CN105777725B - The application of 3- (2- furyls) chromogen ketone compounds and preparation method thereof and plant epiphyte resisting - Google Patents

The application of 3- (2- furyls) chromogen ketone compounds and preparation method thereof and plant epiphyte resisting Download PDF

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CN105777725B
CN105777725B CN201610220171.4A CN201610220171A CN105777725B CN 105777725 B CN105777725 B CN 105777725B CN 201610220171 A CN201610220171 A CN 201610220171A CN 105777725 B CN105777725 B CN 105777725B
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compound
yield
diacetyl
hydroxyl
phenyl
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CN105777725A (en
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张尊听
韩杰
王涛
张瑾
李晨晨
冯斯琪
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Shaanxi Normal University
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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
    • C07D407/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses 3- (2- furyls) chromogen ketone compounds and preparation method and application that one kind meets general formula 1；Its technique includes：1- (2- hydroxy phenyls) -1 is added in a kettle, 3- diacetyl class compounds, add K10 montmorillonites and 2,5- dimethoxys -2,5- dihydrofuran, heat reactant and 2,5- dimethoxys -2,5- dihydrofuran is chemically reacted, reactant removes K10 montmorillonite catalysts after ethyl alcohol washs three times, the ethanol solution vacuum distillation recovered solvent of washing obtains the mixture of the compounds of this invention and unreacted reactant, so that it is isolated and purified with column chromatography, obtains the compound of the present invention sterling.The synthetic method of the present invention is solvent-free, and easy to operate, the reaction being catalyzed using cheap raw material and K10 montmorillonites has simple process, the advantages such as equipment used is simple, the high income of product and production cost are low.The compound of the present invention has good plant epiphyte resisting effect, can be developed into the novel agrochemical with plant epiphyte resisting.

Description

3- (2- furyls) chromogen ketone compounds and preparation method thereof and plant epiphyte resisting Using
Technical field
The invention belongs to heterocyclic compound technical fields, and in particular to contain six-membered ring to what heterocycle did not hydrogenated, there are one oxygen Atom is as only having ring hetero atom, the condensed heterocyclic compound with other rings.
Background technology
The chromogen ketone compounds of 3- substitutions have extensive physiological activity as a kind of important heterocyclic compound, Anticancer, antibiotic, tranquilizer and antiphlogistic can be done in biological medicine, make insecticide and the weeding of wide spectrum in pesticide research Agent.In recent years, the chromogen ketone compounds of 3- substitutions because of it efficiently, low toxicity, structure diversity and extensive bioactivity, by The highest attention of chemist.Currently, there are two types of the common synthetic methods of chromogen ketone compounds of 3- substitutions：(1)Suzuki Or Stille coupling reactions；(2) illumination coupling reaction.The present invention is with 1- (2- hydroxy phenyls) -1,3- diacetyl cheap and easy to get Class compound and 2,5- dimethoxys -2,5-dihydrofuran are raw material, and catalyst is made with one with the K10 montmorillonites of cheap commercial Pot method has synthesized a series of 3- (2- furyls) chromogen ketone compound.This method has the following advantages：
1. using " one pot synthesis ", the route of synthesis is short (step can be obtained target compound), high income.
2. solvent-free reaction, easily operated, the reaction time is short.
3. atom utilization is high, purifying products aftertreatment technology is simple.
4. not using environmentally harmful catalyst in reaction process, the solvent used is common and solvent-recoverable.
Simultaneously, it has been found that 3- (2- furyls) chromogen ketone compounds have the activity of plant epiphyte resisting, can make It is applied in the drug of standby plant epiphyte resisting.
Invention content
The purpose of the present invention is to provide noval chemical compound 3- (2- furyls) chromogen ketone compounds.
It is original that it is another object of the present invention to provide one kind with 1- (2- hydroxy phenyls) -1,3- diacetyl class compounds The method for expecting to prepare 3- (2- furyls) chromogen ketone compounds.
It is a further object of the present invention to provide a kind of 3- (2- furyls) chromone with plant epiphyte resisting activity The application of class compound, it is characterized in that being used to prepare the drug and medicament of plant epiphyte resisting；It is used to prepare anti-apple decay fungi, Apple anthrax fungi, tomato gray mould fungi, tomato early epidemic fungi, the drug and medicament of potato dry rot fungi.
The chemical structure of general formula of 3- (2- furyls) chromogen ketone compounds according to the present invention is formula 1.
Substituent R in formula 11For hydrogen or hydroxyl or methoxyl group or methyl or fluorine or chlorine or bromine or nitro, R2For hydrogen or hydroxyl or Methoxyl group or methyl or fluorine or chlorine or bromine or nitro, R3For hydrogen or C1~C6Any one in alkyl or aryl, described aryl is Phenyl or naphthyl or furyl or thienyl or pyrrole radicals or anthryl or phenanthryl and hydroxyl or methoxyl group or methyl or fluorine or The phenyl or naphthyl or furyl or thienyl or pyrrole radicals or anthryl or phenanthryl of chlorine or bromine or nitro substituent.It is respectively taken in formula 1 When atom shown in Dai Jiwei following tables or group, specific substance chemical name such as the following table 1.
The substituent group and chemical name of 1 compound 1~19 of table
The preparation method of above-mentioned chemical combination is as follows：
1- (2- hydroxy phenyls) -1,3- diacetyl class compounds are added in a kettle, are added with stirring 1- (2- hydroxy benzenes Base) -1,3- diacetyl classes, 1~4 times of weight of compound K10 montmorillonites, with register make reaction solution temperature be 60~100 DEG C, it is added with stirring rubbing for 1- (2- hydroxy phenyls) -1,3- diacetyl class compounds and 2,5- dimethoxys -2,5-dihydrofuran You react 0.5~2h than 2,5- dimethoxys -2,5-dihydrofuran for 1~4；Make the temperature of reaction solution with register again It is 100~140 DEG C, reacts 0.5h；Last gained reactant 1- (2- hydroxy phenyls) -1,3- diacetyl classes, 30 times of weights of compound Amount ethyl alcohol washs removing K10 montmorillonite catalysts three times respectively, and the ethanol solution of washing merges vacuum distillation recovered solvent and obtains The mixture of the compounds of this invention and unreacted reactant makes it isolate and purify (eluant, eluent: petroleum ether and acetic acid second through silica gel column chromatography Ester volume ratio is 1: 0.1~0.5), obtain the sterling of 3- of the present invention (2- furyls) chromogen ketone compounds.Its chemical reaction side Formula is as follows：
Reaction mechanism：The mechanism of this reaction is divided into two steps, and a step is the alkylation of alpha-alkoxy base, and in addition a step is intramolecular Dehydration.First, at T DEG C, K10 montmorillonites are catalyzed 2,5- dimethoxys -2,5-dihydrofuran and form cation A.No. 2 of 1a Carbon atom on position obtains intermediate B as nucleopilic reagent attack cation A.Intermediate B loses a molecule methanol and obtains 4a. Secondly, the carbon atom that the hydroxyl oxygen atom attack third place of 4a is set is formed into its hemiacetal form, and then at T DEG C, K10 covers de- Intramolecular dehydration obtains final compound 3a under the action of soil.
A kind of application of 3- (2- furyls) chromogen ketone compounds of the present invention, is to be used to prepare plant epiphyte resisting Drug and medicament.
A kind of application of 3- (2- furyls) chromogen ketone compounds of the present invention, is to be used to prepare anti-apple decay Fungi, apple anthrax fungi, tomato gray mould fungi, tomato early epidemic fungi, the drug and medicament of potato dry rot fungi.
The invention is realized by the following technical scheme：
The present invention prepares the formula of plant epiphyte resisting pesticide, it is characterised in that is produced by the raw material of following mass fraction：Change Close object 1~19 5~20 part, remaining be auxiliary agent and water, the auxiliary agent is respectively 1~3 part of wetting agent, 2~5 parts of dispersant, is prevented 1~2 part of agglomeration agent, 0.01~0.05 part of antifoaming agent, 0.5~1 part of suspending agent.
The wetting agent is one or any two in lauryl sodium sulfate, dodecyl sodium sulfate, pull open powder Kind or more, dispersant is one kind in calcium lignosulfonate, sodium lignin sulfonate, polyvinyl alcohol, sodium tripolyphosphate, anticaking agent For white carbon, antifoaming agent SAG-630, suspending agent JY-3.
Inventor has chosen compound 2 from the compound of the present invention 1~19, and compound 6, compound 14 is to apple decay Fungi, apple anthrax fungi, tomato gray mould fungi, tomato early epidemic fungi and potato dry rot fungi carry out the anti-plant of preliminary screening The activity of fungi show that this 3 kinds of compounds all have good plant epiphyte resisting activity, and compound 6 is to five kinds of plant epiphytes Inhibiting rate is both greater than 75%, therefore the present inventor carries out plant epiphyte resisting IC to compound 650Test.3- prepared by the present invention (2- furyls) chromogen ketone compounds are the compounds of a kind of structure proximate, they all have 3- (2- furyls) chromone Basic structure.Thus infer that the compound of the present invention 1~19 all has good plant epiphyte resisting activity.If by them for making The pesticide of standby plant epiphyte resisting, it is contemplated that preferable plant protection effect will be had.The synthetic method of the present invention is using cheap and easy to get 1- (2- hydroxy phenyls) -1,3- diacetyl class compounds and 2,5- dimethoxys -2,5-dihydrofuran be raw material, with cheap quotient The a series of 3- of catalyst one pot process (2- furyls) chromogen ketone compound is done in the K10 montmorillonites of industry, has work The advantages such as skill is easy, and equipment used is simple, the high income of product and production cost are low.
Specific implementation mode
With reference to spectroscopic data and embodiment, the present invention is described in more detail, but the present invention is not restricted to these implement Example.
Used reagent is that chemistry is pure in embodiment.Compound structure determines that Nuclear Magnetic Resonance used is Bruker AM-400 or 600 NMR spectrometer with superconducting magnet, TMS is as internal standard；Infrared spectrum uses Nicolet 170SX FT-IR infrared spectrums Instrument measures；Bruker MAXIS high-resolution mass spectrometers (German Bruker companies)；Fusing point uses WRS-113 digital melting point analyzers It measures.
Embodiment 1
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h；Make the temperature of reaction solution be 120 DEG C with register again, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 78%) of object.Using compound 1 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 92.8-93.6 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 1 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 2.60 (s, 3H), 6.52 (dd, 1H, J=3.0,1.7Hz), 6.98 (d, 1H, J=3.0Hz), 7.35-7.39 (m, 1H), 7.41 (d, 1H, J=8.4Hz), 7.50 (d, 1H, J=1.7Hz), 7.60- 7.65 (m, 1H), 8.23 (d, 1H, J=7.9Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 1 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 20.5,111.3,112.4,114.3,117.7,123.1,125.1, 126.3,133.5,141.8,145.9,155.5,164.6,175.5.
Test result is as follows with mass spectrograph for the molecular weight of the compound 1 of the present embodiment：
HRMS(ESI)：calc.for C14H10O3[M+Na]+249.0528 found 249.0525.
The preparation of compound 2-19
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, ingredient proportion, reaction respectively Condition and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 64%), compound 3 (yields 79%), compound 4 (yield 77%), compound 5 (yield 75%), compound 6 (yield 78%), (production of compound 7 Rate 86%), compound 8 (yield 75%), compound 9 (yield 68%), compound 10 (yield 65%), 11 (yield of compound 89%), compound 12 (yield 68%), compound 13 (yield 80%), compound 14 (yield 27%), 15 (yield of compound 29%), compound 16 (yield 29%), compound 17 (yield 26%), compound 18 (yield 27%), 19 (yield of compound 53%).
Using compound 2 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 225.7-226.4 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 2 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, DMSO-d6), δ (ppm) 2.46 (s, 3H), 6.58 (dd, 1H, J=3.2,1.8Hz), 6.80 (d, 1H, J=3.2Hz), 6.81 (d, 1H, J=2.2Hz), 6.90 (dd, 1H, J=8.7,2.2Hz), 7.74 (d, 1H, J= 1.8Hz), 7.89 (d, 1H, J=8.7Hz), 10.81 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by C in 2 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, DMSO-d6), δ (ppm) 19.8,101.9,111.1,111.7,112.9,115.1, 115.2,127.1,142.4,145.8,156.7,162.7,164.4,173.6.
Test result is as follows with mass spectrograph for the molecular weight of the compound 2 of the present embodiment：
HRMS(ESI)：calc.for C14H10O4[M+Na]+265.0477 found 265.0468.
