JPH0240078B2 - JIARUKIRUHOSUHONAATOJUDOTAIOYOBISONOSEIZOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to dialkylphosphonate derivatives and methods for producing the same. The compounds of the present invention are novel compounds and are useful as fungicides. The present invention is based on the general formula

[Formula] (In the formula, R ₁ , R ₂ , and R ₃ represent lower alkyl groups.)
A dialkylphosphonate derivative represented by (hereinafter referred to as the compound of the present invention), and the general formula

4-alkyl-1-ethoxycarbonyl-1,2-dihydroquinoline- represented by [Formula] (wherein R ₁ and R ₃ are the same as above)
2-dialkylphosphonate () is used as an alkali metal salt, and then R ₂ X (wherein R ₂ is the same as above).
X represents halogen. ) A general formula characterized by reacting with an alkyl halide represented by

The present invention provides a method for producing a dialkylphosphonate derivative represented by the formula: (wherein R ₁ , R ₂ , and R ₃ are the same as above). Next, the method for producing the compound of the present invention will be described in more detail. 4-Alkyl-1-ethoxycarbonyl-1,2-dihydroquinoline-2-dialkylphosphonate (), which is a raw material used in the production of the compound of the present invention, is available from Tetrahedron Letters, Volume 23, No. 16, 1709-
1712 (1982)), quinoline and ethyl chlorocarbonate were reacted, and then trialkyl phosphite was reacted in the presence of sodium iodide to form the general formula

