CN106279082B - Substituted furans chalcone derivative and preparation method thereof - Google Patents

Substituted furans chalcone derivative and preparation method thereof Download PDF

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CN106279082B
CN106279082B CN201610631120.0A CN201610631120A CN106279082B CN 106279082 B CN106279082 B CN 106279082B CN 201610631120 A CN201610631120 A CN 201610631120A CN 106279082 B CN106279082 B CN 106279082B
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methyl
hydroxy
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ethyl
ketone
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CN106279082A (en
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吴军
何兴瑞
娄永根
商志才
顾海宁
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention relates to medicinal chemistry arts, it is desirable to provide a kind of substituted furans chalcone derivative and preparation method thereof.The substituted furans chalcone derivative has the structure as shown in formula (I): where B ring is selected from phenyl, furyl or thienyl；R1、R2、R3It is each independently selected from the alkoxy of hydrogen atom, halogen, hydroxyl, cyano, nitro, the alkyl chain of C1~C7, C1~C7, dimethylamino or diethylin.The product is a kind of natural furans chalcone analog with new skeleton, has potential pharmaceutical activity, and the preparation of such compound can be studied for the pharmaceutical activity of furans chalcone provides support.Preparation methods steps are simple, and loss late is low, are the routes that the completely new slave nonaro-maticity raw material of one kind synthesizes furans chalcone derivative.It is significant for industrialized production.

Description

Substituted furans chalcone derivative and preparation method thereof
Technical field
The present invention relates to field of medicaments, more particularly, to a kind of substituted furans chalcone derivative and its preparation Method.
Background technique
Chalcone Compounds belong to flavone compound, are distributed widely in natural plants, chemical structure 1,3- Diphenyl -2- propylene -1- ketone, receives significant attention due to multiple biological activities.The study found that Chalcone Compounds And its derivative has anticancer, anti-inflammatory, anti-oxidant, anti parasitic, antibacterial isoreactivity.
Methyl substituted furan ring structure is widely present in natural products, and has the bioactivity of multiplicity, such as red Ginseng ketone can treat cardiovascular disease, and furans Buddhist art alkane has Allelopathic Effect in Plants, and sesquiterpenoids cacalol has anti- The effect of hyperglycemia and antibacterial.
Therefore furan nucleus has potential pharmaceutical activity by methyl substituted furans Chalcone Compounds and its derivative, And this kind of compound is not reported yet so far.Invention is a kind of simple, high yield to prepare furans chalcone derivative The completely new synthetic route of object.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of substituted furans and look into ear Ketones derivant and preparation method thereof.
In order to solve the technical problem, solution of the invention is:
A kind of substituted furans chalcone derivative is provided, there is the structure as shown in formula (I):
Wherein,
B ring is selected from phenyl, furyl or thienyl；
R1、R2、R3It is each independently selected from hydrogen atom, halogen, hydroxyl, cyano, nitro, the alkyl chain of C1~C7, C1~C7 Alkoxy, dimethylamino or diethylin.
In the present invention, which has any one following structure:
The present invention still further provides the preparation method of the substituted furans chalcone derivative, including following Step:
(1) by 1, hydroresorcinol and potassium hydroxide are dispersed in water, and after stirring at normal temperature 5min, chloracetyl second is added The methanol solution of acetoacetic ester；After reaction system is stirred at room temperature 5 days, it is acidified with the hydrochloric acid of 4N；Reaction after filtering acidification Liquid obtains solid product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formates；
Described 1, hydroresorcinol and potassium hydroxide, chloroacetyl acetacetic ester molar ratio be 1:1:1, every milliliter of water is corresponding 1, the inventory of hydroresorcinol is 0.1g, and the inventory of the corresponding chloroacetyl acetacetic ester of every ml methanol is 0.2g；
(2) by 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate, potassium hydroxide methanol and water Mixed solvent dissolution；After reaction 5h is stirred at room temperature in reaction system, with the hydrochloric acid tune pH to 1 of 6N；Filtering reacting liquid obtains Solid product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid；
The mixed solvent is that methanol and water are formulated by the volume ratio of 2.5:1；The corresponding 3- of every milliliter of mixed solvent Methyl -4- oxygen -4,5, the inventorys of 6,7- tetrahydrochysene benzfuran -2- Ethyl formates are 0.2g, 3- methyl -4- oxygen -4,5,6,7- The molar ratio of tetrahydrochysene benzfuran -2- Ethyl formate and potassium hydroxide is 1:6；
(3) by 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid are dispersed in diethylene glycol (DEG), and copper is added Powder and pyridine；Reaction system is heated to 175 DEG C, is kept stirring 10h；Reaction system is cooled to room temperature, ice water is added, is used in combination The hydrochloric acid of 4N is acidified；Three times, combined extract liquor is washed with water once for reaction solution after being acidified with petroleum ether extraction, then will Extract liquor anhydrous sodium sulfate is dry, is spin-dried for, and obtains solid product: 3- methyl -6,7- Dihydrobenzofuranes -4- (5H) -one；
Wherein, the corresponding 3- methyl -4- oxygen -4,5 of every milliliter of diethylene glycol (DEG), 6,7- tetrahydrochysene benzfuran -2- formic acid feed intake Amount is 0.1g；The molar ratio of 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid and copper powder and pyridine is 1:1:2；
(4) under nitrogen protection, it uniformly disperses sodium hydride in ethylene glycol dimethyl ether solution, reaction system is cooling To 0 DEG C, the ethylene glycol dimethyl ether solution of 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) -one is then added, keeping body ties up to 0 DEG C stirring 30min；The ethylene glycol dimethyl ether solution of ethyl acetate is added into system, system is then heated to 90 DEG C；It keeps After 3h, system is cooled to room temperature, the ammonium chloride solution quenching reaction of saturation is added；It is extracted with ethyl acetate 3 times, organic phase is used Anhydrous sodium sulfate is dry, is concentrated, and obtains product: the crude product of -4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes；
- 4 (5H) -one of 3- methyl -6,7- Dihydrobenzofuranes and the molar ratio of sodium hydride, ethyl acetate are 1:5:3, Corresponding 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) the -one inventory of every milliliter of glycol dimethyl ether is 0.04g；
(5) -4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes is dispersed in toluene solution, Xiang Ti Chloro- 5, the 6- dicyanoquinone of 2,3- bis- is added in system, is heated to 130 DEG C of holding 6h；System is cooled to room temperature, is concentrated after filtering Filtrate；By filtrate silica gel chromatograph post separation, the pure of 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is obtained Product；
- 4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes and the chloro- 5,6- dicyanoquinone of 2,3- bis- Molar ratio be 1:1.2, corresponding -4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes of every milliliter of toluene feeds intake Amount is 0.1g；
(6) under nitrogen protection, by 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone obtained by step (5) It is uniformly scattered in reaction dissolvent a, keeping body ties up at room temperature；Then highly basic is added, stirs 10min~1h；Again to system The middle a solution that reactive group is added, reacts 1 hour to 24 hours；Then the water quenching reaction of twice solvent a volume is added, System is adjusted to acidity with hydrochloric acid again；Crude product is precipitated in filtering, obtains pure substituted furans with ethyl alcohol recrystallization and looks into Ear ketones derivant；
In reaction system, 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and reactive group, highly basic rub You are than being 1:1~5:1~5；The corresponding 1- of every milliliter of reaction dissolvent a (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- The inventory of ketone is 0.02 to 0.06g；The reaction dissolvent a is tetrahydrofuran or dioxane；
The structural formula of the reactive group are as follows:
Wherein, B ring is selected from phenyl, furyl or thienyl；R1、R2、R3It is each independently selected from hydrogen atom, halogen, hydroxyl Base, cyano, nitro, the alkyl chain of C1~C7, C1~C7 alkoxy, dimethylamino or diethylin.
In the present invention, step (6) highly basic is that (highly basic is preferably sodium hydride, described molten for sodium hydride or hydrofining Agent is preferably tetrahydrofuran).
Compared with prior art, the present invention can obtain the utility model has the advantages that
(1) furans chalcone derivative provided by the invention is that one kind has the natural furans chalcone of new skeleton seemingly Object has potential pharmaceutical activity, and the preparation of such compound can be studied for the pharmaceutical activity of furans chalcone provides branch Support.
(2) preparation method of furans chalcone derivative provided by the invention, step is simple, and loss late is low, is a kind of Completely new slave nonaro-maticity raw material synthesizes the route of furans chalcone derivative.There is important meaning for industrialized production Justice.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of substituted furans chalcone derivative provided by the invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection scope.
Embodiment 1
By 1, hydroresorcinol and potassium hydroxide are uniformly dispersed in water, and after stirring at normal temperature 5min, chloracetyl second is added Then system is stirred at room temperature 5 days, is then acidified the system hydrochloric acid of 4N, filtering acidification by the methanol solution of acetoacetic ester Reaction solution afterwards, obtained solid is product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formates.It should 1 in step, the molar ratio of hydroresorcinol and potassium hydroxide and chloroacetyl acetacetic ester is 1:1:1, every milliliter of water corresponding 1, The inventory of hydroresorcinol is 0.1g, and the inventory of the corresponding chloroacetyl acetacetic ester of every ml methanol is 0.2g.The step Yield is 65%.The structure of products therefrom are as follows:
Molecular formula: C12H14O4
Chinese name: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate
English name: ethyl 3-methyl-4-oxo-4,5,6,7-tetrahydrobenzofuran-2- carboxylate
Molecular weight: 222.09
Appearance: white solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 4.38 (q, J=7.1Hz, 2H), 2.94 (t, J= 6.3Hz, 2H), 2.60-2.46 (m, 5H), 2.20 (p, J=6.4Hz, 2H), 1.40 (t, J=7.1Hz, 3H) ppm.
Embodiment 2
By the mixed of 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate and potassium hydroxide first alcohol and water After dissolution reaction 5h is stirred at room temperature in system by bonding solvent dissolution.Then by the hydrochloric acid tune pH to 1 of reaction solution 6N, filtering Reaction solution, filtering resulting solid is product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid.The step Used in mixed solvent be that methanol and water are formulated with 2.5:1.Corresponding oxygen -4 3- methyl -4- of every milliliter of mixed solvent, The inventory of 5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate is 0.2g.3- methyl -4- oxygen -4,5,6,7- tetrahydro in the step The molar ratio of coumarilic acid ethyl ester and potassium hydroxide is 1:6.The yield of the step is 90%.The structure of products therefrom are as follows:
Molecular formula: C10H10O4
Chinese name: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid
English name: 3-methyl-4-oxo-4,5,6,7-tetrahydrobenzofuran-2-carboxylic acid
Molecular weight: 194.06
Appearance: white solid
Nuclear magnetic resonance spectroscopy: (400MHz, DMSO-d6) δ 2.91 (t, J=6.2Hz, 2H), 2.44 (m, 5H), 2.08 (p, J =6.4Hz, 2H) ppm.
Embodiment 3
By 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid are uniformly scattered in diethylene glycol (DEG), and copper is added Then system is heated to 175 DEG C, is kept stirring 10h by powder and pyridine.System is cooled to room temperature, ice water is added, and with 4N's Three times, combined extract liquor is washed with water once for hydrochloric acid acidification, the reaction solution after being acidified with petroleum ether extraction, then will extraction Liquid is dry with anhydrous sodium sulfate, is spin-dried for.Resulting solid is product: 3- methyl -6,7- Dihydrobenzofuranes -4- (5H) -one. The inventory of the corresponding 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid of every milliliter of diethylene glycol (DEG) is in the step 0.1g.The molar ratio of 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid and copper powder and pyridine is 1 in the step: 1:2.The yield of the step is 85%.The structure of products therefrom are as follows:
Molecular formula: C9H10O2
Chinese name: 3- methyl -6,7- Dihydrobenzofuranes -4- (5H) -one
English name: 3-methyl-6,7-dihydrobenzofuran-4 (5H)-one
Molecular weight: 150.07
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 7.11-6.98 (m, 1H), 2.83 (t, J=6.3Hz, 2H), 2.47 (dd, J=7.2,5.8Hz, 2H), 2.26-2.06 (m, 5H) ppm.
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 195.70,167.40,138.90,120.41,119.07, 38.29,23.63,22.75,9.07ppm。
Embodiment 4
Under nitrogen protection, it uniformly disperses sodium hydride in ethylene glycol dimethyl ether solution, system is cooled to 0 DEG C, Then the ethylene glycol dimethyl ether solution of 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) -one is added into system, keeping body ties up to 0 DEG C of stirring 30min.Then the ethylene glycol dimethyl ether solution of ethyl acetate is added into system, system is then heated to 90 DEG C. After keeping 3h, system is cooled to room temperature, the ammonium chloride solution quenching reaction of saturation is added, is extracted with ethyl acetate 3 times, it is organic Mutually dry with anhydrous sodium sulfate, step product 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes -4 (5H)-can be obtained in concentration The crude product of ketone.The molar ratio of -4 (5H) -one of 3- methyl -6,7- Dihydrobenzofuranes and sodium hydride and ethyl acetate in the step For 1:5:3, corresponding 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) the -one inventory of every milliliter of glycol dimethyl ether is 0.04g。
Resulting -4 (5H) -one of product 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes is dispersed in toluene solution In, chloro- 5, the 6- dicyanoquinone of 2,3- bis- is added into system, is heated to 130 DEG C of holding 6h.System is cooled to room temperature, mistake Filter is concentrated filtrate, pure product 1- (4- hydroxy-3-methyl benzo furan can be obtained with silica gel chromatograph post separation in crude product Mutter -5- base) ethyl -1- ketone.- 4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes and 2,3- bis- are chloro- in the step The molar ratio of 5,6- dicyanoquinones is 1:1.2, corresponding 5- acetyl -3- methyl -6, the 7- Dihydrobenzofuranes-of every milliliter of toluene The inventory of 4 (5H) -one is 0.1g.The yield of this two step is 70%.The structure of products therefrom are as follows:
Molecular formula: C11H10O3
Chinese name: 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone
English name: 1- (4-hydroxy-3-methylbenzofuran-5-yl) ethan-1-one
Molecular weight: 190.06
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.28 (s, 1H), 7.58 (d, J=8.8Hz, 1H), 7.28 (q, J=1.4Hz, 1H), 6.93 (d, J=8.9Hz, 1H), 2.63 (s, 3H), 2.41 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 204.10,160.50,160.42,140.79,126.97, 117.87,117.26,114.05,103.71,26.93,9.57.
Embodiment 5-1:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then p-tolyl aldehyde is added into system Tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent is then added into system System is adjusted to acidity with hydrochloric acid by the water quenching reaction of volume.The crude product being precipitated is filtered, by crude product ethyl alcohol recrystallization Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to methylbenzene first The molar ratio of aldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone Derivative are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-methylphenyl) -2- propylene -1- ketone, yield 85%, the structure of the derivative are as follows:
Molecular formula: C19H16O3
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-methylphenyl) -2- propylene -1- Ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (p-tolyl) prop-2- en-1-one
Molecular weight: 292.11
Appearance: red solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.03 (s, 1H), 7.91 (d, J=15.4Hz, 1H), 7.80 (d, J=8.9Hz, 1H), 7.64 (d, J=15.5Hz, 1H), 7.60-7.54 (m, 2H), 7.30 (q, J=1.4Hz, 1H), 7.23 (s, 1H), 6.99 (d, J=8.9Hz, 1H), 2.44 (d, J=1.4Hz, 3H), 2.41 (s, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.44,161.97,160.46,144.70, 141.34,140.77,132.06,129.77,128.63,125.99,119.69,118.12,117.33,114.27,103.69, 21.59,9.65.
Embodiment 5-2:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 10 minutes.Then cumaldehyde is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 24 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and p-isopropyl in the step The molar ratio of benzaldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans looks into ear Ketones derivant are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-isopropyl phenyl) -2- propylene -1- ketone, Yield 87%, the structure of the derivative are as follows:
Molecular formula: C21H20O3
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-isopropyl phenyl) -2- propylene - 1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (4- isopropylphenyl)prop-2-en-1-one
Molecular weight: 320.14
Appearance: brown solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.04 (s, 1H), 7.89 (d, J=15.4Hz, 1H), 7.77 (d, J=8.9Hz, 1H), 7.66-7.52 (m, 3H), 7.31-7.25 (m, 3H), 6.97 (d, J=8.9Hz, 1H), 2.94 (hept, J=6.9Hz, 1H), 2.42 (d, J=1.4Hz, 3H), 1.27 (d, J=6.9Hz, 6H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.40,161.97,160.45,152.18, 144.69,140.75,132.44,128.76,127.14,125.98,119.73,118.10,117.32,114.28,103.68, 34.18,23.79,9.65.
Embodiment 5-3:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 1h.Then the four of p-t-Butylbenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 1 hour, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to tert-butyl benzene first The molar ratio of aldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.02g.Gained furans chalcone Derivative are as follows: (E) -3- (to tert-butyl-phenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 84%, the structure of the derivative are as follows:
Molecular formula: C22H22O3
Chinese name: (E) -3- (to tert-butyl-phenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene - 1- ketone
English name:
(E)-3-(4-(tert-butyl)phenyl)-1-(4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 334.16
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (500MHz, Chloroform-d) δ 14.03 (s, 1H), 7.91 (d, J=15.4Hz, 1H), 7.79 (d, J=9.0Hz, 1H), 7.70-7.55 (m, 3H), 7.49-7.42 (m, 2H), 7.29 (t, J=1.6Hz, 1H), 6.99 (d, J=8.9Hz, 1H), 2.44 (d, J=1.5Hz, 3H), 1.35 (s, 9H)
Carbon-13 nmr spectra: (126MHz, Chloroform-d) δ 193.12,161.98,160.47,153.50, 144.75,140.81,140.60,130.25,125.94,119.89,118.14,117.33,114.21,105.80,103.70, 61.04,56.25,9.63.
Embodiment 5-4:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then p-ethoxybenzaldehyde is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 2 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to ethyoxyl The molar ratio of benzaldehyde and sodium hydride is 1:2:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.06g.Gained furans looks into ear Ketones derivant are as follows: (E) -3- (to ethoxyl phenenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, Yield 85%, the structure of the derivative are as follows:
Molecular formula: C20H18O4
Chinese name: (E) -3- (to ethoxyl phenenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene - 1- ketone
English name: (E) -3- (4-ethoxyphenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 322.12
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.11 (s, 1H), 7.93-7.74 (m, 2H), 7.66- 7.50 (m, 3H), 7.29 (t, J=1.5Hz, 1H), 7.01-6.89 (m, 3H), 4.09 (q, J=7.0Hz, 2H), 2.44 (d, J= 1.4Hz, 3H), 1.44 (d, J=7.0Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.35,161.91,161.27,160.38, 144.54,140.71,130.44,127.33,125.91,118.09,117.32,114.93,114.29,103.60,63.70, 14.74,9.65.
Embodiment 5-5:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then it is added into system to fluorine-based benzaldehyde Tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 12 hours, twice solvent is then added into system System is adjusted to acidity with hydrochloric acid by the water quenching reaction of volume.The crude product being precipitated is filtered, by crude product ethyl alcohol recrystallization Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to fluorine-based benzene first The molar ratio of aldehyde and sodium hydride is 1:3:3, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone Derivative are as follows: (E) -3- (p-fluorophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 74%, the structure of the derivative are as follows:
Molecular formula: C18H13FO3
Chinese name: (E) -3- (p-fluorophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (4-fluorophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 296.08
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.97 (s, 1H), 7.90 (d, J=15.4Hz, 1H), 7.80 (d, J=8.9Hz, 1H), 7.74-7.57 (m, 3H), 7.33 (q, J=1.4Hz, 1H), 7.22-7.10 (m, 2H), 7.02 (d, J=8.9Hz, 1H), 2.47 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.12,162.01,160.53,143.24, 140.84,131.05 (d, J=3.3Hz), 130.48 (d, J=8.7Hz), 125.93,120.48 (d, J=2.5Hz), 118.15,117.33,116.31,116.09,114.17,103.81,9.63.
Embodiment 5-6:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of p-chlorobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and p-chlorobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (rubigan) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 81% should The structure of derivative are as follows:
Molecular formula: C18H13ClO3
Chinese name: (E) -3- (rubigan) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (4-chlorophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 312.06
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.93 (d, J=2.7Hz, 1H), 7.96-7.74 (m, 2H), 7.73-7.55 (m, 3H), 7.53-7.37 (m, 2H), 7.32 (s, 1H), 7.01 (dd, J=9.0,3.1Hz, 1H), 2.46 (d, J=3.5Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.51,161.54,160.06,142.53, 140.37,136.10,132.75,129.18,128.79,125.42,120.71,117.64,116.83,113.66,103.35, 9.13.
Embodiment 5-7:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of p-bromobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and p-bromobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (p-bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 76% should The structure of derivative are as follows:
Molecular formula: C18H13BrO3
Chinese name: (E) -3- (p-bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (4-bromophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 356.00
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.90 (s, 1H), 7.86-7.69 (m, 2H), 7.67- 7.45 (m, 5H), 7.29 (t, J=1.4Hz, 1H), 6.98 (d, J=8.9Hz, 1H), 2.43 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.99,162.05,160.56,143.10, 140.87,133.66,132.25,129.88,125.93,125.00,121.28,118.15,117.33,114.15,103.87, 9.64.
Embodiment 5-8:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then it is added into system to Dimethylaminobenzene first The tetrahydrofuran solution of aldehyde, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, be then added into system twice System is adjusted to acidity with hydrochloric acid by the water quenching reaction of solvent volume.The crude product being precipitated is filtered, by crude product ethyl alcohol weight Clean product can be obtained in crystallization.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to diformazan The molar ratio of amido benzaldehyde and sodium hydride is 1:1:1, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans Chalcone derivative are as follows: (E) -3- (to dimethylaminophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone, yield 86%, the structure of the derivative are as follows:
Molecular formula: C20H19NO3
Chinese name: (E) -3- (to dimethylaminophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone
English name: (E) -3- (4- (dimethylamino) phenyl) -1- (4-hydroxy-3- methylbenzofuran-5-yl)prop-2-en-1-one
Molecular weight: 321.14
Appearance: red solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.35 (s, 1H), 7.90 (d, J=15.2Hz, 1H), 7.79 (d, J=8.9Hz, 1H), 7.64-7.52 (m, 2H), 7.46 (d, J=15.2Hz, 1H), 7.28 (q, J=1.4Hz, 1H), 6.97 (d, J=8.9Hz, 1H), 6.75-6.66 (m, 2H), 3.05 (s, 6H), 2.44 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.29,161.80,160.18,152.12, 145.61,140.56,130.68,125.82,122.56,118.05,117.30,114.99,114.44,111.84,103.33, 40.15,9.69.
Embodiment 5-9:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in dioxane, at room temperature, sodium hydride is added, stirs 15 minutes.Then it is added into system to cyanobenzaldehyde Dioxane solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent is then added into system System is adjusted to acidity with hydrochloric acid by the water quenching reaction of volume.The crude product being precipitated is filtered, by crude product ethyl alcohol recrystallization Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to cyano benzene first The molar ratio of aldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone Derivative are as follows: (E) -4- (3- (4- hydroxy-3-methyl benzofuran -5- base) -3- oxo -1- propylene -1- base) benzonitrile, yield 73%, the structure of the derivative are as follows:
Molecular formula: C19H13NO3
Chinese name: (E) -4- (3- (4- hydroxy-3-methyl benzofuran -5- base) -3- oxo -1- propylene -1- base) benzene Formonitrile HCN
English name: (E) -4- (3- (4-hydroxy-3-methylbenzofuran-5-yl) -3-oxoprop-1-en- 1-yl)benzonitrile
Molecular weight: 303.09
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.77 (s, 1H), 7.87 (d, J=15.5Hz, 1H), 7.82-7.64 (m, 6H), 7.32 (s, 1H), 7.01 (d, J=8.9Hz, 1H), 2.44 (s, 3H)
Carbon-13 nmr spectra: (101MHz, DMSO-d6)δ192.07,161.07,160.26,141.32,140.55, 138.58,132.22,128.29,125.43,123.64,117.87,117.74,116.87,113.62,113.11,103.62, 9.10.
Embodiment 5-10:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then it is added into system to diethylin benzene first The tetrahydrofuran solution of aldehyde, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, be then added into system twice System is adjusted to acidity with hydrochloric acid by the water quenching reaction of solvent volume.The crude product being precipitated is filtered, by crude product ethyl alcohol weight Clean product can be obtained in crystallization.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone with to diethyl The molar ratio of amido benzaldehyde and sodium hydride is 1:5:5, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans Chalcone derivative are as follows: (E) -3- (to diethylin phenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone, yield 88%, the structure of the derivative are as follows:
Molecular formula: C22H23NO3
Chinese name: (E) -3- (to diethylin phenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone
English name: (E) -3- (4- (diethylamino) phenyl) -1- (4-hydroxy-3- methylbenzofuran-5-yl)prop-2-en-1-one
Molecular weight: 349.17
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.40 (s, 1H), 7.90 (d, J=15.1Hz, 1H), 7.80 (d, J=8.9Hz, 1H), 7.55 (d, J=8.5Hz, 2H), 7.44 (d, J=15.1Hz, 1H), 7.30-7.24 (m, 1H), 6.97 (d, J=8.9Hz, 1H), 6.66 (d, J=8.4Hz, 2H), 3.42 (q, J=7.1Hz, 4H), 2.44 (d, J=1.4Hz, 3H), 1.21 (t, J=7.1Hz, 6H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.27,161.78,160.14,149.88, 145.71,140.53,131.05,125.78,121.75,118.05,117.31,114.49,114.32,111.29,103.28, 44.56,12.62,9.69.
Embodiment 5-11:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then paranitrobenzaldehyde is added into system Tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent is then added into system System is adjusted to acidity with hydrochloric acid by the water quenching reaction of volume.The crude product being precipitated is filtered, by crude product ethyl alcohol recrystallization Clean product can be obtained.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and p-nitrophenyl first in the step The molar ratio of aldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.02g.Gained furans chalcone Derivative are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-nitrophenyl) -2- propylene -1- ketone, yield 81%, the structure of the derivative are as follows:
Molecular formula: C18H13NO5
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (p-nitrophenyl) -2- propylene -1- Ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (4-nitrophenyl) prop-2-en-1-one
Molecular weight: 323.08
Appearance: dark red solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.78 (s, 1H), 8.36-8.29 (m, 2H), 7.95 (d, J=15.6Hz, 1H), 7.87-7.78 (m, 4H), 7.35 (d, J=1.5Hz, 1H), 7.06 (d, J=8.9Hz, 1H), 2.48 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.93,162.06,160.57,142.77, 140.85,134.90,133.62,131.45,127.96,127.73,126.04,123.61,117.34,114.14,103.86, 9.63.
Embodiment 5-12:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 2- fluorobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2- fluorobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.06g.Gained furans chalcone is derivative Object are as follows: (E) -3- (2- fluorophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 73% should The structure of derivative are as follows:
Molecular formula: C18H13FO3
Chinese name: (E) -3- (2- fluorophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (2-fluorophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 296.08
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.94 (d, J=2.5Hz, 1H), 7.99 (d, J= 15.7Hz, 1H), 7.90-7.72 (m, 2H), 7.66 (t, J=7.7Hz, 1H), 7.41 (q, J=7.0,6.5Hz, 1H), 7.30 (s, 1H), 7.19 (dt, J=27.0,8.8Hz, 2H), 7.00 (d, J=8.8Hz, 1H), 2.45 (s, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.76,161.53,160.04,140.31,136.80 (d, J=1.8Hz), 131.48 (d, J=8.7Hz), 129.52 (d, J=3.1Hz), 125.55,124.04 (d, J=3.7Hz), 122.89 (d, J=11.4Hz), 122.45,122.34,117.58,115.96,115.74,113.69,103.33,9.13.
Embodiment 5-13:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 2- chlorobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2- chlorobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (2- chlorphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 83% should The structure of derivative are as follows:
Molecular formula: C18H13ClO3
Chinese name: (E) -3- (2- chlorphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (2-chlorophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 312.06
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.89 (s, 1H), 8.32 (d, J=15.5Hz, 1H), 7.85-7.75 (m, 2H), 7.68 (d, J=15.5Hz, 1H), 7.52-7.44 (m, 1H), 7.41-7.31 (m, 3H), 7.02 (d, J =8.9Hz, 1H), 2.47 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.56,161.58,160.09,140.38, 139.80,135.12,132.65,130.82,129.89,127.40,126.61,125.55,122.98,117.67,116.87, 113.68,103.38,9.15.
Embodiment 5-14:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, hydrofining is added, stirs 15 minutes.Then the four of 2- bromobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2- bromobenzaldehyde and The molar ratio of hydrofining is 1:1:1, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (2- bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 81% should The structure of derivative are as follows:
Molecular formula: C18H13BrO3
Chinese name: (E) -3- (2- bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (2-bromophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 356.00
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.87 (s, 1H), 8.26 (d, J=15.4Hz, 1H), 7.78 (d, J=8.7Hz, 2H), 7.71-7.55 (m, 2H), 7.45-7.27 (m, 3H), 7.01 (d, J=8.9Hz, 1H), 2.46 (s,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.93,162.06,160.57,142.77, 140.85,134.90,133.62,131.45,127.96,127.73,126.04,123.61,118.13,117.34,114.14, 103.86,9.63.
Embodiment 5-15:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, hydrofining is added, stirs 15 minutes.Then Benzaldehyde,2-methoxy is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 2 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2- methoxyl group in the step The molar ratio of benzaldehyde and hydrofining is 1:2:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans looks into ear Ketones derivant are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (2- methoxyphenyl) -2- propylene -1- ketone, Yield 86%, the structure of the derivative are as follows:
Molecular formula: C19H16O4
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (2- methoxyphenyl) -2- propylene - 1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (2- methoxyphenyl)prop-2-en-1-one
Molecular weight: 308.10
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.10 (s, 1H), 8.20 (d, J=15.6Hz, 1H), 7.84-7.69 (m, 2H), 7.63 (dd, J=7.7,1.8Hz, 1H), 7.37 (ddd, J=8.6,7.5,1.7Hz, 1H), 7.27 (s, 1H), 6.96 (td, J=13.0,11.9,7.9Hz, 3H), 3.92 (s, 3H), 2.43 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.89,161.95,160.39,158.92, 140.69,140.19,131.97,129.52,126.09,123.77,121.37,120.77,118.05,117.32,114.38, 111.25,103.59,55.57,9.66.
Embodiment 5-16:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, hydrofining is added, stirs 15 minutes.Then 2,4- dimethyl benzene first is added into system The tetrahydrofuran solution of aldehyde, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, be then added into system twice System is adjusted to acidity with hydrochloric acid by the water quenching reaction of solvent volume.The crude product being precipitated is filtered, by crude product ethyl alcohol weight Clean product can be obtained in crystallization.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2,4- bis- in the step The molar ratio of tolyl aldehyde and hydrofining is 1:5:5, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans Chalcone derivative are as follows: (E) -3- (2,4- 3,5-dimethylphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone, yield 85%, the structure of the derivative are as follows:
Molecular formula: C20H18O3
Chinese name: (E) -3- (2,4- 3,5-dimethylphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- third Alkene -1- ketone
English name: (E) -3- (2,4-dimethylphenyl) -1- (4-hydroxy-3-methylbenzofuran- 5-yl)prop-2-en-1-one
Molecular weight: 306.13
Appearance: dark yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.03 (s, 1H), 8.19 (d, J=15.2Hz, 1H), 7.78 (d, J=8.9Hz, 1H), 7.63 (d, J=8.0Hz, 1H), 7.55 (d, J=15.3Hz, 1H), 7.29 (q, J=1.4Hz, 1H), 7.07 (d, J=7.2Hz, 2H), 6.98 (d, J=8.9Hz, 1H), 2.47 (s, 3H), 2.44 (d, J=1.4Hz, 3H), 2.35(s,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.43,161.96,160.42,142.13, 140.93,140.73,138.54,131.79,130.92,127.19,126.49,125.99,120.69,118.08,117.31, 114.27,103.66,21.40,19.81,9.63.
Embodiment 5-17:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then 2,4,6- trimethylbenzene is added into system The tetrahydrofuran solution of formaldehyde, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, be then added into system twice In the water quenching reaction of solvent volume, system is adjusted to acidity with hydrochloric acid.The crude product being precipitated is filtered, by crude product ethyl alcohol Clean product can be obtained in recrystallization.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2,4 in the step, The molar ratio of 6- trimethylbenzaldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained Furans chalcone derivative are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (2,4,6- trimethylphenyl) - 2- propylene -1- ketone, yield 86%, the structure of the derivative are as follows:
Molecular formula: C21H20O3
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (2,4,6- trimethylphenyl) -2- third Alkene -1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3-mesitylprop-2- en-1-one
Molecular weight: 320.14
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.94 (s, 1H), 8.07 (d, J=15.8Hz, 1H), 7.67 (d, J=8.9Hz, 1H), 7.34-7.26 (m, 2H), 7.01-6.88 (m, 3H), 2.45 (d, J=1.4Hz, 3H), 2.42 (s,6H),2.31(s,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.50,161.99,160.46,143.06, 140.79,138.78,137.26,131.46,129.37,126.06,125.99,118.11,117.33,114.23,103.77, 21.31,21.12,9.64.
Embodiment 5-18:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then 3,4,5- trimethoxy is added into system The tetrahydrofuran solution of benzaldehyde, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, two are then added into system The water quenching reaction of times solvent volume, is adjusted to acidity for system with hydrochloric acid.The crude product being precipitated is filtered, by crude product second Clean product can be obtained in alcohol recrystallization.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 3 in the step, 4,5- trimethoxybenzaldehyde and the molar ratio of sodium hydride are 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g. Gained furans chalcone derivative are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (3,4,5- trimethoxy Phenyl) -2- propylene -1- ketone, yield 87%, the structure of the derivative are as follows:
Molecular formula: C21H20O6
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (3,4,5- trimethoxyphenyl) -2- Propylene -1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (3,4,5- trimethoxyphenyl)prop-2-en-1-one
Molecular weight: 368.13
Appearance: bright yellow solid
Nuclear magnetic resonance spectroscopy: (500MHz, Chloroform-d) δ 14.01 (s, 1H), 7.86-7.76 (m, 2H), 7.54 (d, J=15.3Hz, 1H), 7.30 (d, J=1.7Hz, 1H), 7.00 (d, J=8.8Hz, 1H), 6.88 (s, 2H), 3.94 (s, 6H), 3.92 (s, 3H), 2.44 (d, J=1.5Hz, 3H)
Carbon-13 nmr spectra: (126MHz, Chloroform-d) δ 193.42,161.95,160.44,154.41, 144.57,140.74,132.02,128.47,125.99,125.96,119.86,118.10,117.31,114.27,103.68, 34.98,31.15,9.63.
Embodiment 5-19:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then 2,4 dichloro benzene formaldehyde is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 2 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2,4- dichloro in the step The molar ratio of benzaldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans looks into ear Ketones derivant are as follows: (E) -3- (2,4- dichlorophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, Yield 80%, the structure of the derivative are as follows:
Molecular formula: C18H12Cl2O3
Chinese name: (E) -3- (2,4 dichloro benzene base) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene - 1- ketone
English name: (E) -3- (2,4-dichlorophenyl) -1- (4-hydroxy-3-methylbenzofuran- 5-yl)prop-2-en-1-one
Molecular weight: 346.02
Appearance: dark yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.84 (s, 1H), 8.24 (d, J=15.5Hz, 1H), 7.83-7.59 (m, 3H), 7.51 (d, J=2.1Hz, 1H), 7.37-7.31 (m, 2H), 7.02 (d, J=8.9Hz, 1H), 2.47 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.26,161.63,160.15,140.43, 138.52,136.14,135.69,131.22,129.73,128.10,127.09,125.47,123.27,117.69,116.86, 113.62,103.47,9.14.
Embodiment 5-20:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the bromo- 4- fluorobenzaldehyde of 2- is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 2 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and the bromo- 4- fluorine of 2- in the step The molar ratio of benzaldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans looks into ear Ketones derivant are as follows: (E) -3- (the bromo- 4- fluorophenyl of 2-) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- Ketone, yield 82%, the structure of the derivative are as follows:
Molecular formula: C18H12BrFO3
Chinese name: (E) -3- (the bromo- 4- fluorophenyl of 2-) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene - 1- ketone
English name: (E) -3- (2-bromo-4-fluorophenyl) -1- (4-hydroxy-3- methylbenzofuran-5-yl)prop-2-en-1-one
Molecular weight: 374.00
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.82 (s, 1H), 8.17 (d, J=15.3Hz, 1H), 7.75 (t, J=8.4Hz, 2H), 7.53 (d, J=15.4Hz, 1H), 7.39 (dd, J=8.2,2.5Hz, 1H), 7.30 (s, 1H), 7.16-7.05 (m, 1H), 6.98 (d, J=8.9Hz, 1H), 2.43 (s, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.77,164.49,162.09,160.61, 141.60,140.91,131.30 (d, J=3.5Hz), 129.15 (d, J=8.9Hz), 126.40 (d, J=9.6Hz), 125.98,123.41 (d, J=2.07Hz), 120.88 (d, J=24.6Hz), 118.18,117.37,115.35 (d, J= 21.6Hz),114.10,103.92,9.63.
