JPS6048983A - 2-halo-4,5-ethylenedioxynitrobenzene and its production - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is halogen). EXAMPLE:2-Chloro-4,5-ethylenedioxynitrobenzene. USE:Agent for controlling the plant blights such as downy mildew, late blight, etc. PREPARATION:The objective compound can be produced by reacting the beta-(2,4- dihalo-5-nitrophenoxy)ethanol of formula II (Y is halogen) in a solvent such as dimethyl sulfoxide, in the presence of >=1 equivalent of an alkali metal hydroxide or metal fluoride (e.g. sodium hydroxide, potassium fluoride, etc.) usually at 30-200 deg.C (30-60 deg.C for alkali metal compound, and 70-200 deg.C for metal fluoride) for 1-30hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (I) where X represents a halogen atom. ] 2-
The present invention relates to halo 4,5-ethylenedioxynitrobenzene and its manufacturing method.

2-halo 4,5-ethylenedioxynitrobenzene represented by the general formula (I) is an intermediate of the active ingredient of the 411 disease control agent. 4,5-ethylenedioxy-2-ditrophenol obtained by reacting it in the presence of an oxide or metal fluoride is converted into 〇-ethyl
N-5ee-butyl 〇-ethyl 〇-4,5-ethylenedioxy-2-nitrophenyl N-sec-butyl phosphoroamide thioate, which can be produced by reacting with thiophosphoric acid amide chloride, is useful for plant disease control. It is the active ingredient of the agent and has a control effect against plant diseases such as downy mildew and late blight.

The present inventors investigated the method for producing 2-halo-4,5-ethylenedioxynitrobenzene represented by the above general formula CI), and found that ] Reacting β-(2,4-dihalo-5-nitrophenoxy)ethanol represented by the following in the presence of 1 equivalent or more of an alkali metal hydroxide or metal fluoride in a solvent. It was discovered that it can be manufactured by

Next, the manufacturing method of the present invention will be described in detail.

Examples of solvents used in the production method of the present invention include dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, nitriles such as acetonitrile and imbutyronitrile, N,N-dimethylformamide N,
.

Examples include acid amides such as N-dimethylacetamide, and sulfur compounds such as dimethyl sulfoxide and sulfolane. Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide, and examples of metal fluorides include:
Examples include potassium fluoride and cesium fluoride.

The reaction temperature is usually 30 to 60°C in the presence of an alkali metal hydroxide, and usually 70 to 200°C in the presence of a metal fluoride. The reaction time is usually 1
~80 hours.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, recrystallization, etc.

The raw material compound, rel β-(2
,4-dihalo-5-nitrophenoxy)ethanol is
For example, general formula (III) 5- [wherein, X and Y represent the same meanings as above. ] 2,4-dihalo-5-2)0 phenol and 1
~5 equivalents of ethylene halohydrin and acetonitrile,
1-2 at 60-150°C in the presence of 1-6 equivalents of an inorganic base such as sodium hydroxide or potassium carbonate in a solvent such as N,N-dimethylformamide or dimethyl sulfoxide.
It can be produced by reacting for 4 hours.

Next, examples will be shown.

Example 1 7.11 of β-(2,4-dichloro-5-nitrophenoxy)ethanol was dissolved in 50 g of dimethyl sulfoxide, and 8.11 of β-(2,4-dichloro-5-nitrophenoxy)ethanol was dissolved in 50 g of dimethyl sulfoxide. Of was added at 30-40°C. After reacting at the same temperature for 24 hours, the mixture was poured into 200#I ice water and extracted twice with 100 ml of ethyl acetate. The extract was washed with water and dried over magnesium sulfate. Ethyl acetate was distilled off, and the residue was recrystallized from 6-ethanol to obtain 4.809 g of 2-chloro-4.5-ethylenedioxy-trobenzene. m, p
, 151-152℃ Example 2 5.00f of β-(2-chloro-4-fluoro-5-nitrophenoxy)ethanol was dissolved in Sr Reholan 20, and 2.5Of potassium fluoride was added at 100℃. Keep at temperature for 2 hours and then at 180-150°C for 5 hours. After cooling, the same treatment as in Example 1 was carried out to obtain 2-fluoro-4.
, 8.849% of 5-ethylenedioxydi"trobenzene was obtained.

m, 9. 140 to 141°C Next, a production example of 4,5-ethylenedioxy-2-ditrophenol will be shown for reference.

