CN1052981C - 1,3,2-phospho heterocyclic octane-novel germicide - Google Patents
1,3,2-phospho heterocyclic octane-novel germicide Download PDFInfo
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- CN1052981C CN1052981C CN96100043A CN96100043A CN1052981C CN 1052981 C CN1052981 C CN 1052981C CN 96100043 A CN96100043 A CN 96100043A CN 96100043 A CN96100043 A CN 96100043A CN 1052981 C CN1052981 C CN 1052981C
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Abstract
The present invention relates to a 1, 3, 2-dioxide phosphorus heterocyclic octane type compound with a novel chemical structure and a general formula I, a synthetic method of the compound, a preparation and application used as an agricultural disinfecting agent. In the general formula I: A is an H or CC l 3; B is 2 to 3 Cl atoms; R is alkyl of C1 to C4, alkenyl or halogenating alky, CH2COOR<1> alkyl, CH2CONR2<2> alkyl, CH2Ar and halogenating alkyl, CH2, etc., wherein R<1> is equal to C1-C4, R<2> is equal to H and Ar is equal to C6H5. The compound of the general formula Iis synthesized by the reaction, A, B and R in the formula I are the same in meaning; X is equal to halogen.
Description
The present invention relates to a class chemical structure novelty, general formula I 1,3,2-dioxy phosphorus heterocycle octane compounds and synthetic method thereof, contain this compounds preparation and the control corps diseases application.
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;
Deng.
The I compounds is through two (2-hydroxyl-chlorophenyl) methane (II) and P
4S
10, triethylamine, in the benzene,toluene,xylene equal solvent, close ring, obtain intermediate-6-sulphur-6-sulfydryl-1,3,2-dioxy phosphorus heterocycle octane triethylamine salt (III), III obtain with corresponding RX esterification again.Its reaction formula is as follows:
The implication of A, B and R is the same in the formula; The X=halogen.
Filler and tensio-active agents such as the compound of general formula I and talcum powder, diatomite, kaolin, mixed as sodium lauryl sulphate, sodium alkylarysulfonate etc. by certain weight ratio, after mechanical mill, obtain containing pulvis or the wettable powder of I 5%～40%.
The compound of general formula I and preparation thereof; botrytis cinerea pers (Pseudomonas lachrymans), wheat leaf rust bacterium (Puccinia rubigo-vera), ring rot of apple bacterium (Macrophoma kuwatsukai), bacterium of downy mildew of cucumber various plants pathogenic bacterias such as (Pseudoperonospora cubensis) had bacteriostatic action; particularly, be better than the protective fungicide m-tetrachlorophthalodinitrile to the restraining effect of bacterium of downy mildew of cucumber.
The present invention can be further described with following example, but the present invention is not limited in these examples.Synthetic A, the IIIA's of example 1 intermediate III is synthetic
Put two (2-hydroxyl-3, the 5-dichlorophenyl) methane of 0.04mol, 0.01molP
4S
10, 0.04mol triethylamine and 200mL toluene in reaction flask, under agitation, refluxed 2～3 hours.Reaction is finished, cooling, and suction filtration gets solid.Get product IIIA through acetone recrystallization.M.p.273～275 ℃, yield 87.6%.
1H-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)。Ultimate analysis, measured value (calculated value) %:C, 42.80 (42.79); H, 4.07 (4.16); N, 2.48 (2.63).B, IIIB's is synthetic
It is synthetic to press the A method, with two (2-hydroxyl-3,5,6-trichlorophenyl) methane and P
4S
10, triethylamine reaction, IIIB.M.p.189～190 ℃, yield 49.5%.
1H-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)。Ultimate analysis, measured value (calculated value) %:C, 37.89 (37.90); H, 3.28 (3.35); N, 2.75 (2.33).C, IIIC's is synthetic
It is synthetic to press the A method, with two (2-hydroxyl-3,5-dichlorophenyl) trichloromethyl methane and P
4S
10, triethylamine reaction, IIIC.Mp.183～184 ℃, yield 55.3%.
1H-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)。Ultimate analysis, measured value (calculated value) %:C, 37.21 (36.92); H, 3.12 (3.25); N, 2.23 (2.15).Synthesizing of example 2 Compound I
Put IIIA, IIIB or the IIIC of 0.005mol, the halides of 0.005-0.006mol (RX) and 50-100mL butanone reflux and stirred 2-24 hour in reaction flask.Reaction is finished, and filters by product triethylamine halogen hydracid salt.Behind the filtrate precipitation, obtain corresponding IA, IB or IC, obtain pure compound behind recrystallization, recrystallization solvent is acetone, chloroform or acetone-alcohol mixture.
Halides (RX) used in the reaction is respectively:
X＝I， R＝CH
3；
X＝Br， R＝C
2H
5，C
3H
7(n)，C
3H
7(i)，CH
2Br，C
2H
4Br，CH
2-CH＝CH
2；
X＝Cl， R＝C
4H
9(n)，C
4H
9(i)，C
4H
9(s)，CH
2COOCH
3，CH
2COOC
2H
5，
CH
2CONH
2，CH
2CON(C
2H
5)
2，CH
2C
6H
5，CH
2-C
6H
4Cl(p)，
CH
2-C
6H
4Br (p), CH
2-C
6H
4F (p);
The results are shown in Table 1.
