CN1052981C - 1,3,2-phospho heterocyclic octane-novel germicide - Google Patents

Abstract

The present invention relates to a class of 1,3,2-dioxaphosphorane compound with novel chemical structure and general formula I, its synthesis method, preparation and application as agricultural fungicide.

In the formula: A is H or CCl ₃ ;

B is 2-3 Cl atoms;

R is C ₁ -C ₄ alkyl, alkenyl or haloalkyl;

CH ₂ COOR ¹ , R ¹ =C ₁ -C ₄ alkyl; CH ₂ CONR ² ₂ , R ² =H, alkyl;

CH ₂ Ar, AR=C ₆ H ₅ , halophenyl,

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Description

1,3,2-Dioxaphosphoctanes—a class of fungicides

式中：A为H或CCl₃；The present invention relates to a class of 1,3,2-dioxaphosphocyclooctane compound with novel chemical structure and general formula I, its synthesis method, preparation containing the compound and its application for preventing and controlling crop diseases.

In the formula: A is H or CCl ₃ ;

B is 2-3 Cl atoms;

R is C ₁ -C ₄ alkyl, alkenyl or haloalkyl;

CH ₂ COOR ¹ , R ¹ =C ₁ -C ₄ alkyl;

CH ₂ CONR ² ₂ , R ² =H, alkyl;

等。CH ₂ Ar, Ar=C ₆ H ₅ , halophenyl;

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Class I compounds are ring-closed by bis(2-hydroxy-chlorophenyl)methane(II) and P ₄ S ₁₀ , triethylamine in benzene, toluene, xylene and other solvents to obtain the intermediate-6-thio -6-Mercapto-1,3,2-dioxaphosphorane triethylamine salt (III), obtained by esterification of III with the corresponding RX. Its reaction formula is as follows: In the formula, A, B and R have the same meaning as above; X=halogen.

The compound of general formula I is mixed with talcum powder, diatomaceous earth, kaolin and other fillers and surfactants, such as sodium lauryl sulfate, sodium alkylaryl sulfonate, etc., in a certain weight ratio, and after mechanical grinding, to obtain Containing 1 5%～40% powder or wettable powder.

The compound of general formula I and preparation thereof, to cucumber downy mildew (Pseudomonas lachrymans), wheat leaf rust (Puccinia rubigo-vera), apple ring grain (Macrophoma kuwatsukai), cucumber downy mildew (Pseudoperonospora cubensis) etc. Phytopathogenic bacteria have antibacterial effect, especially the inhibitory effect on cucumber downy mildew, which is better than the protective fungicide chlorothalonil.

The invention is further illustrated by the following examples, but the invention is not limited to these examples. Example 1 Synthesis of Intermediate III Synthesis of A, IIIA

Put 0.04mol of bis(2-hydroxy-3,5-dichlorophenyl)methane, 0.01mol of P ₄ S ₁₀ , 0.04mol of triethylamine and 200mL of toluene in the reaction flask, and reflux for 2-3 hours under stirring. After the reaction was completed, it was cooled and filtered with suction to obtain a solid. Product IIIA was obtained by recrystallization from acetone. mp273～275°C, yield 87.6%. ¹ H-NMR (DMSO-d6): 7.25-7.10 (m, 4H, ArH), 3.92 (d, 2H, CH ₂ ), 3.22 (q, 6H, 3CH ₂ ), 1.28 (t, 9H, 3CH ₃ ) . Elemental analysis, found (calculated) %: C, 42.80 (42.79); H, 4.07 (4.16); N, 2.48 (2.63). B. Synthesis of IIIB

Synthesized according to method A, reacting bis(2-hydroxy-3,5,6-trichlorophenyl)methane with P ₄ S ₁₀ and triethylamine to obtain IIIB. mp189～190°C, yield 49.5%. ¹ H-NMR (DMSO-d6): 7.78 (s, 2H, ArH), 4.42 (s, 2H, CH ₂ ), 3.16 (q, 6H, 3CH ₂ ), 1.24 (t, 9H, 3CH ₃ ). Elemental analysis, found (calculated) %: C, 37.89 (37.90); H, 3.28 (3.35); N, 2.75 (2.33). C. Synthesis of IIIC

Synthesized according to method A, reacting bis(2-hydroxy-3,5-dichlorophenyl)trichloromethylmethane with P ₄ S ₁₀ and triethylamine to obtain IIIC. mp.183～184°C, yield 55.3%. ¹ H-NMR (DMSO-d6): 8.10-7.50 (m, 4H, ArH), 6.28 (d, 2H, CH ₂ ), 3.12 (m, 6H, 3CH ₂ ), 1.20 (m, 9H, 3CH ₃ ) . Elemental analysis, found (calculated) %: C, 37.21 (36.92); H, 3.12 (3.25); N, 2.23 (2.15). Synthesis of Example 2 Compound I

Put 0.005 mol of IIIA, IIIB or IIIC, 0.005-0.006 mol of halide (RX) and 50-100 mL of methyl ethyl ketone in the reaction flask, reflux and stir for 2-24 hours. After the reaction is complete, the by-product triethylamine halide hydrogen salt is filtered off. After the filtrate is precipitated, the corresponding IA, IB or IC is obtained, and the pure compound is obtained after recrystallization. The recrystallization solvent is acetone, chloroform or acetone-ethanol mixture.

