CN106279083A - A kind of furocoumarin analog derivative and preparation method thereof - Google Patents
A kind of furocoumarin analog derivative and preparation method thereof Download PDFInfo
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- CN106279083A CN106279083A CN201610629772.0A CN201610629772A CN106279083A CN 106279083 A CN106279083 A CN 106279083A CN 201610629772 A CN201610629772 A CN 201610629772A CN 106279083 A CN106279083 A CN 106279083A
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- methyl
- oxygen
- furan
- formaldehyde
- furocoumarin
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- ZPTMWVDSVJOEEB-UHFFFAOYSA-N Cc1c(C(O)=O)[o]c(CCC2)c1C2=O Chemical compound Cc1c(C(O)=O)[o]c(CCC2)c1C2=O ZPTMWVDSVJOEEB-UHFFFAOYSA-N 0.000 description 1
- HVXIXLZOMVQEPY-UHFFFAOYSA-N Cc1c[o]c(CCC2)c1C2=O Chemical compound Cc1c[o]c(CCC2)c1C2=O HVXIXLZOMVQEPY-UHFFFAOYSA-N 0.000 description 1
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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
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D307/85—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to field of medicaments, it is desirable to provide a kind of furocoumarin analog derivative and preparation method thereof.This kind of furocoumarin analog derivative is that furan nucleus is by methyl substituted furocoumarin analog derivative；The preparation method of this furocoumarin analog derivative is: take 4 hydroxyl 3 methyl benzofuran 5 formaldehyde, weak base is dispersed in reaction dissolvent a, obtain raw mixture, then at 70 DEG C, react 1～3 hour, filtering reacting liquid is precipitated thing, and the precipitate after washing is furocoumarin analog derivative.The furocoumarin analog derivative of the present invention is the isopsoralen analog that a class has new skeleton, there is potential pharmaceutically active, the preparation of this compounds can be that the pharmaceutically active research of furocoumarin class provides support, and the preparation method step that the present invention provides is simple, and loss rate is low.
Description
Technical field
The present invention is about field of medicaments, particularly to a kind of furocoumarin analog derivative and preparation method thereof.
Background technology
Furocoumarin is widespread in nature, China's Chinese medicine Radix Angelicae Dahuricae, Radix Angelicae Pubescentis, Radix Peucedani, Radix Angelicae Sinensis, Fructus Psoraleae
Deng, and the multiple medicinal plants of external report all contains furocoumarin compound.Furocoumarin has many medicines
Reason activity, be mainly manifested in antitumor, AntiHIV1 RT activity, antioxidation, photochemical effect, resisting pathogenic microbes, anti-inflammatory and antalgic, antidepressant,
And on aspects such as the impacts of drug metabolism enzyme.Wherein, dihedral furocoumarin isopsoralen (isopsoralen), there is tool
There are the effects such as stronger optical sensibilization and calmness, spasmolytic, hemostasis, are treatment vitiligo, alopecia areata, psoriasis and tumor sample skin
Sick active drug.Isopsoralen have with estrogens as proliferation, the endocrine of scalable body is lost
Tune state thus reach alleviate climacteric syndrome effect.
Methyl substituted furan ring structure is widely present in natural product, and has various biological activity, such as red
Ginseng ketone can treat cardiovascular disease, and furan Buddhist art alkane has Allelopathic Effect in Plants, and sesquiterpenoids cacalol has anti-
Hyperglycemia and antibacterial effect.
Therefore furan nucleus is had potential pharmaceutically active, and such by methyl substituted isopsoralen and derivant thereof
Compound is in the news the most not yet.
Summary of the invention
Present invention is primarily targeted at and overcome deficiency of the prior art, it is provided that a kind of furan nucleus is by methyl substituted furan
Mutter coumarin derivatives and preparation method thereof.For solving above-mentioned technical problem, the solution of the present invention is:
There is provided a kind of furocoumarin analog derivative, shown in the following formula I of structural formula:
Wherein, R be methyl, ethyl, ethyoxyl, propyl group, isopropyl, phenyl, 3,4-Dimethoxyphenyl or 4-pyridine radicals.
In the present invention, following compound is specifically included: 3-acetyl group-9-methyl-2H-furan [2,3-h] .alpha.-5:6-benzopyran-
2-ketone, 9-methyl-2-oxygen-2H-furan [2,3-h] .alpha.-5:6-benzopyran-3-Ethyl formate, 9-methyl-3-propiono-2H-furan [2,
3-h] chromen-2-one, 3-isobutyryl-9-methyl-2H-furan [2,3-h] chromen-2-one, 3-bytyry-9-first
Base-2H-furan [2,3-h] chromen-2-one, 3-benzoyl-9-methyl-2H-furan [2,3-h] chromen-2-one,
3-(3,4-Dimethoxybenzoyl)-9-methyl-2H-furan [2,3-h] chromen-2-one, 3-different nicotinoyl-9-methyl-
2H-furan [2,3-h] chromen-2-one.
The method preparing described furocoumarin analog derivative is provided, specifically includes following step:
(1) by 1, hydroresorcinol, potassium hydroxide are dispersed in water, after stirring at normal temperature 5min, add chloracetyl second
The methanol solution of acetoacetic ester, is then stirred at room temperature system 5 days；Then the hydrochloric acid of system 4N is acidified, filters acidifying
After reactant liquor, the solid obtained is product: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formates；
Wherein, 1, hydroresorcinol, potassium hydroxide, the mol ratio of chloroacetyl acetacetic ester are 1:1:1；Every milliliter of water correspondence
The inventory of hydroresorcinol be 0.1g；The inventory of the chloroacetyl acetacetic ester that every ml methanol is corresponding is 0.2g；
(2) by product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate and the hydroxide of step (1)
Potassium, dissolves with the mixed solvent of first alcohol and water, and system is stirred at room temperature after dissolving reaction 5h；Then by reactant liquor 6N's
Hydrochloric acid tune pH to 1, filtering reacting liquid, the solid i.e. product of filtration gained: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfurans-
2-formic acid；
Wherein, in the mixed solvent of described first alcohol and water, methanol is 2.5:1 with the volume ratio of water；Every ml methanol and water
The inventory of 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate corresponding to mixed solvent be 0.2g；3-
Methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate is 1:6 with the mol ratio of potassium hydroxide；
(3) product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid in step (2) is dispersed in two
In glycol, add copper powder and pyridine, then system is heated to 175 DEG C, is kept stirring for 10h；System is cooled to room temperature, adds
Frozen water, and be acidified with the hydrochloric acid of 4N, the reactant liquor after being acidified with petroleum ether extraction three times, wash the extract of merging with water one
Secondary, then extract anhydrous sodium sulfate is dried, is spin-dried for, gained solid is product: 3-methyl-6,7-dihydrobenzo furan
Mutter-4-(5H)-one；
Wherein, 3-methyl-4-oxygen-4 that every milliliter of diethylene glycol is corresponding, feeding intake of 5,6,7-tetrahydrochysene benzfuran-2-formic acid
Amount is 0.1g；3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid, copper powder, the mol ratio of pyridine are 1:1:2；
(4) under nitrogen protection, sodium hydride is dispersed in toluene solution, system is cooled to 0 DEG C, then to body
System adds 3-methyl-6, the toluene solution of 7-Dihydrobenzofuranes-4 (5H)-one, keeps system to stir 30min at 0 DEG C；So
In backward system, (slow with 30min) adds the toluene solution of Ethyl formate, and system continues to stir at 0 DEG C 1h；Then will
System is warmed to room temperature, and continues stirring 8h；React complete, in system, be slowly added to saturated aqueous ammonium chloride solution cancellation reaction,
Being extracted with ethyl acetate by reactant liquor 3 times, organic facies anhydrous sodium sulfate is dried, and concentrates, i.e. can get product: 3-methyl-4-
Oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde；
Wherein, 3-methyl-6,7-Dihydrobenzofuranes-4 (5H)-one, sodium hydride, the mol ratio of Ethyl formate are 1:5:3；
3-methyl-6,7-Dihydrobenzofuranes-4 (5H) the-one inventory that every milliliter of toluene is corresponding is 0.04g；
(5) by dispersed for the product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde of step (4) gained
In toluene solution, addition 2,3-bis-chloro-5,6-dicyan 1,4-benzoquinone in system, it is heated to 130 DEG C and keeps 6h；System is cooled down
To room temperature, filtering, concentrated filtrate, the filtrate after concentrating separates with silica gel chromatographic column and i.e. can get product: 4-hydroxy-3-methyl
Benzofuran-5-formaldehyde；
Wherein, 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde, 2,3-bis-chloro-5,6-dicyan 1,4-benzoquinone
Mol ratio be 1:1.2；Feeding intake of the 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde that every milliliter of toluene is corresponding
Amount is 0.1g；
(6) by the product 4-hydroxy-3-methyl benzofuran-5-formaldehyde of step (5) gained,Weak base is uniform
It is scattered in reaction dissolvent a, it is thus achieved that raw mixture；
Wherein, 4-hydroxy-3-methyl benzofuran-5-formaldehyde,The mol ratio of weak base is 1:1:0.5；Often
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that milliliter reaction dissolvent a is corresponding is 0.1g；
DescribedIn, R be methyl, ethyl, ethyoxyl, propyl group, isopropyl, 4-pyridine radicals, 3,4-dimethoxy
Phenyl or phenyl；
Described weak base is piperidines or nafoxidine；
Described reaction dissolvent a is ethanol or methanol；
(7) raw mixture step (6) prepared, at 70 DEG C, reacts 1～3 hour, and filtering reacting liquid is precipitated
Thing, by precipitates washed with EtOH, the precipitate after being washed is product, i.e. furocoumarin analog derivative.
In the present invention, described weak base uses piperidines.
In the present invention, described reaction dissolvent a uses ethanol.
Compared with prior art, the invention has the beneficial effects as follows:
1, the furocoumarin analog derivative that the present invention provides is the isopsoralen analog that a class has new skeleton, tool
Having potential pharmaceutically active, the preparation of this compounds can be that the pharmaceutically active research of furocoumarin class provides support.
2, the preparation method of the furocoumarin analog derivative that the present invention provides, step of condensation is simple, and loss rate is low.
Significant for industrialized production.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of furocoumarin analog derivative.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings:
The following examples can make the professional and technical personnel of this specialty that the present invention is more fully understood, but not with any side
Formula limits the present invention.
Embodiment 1
By 1, hydroresorcinol and potassium hydroxide are dispersed in water uniformly, after stirring at normal temperature 5min, add chloracetyl second
The methanol solution of acetoacetic ester, is then stirred at room temperature system 5 days, is then acidified by the hydrochloric acid of system 4N, filter acidifying
After reactant liquor, the solid obtained is product: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formates.Should
In step 1, hydroresorcinol is 1:1:1 with the mol ratio of potassium hydroxide and chloroacetyl acetacetic ester, every milliliter of water corresponding 1,
The inventory of hydroresorcinol is 0.1g, and the inventory of the chloroacetyl acetacetic ester that every ml methanol is corresponding is 0.2g.This step
Productivity is 65%.The structure of products therefrom is:
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
Outward appearance: white solid
Proton nmr spectra: (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
The mixing with first alcohol and water by 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate and potassium hydroxide
Bonding solvent dissolves, and system is stirred at room temperature after dissolving reaction 5h.Then the hydrochloric acid of reactant liquor 6N is adjusted pH to 1, filter
Reactant liquor, the solid filtering gained is product: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid.This step
Mixed solvent used by is that methanol is formulated with 2.5:1 with water.3-methyl-4-oxygen-4 that every milliliter of mixed solvent is corresponding,
The inventory of 5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate is 0.2g.3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene in this step
Coumarilic acid ethyl ester is 1:6 with the mol ratio of potassium hydroxide.The productivity of this step is 90%.The structure of products therefrom is:
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
Outward appearance: white solid
Proton nmr spectra: (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 scattered in diethylene glycol uniformly, add copper
Powder and pyridine, be then heated to system 175 DEG C, be kept stirring for 10h.System is cooled to room temperature, adds frozen water, and with 4N's
Hydrochloric acid is acidified, the reactant liquor after being acidified with petroleum ether extraction three times, washes with water once by the extract of merging, then will extraction
Liquid anhydrous sodium sulfate is dried, and is spin-dried for.The solid of gained is product: 3-methyl-6,7-Dihydrobenzofuranes-4-(5H)-one.
In this step, the inventory of the 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid that every milliliter of diethylene glycol is corresponding is
0.1g.In this step, 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid is 1 with the mol ratio of copper powder and pyridine:
1:2.The productivity of this step is 85%.The structure of products therefrom is:
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
Outward appearance: yellow solid
Proton nmr spectra: (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
(1) under nitrogen protection, sodium hydride is scattered in toluene solution uniformly, system is cooled to 0 DEG C, then to
System adds 3-methyl-6, the toluene solution of 7-Dihydrobenzofuranes-4 (5H)-one, keeps system to stir 30min at 0 DEG C.
Then in system, add the toluene solution of Ethyl formate with 30min, system continues to stir at 0 DEG C 1h.Then by system
It is warmed to room temperature, continues stirring 8h.React complete, in system, be slowly added to saturated aqueous ammonium chloride solution cancellation reaction, will be anti-
Answering liquid to be extracted with ethyl acetate 3 times, organic facies anhydrous sodium sulfate is dried, and concentrates, i.e. can obtain the product of this step: 3-methyl-
4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde.3-methyl-6,7-Dihydrobenzofuranes-4 (5H)-one and hydrogen in this step
The mol ratio changing sodium and Ethyl formate is 1:5:3,3-methyl-6 that every milliliter of toluene is corresponding, 7-Dihydrobenzofuranes-4 (5H)-
Ketone inventory is 0.04g.