1-ethoxycarbonyl- represented by [Formula] (in the formula, R ₃ is the same as above)
1,2-dihydroquinoline-2-dialkylphosphonate (), and then the compound is made into an alkali metal salt and is obtained by reacting it with an alkyl halide represented by R ₁ X (wherein R ₁ is the same as above). It will be done. The compound of the general formula () is reacted with an approximately equivalent amount of an alkali metal to form an alkali metal salt of a 1,2-dihydroquinoline derivative, and then reacted with an approximately equivalent amount of an alkyl halide to form the compound of the present invention ( ) can be manufactured. The reaction is generally preferably carried out in the presence of a solvent. Examples of the solvent used include ether, isopropyl ether, tetrahydrofuran, dioxane, benzene, toluene, and xylene. As the alkali metal, for example, sodium, potassium, lithium, or n-butyllithium, and their alkyl compounds, or sodium hydride, sodium amide, lithium diisopropylamide, etc. are used. The reaction temperature is usually selected between about -80°C and room temperature. Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 1-ethoxycarbonyl-4-methyl-1,2-dihydroquinoline was placed in a 100 ml three-necked flask equipped with a condenser, nitrogen suction tube, and rubber septum.
Take 1g of 2-diethylphosphonate and 15ml of tetrahydrofuran and put in a dry ice-acetone bath.
Cooled to 78°C. While stirring with a magnetic stirrer, the inside of the flask was sufficiently purged with nitrogen. Next, 1.78 ml of 1.59M n-butyllithium-n-hexane solution was added and stirred for 30 minutes. after that,
Add 0.18 ml of methyl iodide, stir for 20 minutes, remove the dry ice-acetone bath, and warm to room temperature.
Stirred for 1 hour. After the reaction was completed, tetrahydrofuran was distilled off, 25 ml of a 5% aqueous sodium hydrogen carbonate solution was added to the residue, and the product was extracted with dichloromethane. After drying the dichloromethane solution over anhydrous magnesium sulfate, dichloromethane was distilled off. The residue was subjected to column chromatography (silica gel, ethyl acetate:n-hexane=
4:1 developing solvent) to produce 4,4-dimethyl-
0.81 gr of 1-ethoxycarbonyl-1,4-dihydroquinoline-2-diethylphosphonate was obtained.
n ²⁵ _D 1.5172) Infrared absorption spectrum (NaCl) 2980 (C-H), 1720 (C=O), 1260 (P=O),
1050, 1020 (P-O-C) cm ^-1 nuclear magnetic resonance absorption spectrum (CCl ₄ , internal standard
TMS) δ 1.10-1.60 (m) ppm (15H) δ 3.70-4.60 (m) ppm (6H) δ 6.30 (d) ppm (1H) δ 7.00-7.40 (m) ppm (3H) δ 7.70-8.00 (m) ) ppm (1H) Elemental analysis (as C ₁₈ H ₂₆ NO ₅ P) C H N Analysis value (%) 58.79 7.36 3.69 Theoretical value (%) 58.85 7.13 3.81 Molecular weight by GC-MSS 367 Next, 4,4-dimethyl- An example of the use of 1-ethoxycarbonyl-1,4-dihydroquinoline-2-diethylphosphonate as a fungicide is shown. 4,
4-dimethyl-1-ethoxycarbonyl-1,4
-Dissolve dihydroquinoline-2-diethylphosphonate in a 10% aqueous methanol solution, and then add Tween 20 [trade name, manufactured by Kao Atlas Co., Ltd.]
The drug was prepared at a concentration of 300 ppm. Wheat seedlings were sprayed with 300 ppm of the chemical, and 30 hours later they were inoculated with black rust fungus (Puccinia graminis tritis race) and grown in a greenhouse. When observed two weeks later, the disease was found to be
It was not recognized at all. It was also found to be effective against powdery mildew (Erysiple graminis). Example 2 1g of 1-ethoxycarbonyl-4-methyl-1,2-dihydroquinoline-2-diethylphosphonate and 15ml of tetrahydrofuran were placed in the same reactor as in Example 1, and heated to -78°C in a dry ice-acetone bath. It was cooled to While stirring with a magnetic stirrer, the inside of the flask was sufficiently purged with nitrogen. Next, 1.83 ml of 1.55M n-butyllithium-hexane solution was added and stirred for 30 minutes. Then, 0.21 ml of ethyl bromide was added, stirred for 20 minutes, removed the dry ice-acetone bath, heated to room temperature, and heated to room temperature.
Stir for hours. After the reaction was completed, the same operation as in Example 1 was carried out to obtain 1
0.55 gr of -ethoxycarbonyl-4-ethyl-4-methyl-1,4-dihydroquinoline-2-diethylphosphonate was obtained. (n ²⁵ _D 1.5186) Infrared absorption spectrum (NaCl) 2970 (C-H), 1716 (C=O), 1250 (P=O),
1050, 1020 (P-O-C) cm ^-1 nuclear magnetic resonance absorption spectrum (CCl ₄ , internal standard
TMS) δ 0.60-1.90 (m) ppm (17H) δ 3.48-4.48 (m) ppm (6H) δ 6.12 (d) ppm (1H) δ 6.73-7.33 (m) ppm (3H) δ 7.57-7.96 (m) ) ppm (1H) Elemental analysis value (C ₁₉ H ₂₆ NO ₅ P) C H N analysis value (%) 59.80 7.44 3.71 Theoretical value (%) 59.83 7.40 3.67 Molecular weight by GC-MSS 381 Example 3 Same as Example 1 In a reactor, add 1g of 1-ethoxycarbonyl-1,2-dihydroquinoline-2-diisopurphosphonate and 20ml of tetrahydrofuran.
The sample was taken and cooled to -78°C in a dry ice-acetone bath. While stirring with a magnetic stirrer,
The inside of the flask was sufficiently purged with nitrogen. Next, 2.03 ml of 1.59M n-butyllithium n-hexane solution was added and stirred for 30 minutes. Furthermore, 0.17 ml of methyl iodide was added and stirred for 20 minutes, and the dry ice-acetone bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 1 hour. The mixture was again cooled to -78°C in a dry ice-acetone bath, 2.03 ml of a 1.59M n-butyllithium-n-hexane solution and 0.17 ml of methyl iodide were added, and the same reaction was carried out. After the reaction is completed, perform the same operation as in Example 1 to obtain 4,4-dimethyl-1-ethoxycarbonyl-
0.5 gr of 1,4-dihydroquinoline-2-diisopropylphosphonate was obtained. (n ²⁵ _D 1.5045) Infrared absorption spectrum (NaCl) 2975 (C-H), 1720 (C=O), 1260 (P=O),
1010,980 (P-O-C) cm ^-1 nuclear magnetic resonance absorption spectrum (CCl ₄ internal standard
TMS) δ 1.00-1.88 (m) ppm (21H) δ 4.00-5.00 (m) ppm (4H) δ 6.33 (d) ppm (1H) δ 6.93-7.43 (m) ppm (3H) δ 7.60-8.00 (m) ) ppm (1H) Elemental analysis value (as C ₂₀ H ₃₀ NO ₅ P) C H N Analysis value (%) 60.81 7.60 3.57 Theoretical value (%) 60.75 7.65 3.54 Molecular weight by GC-MSS 395

Claims (1)

[Claims] 1. A dialkylphosphonate derivative represented by the general formula [Formula] (wherein R ₁ , R ₂ , and R ₃ represent lower alkyl groups). 2 4-alkyl-1-ethoxycarbonyl-1,2 represented by the general formula [formula] (in the formula, R ₁ and R ₃ represent lower alkyl groups)
-dihydroquinoline-2-dialkylphosphonate is converted into an alkali metal salt, and then R ₂ X (in the formula R ₂
is the same as above, and X represents halogen. ) A method for producing a dialkylphosphonate derivative represented by the general formula [Formula] (wherein R ₁ , R ₂ , and R ₃ represent a lower alkyl group), which comprises reacting with an alkyl halide represented by the following formula: