CN108864188B - Phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, and preparation method and application thereof - Google Patents

Phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, and preparation method and application thereof Download PDF

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CN108864188B
CN108864188B CN201811037049.9A CN201811037049A CN108864188B CN 108864188 B CN108864188 B CN 108864188B CN 201811037049 A CN201811037049 A CN 201811037049A CN 108864188 B CN108864188 B CN 108864188B
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薛伟
陈丽娟
汤旭
陈英
夏榕娇
张橙
郭涛
蒋仕春
王一会
贺鸣
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4875—Esters with hydroxy aryl compounds
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/5475—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and selenium with or without oxygen or sulfur as ring hetero atoms; having nitrogen and tellurium with or without oxygen or sulfur as ring hetero atoms

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Abstract

The invention discloses a phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, a preparation method and application thereof, wherein the general formula (I) is shown as follows: r1Is phenyl, substituted phenyl or substituted aromatic heterocyclic radical; r2Is C1-C6 alkyl. Said R1The substituted phenyl is the phenyl ring which contains more than one methoxyl, nitryl, methyl, trifluoromethyl or halogen atom at the ortho, meta, para or the two ortho, meta and para positions; said R1The substituted aromatic heterocyclic group is furyl, pyridyl, thienyl, pyrrolyl, thiazolyl, 2-chloropyridyl or 2-chlorothiazolyl. The invention can inhibit the activity of plant bacteria, and has the advantages of easily obtained raw materials, mild reaction conditions, simple post-treatment and high yield.

Description

Phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical industry, in particular to a phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, a preparation method of the phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, and application of the phosphite ester-containing 1, 4-pentadiene-3-ketone derivative in the aspect of inhibiting plant bacterial activity.
Background
The natural product and the bionic pesticide thereof have the characteristics of environmental friendliness, unique action site and high selectivity, and play an increasingly important role in preventing and treating plant diseases. Curcumin, a polyphenol compound derived from turmeric, is widely used as a spice, a food preservative, monosodium glutamate and a dye. 1, 4-pentadiene ketone compound, as an important curcumin derivative, has gradually become one of the hot spots in the field of medicament creation because of having broad-spectrum biological activities such as insecticidal, bacteriostatic, plant virus resistant, anticancer, anti-inflammatory and antioxidant activities. Recent reports show that 1, 4-pentadiene-3-ketone compounds have extremely good anti-plant virus activity, so that the compounds are taken as leads, and the structure of the compounds is modified, so that organic active molecules with excellent anti-plant virus activity can be obtained.
In 2014 Ma et al (J.Agric.food Chem,2014,62,8928-8934.) introduce a 4(3H) -quinazolinone structure into the skeleton of 1, 5-diaryl-1, 4-pentadien-3-one, so as to synthesize a series of quinazolinone-containing pentadienone compounds, and perform an activity test on the quinazolinone compounds against TMV. The test result shows that: at a medicament concentration of 500 mug/mL, most of the synthesized compounds have certain in-vivo inhibition and cure effects on TMV. Some of the compounds have excellent effects on in vivo treatment, and the inhibition rate of the compounds is better than that of a control medicament, namely ningnanmycin.
A series of 2-imidazolyl-1, 4-pentadiene-3-ketone derivatives are synthesized by Liuchunli and the like (Liuchunli, Schuman, Liujinyan, Weibingo, Maofei, Yanjie, Li Jian. 2-imidazolyl-1, 4-pentadiene-3-ketone derivatives are synthesized and antibacterial activity research [ J ]. Chinese medicinal chemistry J, 2015,25:15-23.) shows that the compounds have a certain inhibiting effect on staphylococcus epidermidis and staphylococcus aureus.
Baldwin et al (Eur J Med Chem,2015,92:693-699.) designed and synthesized 8 monocarbonyl curcumin derivatives, found that the compounds have good inhibitory effect on Mycobacterium marinum.
In 2016, Gan et al (Pest Manag. Sci,2016,72: 534-. The test result shows that: the synthesized compound has better anti-TMV activity when the concentration of the medicament is 500 mu g/mL. Wherein the partially differentiated compound has excellent activity in the aspect of anti-TMV protective activity, and the EC thereof50The value is far better than that of the control medicament ribavirin.
In 2017, Wang (Chem pap,2017,71(7):1225-1233.) and the like take curcumin derivatives as lead compounds, and an oxime ether structure is introduced into 1, 4-pentadiene-3-ketone containing a pyridine ring to obtain a series of 1, 4-pentadiene-3-ketone oxime ether compounds with better TMV (tetramethylpyrazine) resistance activity. The test result shows that: EC of compounds on TMV in therapeutic action50The value is superior to that of the control medicament ribavirin.
The H-phosphite ester and its derivative are used as pesticide, bactericide, herbicide, plant growth regulator, food additive and anticancer medicine, and may be also used as phosphorylating reagent in synthesizing phosphorus-containing compound.
2017, Huang Min, etc. (Huang Min, Ruan Xiang Hui, Zhang Ju Ping, etc.. Studies on the synthesis and antibacterial activity of substituted flavone phosphites [ J ]. organic chemistry, 2017,37(08):2145-
2152.) substituted flavonol is introduced into phosphite ester, a series of phosphite ester compounds containing flavone group are designed and synthesized, the bacteriostatic activity of a target compound is tested by a turbidity method, and a primary measurement result shows that the inhibition rate of most compounds on rice bacterial leaf blight is far higher than that of contrast agents, namely thiabendazole and bismerthiazol under the concentration of 100 mu g/mL; part of the compounds also have better inhibitory activity on citrus canker pathogenic bacteria.
In 2017, Huang et al (phosphor sulfide Silicon Relat,2017,192(8): 954) -959.) introduced substituted flavonol into phosphite ester to design and synthesize a series of flavonoid-containing phosphite ester compounds with antibacterial activity, and preliminary measurement and calculation results show that the compounds have EC for rice bacterial leaf blight50The value is from 40.29 to 66.87. mu.g/mL; is superior to the control medicament thiabendazole copper (88.51 mu g/mL).
In conclusion, the compounds containing 1, 4-pentadiene-3-ketone and phosphite have better biological activity, but no reports about the introduction of phosphite into the pentadiene-ketone structure and the test of inhibiting the activity of plant bacteria are found.
Disclosure of Invention
The invention aims to overcome the defects and provide the phosphite ester-containing 1, 4-pentadiene-3-ketone derivative which can inhibit the activity of plant bacteria, is easy to obtain raw materials, mild in reaction conditions, simple in post-treatment and high in yield.
Another object of the present invention is to provide a process for preparing the phosphite-containing 1, 4-pentadien-3-one derivatives.
The invention further aims to provide the application of the 1, 4-pentadiene-3-ketone derivative containing phosphite ester in inhibiting the activity of plant bacteria.
The invention relates to a1, 4-pentadiene-3-ketone derivative containing phosphite ester, which has the following general formula:
Figure BDA0001791136760000041
wherein: r1Is phenyl, substituted phenyl or substituted aromatic heterocyclic radical; r2Is C1-C6 alkyl.
The aboveA phosphite-containing 1, 4-pentadien-3-one derivative wherein: said R1The substituted phenyl is the phenyl ring which contains more than one methoxyl, nitryl, methyl, trifluoromethyl or halogen atom at the ortho, meta, para or the two ortho, meta and para positions; said R1The substituted aromatic heterocyclic group is furyl, pyridyl, thienyl, pyrrolyl, thiazolyl, 2-chloropyridyl or 2-chlorothiazolyl.
The invention relates to a phosphite ester-containing 1, 4-pentadiene-3-ketone derivative, which has the following synthetic route:
(1) preparing 2- (hydroxyphenyl) -3-butene-2-one or 4- (hydroxyphenyl) -3-butene-2-one from acetone, salicylaldehyde or 4-hydroxybenzaldehyde under alkaline conditions:
Figure BDA0001791136760000051
(2) preparing 1-substituted aryl-5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone or 1-substituted aryl-5- (2-hydroxyphenyl) -1, 4-pentadiene-3-ketone under alkaline conditions by using substituted aromatic aldehyde, 2- (hydroxyphenyl) -3-buten-2-ketone or 4- (hydroxyphenyl) -3-buten-2-ketone as raw materials:
Figure BDA0001791136760000052
(3)1- (2-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadien-3-one and 1- (4-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadien-3-one are reacted with phosphite containing substituent to produce 1, 4-pentadien-3-one derivative containing phosphite. The synthetic route is as follows:
Figure BDA0001791136760000053
the invention relates to application of phosphite ester-containing 1, 4-pentadiene-3-ketone derivatives in medicaments for inhibiting plant bacterial activity.
The invention relates to application of phosphite ester-containing 1, 4-pentadiene-3-ketone derivatives in medicaments for inhibiting rice bacterial blight, citrus canker pathogen and tobacco bacterial wilt.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can show that: the invention takes 1- (2-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-ketone and 1- (4-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-ketone to react with phosphite ester containing substituent group with excellent bioactivity to generate 1, 4-pentadiene-3-ketone derivative containing phosphite ester, and the plant bacteria inhibiting activity of the target compound is measured at the concentration of 100 mu g/mL and 50 mu g/mL, and the result of the bacteriostatic activity test shows that: under the concentration tested by experiments, the compound has good inhibitory activity on rice bacterial blight, tobacco bacterial wilt and citrus canker pathogen, and can be used for preparing a medicament for inhibiting plant pathogens. The preparation method comprises the steps of carrying out aldol condensation reaction on salicylaldehyde and p-hydroxybenzaldehyde with acetone to generate 4- (2-hydroxyphenyl) -3-butene-2-one and 4- (4-hydroxyphenyl) -3-butene-2-one, carrying out aldol condensation reaction on 4- (2-hydroxyphenyl) -3-butene-2-one and 4- (4-hydroxyphenyl) -3-butene-2-one with substituted aromatic formaldehyde to generate 1- (2-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-one and 1- (4-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-ketone, 1- (2-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-ketone and 1- (4-hydroxyphenyl) -5- (substituted aryl) -1, 4-pentadiene-3-ketone react with phosphite ester containing substituent to generate 1, 4-pentadiene-3-ketone derivative containing phosphite ester. The preparation method takes salicylaldehyde, p-hydroxybenzaldehyde, acetone and substituent phosphite ester as raw materials, which are common organic reagents and solvents and are easy to obtain. The method can react at normal temperature or lower temperature, the reaction condition is mild, the post-treatment is simple, and the yield is high and can reach 44-70%.
Detailed Description
Example 1
Synthesis of diethyl (4- ((1E,4E) -5- (3-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate (Compound No. A1), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: 4-hydroxybenzaldehyde (6.1g) was added to 60mL of acetone, stirred for about 15min, and after ice-cooling the reaction system for about 30min, about 100mL of 5% NaOH solution was added to the system, after the dropwise addition, the ice-cooling chamber was removed, and the mixture was stirred at room temperature for about 24 h. And after the reaction is finished, transferring the system into a 500mL beaker, adding a proper amount of ice water, adjusting the pH of the system to be about 5-6 by using a 5% dilute hydrochloric acid solution, separating out a large amount of yellow solid, pumping out the solid, and finally recrystallizing by using an ethanol/water system to obtain the yellow solid with the yield of 68%.
(2) Synthesis of 1- (3-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: adding 4- (hydroxyphenyl) -3-buten-2-one (4.0g), thiophene-2-formaldehyde (2.86mL) and 50mL of ethanol into a 250mL three-neck flask, stirring for about 30min, adding 60mL of 5% NaOH solution into the system, removing the ice bath chamber after dropwise addition, and stirring at normal temperature for about 24 h. After the reaction is finished, transferring the system to a 500mL beaker, adding a proper amount of ice water, adjusting the pH of the system to be about 5-6 by using a 5% dilute hydrochloric acid solution, separating out a large amount of yellow solid, and extracting the solid to obtain the yellow solid with the yield of 82%.