(2) the product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde of gained is dispersed in toluene
In solution, addition 2,3-bis-chloro-5,6-dicyan 1,4-benzoquinone in system, it is heated to 130 DEG C and keeps 6h.System is cooled to room
Temperature, filters, concentrated filtrate, is separated by thick product silica gel chromatographic column and i.e. can obtain the product of this step: 4-hydroxy-3-methyl benzo
Furan-5-formaldehyde.3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde and the chloro-5,6-of 2,3-bis-bis-in this step
The mol ratio of cyanogen 1,4-benzoquinone is 1:1.2,3-methyl-4-oxygen-4 that every milliliter of toluene is corresponding, 5,6,7-tetrahydrochysene benzfuran-5-first
The inventory of aldehyde is 0.1g.The productivity of two steps is 70%.The structure of products therefrom is:
Molecular formula: C10H8O3
Chinese name: 4-hydroxy-3-methyl benzofuran-5-formaldehyde
English name: 4-hydroxy-3-methylbenzofuran-5-carbaldehyde
Molecular weight: 176.05
Outward appearance: yellow solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 11.97 (s, 1H), 9.87 (s, 1H), 7.37 (d, J=
8.6Hz, 1H), 7.31 (q, J=1.4Hz, 1H), 7.04 (d, J=8.6Hz, 1H), 2.41 (d, J=1.4Hz, 3H) ppm.
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 195.98,161.03,159.49,141.21,129.73,
117.71,117.00,115.28,104.85,9.46ppm。
Embodiment 5
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, ethyl acetoacetate and piperidines are dispersed in ethanol, make
Obtaining 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of ethyl acetoacetate and piperidines is 1:1:0.5, every milliliter of reaction
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that solvent is corresponding is 0.1g, it is thus achieved that raw mixture.Raw material is mixed
Compound, at 70 DEG C, reacts 3 hours, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furocoumarin
Analog derivative is: 3-acetyl group-9-methyl-2H-furan [2,3-h] chromen-2-one, yield 90%, the knot of this derivant
Structure is:
Molecular formula: C14H10O4
Chinese name: 3-acetyl group-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-acetyl-9-methyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 242.06
Outward appearance: bright yellow solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.55 (s, 1H), 7.47 7.36 (m, 2H), 7.33 (d,
J=8.6Hz, 1H), 2.67 (s, 3H), 2.46 (d, J=1.3Hz, 3H) ppm.
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 194.55,158.46,158.24,150.55,147.86,
141.68,124.99,120.29,116.14,115.13,111.87,108.82,29.59,8.47ppm。
Embodiment 6
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, diethyl malonate and nafoxidine are dispersed in ethanol
In so that 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of diethyl malonate and nafoxidine is 1:1:0.5,
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that every milliliter of reaction dissolvent is corresponding is 0.1g, it is thus achieved that raw material mixes
Thing.By raw mixture, at 70 DEG C, react 3 hours, cooled and filtered, by washing with alcohol, obtain filter cake and be product.Institute
Obtaining furocoumarin analog derivative is: 9-methyl-2-oxygen-2H-furan [2,3-h] .alpha.-5:6-benzopyran-3-Ethyl formate, yield
92%, the structure of this derivant is:
Molecular formula: C15H12O5
Chinese name: 9-methyl-2-oxygen-2H-furan [2,3-h] .alpha.-5:6-benzopyran-3-Ethyl formate
English name: ethyl 9-methyl-2-oxo-2H-furo [2,3-h] chromene-3-carboxylate
Molecular weight: 272.07
Outward appearance: Off-white solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.63 (s, 1H), 7.51 7.33 (m, 3H), 4.42 (q,
J=7.1Hz, 2H), 2.51 (d, J=1.4Hz, 3H), 1.43 (t, J=7.1Hz, 3H) ppm.
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 163.37,159.37,156.53,151.35,149.89,
142.64,125.27,117.18,116.16,114.93,112.43,109.58,61.76,14.27,9.51ppm。
Embodiment 7
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, Propionylacetic acid ethyl ester and piperidines are dispersed in ethanol, make
Obtaining 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of Propionylacetic acid ethyl ester and piperidines is 1:1:0.5, every milliliter of reaction
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that solvent is corresponding is 0.1g, it is thus achieved that raw mixture.Raw material is mixed
Compound, at 70 DEG C, reacts 3 hours, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furocoumarin
Analog derivative is: 9-methyl-3-propiono-2H-furan [2,3-h] chromen-2-one, yield 92%, the knot of this derivant
Structure is:
Molecular formula: C15H12O4
Chinese name: 9-methyl-3-propiono-2H-furan [2,3-h] chromen-2-one
English name: 9-methyl-3-propionyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 256.07
Outward appearance: faint yellow solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.64 (s, 1H), 7.52 7.45 (m, 2H), 7.41 (d,
J=8.6Hz, 1H), 3.19 (q, J=7.2Hz, 2H), 2.54 (d, J=1.4Hz, 3H), 1.20 (t, J=7.2Hz, 3H) ppm.
Carbon-13 nmr spectra (101MHz, Chloroform-d) δ 198.63,159.40,159.14,151.45,148.82,
142.66,125.94,121.30,117.15,116.15,112.97,109.79,36.00,9.53,8.00ppm。
Embodiment 8
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, ethyl isobutyryl and piperidines are dispersed in methanol,
Making 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of ethyl isobutyryl and piperidines is 1:1:0.5, every milliliter
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that reaction dissolvent is corresponding is 0.1g, it is thus achieved that raw mixture.By former
Material mixture, at 70 DEG C, reacts 1 hour, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furan is fragrant
Legumin analog derivative is: 3-isobutyryl-9-methyl-2H-furan [2,3-h] chromen-2-one, yield 84%, and this derives
The structure of thing is:
Molecular formula: C16H14O4
Chinese name: 3-isobutyryl-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-isobutyryl-9-methyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 270.09
Outward appearance: faint yellow solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.59 (s, 1H), 7.52 7.44 (m, 2H), 7.40 (d,
J=8.6Hz, 1H), 3.90 (hept, J=6.8Hz, 1H), 2.54 (d, J=1.4Hz, 3H), 1.21 (d, J=6.8Hz, 6H)
ppm。
Carbon-13 nmr spectra: δ 202.41,159.33,158.82,151.40,149.21,142.66,125.77,
121.37,117.14,116.13,113.06,109.73,38.42,18.33,9.50ppm。
Embodiment 9
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, ethyl butyrylacetate and piperidines are dispersed in ethanol, make
Obtaining 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of ethyl butyrylacetate and piperidines is 1:1:0.5, every milliliter of reaction
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that solvent is corresponding is 0.1g, it is thus achieved that raw mixture.Raw material is mixed
Compound, at 70 DEG C, reacts 2 hours, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furocoumarin
Analog derivative is: 3-bytyry-9-methyl-2H-furan [2,3-h] chromen-2-one, yield 86%, the knot of this derivant
Structure is:
Molecular formula: C16H14O4
Chinese name: 3-bytyry-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-butyryl-9-methyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 270.09
Outward appearance: faint yellow solid
Proton nmr spectra: δ 8.62 (s, 1H), 7.52 7.44 (m, 2H), 7.41 (d, J=8.5Hz, 1H), 3.13 (t, J
=7.2Hz, 2H), 2.54 (d, J=1.4Hz, 3H), 1.74 (h, J=7.4Hz, 2H), 1.01 (t, J=7.4Hz, 3H) ppm.
Carbon-13 nmr spectra: 198.14,159.39,159.11,151.46,148.80,142.66,125.92,121.53,
117.16,116.16,112.99,109.78,44.40,17.44,13.81,9.52ppm。
Embodiment 10
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, ethyl benzoylacetate and piperidines are dispersed in ethanol,
Making 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of ethyl benzoylacetate and piperidines is 1:1:0.5, every milliliter
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that reaction dissolvent is corresponding is 0.1g, it is thus achieved that raw mixture.By former
Material mixture, at 70 DEG C, reacts 3 hours, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furan is fragrant
Legumin analog derivative is: 3-benzoyl-9-methyl-2H-furan [2,3-h] chromen-2-one, yield 85%, and this derives
The structure of thing is:
Molecular formula: C19H12O4
Chinese name: 3-benzoyl-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-benzoyl-9-methyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 304.07
Outward appearance: faint yellow solid
Proton nmr spectra: (400MHz, DMSO-d6)δ8.55(s,1H),8.03–7.87(m,3H),7.81–7.65(m,
2H), 7.67 7.50 (m, 3H), 2.45 (d, J=1.3Hz, 3H) ppm.
Carbon-13 nmr spectra: (101MHz, DMSO-d6)δ191.78,158.10,157.80,149.96,147.11,
143.50,136.32,133.63,129.46,128.62,125.84,123.31,116.28,114.93,112.91,109.24,
9.15ppm。
Embodiment 11
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, 3,4-dimethoxybenzoyl ethyl acetate and piperidines uniformly divide
Dissipate in ethanol so that 4-hydroxy-3-methyl benzofuran-5-formaldehyde, 3,4-dimethoxybenzoyl ethyl acetate and piperidines
Mol ratio be 1:1:0.5, the inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that every milliliter of reaction dissolvent is corresponding is
0.1g, it is thus achieved that raw mixture.By raw mixture, at 70 DEG C, react 3 hours, cooled and filtered, by washing with alcohol, obtain
It is product to filter cake.Gained furocoumarin analog derivative is: 3-(3,4-Dimethoxybenzoyl)-9-methyl-2H-furan
Mutter [2,3-h] chromen-2-one, yield 85%, the structure of this derivant is:
Molecular formula: C19H12O4
Chinese name: 3-(3,4-Dimethoxybenzoyl)-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-(3,4-dimethoxybenzoyl)-9-methyl-2H-furo [2,3-h] chromen-2-
one
Molecular weight: 364.09
Outward appearance: white solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.15 (s, 1H), 7.57 (d, J=2.0Hz, 1H),
7.51 7.38 (m, 4H), 6.89 (d, J=8.4Hz, 1H), 3.96 (d, J=1.6Hz, 6H), 2.58 2.53 (m, 3H) ppm.
Carbon-13 nmr spectra: δ 190.43,158.86,158.49,153.98,150.68,149.22,146.26,
142.66,129.40,125.41,124.83,124.32,117.43,116.10,112.78,111.14,109.90,109.57,
56.15,56.09,9.58ppm。
Embodiment 12
By 4-hydroxy-3-methyl benzofuran-5-formaldehyde, different nicotinoyl ethyl acetate and piperidines are dispersed in ethanol,
Making 4-hydroxy-3-methyl benzofuran-5-formaldehyde, the mol ratio of different nicotinoyl ethyl acetate and piperidines is 1:1:0.5, every milliliter
The inventory of the 4-hydroxy-3-methyl benzofuran-5-formaldehyde that reaction dissolvent is corresponding is 0.1g, it is thus achieved that raw mixture.By former
Material mixture, at 70 DEG C, reacts 3 hours, cooled and filtered, by washing with alcohol, obtains filter cake and be product.Gained furan is fragrant
Legumin analog derivative is: 3-different nicotinoyl-9-methyl-2H-furan [2,3-h] chromen-2-one, yield 85%, this derivant
Structure be:
Molecular formula: C18H11NO4
Chinese name: 3-different nicotinoyl-9-methyl-2H-furan [2,3-h] chromen-2-one
English name: 3-isonicotinoyl-9-methyl-2H-furo [2,3-h] chromen-2-one
Molecular weight: 305.07
Outward appearance: yellow solid
Proton nmr spectra: (400MHz, Chloroform-d) δ 8.85 8.79 (m, 2H), 8.44 (s, 1H), 7.69
7.62 (m, 2H), 7.55 7.43 (m, 3H), 2.55 (d, J=1.4Hz, 3H) ppm.
Carbon-13 nmr spectra: (101MHz, Chloroform-d) δ 191.35,159.61,158.28,151.54,
150.24,149.62,143.75,142.97,125.58,122.09,121.79,117.55,116.20,112.74,110.11,
9.51ppm。
It is only the specific embodiment of the present invention finally it should be noted that listed above.It is clear that the invention is not restricted to
Above example, it is also possible to have many variations.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation gone out or associate, are all considered as protection scope of the present invention.
Claims (5)
1. a furocoumarin analog derivative, it is characterised in that shown in the following formula I of structural formula:
Wherein, R be methyl, ethyl, ethyoxyl, propyl group, isopropyl, phenyl, 3,4-Dimethoxyphenyl or 4-pyridine radicals.
A kind of furocoumarin analog derivative the most according to claim 1, it is characterised in that specifically include following chemical combination
Thing: 3-acetyl group-9-methyl-2H-furan [2,3-h] chromen-2-one, 9-methyl-2-oxygen-2H-furan [2,3-h] benzo
Pyrans-3-Ethyl formate, 9-methyl-3-propiono-2H-furan [2,3-h] chromen-2-one, 3-isobutyryl-9-first
Base-2H-furan [2,3-h] chromen-2-one, 3-bytyry-9-methyl-2H-furan [2,3-h] chromen-2-one, 3-
Benzoyl-9-methyl-2H-furan [2,3-h] chromen-2-one, 3-(3,4-Dimethoxybenzoyl)-9-methyl-
2H-furan [2,3-h] chromen-2-one, 3-different nicotinoyl-9-methyl-2H-furan [2,3-h] chromen-2-one.
