JPS6041671A - 4,5-ethylenedioxy-2-nitrophenol and its preparation - Google Patents

Abstract

NEW MATERIAL:4,5-Ethylenedioxy-2-nitropehnol. USE:Useful as an intermediate of the active component of a plant blight controlling agent. For example, O-ethyl O-4,5-ethylenedioxy-2-nitropheyl N-sec-butyl phosphoramide thioate prepared by the reaction of the compound with O-ethyl N-sec-butyl thiophosphoric acid amide chloride is an active component of a plant blight controlling agent effective to control the plant blights such as downey mildew, blight, etc. PREPARATION:3,4-Ethylenedioxyphenyl acetate is made to react with e.g. a mixture of sulfuric acid and nitric acid at 0-10 deg.C to obtain 4,5-ethylenedioxy-2- nitrophenyl acetate. The titled compound can be produced by hydrolyzing the obtained 4,5-ethylenedioxy-2-nitrophenyl acetate in the presence of an alkali or acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 4,5-ethylenedioxy-2-ditrophenol and a process for producing the same.

The compound of the present invention is among the active ingredients of plant disease control agents]
It is the body. That is, 0-ethyl O-4,5-ethylenedioxy-2-nitrophenyl N-5ea can be produced by reacting the compound of the present invention with, for example, 0-ethyl N-5eC-butyl thionolinic acid amide chloride. -Butyl phosphoroamide thioate is an active ingredient of a plant disease control agent, and has a controlling effect on plant diseases such as downy mildew and late blight.

The inventors have discovered that 4,5-ethylenedioxy-2-nide 1
We investigated the production method of cophenol and developed totaN and El.
i acid: 4.5 in high yield and purity by nitration and hydrolysis of 3,4-ethylenedioxyphenyl
It has been found that -ethylenedioxy-2-ditrophenol can be produced in fM.

Next, the method for producing the compound of the present invention will be described in detail.

The nitration of 8.4-ethylenedioxyphenyl acetate is
For example, using a mixed acid of sulfuric acid and nitric acid, a mixed acid of acetic acid and nitric acid, fuming nitric acid, or nitric acid in a halogenated hydrogen ash solvent, usually θ ~ 1
The reaction is carried out at 0'C within 12 hours. reaction path T
Thereafter, D n 4 + 5-ethylenedioxy-2-nitrophenyl is obtained by a conventional method.

The hydrolysis H of 4.5-r-ethylenedioxy-2-nitrophenyl acetate obtained by f() as described above is carried out in the presence of an alkali or acid catalyst.

Hydrolysis with an alkali catalyst is carried out, for example, by adding an alkaline aqueous solution such as sodium hydroxide to an alcoholic solution of 4°5-ethylenedioxy-2-nitrophenyl acetate and reacting it at 40 to 60'C for 1 to 5 hours. Alternatively, 4,5-ethylenedioxy-2-nitrophenyl acetate is added to an alcoholic solution of Alcorade to give a
The mixture is heated under reflux for 7 hours. For hydrolysis with an acid catalyst, for example, W& acid or sulfuric acid is added as a catalyst to an alcoholic solution of 4,5-diethylenedioxy-2-nitrophenyl acetate, and the hydrolysis is usually carried out at 60 to 80°C for 4 to 8 hours. Let it react over time.

After the reaction is complete, neutralize, distill off the solvent if necessary, collect the resulting crystals in IF5, wash with water, and dry to obtain 4,5-ethylenedioxy-2-nitrophenol. .

The acid 19M1.4-ethylenedioxyphenyl, which is a compound, can be prepared by reacting 8,4-ethylenedioxyphenylmethylketone with a peracid such as peracetic acid, metachloroperbenzoic acid, or 3,4-ethylenedioxyphenyl. It can be produced by reacting dioquinphenol with an acetylation agent such as anhydrous vinegar rll or acetyl mide. In addition, 8.4-
Ethylenedioxyphenylmethylketone and 8.4-
Ethylenedioquinephenol, J Chem, Sa
j! by the method described in J. C., 1957 3445-13447. I! iM is possible.