(3) Synthesis of diethyl 4- ((1E,4E) -5- (3-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate: 1- (3-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one (0.8g), 60mL of carbon tetrachloride and 1.3mL of triethylamine were added to a 100mL round-bottomed flask, and after stirring at room temperature for 0.5 hour, 1.61Ml of diethyl phosphite was added, and stirring was carried out at room temperature, TCL was detected until generation of a new spot and no change in the raw material occurred, and the mixture was extracted with ethyl acetate, and then, a crude product was obtained by distillation under reduced pressure, and diethyl 4- ((1E,4E) -5- (3-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate was obtained by chromatography on a silica gel column [ V (petroleum ether: V ethyl acetate ═ 2.1 ]. Yield 64%, melting point: 128.8-129.0.
Example 2
Synthesis of dimethyl (4- ((1E,4E) -3-oxo-5-phenylpenta-1, 4-dien-1-yl) phenyl) phosphite (Compound No. A2), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-phenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that benzaldehyde is used as a starting material.
(3) Synthesis of dimethyl (4- ((1E,4E) -3-oxo-5-phenylpenta-1, 4-dien-1-yl) phenyl) phosphite: as in step (3) of example 1. The difference lies in that 1- (4-phenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-methyl phosphite are used as raw materials.
Example 3
Synthesis of diethyl (4- ((1E,4E) -3-oxo-5-phenylpenta-1, 4-dien-1-yl) phenyl) phosphate (Compound No. A3) comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (phenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that benzaldehyde is used as a starting material.
(3) Synthesis of diethyl (4- ((1E,4E) -3-oxo-5-phenylpenta-1, 4-dien-1-yl) phenyl) phosphate: as in step (3) of example 1. The difference lies in that 1- (4-phenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-ethyl phosphite are used as raw materials.
Example 4
Synthesis of 4- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyldimethyl phosphite (Compound No. A4), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-chlorophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 4-Cl-benzaldehyde is used as the starting material.
(3) Synthesis of 4- ((1E,4E) -5- (4-chlorophenyl) -3-oxopentan-1, 4-dien-1-yl) phenyldimethyl phosphite: as in step (3) of example 1. The difference lies in that 1- (4-chlorphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-methyl phosphite are used as raw materials.
Example 5
Synthesis of 4- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyldiethyl phosphite (Compound No. A5), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-chlorophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 4-Cl-benzaldehyde is used as the starting material.
(3) Synthesis of 4- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl diethyl phosphite: as in step (3) of example 1. The difference lies in that 1- (4-chlorphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-ethyl phosphite are used as raw materials.
Example 6
Synthesis of 4- ((1E,4E) -5- (2-methoxyphenyl) -3-oxopent-1, 4-dien-1-yl) phenyldimethyl phosphite (Compound No. A6), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (2-methoxyphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 4-nitrobenzaldehyde is used as the starting material.
(3) Synthesis of 4((1E,4E) -5- (2-methoxyphenyl) -3-oxopent-1, 4-dien-1-yl) phenyldimethyl phosphite: as in step (3) of example 1. The difference lies in that 1- (2-methoxyphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-methyl phosphite are used as raw materials.
Example 7
Synthesis of diethyl (4- ((1E,4E) -5- (2-methoxyphenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate (Compound No. A7), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (2-methoxyphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in (2) of example 1, except that 4-chlorobenzaldehyde is used as the starting material.
(3) Synthesis of diethyl (4- ((1E,4E) -5- (2-methoxyphenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate: as in step (3) of example 1. The difference lies in that 1- (2-methoxyphenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H ethyl phosphite are used as raw materials.
Example 8
Synthesis of diethyl (4- ((1E,4E) -3-oxo-5- (thiophen-2-yl) penta-1, 4-dien-1-yl) phenyl) phosphate (Compound No. A8) comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (2-thienyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 2-methoxybenzaldehyde is used as a starting material.
(3) Synthesis of diethyl (4- ((1E,4E) -3-oxo-5- (thiophen-2-yl) pent-1, 4-dien-1-yl) phenyl) phosphate: as in step (3) of example 1. The difference lies in that 1- (2-thienyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-ethyl phosphite are used as raw materials.