3. the method for furocoumarin analog derivative described in preparation claim 1, it is characterised in that specifically include following step:
(1) by 1, hydroresorcinol, potassium hydroxide are dispersed in water, after stirring at normal temperature 5min, add chloracetyl acetic acid second
The methanol solution of ester, is then stirred at room temperature system 5 days；Then the hydrochloric acid of system 4N is acidified, after filtering acidifying
Reactant liquor, the solid obtained is product: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formates；
Wherein, 1, hydroresorcinol, potassium hydroxide, the mol ratio of chloroacetyl acetacetic ester are 1:1:1；Every milliliter of water corresponding 1,
The inventory of hydroresorcinol is 0.1g；The inventory of the chloroacetyl acetacetic ester that every ml methanol is corresponding is 0.2g；
(2) by product 3-methyl-4-oxygen-4 of step (1), 5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate and potassium hydroxide,
Dissolve with the mixed solvent of first alcohol and water, after dissolving, system is stirred at room temperature reaction 5h；Then by the salt of reactant liquor 6N
PH to 1, filtering reacting liquid, the solid i.e. product of filtration gained: 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-are adjusted in acid
Formic acid；
Wherein, in the mixed solvent of described first alcohol and water, methanol is 2.5:1 with the volume ratio of water；Every ml methanol and water mixed
The inventory of the 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate that bonding solvent is corresponding is 0.2g；3-methyl-
4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-Ethyl formate is 1:6 with the mol ratio of potassium hydroxide；
(3) product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid in step (2) is dispersed in diethylene glycol
In, add copper powder and pyridine, then system is heated to 175 DEG C, is kept stirring for 10h；System is cooled to room temperature, adds ice
Water, and be acidified with the hydrochloric acid of 4N, the reactant liquor after being acidified with petroleum ether extraction three times, wash the extract of merging with water one
Secondary, then extract anhydrous sodium sulfate is dried, is spin-dried for, gained solid is product: 3-methyl-6,7-dihydrobenzo furan
Mutter-4-(5H)-one；
Wherein, 3-methyl-4-oxygen-4 that every milliliter of diethylene glycol is corresponding, the inventory of 5,6,7-tetrahydrochysene benzfuran-2-formic acid is
0.1g；3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-2-formic acid, copper powder, the mol ratio of pyridine are 1:1:2；
(4) under nitrogen protection, sodium hydride is dispersed in toluene solution, system is cooled to 0 DEG C, then in system
Add 3-methyl-6, the toluene solution of 7-Dihydrobenzofuranes-4 (5H)-one, keep system to stir 30min at 0 DEG C；Then to
System adds the toluene solution of Ethyl formate, system continues to stir at 0 DEG C 1h；Then system is warmed to room temperature, continues
Stirring 8h；React complete, in system, be slowly added to saturated aqueous ammonium chloride solution cancellation reaction, by reactant liquor ethyl acetate
Extracting 3 times, organic facies anhydrous sodium sulfate is dried, and concentrates, i.e. can get product: 3-methyl-4-oxygen-4,5,6,7-tetrahydro benzos
Furan-5-formaldehyde；
Wherein, 3-methyl-6,7-Dihydrobenzofuranes-4 (5H)-one, sodium hydride, the mol ratio of Ethyl formate are 1:5:3；Every milli
3-methyl-6,7-Dihydrobenzofuranes-4 (5H) the-one inventory rising toluene corresponding is 0.04g；
(5) the product 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde of step (4) gained is dispersed in first
In benzole soln, addition 2,3-bis-chloro-5,6-dicyan 1,4-benzoquinone in system, it is heated to 130 DEG C and keeps 6h；System is cooled to room
Temperature, filters, concentrated filtrate, and the filtrate after concentrating separates with silica gel chromatographic column and i.e. can get product: 4-hydroxy-3-methyl benzo
Furan-5-formaldehyde；
Wherein, 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde, 2,3-bis-chloro-5, rubbing of 6-dicyan 1,4-benzoquinone
That ratio is 1:1.2；The inventory of the 3-methyl-4-oxygen-4,5,6,7-tetrahydrochysene benzfuran-5-formaldehyde that every milliliter of toluene is corresponding is
0.1g；
(6) by the product 4-hydroxy-3-methyl benzofuran-5-formaldehyde of step (5) gained,Weak base is dispersed
In reaction dissolvent a, it is thus achieved that raw mixture；
Wherein, 4-hydroxy-3-methyl benzofuran-5-formaldehyde,The mol ratio of weak base is 1:1:0.5；Every milliliter
The inventory of 4-hydroxy-3-methyl benzofuran-5-formaldehyde corresponding for reaction dissolvent a is 0.1g；
DescribedIn, R be methyl, ethyl, ethyoxyl, propyl group, isopropyl, 4-pyridine radicals, 3,4-Dimethoxyphenyl
Or phenyl；
Described weak base is piperidines or nafoxidine；
Described reaction dissolvent a is ethanol or methanol；
(7) raw mixture step (6) prepared, at 70 DEG C, reacts 1～3 hour, and filtering reacting liquid is precipitated thing,
By precipitates washed with EtOH, the precipitate after being washed is product, i.e. furocoumarin analog derivative.