Using compound 3 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 118.4-119.2 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 3 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 2.54 (s, 3H), 3.86 (s, 3H), 6.51 (dd, 1H, J=3.2, 1.0Hz), 6.77 (d, 1H, J=3.2Hz), 6.91 (dd, 1H, J=8.9,1.7Hz), 6.94 (d, 1H, J=1.7Hz), 7.48 (d, 1H, J=1.0Hz), 8.10 (d, 1H, J=8.9Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 3 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 20.3,55.8,99.9,111.2,112.3,114.0,114.4, 116.9,127.6,141.7,146.0,157.2,163.9,164.2,174.8.
Test result is as follows with mass spectrograph for the molecular weight of the compound 3 of the present embodiment：
HRMS(ESI)：calc.for C15H12O4[M+Na]+279.0633 found 279.0630.
Using compound 4 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow liquid；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 4 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 2.41 (s, 3H), 2.55 (s, 3H), 6.51 (dd, 1H, J=3.2, 1.8Hz), 6.95 (d, 1H, J=3.2Hz), 7.27 (d, 1H, J=8.5Hz), 7.40 (d, 1H, J=8.5Hz), 7.48 (d, 1H, J=1.8Hz), 7.98 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by the C of the compound 1 of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 20.4,21.0,111.2,112.2,114.1,117.4,122.7, 125.5,134.7,135.0,141.7,146.1,153.8,164.6,175.3.
Test result is as follows with mass spectrograph for the molecular weight of the compound 4 of the present embodiment：
HRMS(ESI)：calc.for C15H12O3[M+Na]+263.0684 found 263.0679.
Using compound 5 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 104.8-105.4 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 5 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 2.58 (s, 3H), 6.52 (dd, 1H, J=3.2,1.8Hz), 6.97 (d, 1H, J=3.2Hz), 7.28 (d, 1H, J=8.8Hz), 7.49 (d, 1H, J=1.8Hz), 7.67 (dd, 1H, J=8.8, 2.3Hz), 8.30 (d, 1H, J=2.3Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 5 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 20.6,111.3,112.7,114.3,118.4,119.7,124.3, 128.8,136.4,141.9,145.4,154.2,164.9,173.9.
Test result is as follows with mass spectrograph for the molecular weight of the compound 5 of the present embodiment：
HRMS(ESI)：calc.for C14H9BrO3[M+Na]+326.9633 found 326.9629.
Using compound 6 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 102.2-102.8 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 6 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 2.55 (s, 3H), 6.49 (dd, 1H, J=3.3,1.8Hz), 6.95 (d, 1H, J=3.3Hz), 7.27-7.31 (m, 1H), 7.36 (dd, 1H, J=9.1,4.2Hz), 7.46 (d, 1H, J=1.8Hz), 7.78 (dd, 1H, J=8.3,3.1Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 6 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 20.5,110.9 (d,2J=23.6Hz), 111.3,112.6, 113.6,119.9 (d,3J=8.1Hz), 121.6 (d,2J=25.3Hz), 124.1 (d,3J=7.4Hz), 141.9,145.5, 151.6,159.5 (d,1J=244.9Hz), 165.0,174.4 (d,4J=1.7Hz).
Test result is as follows with mass spectrograph for the molecular weight of the compound 6 of the present embodiment：
HRMS(ESI)：calc.for C14H9FO3[M+Na]+267.0433 found 267.0426.
The compound 7 prepared using this example, after tested, physicochemical property is as follows：
White powder, fusing point are 56.5-57.4 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 7 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 1.33 (s, 3H), 1.35 (s, 3H), 3.32 (hept, 1H, J= 6.8Hz), 6.52 (dd, 1H, J=3.2,1.8Hz), 6.75 (d, 1H, J=3.2Hz), 7.36-7.39 (m, 1H), 7.46 (d, 1H, J=8.4Hz), 7.52 (d, 1H, J=1.8Hz), 7.60-7.69 (m, 1H), 8.23 (d, 1H, J=7.9Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 7 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 20.3,31.9,111.2,112.2,112.8,117.7,123.2, 125.1,126.3,133.5,142.2,145.6,155.7,172.3,176.2.
Test result is as follows with mass spectrograph for the molecular weight of the compound 7 of the present embodiment：
HRMS(ESI)：calc.for C16H14O3[M+Na]+277.0841 found 277.0842.
Using compound 8 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 88.5-89.4 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 8 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 1.32 (s, 3H), 1.33 (s, 3H), 3.29 (hept, 1H, J= 6.8Hz), 3.89 (s, 3H), 6.51 (dd, 1H, J=3.2,1.9Hz), 6.72 (d, 1H, J=3.2Hz), 6.84 (d, 1H, J= 2.3Hz), 6.93 (dd, 1H, J=8.9,2.3Hz), 7.50 (d, 1H, J=1.9Hz), 8.11 (d, 1H, J=8.9Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 8 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 20.3,31.7,55.9,99.9,111.1,112.1,112.6, 114.5,117.1,127.7,142.2,145.8,157.4,164.1,171.8,175.6.
Test result is as follows with mass spectrograph for the molecular weight of the compound 8 of the present embodiment：
HRMS(ESI)：calc.for C17H16O4[M+Na]+307.0946 found 307.0943.
Using compound 9 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 106.9-107.8 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 9 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 1.32 (s, 3H), 1.33 (s, 3H), 3.33 (hept, 1H, J= 6.8Hz), 6.52 (dd, 1H, J=3.2,1.9Hz), 6.75 (d, 1H, J=3.2Hz), 7.36 (d, 1H, J=8.9Hz), 7.52 (d, 1H, J=1.9Hz), 7.71 (dd, 1H, J=8.9,2.4Hz), 8.33 (d, 1H, J=2.4Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 9 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 20.2,31.9,111.2,112.5,113.0,118.5,119.8, 124.6,128.9,136.5,142.4,145.1,154.5,172.5,174.8.
Test result is as follows with mass spectrograph for the molecular weight of the compound 9 of the present embodiment：
HRMS(ESI)：calc.for C16H13BrO3[M+Na]+354.9946 found 354.9942.
Using compound 10 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 78.0-78.6 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 10 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 1.32 (s, 3H), 1.33 (s, 3H), 3.33 (hept, 1H, J= 6.9Hz), 6.51 (dd, 1H, J=3.3,1.9Hz), 6.75 (d, 1H, J=3.3Hz), 7.33-7.38 (m, 1H), 7.44-7.48 (m, 1H), 7.51 (d, 1H, J=1.9Hz), 7.83 (dd, 1H, J=8.2,3.1Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 10 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 20.2,31.9,110.9 (d,2J=23.6Hz), 111.2,112.2, 112.3,119.9 (d,3J=8.0Hz), 121.7 (d,2J=25.4Hz), 124.3 (d,3J=7.4Hz), 142.3,145.2, 151.9 (d,4J=1.3Hz), 159.5 (d,1J=244.8Hz), 172.6,175.3 (d,4J=2.1Hz).
Test result is as follows with mass spectrograph for the molecular weight of the compound 10 of the present embodiment：
HRMS(ESI)：calc.for C16H13FO3[M+Na]+295.0746 found 295.0743.
Using compound 11 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 133.8-134.4 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 11 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 6.47 (dd, 1H, J=3.3,1.8Hz), 6.74 (d, 1H, J= 3.3Hz), 7.31 (d, 1H, J=1.8Hz), 7.35-7.45 (m, 6H), 7.52 (d, 1H, J=8.4Hz), 7.65-7.69 (m, 1H), 8.30 (d, 1H, J=7.9Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 11 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 111.6,112.8,113.5,118.1,123.3,125.4,126.4, 128.3,128.8,130.6,133.6,134.0,142.0,145.3,155.9,162.8,176.4.
Test result is as follows with mass spectrograph for the molecular weight of the compound 11 of the present embodiment：
HRMS(ESI)：calc.for C19H12O3[M+Na]+311.0684 found 311.0678.
Using compound 12 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 161.4-162.3 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 12 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 6.28 (d, 1H, J=3.6Hz), 6.48 (dd, 1H, J=3.6, 1.6Hz), 6.59 (dd, 1H, J=3.2,1.9Hz), 6.66 (d, 1H, J=3.2Hz), 7.40-7.42 (m, 1H), 7.54 (d, 1H, J=1.9Hz), 7.55 (d, 1H, J=8.4Hz), 7.57 (d, 1H, J=1.6Hz), 7.67-7.71 (m, 1H), 8.24 (dd, 1H, J=7.9,1.4Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 12 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 111.1,111.9,112.4,112.5,116.4,118.0,123.4, 125.5,126.3,134.0,142.5,144.6,145.7,145.8,153.9,155.4,176.3.
Test result is as follows with mass spectrograph for the molecular weight of the compound 12 of the present embodiment：
HRMS(ESI)：calc.for C17H10O4[M+Na]+301.0477 found 301.0474.
Using compound 13 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 132.7-133.2 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 13 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 6.61 (dd, 1H, J=3.2,1.9Hz), 6.65 (d, 1H, J= 3.2Hz), 7.00-7.07 (m, 1H), 7.16 (d, 1H, J=3.8Hz), 7.38-7.41 (m, 1H), 7.50-7.57 (m, 2H), 7.57 (d, 1H, J=1.9Hz), 7.65-7.70 (m, 1H), 8.22 (dd, 1H, J=7.9,1.4Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 13 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 111.3,112.0,113.2,117.8,123.1,125.4,126.3, 127.8,131.3,131.7,134.0,134.5,142.9.144.5,155.5,158.2,176.5.
Test result is as follows with mass spectrograph for the molecular weight of the compound 13 of the present embodiment：
HRMS(ESI)：calc.for C17H10O3S[M+Na]+317.0248 found 317.0246.
Using compound 14 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 135.3-136.1 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 14 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 6.48 (dd, 1H, J=3.2,1.8Hz), 7.34 (d, 1H, J= 3.2Hz), 7.36-7.40 (m, 2H), 7.43 (d, 1H, J=8.4Hz), 7.60-7.63 (m, 1H), 8.27 (dd, 1H, J=8.0, 1.5Hz), 8.42 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by C in 14 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 111.2,111.8,116.2,118.2,124.1,125.3,126.1, 133.6,141.2,145.5,151.4,155.7,173.9.
Test result is as follows with mass spectrograph for the molecular weight of the compound 14 of the present embodiment：
HRMS(ESI)：calc.for C13H8O3[M+Na]+235.0371 found 235.0369.
Using compound 15 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 161.9-162.5 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 15 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, CDCl3), δ (ppm) 3.87 (s, 3H), 6.49 (dd, 1H, J=3.3,1.8Hz), 6.81 (d, 1H, J=3.3Hz), 6.96 (dd, 1H, J=8.9,2.4Hz), 7.33 (d, 1H, J=2.4Hz), 7.38 (d, 1H, J= 1.8Hz), 8.17 (d, 1H, J=8.9Hz), 8.36 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by C in 15 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, CDCl3), δ (ppm) 55.9,100.2,111.2,111.8,114.8,116.2,118.1, 127.5,141.1,145.7,151.2,157.6,164.1,173.5.
Test result is as follows with mass spectrograph for the molecular weight of the compound 15 of the present embodiment：
HRMS(ESI)：calc.for C14H10O4[M+Na]+265.0477 found 265.0473.
Using compound 16 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 137.2-137.8 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 16 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 6.50 (dd, 1H, J=3.2,1.8Hz), 7.33 (d, 1H, J= 3.2Hz), 7.35-7.39 (m, 1H), 7.40 (d, 1H, J=1.8Hz), 7.48 (dd, 1H, J=9.2,4.2Hz), 7.91 (dd, 1H, J=8.3,3.1Hz), 8.46 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by C in 16 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 111.0 (d,2J=23.7Hz), 111.5,111.9,115.8, 120.4 (d,3J=8.1Hz), 122.0 (d,2J=25.5Hz), 125.3 (d,3J=7.3Hz), 141.5,145.2,151.7, 152.1 (d,4J=1.3Hz), 159.7 (d,1J=245.5Hz), 173.3 (d,4J=2.2Hz).
Test result is as follows with mass spectrograph for the molecular weight of the compound 16 of the present embodiment：
HRMS(ESI)：calc.for C13H7FO3[M+Na]+253.0277 found 253.0269.
Using compound 17 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 204.2-205.6 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 17 molecular structural formula of compound of the present embodiment：
1H NMR (400MHz, DMSO-d6), δ (ppm) 6.65 (dd, 1H, J=3.3,1.8Hz), 7.25 (d, 1H, J= 3.3Hz), 7.80 (d, 1H, J=1.8Hz), 7.98 (d, 1H, J=9.2Hz), 8.58 (dd, 1H, J=9.2,2.7Hz), 8.84 (d, 1H, J=2.7Hz), 8.94 (s, 1H).
Test result is as follows with Nuclear Magnetic Resonance by C in 17 molecular structural formula of compound of the present embodiment：
13C NMR (100MHz, DMSO-d6), δ (ppm) 111.5,111,9,115.5,120.9,121.5,123.3, 128.3,142.7,144.3,144.5,153.1,158.2,172.2.
Test result is as follows with mass spectrograph for the molecular weight of the compound 17 of the present embodiment：
HRMS(ESI)：calc.for C13H7NO5[M+Na]+280.0222 found 280.0216.
Using compound 18 manufactured in the present embodiment, after tested, physicochemical property is as follows：
Yellow powder, fusing point are 153.2-154.3 DEG C；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 18 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 2.68 (s, 3H), 6.54 (dd, 1H, J=3.2,1.8Hz), 7.06 (d, 1H, J=3.2Hz), 7.52 (d, 1H, J=1.8Hz), 7.58 (d, 1H, J=9.1Hz), 8.46 (dd, 1H, J=9.1, 2.7Hz), 9.07 (d, 1H, J=2.7Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 18 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 20.6,111.6,113.4,114.9,119.6,123.1,127.8, 142.3,144.6,144.8,158.2,165.1,173.7.
Test result is as follows with mass spectrograph for the molecular weight of the compound 18 of the present embodiment：
HRMS(ESI)：calc.for C14H9NO5[M+Na]+294.0378 found 294.0374.
Using compound 19 manufactured in the present embodiment, after tested, physicochemical property is as follows：
White powder, fusing point are 120.5-121.4 DEG C of；It is soluble in ethyl alcohol, the organic solvents such as methanol.
Test result is as follows with Nuclear Magnetic Resonance by H in 19 molecular structural formula of compound of the present embodiment：
1H NMR (600MHz, CDCl3), δ (ppm) 2.58 (s, 3H), 6.57 (dd, 1H, J=3.2,1.8Hz), 7.02 (d, 1H, J=3.2Hz), 7.40 (d, 1H, J=9.0Hz), 7.56 (d, 1H, J=1.8Hz), 7.57-7.59 (m, 1H), 7.70- 7.73 (m, 1H), 7.84 (d, 1H, J=8.0Hz), 7.98 (d, 1H, J=9.0Hz), 10.05 (d, 1H, J=8.7Hz).
Test result is as follows with Nuclear Magnetic Resonance by C in 19 molecular structural formula of compound of the present embodiment：
13C NMR (150MHz, CDCl3), δ (ppm) 19.9,111.3,112.5,116.2,116.6,117.3,126.5, 127.1,128.3,129.2,130.6,130.7,135.3,142.0,146.2,156.6,162.3,177.1.
Test result is as follows with mass spectrograph for the molecular weight of the compound 19 of the present embodiment：
HRMS(ESI)：calc.for C18H12O3[M+Na]+299.0684 found 299.0678.
Embodiment 2
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h, then makes the temperature of reaction solution be 100 DEG C with register, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 56%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 44%), compound 3 (yield 59%), compound 4 (yield 57%), compound 5 (yield 55%), compound 6 (yield 58%), 7 (yield of compound 66%), compound 8 (yield 55%), compound 9 (yield 58%), compound 10 (yield 55%), 11 (yield of compound 59%), compound 12 (yield 58%), compound 13 (yield 60%), compound 14 (yield 16%), 15 (yield of compound 18%), compound 16 (yield 17%), compound 17 (yield 16%), compound 18 (yield 17%), 19 (yield of compound 39%).
Embodiment 3
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h, then makes the temperature of reaction solution be 140 DEG C with register, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 68%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 60%), compound 3 (yield 70%), compound 4 (yield 70%), compound 5 (yield 68%), compound 6 (yield 71%), 7 (yield of compound 78%), compound 8 (yield 64%), compound 9 (yield 48%), compound 10 (yield 45%), 11 (yield of compound 70%), compound 12 (yield 58%), compound 13 (yield 74%), compound 14 (yield 18%), 15 (yield of compound 19%), compound 16 (yield 17%), compound 17 (yield 19%), compound 18 (yield 17%), 19 (yield of compound 42%).
Embodiment 4
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl class compounds and 2,5- dimethoxys -2,5-dihydrofuran molar ratio be 1 dimethoxy -2 2,5-, 5- dihydrofuran reacts 0.5h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant Removing K10 montmorillonite catalysts three times are washed respectively with 1- (2- hydroxy phenyls) -1,3- diacetyl, 30 times of w ethanols, washing Ethanol solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes through silica gel column chromatography It isolates and purifies (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), obtains 2- methyl -3- (2- furyls) chromogen The sterling (yield 75%) of ketone compound.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 61%), compound 3 (yield 73%), compound 4 (yield 74%), compound 5 (yield 71%), compound 6 (yield 72%), 7 (yield of compound 76%), compound 8 (yield 69%), compound 9 (yield 62%), compound 10 (yield 60%), 11 (yield of compound 79%), compound 12 (yield 60%), compound 13 (yield 70%), compound 14 (yield 19%), 15 (yield of compound 17%), compound 16 (yield 19%), compound 17 (yield 22%), compound 18 (yield 19%), 19 (yield of compound 50%).
Embodiment 5
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydro furans that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 2 It mutters, reacts 0.5h, then make the temperature of reaction solution be 120 DEG C with register, react 0.5h；Last gained reactant 1- (2- Hydroxy phenyl) 30 times of w ethanols of -1,3- diacetyl wash removing K10 montmorillonite catalysts three times respectively, and the ethyl alcohol of washing is molten Liquid merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its separation through silica gel column chromatography Purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), obtains 2- methyl -3- (2- furyls) chromone chemical combination The sterling (yield 74%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 65%), compound 3 (yield 76%), compound 4 (yield 74%), compound 5 (yield 70%), compound 6 (yield 70%), 7 (yield of compound 75%), compound 8 (yield 69%), compound 9 (yield 62%), compound 10 (yield 60%), 11 (yield of compound 79%), compound 12 (yield 65%), compound 13 (yield 70%), compound 14 (yield 19%), 15 (yield of compound 19%), compound 16 (yield 19%), compound 17 (yield 21%), compound 18 (yield 19%), 19 (yield of compound 52%).
Embodiment 6
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydro furans that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 4 It mutters, reacts 0.5h, then make the temperature of reaction solution be 120 DEG C with register, react 0.5h；Last gained reactant 1- (2- Hydroxy phenyl) 30 times of w ethanols of -1,3- diacetyl wash removing K10 montmorillonite catalysts three times respectively, and the ethyl alcohol of washing is molten Liquid merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its separation through silica gel column chromatography Purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), obtains 2- methyl -3- (2- furyls) chromone chemical combination The sterling (yield 73%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 63%), compound 3 (yield 73%), compound 4 (yield 74%), compound 5 (yield 72%), compound 6 (yield 70%), 7 (yield of compound 74%), compound 8 (yield 67%), compound 9 (yield 60%), compound 10 (yield 60%), 11 (yield of compound 79%), compound 12 (yield 65%), compound 13 (yield 70%), compound 14 (yield 19%), 15 (yield of compound 21%), compound 16 (yield 20%), compound 17 (yield 21%), compound 18 (yield 22%), 19 (yield of compound 50%).
Embodiment 7
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 60 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 44%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 44%), compound 3 (yield 59%), compound 4 (yield 56%), compound 5 (yield 57%), compound 6 (yield 54%), 7 (yield of compound 66%), compound 8 (yield 54%), compound 9 (yield 48%), compound 10 (yield 55%), 11 (yield of compound 69%), compound 12 (yield 58%), compound 13 (yield 60%), compound 14 (yield 16%), 15 (yield of compound 19%), compound 16 (yield 17%), compound 17 (yield 26%), compound 18 (yield 17%), 19 (yield of compound 36%).
Embodiment 8
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 70 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 63%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 53%), compound 3 (yield 66%), compound 4 (yield 65%), compound 5 (yield 65%), compound 6 (yield 68%), 7 (yield of compound 75%), compound 8 (yield 66%), compound 9 (yield 58%), compound 10 (yield 57%), 11 (yield of compound 76%), compound 12 (yield 58%), compound 13 (yield 65%), compound 14 (yield 18%), 15 (yield of compound 17%), compound 16 (yield 17%), compound 17 (yield 19%), compound 18 (yield 20%), 19 (yield of compound 44%).
Embodiment 9
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 90 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 0.5h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；With 1- (2- hydroxy phenyls) -1, 30 times of w ethanols of 3- diacetyl wash removing K10 montmorillonite catalysts three times respectively, and the ethanol solution of washing merges decompression and steams Evaporate recycling design and obtain the mixture of the compounds of this invention and unreacted reactant, through silica gel column chromatography make its isolate and purify (eluant, eluent: Petroleum ether is 1 with ethyl acetate volume ratio: 0.1), obtaining the sterling (yield of 2- methyl -3- (2- furyls) chromogen ketone compound 77%).
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 63%), compound 3 (yield 77%), compound 4 (yield 75%), compound 5 (yield 74%), compound 6 (yield 77%), 7 (yield of compound 85%), compound 8 (yield 74%), compound 9 (yield 66%), compound 10 (yield 64%), 11 (yield of compound 87%), compound 12 (yield 66%), compound 13 (yield 78%), compound 14 (yield 25%), 15 (yield of compound 26%), compound 16 (yield 28%), compound 17 (yield 29%), compound 18 (yield 28%), 19 (yield of compound 52%).
Embodiment 10
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 100 DEG C, are added with stirring 1- (2- hydroxyls with register Phenyl) -1,3- diacetyl and 2,2,5- dimethoxys -2,5- bis- that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Hydrogen furans reacts 0.5h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant 1- 30 times of w ethanols of (2- hydroxy phenyls) -1,3- diacetyl wash removing K10 montmorillonite catalysts three times, the ethyl alcohol of washing respectively Solution merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its point through silica gel column chromatography From purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), 2- methyl -3- (2- furyls) chromogen assimilation is obtained Close the sterling (yield 74%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 61%), compound 3 (yield 75%), compound 4 (yield 76%), compound 5 (yield 70%), compound 6 (yield 77%), 7 (yield of compound 81%), compound 8 (yield 71%), compound 9 (yield 65%), compound 10 (yield 65%), 11 (yield of compound 87%), compound 12 (yield 60%), compound 13 (yield 70%), compound 14 (yield 26%), 15 (yield of compound 28%), compound 16 (yield 20%), compound 17 (yield 20%), compound 18 (yield 17%), 19 (yield of compound 50%).
Embodiment 11
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 1h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant 1- (2- Hydroxy phenyl) 30 times of w ethanols of -1,3- diacetyl wash removing K10 montmorillonite catalysts three times respectively, and the ethyl alcohol of washing is molten Liquid merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its separation through silica gel column chromatography Purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), obtains 2- methyl -3- (2- furyls) chromone chemical combination The sterling (yield 77%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 65%), compound 3 (yield 77%), compound 4 (yield 78%), compound 5 (yield 74%), compound 6 (yield 76%), 7 (yield of compound 87%), compound 8 (yield 76%), compound 9 (yield 67%), compound 10 (yield 64%), 11 (yield of compound 80%), compound 12 (yield 67%), compound 13 (yield 78%), compound 14 (yield 24%), 15 (yield of compound 25%), compound 16 (yield 28%), compound 17 (yield 24%), compound 18 (yield 27%), 19 (yield of compound 48%).
Embodiment 12
The preparation of compound 1 2- methyl -3- (2- furyls) chromone
1- (2- hydroxy phenyls) -1,3- diacetyl is added in a kettle, is added with stirring 1- (2- hydroxy phenyls) -1,3- The K10 montmorillonites of 1 times of weight of diacetyl make the temperature of reaction solution be 80 DEG C, are added with stirring 1- (2- hydroxy benzenes with register Base) -1,3- diacetyl and 2,2,5- dimethoxy -2,5- dihydros that the molar ratio of 5- dimethoxys -2,5-dihydrofuran is 1.5 Furans reacts 2h, then makes the temperature of reaction solution be 120 DEG C with register, reacts 0.5h；Last gained reactant 1- (2- Hydroxy phenyl) 30 times of w ethanols of -1,3- diacetyl wash removing K10 montmorillonite catalysts three times respectively, and the ethyl alcohol of washing is molten Liquid merges vacuum distillation recovered solvent and obtains the mixture of the compounds of this invention and unreacted reactant, makes its separation through silica gel column chromatography Purifying (eluant, eluent: petroleum ether is 1: 0.1 with ethyl acetate volume ratio), obtains 2- methyl -3- (2- furyls) chromone chemical combination The sterling (yield 75%) of object.