Reference production example 1 Dissolve 500 μl of 2-chloro a-4S 5-ethylenedioxynitrobenzene in 5 ml of dimethyl sulfoxide,
The mixture was heated to 100°C, 400 μm of potassium hydroxide powder was added, and the temperature was kept at 120-140°C for 1 hour. After cooling, add 50 ml of ice water
The mixture was poured into tptl, extracted twice with 50 ml of ethyl acetate, and the extract was washed with water and dried over magnesium sulfate. Ethyl acetate was distilled off, and the residue was purified by silica gel column chromatography to obtain 4,5-ethylenedioxy-2
290 mq of -nitrophenol was obtained.

m-P, 170-173°C Reference production example 2 2-fluoro-4,5-ethylenedioxynitrobenzene 2.61 was dissolved in 15 rats of sulfolane, 2.22 ml of potassium hydroxide powder was added and heated to 80-100°C for 3 hours. I kept it. After cooling, ice water 100+/! Pour into reference manufacturing example 1
It was treated in the same manner as above to obtain 1.38f of 4,5-ethylenedioxy-2-nitrophenol. m, P, 170~
L78°C Next, for reference, production examples and test examples of 〇-ethyl O-4,5-ethylenedioxy-2-nitrophenyl N-l1eC-butyl phosphoroamide thioate are shown.

Reference production example 8 4.5-ethylenedioxy-2-nitrophenol (1
,975', 10 mmol) in acetonitrile 100+
+It, and add anhydrous potassium carbonate powder (1,4O
f) and cuprous chloride (10) at 40-50°C.
Stirred for 0 minutes. Then, 〇-ethyl N-5ec-butyl thionolamide chloride (2,2F, 10 mmol) was added dropwise over 40 minutes, and the mixture was stirred and refluxed for 8 hours. After removing the inorganic salts, acetonitrile was distilled off under reduced pressure.

The residue was dissolved in toluene, washed successively with a dilute acid aqueous solution, water, a dilute alkali aqueous solution, and water, and dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and purified with silica gel column chromatography (-) to obtain 0-ethyl 〇-4.5
-ethylenedioxy-2-nitrophenyl N -se
2.88f of c-7'-thyl phosphoroar 〇-midothioate was obtained.

m-P, 59-61°C Reference test example Grape mildew disease control effect test (therapeutic effect) A plastic pot was filled with sandy loam, grapes (neomuscat seeds) were sown, and grown in a greenhouse for 50 days. A spore suspension of grapevine and the disease fungus was spray inoculated onto young grape seedlings in which the 4th to 5th true leaves had developed. After inoculation, 1 at 25℃ and high humidity.
The test compound was grown for one day and made into an emulsion, diluted with water to a predetermined concentration, and sprayed on the foliage so that it adhered sufficiently to the leaf surface.

After spraying, the plants were grown for 10 days in a greenhouse at 23°C, and their pesticidal efficacy was investigated. The control efficacy is determined by visually observing the disease state of the test plants at the time of investigation, i.e., the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is approximately 10% at l'-5J. If it is approved, it will be ``4J'', if about 80% is approved, it will be ``3'', 50%.
If about % is recognized, ``2'', if about 70% is recognized, r
lJ, 10- If no difference is observed from the disease onset state when no compound is tested, it is evaluated as rOJ on a 6-point scale from 0 to 5, and expressed as 0, 1, 2, 8, 4, 5. did.

Note that chlorothalonil and aluminum tris(ethylphosphonate) were used for comparison. The result is the second
Shown in the table.

1 1- Table 2 112 completed-

Claims (1)

[Claims] (11) 2-
Halo 4.6-ethylenedioxynitrobenzene. (2) General formula C In the formula, X and Y are the same or different and represent a halogen atom. [In the formula, X has the same meaning as above. ] A method for producing 2-halo 4,5-ethylenedioxynitrobenzene.