Preparation method the most according to claim 3, it is characterised in that described weak base uses piperidines.
Preparation method the most according to claim 3, it is characterised in that described reaction dissolvent a uses ethanol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851688A (en) * | 2021-01-21 | 2021-05-28 | 宁波大学 | Chromene coumarin derivative containing 4-hydroxy-3-methoxyphenyl functional group and preparation method and application thereof |
| CN112920194A (en) * | 2021-01-21 | 2021-06-08 | 宁波大学 | Chromene coumarin derivative containing fluorine functional group and preparation method and application thereof |
| CN112979732A (en) * | 2021-04-01 | 2021-06-18 | 清华大学 | Furocoumarin compound and application thereof in mycobacterium tuberculosis detection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546493A (en) * | 2003-12-08 | 2004-11-17 | 广州白云山制药股份有限公司广州白云 | Synthesis method for preparation of psoralen |
| CN101307056A (en) * | 2007-05-16 | 2008-11-19 | 中国科学院上海药物研究所 | Linear furocoumarin derivates, preparation method and application thereof, pharmaceutical compositions containing the derivates |
| CN101497593A (en) * | 2009-03-18 | 2009-08-05 | 华南理工大学 | 5-hydroxy coumarin and pyranoid type coumarin compounds, synthesizing method and use |
| US20090312406A1 (en) * | 2008-06-12 | 2009-12-17 | Hsing-Pang Hsieh | Coumarin compounds and their use for treating viral infection |
| WO2009152210A2 (en) * | 2008-06-12 | 2009-12-17 | National Health Research Institutes | Coumarin compounds and their use for treating cancer |
-
2016
- 2016-08-02 CN CN201610629772.0A patent/CN106279083B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546493A (en) * | 2003-12-08 | 2004-11-17 | 广州白云山制药股份有限公司广州白云 | Synthesis method for preparation of psoralen |
| CN101307056A (en) * | 2007-05-16 | 2008-11-19 | 中国科学院上海药物研究所 | Linear furocoumarin derivates, preparation method and application thereof, pharmaceutical compositions containing the derivates |
| US20090312406A1 (en) * | 2008-06-12 | 2009-12-17 | Hsing-Pang Hsieh | Coumarin compounds and their use for treating viral infection |
| WO2009152210A2 (en) * | 2008-06-12 | 2009-12-17 | National Health Research Institutes | Coumarin compounds and their use for treating cancer |
| CN101497593A (en) * | 2009-03-18 | 2009-08-05 | 华南理工大学 | 5-hydroxy coumarin and pyranoid type coumarin compounds, synthesizing method and use |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851688A (en) * | 2021-01-21 | 2021-05-28 | 宁波大学 | Chromene coumarin derivative containing 4-hydroxy-3-methoxyphenyl functional group and preparation method and application thereof |
| CN112920194A (en) * | 2021-01-21 | 2021-06-08 | 宁波大学 | Chromene coumarin derivative containing fluorine functional group and preparation method and application thereof |
| CN112920194B (en) * | 2021-01-21 | 2022-04-26 | 宁波大学 | Chromene coumarin derivative containing fluorine functional group and preparation method and application thereof |
| CN112851688B (en) * | 2021-01-21 | 2022-04-26 | 宁波大学 | Chromene coumarin derivative containing 4-hydroxy-3-methoxyphenyl functional group and preparation method and application thereof |
| CN112979732A (en) * | 2021-04-01 | 2021-06-18 | 清华大学 | Furocoumarin compound and application thereof in mycobacterium tuberculosis detection |
| CN112979732B (en) * | 2021-04-01 | 2022-09-09 | 清华大学 | Furocoumarin compound and application thereof in mycobacterium tuberculosis detection |
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