In the present embodiment, with 1- (2,4- dihydroxy phenyl) -1,3- diacetyl, 1- (2- hydroxyl -4- methoxyphenyls) - 1,3- diacetyl, 1- (2- hydroxy-5-methyl bases phenyl) -1,3- diacetyl, 1- (2- hydroxyl -5- bromophenyls) -1,3- diacetyl, 1- (2- hydroxyl-5-fluorines phenyl) -1,3- diacetyl, 1- (2- hydroxy phenyls) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -4- first Phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyl -5- bromos phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxyls -5- Fluorine-based phenyl) -4- methyl-1s, 3- pentanediones, 1- (2- hydroxy phenyls) -3- phenyl -1,3- propanedione, 1- furans -3- (2- hydroxyls Phenyl) -1,3- propanedione, 1- (2- hydroxy phenyls) -3- thiophene -1,3- propanedione, 3- (2- hydroxy phenyls) -3- oxopropanals, 3- (2- hydroxyl -4- methoxyphenyls) -3- oxopropanals, 3- (2- hydroxyl-5-fluorines phenyl) -3- oxopropanals, 3- (2- hydroxyls - 5- nitrobenzophenones) -3- oxopropanals, 1- (2- hydroxyl -5- nitrobenzophenones) -1,3- diacetyl, 1- (1- hydroxyl naphthalenes) -1,3- fourths two Ketone replaces 1- (2- hydroxy phenyls) -1,3- diacetyl in embodiment 1 in the preparation of compound 1, rate of charge to react item respectively Part and technological process prepare identical with compound 1 in embodiment 1, can respectively obtain compound 2 (yield 60%), compound 3 (yield 75%), compound 4 (yield 78%), compound 5 (yield 74%), compound 6 (yield 76%), 7 (yield of compound 86%), compound 8 (yield 74%), compound 9 (yield 65%), compound 10 (yield 64%), 11 (yield of compound 74%), compound 12 (yield 63%), compound 13 (yield 74%), compound 14 (yield 26%), 15 (yield of compound 24%), compound 16 (yield 27%), compound 17 (yield 26%), compound 18 (yield 26%), 19 (yield of compound 50%).
Example of formulations
Embodiment 13
Formulation of pesticide is prepared to prepare the compounds of this invention 6, is produced by the raw material of following mass fraction：
Embodiment 14
Formulation of pesticide is prepared to prepare the compounds of this invention 6, is produced by the raw material of following mass fraction：
Embodiment 15
Formulation of pesticide is prepared to prepare the compounds of this invention 6, is produced by the raw material of following mass fraction：
Embodiment 16
Formulation of pesticide is prepared to prepare the compounds of this invention 6, is produced by the raw material of following mass fraction：
The active ingredient compound 2 of the present invention, compound 6, compound 14 have been carried out the test of pesticide effectiveness, enumerated down by inventor Row experiment content and its test result, it was demonstrated that with the validity of drug plant epiphyte resisting prepared by the present invention.
1. test medicine
Compound 2：2- methyl -3- (2- furyls) -7- hydroxyl chromones, compound 6：2- methyl -3- (2- furyls) - 6- fluorine chromones, compound 14：3- (2- furyls) chromone.
2. material
2.1 instrument
Electromagnetic oven, SHP-250 biochemical cultivation cases (the upper macro experimental facilities Co., Ltd of Nereid), XXQ-LS-50S II are vertical Pressure steam sterilizer (Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.), SKJH-1109 biochemistry superclean bench (are revived in Shanghai Female Industrial Co., Ltd.), MP500Z electronic balances (Shanghai Hengping Science Instrument Co., Ltd.), conical flask, beaker, alcolhol burner, Card punch, transfer needle, culture dish, liquid-transfering gun.
2.2 reagent
Acetone, glucose, agar powder (item), medicinal alcohol, absolute ethyl alcohol.
2.3 for trying strain
There are 5 for examination strain, apple decay, apple anthrax, tomato gray mould, tomato early epidemic, potato dry rot.
2.4 other
Gauze, potato, absorbent cotton etc..
3. preliminary screening plant epiphyte resisting activity assay method
The preparation and its sterilizing of 3.1 culture mediums
By the potato chopping of 200g peelings, 1000mL water is added, boils 20min.With 4 layers of filtered through gauze, Ma Ling is removed Potato wedge.Filtrate tap water constant volume to 1000mL, adds 20g agar powders, is made it dissolve under heating stirring, be eventually adding 20g Glucose, solution are settled to 1000mL with water, are then divided in the triangular flask of 250mL and seal (per bottled 100mL), with going out Bacterium pot (0.11Mp, 115-116 DEG C) sterilizing 35-45min or so rear taking-up is spare.
The sterilizing of 3.2 superclean benches
By tweezers, oese, alcolhol burner, alcohol swab, card punch is put into superclean bench, presses ultraviolet and air-supply button, Ultraviolet sterilization 30min, and workbench and the hand of operator are cleaned with alcohol swab.
The preparation of 3.3 liquids
Take compound 2：2- methyl -3- (2- furyls) -7- hydroxyl chromones, compound 6：2- methyl -3- (2- furans Base) -6- fluorine chromones, compound 14：1mL acetone is added in three centrifuge tubes in each 10.00mg of 3- (2- furyls) chromones It is dissolved, is then respectively poured in the PDA of 100mL, the liquid for being just made into 100 μ g/mL is spare.
3.4 preparations with medicine culture medium
The culture medium to have sterilized heating is dissolved, ready liquid is separately added into, is uniformly mixed, that is, is made into 100 μ g/mL Band medicine culture medium.Then it pours into while hot in culture dish and the uniform tablet of thin and thick is made, mark, irradiated under ultraviolet lamp It is spare after 30min.
3.5 make bacteria cake
Aseptically, a certain number of bacteria cakes will be got for examination strain card punch of 4.5mm under same Radius It is spare.
