CN104356104B - There is the chromen-2-one substituted acrylic ester compounds of fungicidal activity - Google Patents
There is the chromen-2-one substituted acrylic ester compounds of fungicidal activity Download PDFInfo
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- CN104356104B CN104356104B CN201410659502.5A CN201410659502A CN104356104B CN 104356104 B CN104356104 B CN 104356104B CN 201410659502 A CN201410659502 A CN 201410659502A CN 104356104 B CN104356104 B CN 104356104B
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- chromen
- acrylic ester
- compound
- fungicidal activity
- ester compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
- C07D311/44—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3
- C07D311/46—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3 unsubstituted in the carbocyclic ring
- C07D311/52—Enol-esters or -ethers, or sulfur analogues thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
A kind of novel chromen-2-one substituted acrylic ester compounds with fungicidal activity, it relates to a kind of compound, has the novel chromen-2-one substituted acrylic ester compounds of fungicidal activity, and general formula is as follows:Wherein: R1It is selected from phenyl, substituted-phenyl, furan nucleus; R2It is selected from C1-C2Alkyl; The compounds of this invention novel structure, has very high inhibit activities to cucumber downy mildew, gray mold of cucumber is also had certain inhibit activities simultaneously.
Description
Technical field
The present invention relates to a kind of compound, particularly relate to a kind of chromen-2-one substituted acrylic ester compounds with fungicidal activity.
Background technology
Better survive and to the needs of food and environmental safety to meet the mankind, the damage control caused by pest is in the scope that economy allows, due to the succession of mushroom population, transition and to the generation of chemical pesticide resistance with develop rapidly, it is necessary to constantly invention novel with the Fungicidal compounds improved and composition.
Most of chromen-2-one (tonka bean camphor) and derivative thereof all have certain sterilization or anti-microbial activity, methoxy acrylic ester compounds also has been reported as except sterilant, chromen-2-one and acrylic ester compound are combined by the present invention, and the chromen-2-one substituted acrylic ester compounds obtained has no open.
Summary of the invention
It is an object of the invention to provide a kind of chromen-2-one substituted acrylic ester compounds with fungicidal activity, the compounds of this invention novel structure, cucumber downy mildew is had very high inhibit activities, gray mold of cucumber is also had certain inhibit activities simultaneously.
It is an object of the invention to be achieved through the following technical solutions:
There is the chromen-2-one substituted acrylic ester compounds of fungicidal activity, it is characterised in that, described compound general formula is as follows:
Wherein: R2It is selected from C1-C2Alkyl; R1It is selected from phenyl, substituted-phenyl, furan nucleus;
Chromen-2-one substituted acrylic ester shown in general formula has the compound of fungicidal activity.
The chromen-2-one substituted acrylic ester compounds with fungicidal activity, described compound is applied as sterilant; Cucumber downy mildew is had inhibit activities, gray mold of cucumber is also had inhibit activities simultaneously.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
The present invention provides the chromen-2-one substituted acrylic ester compounds of a kind of novel structure, and general formula is as follows:
Wherein: R2It is selected from C1-C2Alkyl; R1It is selected from phenyl, substituted-phenyl, furan nucleus;
The compounds of this invention novel structure, has very high inhibit activities to cucumber downy mildew, gray mold of cucumber is also had certain inhibit activities simultaneously.
The general formula compound (I) of the present invention can be prepared by the following method:
Compound 1(according to method described in DE2155113, US3742669, can be obtained by reacting by Baylis-Hillman by corresponding aldehyde and acrylate) and PBr3Add by a certain percentage in appropriate solvent, at room temperature stir 1 hour, treated obtain compound 2;Solvent can be selected from chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane etc.
Compound 2 and compound 3(can be buied by market) miscible in appropriate solvent, control temperature, at about 60 DEG C, reacts 1～2 hour in the basic conditions, treated obtained target product (chemical compounds I). Solvent is selected from ethyl acetate, ethanol, acetone, DMF, THF or dioxane etc.; Adding alkaloids, such as sodium carbonate, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium hydroxide, potassium hydroxide etc. are favourable to reaction.
Table 1: the compounds of this invention shown in general formula I
| Compound | R1Base | R2Base | Proterties | Receipts rate % |
| Ⅰ-1 | 4-NO2Ph | CH3 | Light yellow viscous liquid | 48 2 --> |
| Ⅰ-2 | 4-NO2Ph | C2H5 | Light yellow liquid | 54 |
| Ⅰ-3 | 2,4-Cl2Ph | C2H5 | Colourless oil liquid | 37 |
| Ⅰ-4 | 2-MeOPh | CH3 | Yellow thick liquid | 39 |
| Ⅰ-5 | 2--Furan | CH3 | Yellow thick liquid | 28 |
| Ⅰ-6 | 2-Furan | C2H5 | Yellow thick liquid | 31 |
Compound in table 11HNMR(CDCl3, 300MHz) and data are as follows:
Chemical compounds I-1:1HNMR(300MHz, CDCl3) δ: 3.96 (s, 3H, CO2CH3),4.85(s,2H,CCH2OC),5.25(s,2H,OCCH2COO), 7.03-7.38 (m, 4H, Ar-H), 7.65 (dd, 2H, J=8.7,1.5Hz, Ar-H), 7.83 (s, 1H, Ar-CH=C), 8.30 (dd, 2H, J=8.7,1.5Hz, Ar-H).