Embodiment 5-21:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 3- chlorobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 3- chlorobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (3- chlorphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 81% should The structure of derivative are as follows:
Molecular formula: C18H13ClO3
Chinese name: (E) -3- (3- chlorphenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (3-chlorophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 312.06
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.86 (s, 1H), 7.85-7.72 (m, 2H), 7.63 (t, J=7.6Hz, 2H), 7.50 (d, J=7.0Hz, 1H), 7.42-7.27 (m, 3H), 6.99 (d, J=8.8Hz, 1H), 2.43 (s,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.88,162.05,160.60,142.75, 140.87,136.59,135.01,130.45,130.22,127.92,126.92,125.97,122.07,118.13,117.32, 114.13,103.90,9.60.
Embodiment 5-22:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 3- bromobenzaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 3- bromobenzaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (3- bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 80% should The structure of derivative are as follows:
Molecular formula: C18H13BrO3
Chinese name: (E) -3- (3- bromophenyl) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (3-bromophenyl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 356.00
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.79 (s, 1H), 7.80-7.62 (m, 3H), 7.55 (d, J=15.4Hz, 1H), 7.51-7.41 (m, 2H), 7.21 (d, J=7.4Hz, 2H), 6.92 (d, J=8.8Hz, 1H), 2.35 (s,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 191.81,161.01,159.56,141.60, 139.83,135.83,132.32,129.80,129.44,126.35,124.94,122.09,121.03,117.09,116.28, 113.09,102.87,8.57.
Embodiment 5-23:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then tolyl aldehyde between being added into system Tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent is then added into system System is adjusted to acidity with hydrochloric acid by the water quenching reaction of volume.The crude product being precipitated is filtered, by crude product ethyl alcohol recrystallization Clean product can be obtained.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and methylbenzene first in the step The molar ratio of aldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone Derivative are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (aminomethyl phenyl) -2- propylene -1- ketone, yield 84%, the structure of the derivative are as follows:
Molecular formula: C19H16O3
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (aminomethyl phenyl) -2- propylene -1- Ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (m-tolyl) prop-2- en-1-one
Molecular weight: 292.11
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.00 (s, 1H), 7.88 (d, J=15.5Hz, 1H), 7.79 (d, J=8.9Hz, 1H), 7.65 (d, J=15.5Hz, 1H), 7.46 (d, J=7.7Hz, 2H), 7.34-7.28 (m, 2H), 7.24 (d, J=7.5Hz, 1H), 6.99 (d, J=8.9Hz, 1H), 2.44 (d, J=1.4Hz, 3H), 2.41 (s, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.38,161.99,160.49,144.80, 140.78,138.68,134.73,131.60,129.11,128.90,126.03,125.91,120.52,118.11,117.33, 114.26,103.73,21.38,9.65.
Embodiment 5-24:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then m-methoxybenzaldehyde is added into system Tetrahydrofuran solution, addition finishes keeping body and ties up to room temperature, be stirred to react 2 hours, be then added into system twice molten System is adjusted to acidity with hydrochloric acid by the water quenching reaction of agent volume.The crude product being precipitated is filtered, crude product is tied again with ethyl alcohol Clean product can be obtained in crystalline substance.1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 3- methoxyl group in the step The molar ratio of benzaldehyde and sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans looks into ear Ketones derivant are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (3- methoxyphenyl) -2- propylene -1- ketone, Yield 86%, the structure of the derivative are as follows:
Molecular formula: C19H16O4
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (3- methoxyphenyl) -2- propylene - 1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (3- methoxyphenyl)prop-2-en-1-one
Molecular weight: 308.10
Appearance: khaki solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 13.96 (s, 1H), 7.86 (d, J=15.4Hz, 1H), 7.77 (d, J=9.0Hz, 1H), 7.62 (d, J=15.4Hz, 1H), 7.34 (t, J=7.9Hz, 1H), 7.29 (q, J=1.4Hz, 1H), 7.27-7.23 (m, 1H), 7.16 (t, J=2.0Hz, 1H), 7.01-6.92 (m, 2H), 3.86 (s, 3H), 2.43 (d, J= 1.3Hz,3H).
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 193.27,162.00,160.51,159.95, 144.48,140.81,136.14,129.99,126.00,121.19,121.02,118.11,117.32,116.40,114.22, 113.61,103.77,55.38,9.63.
Embodiment 5-25:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 2 furan carboxyaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2 furan carboxyaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -3- (furans -2- base) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone, yield 77% should The structure of derivative are as follows:
Molecular formula: C16H12O4
Chinese name: (E) -3- (furans -2- base) -1- (4- hydroxy-3-methyl benzofuran -5- base) -2- propylene -1- ketone
English name: (E) -3- (furan-2-yl) -1- (4-hydroxy-3-methylbenzofuran-5-yl) prop-2-en-1-one
Molecular weight: 268.07
Appearance: yellow solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.05 (s, 1H), 7.79 (d, J=9.0Hz, 1H), 7.68 (d, J=15.1Hz, 1H), 7.63-7.52 (m, 2H), 7.29 (q, J=1.4Hz, 1H), 6.98 (d, J=8.9Hz, 1H), 6.75 (d, J=3.4Hz, 1H), 6.53 (dd, J=3.4,1.8Hz, 1H), 2.44 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.94,161.93,160.50,151.66, 145.21,140.75,130.41,126.02,118.31,118.06,117.31,116.67,114.26,112.81,103.75, 9.66.
Embodiment 5-26:
Under nitrogen protection, intermediate 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is uniformly divided It dissipates in tetrahydrofuran, at room temperature, sodium hydride is added, stirs 15 minutes.Then the four of 2 thiophene carboxaldehyde is added into system Hydrogen tetrahydrofuran solution, addition finish keeping body and tie up to room temperature, be stirred to react 2 hours, twice solvent body is then added into system System is adjusted to acidity with hydrochloric acid by long-pending water quenching reaction.The crude product being precipitated is filtered, is with ethyl alcohol recrystallization by crude product Clean product can be obtained.In the step 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and 2 thiophene carboxaldehyde and The molar ratio of sodium hydride is 1:1:2, and the corresponding inventory of every milliliter of reaction dissolvent is 0.045g.Gained furans chalcone is derivative Object are as follows: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (thiophene -2- base) -2- propylene -1- ketone, yield 79% should The structure of derivative are as follows:
Molecular formula: C16H12O3S
Chinese name: (E) -1- (4- hydroxy-3-methyl benzofuran -5- base) -3- (thiophene -2- base) -2- propylene -1- ketone
English name: (E) -1- (4-hydroxy-3-methylbenzofuran-5-yl) -3- (thiophen-2-yl) prop-2-en-1-one
Molecular weight: 284.05
Appearance: dark red solid
Nuclear magnetic resonance spectroscopy: (400MHz, Chloroform-d) δ 14.04 (s, 1H), 8.07 (dt, J=15.1,0.7Hz, 1H), 7.78 (d, J=8.9Hz, 1H), 7.51-7.44 (m, 2H), 7.41 (dt, J=3.4,0.9Hz, 1H), 7.32 (q, J= 1.4Hz, 1H), 7.14 (dd, J=5.0,3.6Hz, 1H), 7.02 (d, J=8.9Hz, 1H), 2.46 (d, J=1.4Hz, 3H)
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 192.25,161.45,160.00,140.29, 139.84,136.55,131.89,128.72,127.96,125.39,119.01,117.61,116.82,113.63,103.27, 9.15.

