other compounds are also obtained with corresponding modifications to the respective manufacturing instructions. It is clear that these have similar effects to the compounds for which results have been shown due to their structural similarities.

【table】

[Table] The new active substance is of particular interest due to its strong action in controlling oilseeds. Therefore, the commercially available product pirimicarb (formula: Efficacy test example A. Continuous contact action against Musca domestica The inner surface of a Petri dish with a diameter of 10 cm was treated with an acetone solution of the active substance. After the solvent had evaporated, 20 bream flies each 4 days after emergence were placed on a plate. The results are shown in the table below. Mortality was determined after 4 hours.

[Table] Efficacy test example B. Contact effect on cotton bed bug (Deisdercus intermedius) 1 ml of an acetone solution of the active substance was applied to the inner surface of a Petri dish with a diameter of 10 cm. After the solvent evaporates,
Twenty larvae each at the penultimate stage were placed on a plate and efficacy was recorded after 24 hours. Mortality was determined after 4 hours. The results are shown in the table below.

[Table] Efficacy test example
Contact effects in spray tests on potted fava beans (Visia fauba), which were heavily infested with aphids, were sprayed with an aqueous preparation of the active substance to the extent of dripping in a spraying chamber. The results of the evaluation conducted 24 hours later are shown in the table below.

[Table] Efficacy test example D. Systemic effect against oilworm (Aphis fae); Spraying test Plastic pot (diameter 8 cm, compost soil 300 g)
20 ml of an aqueous preparation of the test drug was added to leguminous plants that had been planted in the area and were severely infested with aphids, and the mortality rate was checked after 48 hours. The results are shown in the table below. Compound number % mortality rate (%) 1 0.001 Approx. 90 3 0.04 100 4 0.01 Approx. 90 6 0.02 100 Efficacy test example E Aphid insect (Megoura visiae) on treated plants
Continuous action on young leguminous plants (fava beans), on which the first leaves have formed, are sprayed with an aqueous preparation of the active substance to the extent of dripping in a spray chamber. After drying, the plants were infected with adult aphids and tested for efficacy 24 hours later. When a mortality rate of 80-100% appears, 2 days,
After 4 and 8 days, the plants were infected with insects again and the effects were observed. The results are shown in the table below. Compound number % Mortality rate after 4 days (%) 1 0.01 100 5 0.01 100 Comparative drug 0.01 Approx. 80 Efficacy test example F Continuous action of systemic agent against oilseed insect (Megoura visiae) Planted in a plastic pot (diameter 8 cm) with approximately 300 g of soil aqueous preparations of active substances on young legumes 20
ml was added. They were then infected with adult oilseed worms, and the effects were adjusted after 48 hours. When a mortality rate of 80% or higher was observed, a new infection was given and this was repeated 4 and 8 days later. The results are shown in the table below. Compound number % Mortality rate after 8 days (%) 1 0.01 100 5 0.01 Approximately 80 Comparative drug 0.01 <60 Efficacy test example G Contact effect on ticks (Ornithodorus mutata) Tests were conducted on young ticks that took blood once for the first time. Five animals each were placed in tea bags and immersed for 5 seconds in the aqueous preparation of the active substance. Mortality was assessed after 48 hours. The test temperature was 25-26°C. The results are shown in the table below.

【table】

Claims (1)

[Claims] Linear formula (wherein R ¹ means a branched or straight-chain alkyl group with up to 4 carbon atoms, R ² means a branched or straight-chain alkyl group with up to 6 carbon atoms, or R ¹ and R ² may be taken together with the enclosing molecular moiety to form a 5- to 7-membered heterocycle, n means a number of 1 or 2, and R ³ is up to 6 carbon atoms. a branched or straight-chain alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁴ means a methyl group or a methoxy group). 2. The compound according to claim 1, characterized in that R ³ and R ⁴ represent a methyl group. 3. The compound according to claim 1, wherein R ¹ and R ³ together with the molecular moiety containing them form a tetrahydrofuran ring or a tetrahydropyran ring. Quaternary formula (wherein R ¹ means a branched or straight-chain alkyl group with up to 4 carbon atoms, R ² means a branched or straight-chain alkyl group with up to 6 carbon atoms, or R ¹ and R ² may be taken together with the enclosing molecular moiety to form a 5- to 7-membered heterocycle, n means a number of 1 or 2, and R ³ is up to 6 carbon atoms. or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁴ means a methyl group or a methoxy group. Acaricide. Quintic formula (wherein Z means the equivalent of a monovalent or polyvalent cation),
The following formula characterized by reaction with the corresponding carbamic acid halide represented by the following formula: (wherein R ¹ means a branched or straight-chain alkyl group with up to 4 carbon atoms, R ² means a branched or straight-chain alkyl group with up to 6 carbon atoms, or R ¹ and R ² may be taken together with the enclosing molecular moiety to form a 5- to 7-membered heterocycle, n means a number of 1 or 2, and R ³ is up to 6 carbon atoms. a branched or straight-chain alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁴ means a methyl group or a methoxy group). 6 2-alkyl acrolein, formaldehyde and the corresponding formula with the corresponding formula _H2C = ^CR2CHO
Starting from the alkanol of R ¹ OH, the following formula (symbols R ¹ and R ² in the formula have the meanings given below), oxidize this with nitric acid,
It is characterized by esterifying the resulting malonic acid, reacting it with a corresponding hydrazine of the formula H ₂ N-NHR ³ (R ³ has the meaning given below) to give a pyrazolinone, and carbamoylating it. , the following equation (wherein R ¹ means a branched or straight-chain alkyl group with up to 4 carbon atoms, R ² means a branched or straight-chain alkyl group with up to 6 carbon atoms, or R ¹ and R ² may be taken together with the enclosing molecular moiety to form a 5- to 7-membered heterocycle, n means a number of 1 or 2, and R ³ is up to 6 carbon atoms. a branched or straight-chain alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, and R ⁴ means a methyl group or a methoxy group).