The halides (RX) used in the reaction are respectively:

X=I, R= _CH3 ;

_X =Br, R= _{C2H5 , C3H7} (n ₎ , _C3H7 (i), _CH2Br , _C2H4Br , _CH2 -CH= _{CH2 ;}

X=Cl, R=C ₄ H ₉ (n), C ₄ H ₉ (i), C ₄ H ₉ (s), CH ₂ COOCH ₃ , CH ₂ COOC ₂ H ₅ ,

CH ₂ CONH ₂ , CH ₂ CON(C ₂ H ₅ ) ₂ , CH ₂ C ₆ H ₅ , CH ₂ -C ₆ H ₄ Cl(p),

结果见表1。 _CH2 - _C6H4Br (p _{), CH2-C6H4F ( p} ) _;

The results are shown in Table 1.

Table 1: Physical constants of some Class I (IA, IB, IC) compounds The preparation of example 3 compound I preparations

Compound I 20g

Surfactant 5～10g

Talc powder 65~70g

The mixture prepared in the above ratio was ground by a pulverizer to obtain a wettable powder containing 20% of Compound I. The antibacterial activity of example 4 compound I to cucumber downy mildew

A. The flat plate method inhibits the activity of downy mildew

In flat plate test, compound I has excellent antibacterial activity against cucumber downy mildew. Listed in Table 2 is the inhibitory activity of some class I compounds on the spore germination of Cucumber downy mildew.

Table 2: Part of compound I against cucumber downy mildew (Pseudoperonospora cubensis)

Inhibitory activity of spore germination compound Inhibition percentage (%) 100(mg/L) 50(mg/L) 25(mg/L) 12.5(mg/L) 6.25(mg/L) IA1IA2IA3IA4IA5IA6IA7IA9IA10IA11IA12IA13IA15IB1IB3IB10IB12IC11C2IC3IC101C12IC13IC15 100100100100100100100100100981001001008610010010010010010069100100100 1001001001001001001009910096931001001187100100100100100505099100 17.5100100100100100100894669461001000101610095100100143417100 1310014100100100100784203710010032409525851002803100 1410001001001009842190610010000099165991400100 B. Pot experiment

In the pot test, the inhibitory activity of class I compounds against cucumber downy mildew was also better than that of the control drug chlorothalonil. The results are shown in Table 3.

Table 3: The results of the efficacy test of several IA 20% wettable powders on cucumber downy mildew deal with Condition Index I II III Control effect (%) I II III Average 0.1% IA4 0.05% 0.025% 8.4 11.6 11.6 20.3 10.8 17.914.5 19.4 22.2 87.0 83.3 81.1 83.868.6 84.4 70.8 74.681.8 72.0 63.8 72.5 0.1%IA13 0.05% 0.025% 17.9 25.4 14.519.4 31.3 19.427.0 22.2 30.5 72.3 63.4 76.3 70.770.0 54.9 68.4 64.458.3 68.0 50.2 58.8 0.1%IA2 0.05% 0.025% 22.2 29.8 25.427.0 29.8 29.833.5 28.6 31.3 65.7 57.1 58.6 60.558.3 57.1 51.4 55.648.2 58.8 48.9 52.0 0.1% Chlorothalonil 0.05% 0.025% 28.6 29.8 25.433.3 29.8 30.435.3 39.3 37.2 55.8 57.1 58.6 57.248.5 52.0 50.4 50.345.4 43.4 39.3 42.7 Bacteria liquid 64.7 69.4 61.3 0.0 0.0 0.0 0.0

Claims (9)

1,1,3 shown in the general formula I, the compound with fungicidal activity of 2-dioxy phosphorus heterocycle octane class.

In the formula: A is H or CCl ₃

B is a 2-3 Cl atom;

R is C ₁-C ₄Alkyl, thiazolinyl or haloalkyl;

CH ₂COOR ¹, R ¹=C ₁-C ₄Alkyl;

CH ₂CONR ² ₂, R ²=H, alkyl;

CH ₂Ar, Ar=C ₆H ₅, halogenophenyl;

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2, in the claim 1, B is total up to 2,4,8, the compound of 10-tetrachloro;

3, in the claim 2, A is the compound of H;

4, the synthetic method of compound shown in a kind of synthetic claim 1, its building-up reactions is:

5, the compound in the claim 4, B is total up to 2,4,8, the 10-tetrachloro;

6, the compound in the claim 5, A are H;

7, the wettable powder or the pulvis that are mixed with of the compound in the claim 1;

8, the compound in the claim 1 is as the application of disinfectant use in agriculture;

9, the application of the compound in the claim 8 in the control Pseudoperonospora cubensis.