Table 1: part I class (IA, IB, IC) physical constant of compound
The preparation of example 3 Compound I preparations
Compound I 20g
Tensio-active agent 5～10g
Talcum powder 65～70g
Pei Zhi mixture after pulverizer grinds, obtains containing the wettable powder of Compound I 20% according to the above ratio.Example 4 Compound I are to the bacteriostatic activity of bacterium of downy mildew of cucumber
A, plate method suppress the activity of Pseudoperonospora cubensis
In the test of plate method, Compound I has excellent bacteriostatic activity to bacterium of downy mildew of cucumber.Listed in the table 2 is the inhibition activity of part I compounds to the bacterium of downy mildew of cucumber spore-germination.
Table 2: part of compounds I is to bacterium of downy mildew of cucumber (Pseudoperonospora cubensis)
The inhibition activity of spore-germination
B, pot experiment
| Compound | Suppress percentage (%) | ||||
| 100(mg/L) | 50(mg/L) | 25(mg/L) | 12.5(mg/L) | 6.25(mg/L) | |
| IA1 IA2 IA3 IA4 IA5 IA6 IA7 IA9 IA10 IA11 IA12 IA13 IA15 IB1 IB3 IB10 IB12 IC1 1C2 IC3 IC10 1C12 IC13 IC15 | 100 100 100 100 100 100 100 100 100 98 100 100 100 86 100 100 100 100 100 100 69 100 100 100 | 100 100 100 100 100 100 100 99 100 96 93 100 100 11 87 100 100 100 100 100 50 50 99 100 | 17.5 100 100 100 100 100 100 89 46 69 46 100 100 0 10 16 100 95 100 100 14 34 17 100 | 13 100 14 100 100 100 100 78 42 0 37 100 100 3 24 0 95 25 85 100 28 0 3 100 | 14 100 0 100 100 100 98 42 19 0 6 100 100 0 0 0 99 1 65 99 14 0 0 100 |
In pot experiment, the I compounds also is better than contrasting the medicine m-tetrachlorophthalodinitrile to the inhibition activity of bacterium of downy mildew of cucumber.The results are shown in Table 3.
Table 3: several IA 20% wettable powders are to the potted plant evaluation of pesticide effectiveness result of cucumber downy mildew
| Handle | Disease index I II III | Prevention effect (%) I II III is average |
| 0.1％ IA4 0.05％ 0.025％ | 8.4 11.6 11.6 20.3 10.8 17.9 14.5 19.4 22.2 | 87.0 83.3 81.1 83.8 68.6 84.4 70.8 74.6 81.8 72.0 63.8 72.5 |
| 0.1％ IA13 0.05％ 0.025％ | 17.9 25.4 14.5 19.4 31.3 19.4 27.0 22.2 30.5 | 72.3 63.4 76.3 70.7 70.0 54.9 68.4 64.4 58.3 68.0 50.2 58.8 |
| 0.1％ IA2 0.05％ 0.025％ | 22.2 29.8 25.4 27.0 29.8 29.8 33.5 28.6 31.3 | 65.7 57.1 58.6 60.5 58.3 57.1 51.4 55.6 48.2 58.8 48.9 52.0 |
| 0.1% m-tetrachlorophthalodinitrile 0.05% 0.025% | 28.6 29.8 25.4 33.3 29.8 30.4 35.3 39.3 37.2 | 55.8 57.1 58.6 57.2 48.5 52.0 50.4 50.3 45.4 43.4 39.3 42.7 |
| Bacterium 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;
Deng.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100043A CN1052981C (en) | 1996-01-11 | 1996-01-11 | 1,3,2-phospho heterocyclic octane-novel germicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100043A CN1052981C (en) | 1996-01-11 | 1996-01-11 | 1,3,2-phospho heterocyclic octane-novel germicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1154370A CN1154370A (en) | 1997-07-16 |
| CN1052981C true CN1052981C (en) | 2000-05-31 |
Family
ID=5116445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100043A Expired - Fee Related CN1052981C (en) | 1996-01-11 | 1996-01-11 | 1,3,2-phospho heterocyclic octane-novel germicide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1052981C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415758C (en) * | 2004-03-23 | 2008-09-03 | 天津工业大学 | Fire retardant in use for cellulose and fabricating method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386204A (en) * | 1979-05-15 | 1983-05-31 | Ciba-Geigy Corporation | 6-Piperidino-dibenz[d,g][1,3,6,2]dioxathiophosphocine |
| GB2250990A (en) * | 1990-12-21 | 1992-06-24 | Ciba Geigy Ag | Substituted dibenzo[d,g][1,3,2]dioxaphosphocins |
| US5310890A (en) * | 1992-07-22 | 1994-05-10 | Ciba-Geigy Corporation | Carbohydrate substituted dibenzoi(d,g)(1,3,2)dioxaphosphocin stabilizers |
-
1996
- 1996-01-11 CN CN96100043A patent/CN1052981C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386204A (en) * | 1979-05-15 | 1983-05-31 | Ciba-Geigy Corporation | 6-Piperidino-dibenz[d,g][1,3,6,2]dioxathiophosphocine |
| GB2250990A (en) * | 1990-12-21 | 1992-06-24 | Ciba Geigy Ag | Substituted dibenzo[d,g][1,3,2]dioxaphosphocins |
| US5310890A (en) * | 1992-07-22 | 1994-05-10 | Ciba-Geigy Corporation | Carbohydrate substituted dibenzoi(d,g)(1,3,2)dioxaphosphocin stabilizers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1154370A (en) | 1997-07-16 |
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