Example 3,4-ethylenedioxyphenyl acetate (5,98f,
80.5 mmol) and acetic acid 15rn! , dissolve in 4~
Add nitric acid (d=1.50) 2 while stirring while keeping at 7℃.
．． A mixture of 0 ml and 8.0 me of acetic acid was added dropwise over 80 minutes. After the dropwise addition was completed, the temperature was returned to room temperature, the reaction solution was poured into ice water, the crystals were collected, washed with water, and added with vinegar fi94.5-ethylate/redioxy-2-nitrorophenyl + t + t: < m,
p, 105-106°C).

After heating and dissolving this in 80 mJ of methanol, 50
% sodium hydroxide aqueous solution was added dropwise,
The mixture was kept at ~60°C and stirred for 1 hour. The reaction solution was cooled with ice water, neutralized by adding 10% hydrochloric acid, and methanol was distilled off. The precipitated crystals were collected in P, washed with water, and dried to give 4,5-ethylenedione diphenyl-2-nitrophenol. 4.50
Got FI.

m, p, 178-13447 Yield 74.8% Reference stone example 1 8.4-ethylenedioxyphenylmethylke!・N (6
, 00f/, 88.7 mmol) and m-black perbenzoin (9, Of, 5211 plate 01) were stirred in 200 d of methylene chloride at room temperature for 3 hours. After the reaction is complete,
The mixture was washed with an aqueous sodium thiosulfate solution and an aqueous sodium bicarbonate solution for 1 day, dried over magnesium sulfate, and methylene chloride was distilled off. 5.981 q of 3.4-ethylenedioxyphenyl acetate was equated. Amount: 90.7% Reference example 2 4.5-ethylenedioxy-2-nitrophenol (1
,97y,l Q+mjlol) was dissolved in 7 setsonitrile 10 (tfnt), anhydrous potassium carbonate powder (1,4
Of) and cuprous chloride (10), and add 40 to 50
Keep at 'C' and stir for 30 minutes. To this, there is no ethyl
lq -5ec-butylthionolinic acid amide chloride (
2,21100 pieces o1)j: It was added dropwise over 40 minutes, and the mixture was further stirred and refluxed for 3 hours. After cooling, inorganic salts are separated into ゛C1
The 1-nitrile was distilled off, the residue was dissolved in toluene,
Wash with dilute hydrochloric acid, water, dilute alkali aqueous solution, then water,
Dry with 9mm of anhydrous sulfuric acid magne. Toluene was distilled off, and the residue was further purified by silica gel column chromatography to obtain 0-ethyl 04,5-ethylenedioxy-2-nitrophenyl N-5ee-butylphosporamide thioate 2.3811.

m, P, 59-61″C yield 62.0% Test example Grape mildew disease control test (therapeutic effect) Fill a plastic pot with sandy loam, sow grapes (neomuscat seeds), and place in a greenhouse. The grapes were grown for 50 days.The 4th to 5th true leaves had developed on young grapes, and the spore-suspending liquid of the grapevine and the disease fungus was sprayed on the culm.After inoculation, the grapes were grown for 1 day at 25°C and humid, and then made into an emulsion. Dilute the test compound with water to a specified concentration and spray it on the foliage so that it fully covers the flat surface.After spraying, spray at 23°.
The plants were grown in a greenhouse for 10 days and their pesticidal efficacy was investigated.

In addition, the control efficacy is determined by visually observing the disease state of the test plants at the time of investigation, that is, the degree of R flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is evaluated as "5", 1O%. ``4'' if the degree is recognized, ``3'' if the degree is recognized as 80%, 509c
If it is recognized to a certain extent, it is ``2'', and if it is recognized to be about 70%, it is ``l''.
'', and if no difference was observed from the disease onset state when no compound was tested, it was designated as rOJ, and the Wr value was rated on a 6-level scale from 0 to 5, and expressed as 0.1.2.3.4.5. .

In addition, Chlorochrony J17 Oyo(F tri(ethylphosphonic acid) aluminum) was used as a comparison control.The results are shown in Table 1.

Table 1

Claims (2)

[Claims] (1) 4,5-ethylenedioxy-2-ditrophenol. (2) Vinegar e8, 4,5- characterized in that it nitrates 4-ethylenedioxyphenyl and then hydrolyzes it.
A method for producing ethylenedioxy-2-ditrophenol.