Chemical compounds I-2:1HNMR(300MHz, CDCl3) δ: 1.36 (t, J=7.2Hz, 3H, CO2CH2CH3), 4.32 (q, J=7.2Hz, 2H, CO2CH2CH3),4.75(s,2H,CCH2OC),5.15(s,2H,OCCH2COO), 7.01-7.36 (m, 4H, Ar-H), 7.65 (dd, 2H, J=8.7,1.5Hz, Ar-H), 7.93 (s, 1H, Ar-CH=C), 8.28 (dd, 2H, J=8.7,1.5Hz, Ar-H).
Chemical compounds I-3:1HNMR(300MHz, CDCl3) δ: 1.46 (t, J=7.2Hz, 3H, CO2CH2CH3), 4.39 (q, J=7.2Hz, 2H, CO2CH2CH3),4.83(s,2H,CCH2OC),5.25(s,2H,OCCH2COO), 7.12-7.36 (dd, 2H, Ar-H), 7.43 (s, H, Ar-H), 8.03 (s, 1H, Ar-CH=C).
Chemical compounds I-4:1HNMR(300MHz, CDCl3) δ: 3.89 (s, 3H, OCH3),3.96(s,3H,CO2CH3),4.82(s,2H,CCH2OC),5.23(s,2H,OCCH2COO), 6.83-7.21 (m, 4H, Ar-H), 7.21-7.58 (m, 4H, Ar-H), 8.13 (s, 1H, Ar-CH=C).
Chemical compounds I-5:1HNMR(300MHz, CDCl3) δ: 3.89 (s, 3H, OCH3),3.96(s,3H,CO2CH3),4.82(s,2H,CCH2OC),5.23(s,2H,OCCH2COO), 6.83-7.21 (m, 4H, Ar-H), 7.21-7.58 (m, 4H, Ar-H), 7.51 (s, 1H, Ar-CH=C), 6.85 (d, 1H, J=3.3Hz, Ar-H), 6.57 (dd, 1H, J=1.5,3.3Hz, Ar-H), 7.67 (d, 1H, J=1.5Hz, Ar-H).
Chemical compounds I-6:1HNMR(300MHz, CDCl3) δ: 1.39 (t, 3H, J=7.2Hz, CH2CH3),4.24(s,2H,CH2Br), 4.36 (q, 2H, J=7.2Hz, CH2CH3),4.82(s,2H,CCH2OC),5.23(s,2H,OCCH2COO), 6.83-7.21 (m, 4H, Ar-H), 7.21-7.58 (m, 4H, Ar-H), 8.13 (s, 1H, Ar-CH=C), 7.67 (d, 1H, J=1.5Hz, Ar-H), 7.51 (s, 1H, Ar-CH=C), 6.85 (d, 1H, J=3.3Hz, Ar-H), 6.57 (dd, 1H, J=1.5,3.3Hz, Ar-H).
Embodiment:
The following example and raw test-results of surveying can be used to illustrate further the present invention, but do not mean that restriction the present invention.
Compou nd synthesis example:
The synthesis of Compound I-1:
In 100ml round-bottomed flask, by 5ml ethyl acetate by 2-(brooethyl)-3-(4-nitrophenyl) methyl acrylate (compound 2a) (1.286g, 4.3mmol) dissolve, add 4 hydroxy coumarin (compound 3a) (0.729g again, 4.5mmol) with 15ml dehydrated alcohol, it is heated to 60 DEG C, after 4 hydroxy coumarin all dissolves, maintain 60 DEG C of stirrings, add 0.805g Anhydrous potassium carbonate wherein, carrying out TLC detection reaction process between the reaction period, after when 2, reaction arrives terminal.20ml ethyl acetate and 50ml water is added in reaction solution, the each 20ml of the ethyl acetate layer saturated common salt aqueous solution extracts 3 times, anhydrous magnesium sulfate drying, decompression is de-molten, it is separated (ethyl acetate/petroleum ether=1/2) through silica gel column chromatography, obtain 0.786g light yellow viscous liquid, it is target product (Compound I-1), product rate 48%.
Raw survey example
Test method: take new compound, after a small amount of acetone solution, to be mixed with certain density compound liquid to be measured with the water containing 0.1% polysorbas20. Select two leaf phase potted plant cucumber seedlings as the host plant of cucumber downy mildew and gray mold of cucumber, manual sprayer is adopted to carry out spraying process, spraying is rear naturally air-dry, pathogenic bacteria spore is inoculated after 24h, cucumber downy mildew spore inoculating is in the cucumber leaves back side, after 24h is cultivated in moisturizing, move and put greenhouse normal management, the fungicidal activity of 4d " Invest, Then Investigate " compound. Botrytis cinerea pers spore inoculating is in face of blade, and every leaf inoculates 2 points, directly at temperature indoor cultivation after inoculation, and the fungicidal activity of 7d " Invest, Then Investigate " compound. Adopting visual method investigation blade occurring degree, represent with " 100 " level and do not fall ill completely, " 0 " level represents the most seriously falls ill.
Table 2: the fungicidal activity of compound
。
Claims (2)
1. there is the chromen-2-one substituted acrylic ester compounds of fungicidal activity, it is characterised in that, described structural formula of compound is as follows:
。
2. chromen-2-one substituted acrylic ester compounds according to claim 1, it is characterised in that, cucumber downy mildew is had inhibit activities by this compound, gray mold of cucumber is also had inhibit activities simultaneously.
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| CN201410659502.5A CN104356104B (en) | 2014-11-19 | 2014-11-19 | There is the chromen-2-one substituted acrylic ester compounds of fungicidal activity |
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| CN201410659502.5A CN104356104B (en) | 2014-11-19 | 2014-11-19 | There is the chromen-2-one substituted acrylic ester compounds of fungicidal activity |
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| CN104356104A CN104356104A (en) | 2015-02-18 |
| CN104356104B true CN104356104B (en) | 2016-06-15 |
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