Example 9
Synthesis of dimethyl (4- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite (compound No. A9), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 4-fluorobenzaldehyde is used as the starting material.
(3) Synthesis of dimethyl (4- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite: as in step (3) of example 1. The difference lies in that 1- (4-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-one and H-methyl phosphite are used as raw materials.
Example 10
Synthesis of diethyl (4- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate (Compound No. A10), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadien-3-one: the procedure is as in step (2) of example 1, except that 3-nitrobenzaldehyde is used as the starting material.
(3) Synthesis of diethyl (4- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphate: as in step (3) of example 1. The difference lies in that 1- (4-nitrophenyl) -5- (4-hydroxyphenyl) -1, 4-pentadiene-3-one and H-ethyl phosphite are used as raw materials.
Example 11
Synthesis of 2- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyldimethyl phosphite (Compound No. A11), comprising the following steps:
(1) synthesis of 2- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-chlorophenyl-5- (2-hydroxyphenyl) -1, 4-pentadien-3-one step (2) of example 1 was repeated except that benzaldehyde was used as a starting material.
(3) Synthesis of 2- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyldimethyl phosphite: as in step (3) of example 1. The difference lies in that 1- (4-chloro phenyl) -5- (2-hydroxy phenyl) -1, 4-pentadiene-3-ketone and H-methyl phosphite are used as raw materials.
Example 12
Synthesis of 2- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyldiethyl phosphite (Compound No. A12), comprising the following steps:
(1) synthesis of 2- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-chlorophenyl-5- (2-hydroxyphenyl) -1, 4-pentadien-3-one step (2) of example 1 was repeated except that benzaldehyde was used as a starting material.
(3) Synthesis of 2- ((1E,4E) -5- (4-chlorophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl diethyl phosphite: as in step (3) of example 1. The difference lies in that 1- (4-chloro phenyl) -5- (2-hydroxy phenyl) -1, 4-pentadiene-3-ketone and H-ethyl phosphite are used as raw materials.
Example 13
Synthesis of dimethyl (2- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite (compound No. A13), comprising the following steps:
(1) synthesis of 4- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-nitrophenyl-5- (2-hydroxyphenyl) -1, 4-pentadien-3-one As in (2) of example 1, except that benzaldehyde was used as a starting material.
(3) Synthesis of dimethyl (2- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite: as in step (3) of example 1. The difference lies in that 1- (4-nitrophenyl) -5- (2-hydroxyphenyl) -1, 4-pentadiene-3-one and methyl phosphite are used as raw materials.
Example 14
Synthesis of diethyl (2- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite (compound No. A14), comprising the following steps:
(1) synthesis of 2- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-nitrophenyl-5- (2-hydroxyphenyl) -1, 4-pentadien-3-one As in (2) of example 1, except that benzaldehyde was used as a starting material.
(3) Synthesis of diethyl (2- ((1E,4E) -5- (4-nitrophenyl) -3-oxopent-1, 4-dien-1-yl) phenyl) phosphite: as in step (3) of example 1. The difference lies in that 1- (4-nitrophenyl) -5- (2-hydroxyphenyl) -1, 4-pentadiene-3-one and H-ethyl phosphite are used as raw materials.
Example 15
Synthesis of diethyl (2- ((1E,4E) -3-oxo-5- (p-tolyl) penta-1, 4-dien-1-yl) phenyl) phosphite (Compound No. A15), comprising the following steps:
(1) synthesis of 2- (hydroxyphenyl) -3-buten-2-one: as in step (1) of example 1.
(2) Synthesis of 1- (4-methylphenyl-5- (2-hydroxyphenyl) -1, 4-pentadien-3-one step (2) of example 1 was repeated except that benzaldehyde was used as a starting material.
(3) Synthesis of diethyl (2- ((1E,4E) -3-oxo-5- (p-tolyl) penta-1, 4-dien-1-yl) phenyl) phosphite: as in step (3) of example 1. The difference lies in that 1- (4-methylphenyl) -5- (2-hydroxyphenyl) -1, 4-pentadiene-3-ketone and H-ethyl phosphite are used as raw materials.
TABLE 1 physicochemical Properties of the target Compounds and their Mass spectrometric data
Figure BDA0001791136760000131
Figure BDA0001791136760000141
TABLE 2 NMR and C spectra data for target compounds
Figure BDA0001791136760000142
Figure BDA0001791136760000151
Figure BDA0001791136760000161
Figure BDA0001791136760000171
Figure BDA0001791136760000181
Figure BDA0001791136760000191
Bacteriostatic activity of the target compound
(the target Compound has inhibitory Activity against Xanthomonas oryzae pv. oryzae, Xanthomonas canker (Xanthomonas axonopodis pv. citri) and Nicotiana tabacum (Ralstonia solanacearum)
The in vitro bacteriostatic activity of the target compound is tested by a turbidity method by taking Xanthomonas oryzae pv. oryzae, Xanthomonas oryzae pv. citri and Ralstonia solanacearum as test objects, taking commercial medicaments such as copper Thiodiazole (Thiodiazole chip) and bismerhiazol (Bismerthiazol) as positive control medicaments, and preparing the samples and the control medicaments into toxic NB-containing liquid cultures with the concentrations of 100 mu g/mL and 50 mu g/mL respectively based on a test tube, and determining the OD value of the culture medium, wherein the OD value is the OD value of the sterile medium. Then inoculating the tested strain, shaking and culturing for 48h at 28 ℃ and 180r/min constant temperature shaking table, and measuring OD value of the bacterium liquid with each concentration on a spectrophotometer, wherein the OD value is the OD value of the bacterium-containing culture medium. The inhibition of the tested compounds was calculated as follows and the results are shown in tables 4 and 5.
Inhibition rate (OD value of control culture medium liquid after correction-OD value of toxic medium after correction)/OD value of control culture medium liquid after correction
OD value of bacteria-containing culture medium-OD value of sterile culture medium
TABLE 3 determination of Compound A1-A15 on Paddy rice bacterial blight
Figure BDA0001791136760000201
aThree replicates;bthe commercial drugs thiabendazole and bismerthiazol were used as control agents, respectively.
TABLE 4 measurement of Citrus canker bacteria for Compounds A1-A15
Figure BDA0001791136760000202
Figure BDA0001791136760000211
aThree replicates;bthe commercial drugs thiabendazole and bismerthiazol were used as control agents, respectively.
TABLE 5 determination of Ralstonia solanacearum by Compounds A1-A15
Figure BDA0001791136760000212
aThree replicates;bthe commercial drugs thiabendazole and bismerthiazol were used as control agents, respectively.
The target compounds A1-A15 and the results of the antibacterial activity test are shown in tables 4, 5 and 6, and it can be understood from the tables that part of the compounds show excellent inhibitory activity to rice bacterial blight pathogen at a concentration of 100 μ g/mL, which is significantly higher than that of control medicaments, namely thiabendazole (34%) and bismerthiazol (57%); the compound shows certain bacteriostatic activity on citrus canker germs; most of the compounds show better inhibition activity on tobacco bacterial wilt, wherein A2, A3, A6, A7, A8, A10, A13 and A14 are higher than control medicaments of thiabendazole (68%) and bismerthiazol (58%).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification of the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the technical solution of the present invention.

Claims (3)

1. A phosphite-containing 1, 4-pentadiene-3-one derivative having the formula:
Figure DEST_PATH_IMAGE002
wherein: r1Is phenyl, substituted phenyl or thienyl; r2Is C1-C6 alkyl;
said R1The substituted phenyl is a phenyl ring containing methoxyl, nitryl, methyl or halogen atoms at the ortho, meta or para positions.
2. Use of a phosphite-containing 1, 4-pentadien-3-one derivative according to claim 1 as an agent for inhibiting the activity of plant bacteria.
3. The use of a phosphite-containing 1, 4-pentadien-3-one derivative according to claim 2 for the preparation of a medicament for inhibiting bacterial blight of rice, bacterial canker of citrus and bacterial wilt of tobacco.
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