Claims (3)

1. a kind of preparation method of substituted furans chalcone derivative, which comprises the following steps:
(1) by 1, hydroresorcinol and potassium hydroxide are dispersed in water, and after stirring at normal temperature 5min, chloroethene ethyl acetoacetic acid second is added The methanol solution of ester；After reaction system is stirred at room temperature 5 days, it is acidified with the hydrochloric acid of 4N；Reaction solution after filtering acidification, obtains To solid product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate；
Described 1, hydroresorcinol and potassium hydroxide, chloroacetyl acetacetic ester molar ratio be 1:1:1, every milliliter of water corresponding 1, The inventory of hydroresorcinol is 0.1g, and the inventory of the corresponding chloroacetyl acetacetic ester of every ml methanol is 0.2g；
(2) by the mixing of 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- Ethyl formate, potassium hydroxide methanol and water Solvent dissolution；After reaction 5h is stirred at room temperature in reaction system, with the hydrochloric acid tune pH to 1 of 6N；Filtering reacting liquid obtains solid Product: 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid；
The mixed solvent is that methanol and water are formulated by the volume ratio of 2.5:1；The corresponding 3- methyl-of every milliliter of mixed solvent 4- oxygen -4,5, the inventory of 6,7- tetrahydrochysene benzfuran -2- Ethyl formates are 0.2g, 3- methyl -4- oxygen -4,5,6,7- tetrahydro benzene And the molar ratio of furans -2- Ethyl formate and potassium hydroxide is 1:6；
(3) by 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid are dispersed in diethylene glycol (DEG), be added copper powder and Pyridine；Reaction system is heated to 175 DEG C, is kept stirring 10h；Reaction system is cooled to room temperature, ice water is added, and with 4N's Hydrochloric acid acidification；Three times, combined extract liquor is washed with water once for reaction solution after being acidified with petroleum ether extraction, then will extraction Liquid anhydrous sodium sulfate is dry, is spin-dried for, and obtains solid product: 3- methyl -6,7- Dihydrobenzofuranes -4- (5H) -one；
Wherein, the inventory of the corresponding 3- methyl -4- oxygen -4,5 of every milliliter of diethylene glycol (DEG), 6,7- tetrahydrochysene benzfuran -2- formic acid is 0.1g；The molar ratio of 3- methyl -4- oxygen -4,5,6,7- tetrahydrochysene benzfuran -2- formic acid and copper powder and pyridine is 1:1:2；
(4) under nitrogen protection, it uniformly disperses sodium hydride in ethylene glycol dimethyl ether solution, reaction system is cooled to 0 DEG C, the ethylene glycol dimethyl ether solution of 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) -one is then added, keeping body ties up to 0 DEG C and stirs Mix 30min；The ethylene glycol dimethyl ether solution of ethyl acetate is added into system, system is then heated to 90 DEG C；After keeping 3h, System is cooled to room temperature, the ammonium chloride solution quenching reaction of saturation is added；It is extracted with ethyl acetate 3 times, organic phase is with anhydrous Sodium sulphate is dry, is concentrated, and obtains product: the crude product of -4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes；
- 4 (5H) -one of 3- methyl -6,7- Dihydrobenzofuranes and the molar ratio of sodium hydride, ethyl acetate are 1:5:3, every milli Rising corresponding 3- methyl -6,7- Dihydrobenzofuranes -4 (5H) the -one inventory of glycol dimethyl ether is 0.04g；
(5) -4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes is dispersed in toluene solution, into system Chloro- 5, the 6- dicyanoquinone of 2,3- bis- is added, is heated to 130 DEG C of holding 6h；System is cooled to room temperature, filter is concentrated after filtering Liquid；By filtrate silica gel chromatograph post separation, the pure production of 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone is obtained Object；
- 4 (5H) -one of 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes is rubbed with the chloro- 5,6- dicyanoquinone of 2,3- bis- Your ratio is 1:1.2, and the inventory of corresponding 5- acetyl -3- methyl -6,7- Dihydrobenzofuranes -4 (5H) -one of every milliliter of toluene is 0.1g；
(6) under nitrogen protection, 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone obtained by step (5) is uniform Be scattered in reaction dissolvent a, keeping body ties up at room temperature；Then highly basic is added, stirs 10min~1h；Add again into system Enter a solution of reactive group, reacts 1 hour~24 hours；Then the water quenching reaction of twice solvent a volume is added, then uses System is adjusted to acidity by hydrochloric acid；Crude product is precipitated in filtering, obtains pure substituted furans chalcone with ethyl alcohol recrystallization Analog derivative；The substituted furans chalcone derivative has the structure as shown in formula (I):
Wherein,
B ring is selected from phenyl, furyl or thienyl；
R1、R2、R3It is each independently selected from the alkane of hydrogen atom, halogen, hydroxyl, cyano, nitro, the alkyl chain of C1~C7, C1~C7 Oxygroup, dimethylamino or diethylin；
In reaction system, the molar ratio of 1- (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone and reactive group, highly basic For 1:1~5:1~5；The corresponding 1- of every milliliter of reaction dissolvent a (4- hydroxy-3-methyl benzofuran -5- base) ethyl -1- ketone Inventory is 0.02 to 0.06g；The reaction dissolvent a is tetrahydrofuran or dioxane；
The structural formula of the reactive group are as follows:
Wherein, B ring is selected from phenyl, furyl or thienyl；R1、R2、R3It is each independently selected from hydrogen atom, halogen, hydroxyl, cyanogen Base, nitro, the alkyl chain of C1~C7, C1~C7 alkoxy, dimethylamino or diethylin.
2. method according to claim 1, which is characterized in that the substituted furans chalcone derivative has following any A kind of structure:
3. method according to claim 1, which is characterized in that step (6) highly basic is sodium hydride or hydrofining.
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