3.6 connect bacterium
Carefully bacteria cake is placed on ready culture medium with transfer needle, mycelia one is downwards, (general per 1 bacteria cake of ware Do three repetitions), it marks, is placed in 27 DEG C of insulating boxs and cultivates.
3.7 culture
The culture dish being inoculated with is put upside down and is cultivated in 27 DEG C of incubators.
3.8 test
Culture dish is taken out after cultivating 72h or 96h, (palpus right-angled intersection measures twice, flat with it with slide calliper rule amount colony diameter Mean).
Inhibiting rate=(C-T)/(C-4.5) × 100%
The plant epiphyte resisting activity for analyzing each candidate drug, highest to apple decay fungi inhibiting rate is compound 6, right Highest apple anthrax fungi inhibiting rate is compound 6, and highest to tomato gray mould fungi inhibiting rate is 6 inhibiting rate of compound 100%, highest to the inhibiting rate of tomato early epidemic fungi is compound 6, highest to the inhibiting rate of potato dry rot fungi to be Compound 6 is shown in Table 1.
The preliminary screening compound plant epiphyte resisting activity under the concentration of 100 μ g/mL of table 1
4. plant epiphyte resisting activity IC50Assay method
The preparation and its sterilizing of 4.1 culture mediums
By the potato chopping of 200g peelings, 1000mL water is added, boils 20min.With 4 layers of filtered through gauze, Ma Ling is removed Potato wedge.Filtrate tap water constant volume to 1000mL, adds 20g agar powders, is made it dissolve under heating stirring, be eventually adding 20g Glucose, solution are settled to 1000mL with water, are then divided in the triangular flask of 250mL and seal (per bottled 100mL), with going out Bacterium pot (0.11Mp, 115-116 DEG C) sterilizing 35-45min or so rear taking-up is spare.
The sterilizing of 4.2 superclean benches
By tweezers, oese, alcolhol burner, alcohol swab, card punch is put into superclean bench, presses ultraviolet and air-supply button, Ultraviolet sterilization 30min, and workbench and the hand of operator are cleaned with alcohol swab.
The preparation of 4.3 liquids
Take compound 6：2- methyl -3- (2- furyls) -6- fluorine chromone 0.63mg, 1.25mg, 2.50mg, 5.00mg, 10.00mg is added 1mL acetone and is dissolved, be then respectively poured in the PDA of 100mL, that is, be made into five centrifuge tubes The liquid of 6.25,12.5,25,50,100 μ g/mL is spare.
4.4 preparations with medicine culture medium
The culture medium to have sterilized heating is dissolved, ready liquid is separately added into, is uniformly mixed, that is, be made into (6.25, 12.5,25,50,100 μ g/mL) band medicine culture medium.Then it pours into while hot in culture dish and the uniform tablet of thin and thick is made, carry out It marks, it is spare after irradiation 30min under ultraviolet lamp.
4.5 make bacteria cake
Aseptically, a certain number of bacteria cakes will be got for examination strain card punch of 4.5mm under same Radius It is spare.
4.6 connect bacterium
Carefully bacteria cake is placed on ready culture medium with transfer needle, mycelia one is downwards, (general per 1 bacteria cake of ware Do three repetitions), it marks, is placed in 27 DEG C of insulating boxs and cultivates.
4.7 culture
The culture dish being inoculated with is put upside down and is cultivated in 27 DEG C of incubators.
4.8 test
Culture dish is taken out after cultivating 72h or 96h, (palpus right-angled intersection measures flat with it twice with slide calliper rule amount colony diameter Mean).
Calculate the plant epiphyte resisting activity IC of compound 650Value.
The plant epiphyte resisting activity IC of analysis of compounds 650Value, wherein it is best to the inhibiting effect of tomato early epidemic fungi, it is right Other four kinds of fungies also have certain inhibiting effect to be shown in Table 2.
The plant epiphyte resisting activity IC of 2 compound of table50Value
5 experiment conclusions
The experimental results showed that compound 2, compound 6, compound 14 all have the effect of apparent plant epiphyte resisting, change It closes object 6 and shows best plant epiphyte resisting activity；It thus can inference compound 1-19 all work with good plant epiphyte resisting Property.

Claims (2)

  1. The preparation method of 1.3- (2- furyls) chromogen ketone Formulas (1), substituent R in formula (1)1For hydrogen or hydroxyl or first Oxygroup or methyl or fluorine or chlorine or bromine or nitro, R2For hydrogen or hydroxyl or methoxyl group or methyl or fluorine or chlorine or bromine or nitro, R3For Hydrogen or C1~C6Any one in alkyl or aryl, described aryl are phenyl or naphthyl or furyl or thienyl or pyrrole radicals Or the phenyl or naphthyl or furan of anthryl or phenanthryl and hydroxyl or methoxyl group or methyl or fluorine or chlorine or bromine or nitro substituent It mutters base or thienyl or pyrrole radicals or anthryl or phenanthryl, it is characterised in that this approach includes the following steps：
    1- (2- hydroxy phenyls) -1,3- diacetyl class compounds are added in a kettle, are added with stirring 1- (2- hydroxy phenyls) - The K10 montmorillonites of 1,3- 1~4 times of weight of diacetyl class compound make the temperature of reaction solution be 60~100 DEG C with register, It is added with stirring mole of 1- (2- hydroxy phenyls) -1,3- diacetyl class compounds and 2,5- dimethoxys -2,5-dihydrofuran Than 2,5- dimethoxys -2,5-dihydrofuran for 1~4,0.5~2h is reacted；The temperature of reaction solution is set to be with register again 100~140 DEG C, react 0.5h；Last gained reactant 1- (2- hydroxy phenyls) -1,3- diacetyl classes, 30 times of weight of compound Ethyl alcohol washs removing K10 montmorillonite catalysts three times respectively, and the ethanol solution of washing merges vacuum distillation recovered solvent and obtains mesh The mixture for marking compound and unreacted reactant, makes it isolate and purify, obtains 3- (2- furyls) chromogen ketone chemical combination through column chromatography The sterling of object.
  2. 2. the application of 3- (2- furyls) chromogen ketone compounds in a kind of claim 1, it is characterized in that being used to prepare anti-apple Decay causing fungi, apple anthrax fungi, tomato gray mould fungi, tomato early epidemic fungi, the drug and medicament of potato dry rot fungi.
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