CN105541767A - Method for preparing isosinensetin compound through intramolecular cyclization reaction - Google Patents
Method for preparing isosinensetin compound through intramolecular cyclization reaction Download PDFInfo
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- -1 isosinensetin compound Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 15
- HIUKQMVQSJHRNC-UHFFFAOYSA-N Isosinensetin Natural products C1=C(OC)C(OC)=CC=C1C1=CC(=O)C2=C(O)C=C(OC)C(OC)=C2O1 HIUKQMVQSJHRNC-UHFFFAOYSA-N 0.000 title abstract 3
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 229930015036 aurone Natural products 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical group NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 239000004471 Glycine Chemical group 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 239000002585 base Substances 0.000 description 27
- 238000004440 column chromatography Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical group OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001530 aurones Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 1
- 102000003915 DNA Topoisomerases Human genes 0.000 description 1
- 108090000323 DNA Topoisomerases Proteins 0.000 description 1
- 238000006617 Intramolecular Heck reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930184986 isoaurone Natural products 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- XKFZYVWWXHCHIX-UHFFFAOYSA-N riodoxol Chemical group OC1=C(I)C=C(I)C(O)=C1I XKFZYVWWXHCHIX-UHFFFAOYSA-N 0.000 description 1
- 229950009861 riodoxol Drugs 0.000 description 1
- 206010040872 skin infection Diseases 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 208000004371 toothache Diseases 0.000 description 1
- 210000001635 urinary tract Anatomy 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
Classifications
-
- 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
- C07D307/83—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a method for preparing an isosinensetin compound through an intramolecular cyclization reaction. E-2-(2-bromo aryl)-3-aryl crylic acid compounds are adopted as raw materials, and under the action of a catalyst and ligand, the raw materials react for a period of time in a solvent in the presence of alkali under the condition of a microwave reaction; after the reaction is finished, reaction liquid is poured into water and acidized till the pH ranges from 3 to 4, extracting, drying, solvent spin-drying and purifying are carried out, and the isosinensetin compound is obtained. The method has the advantages that the raw materials are simple and easy to obtain, the reaction time is short, post-treatment is simple, and the yield is high.
Description
Technical field
The present invention relates to organic synthesis field, particularly a kind of method preparing different Aurone compound through Intra-molecular condensation.
Background technology
Different aurones (Isoaurones), chemistry 3-benzene methene base cumarone-2 (3H)-one by name, it is a kind of rare flavonoid class natural product, there is multiple biological activity, as (J.Pharmacol.Sci.2014 such as anti-tobacco virus, anticancer, anti-oxidant, topoisomerase I inhibit activities, 125,193), in the treatment of the diseases such as dysentery, toothache, fever, urinary tract and skin infections, also there is potential application prospect (TetrahedronLett.2000,41,1579).Different aurones, in the content of occurring in nature very rare (Bioorg. & Med.Chem.Lett.2005,15,4313), limits and carries out further Study and appliance exploitation to it.The synthetic method of the different Aurone compound of current report mainly comprises following two classes: one is o-hydroxy phenylacetic acid or benzofuran-2-ones and the condensation reaction (Bioorg.Med.Chem.Lett.2005 of substituted benzaldehyde under Lewis acid or highly basic effect, 15,2065; Tetrahedron2006,62,9855); Two is the esterification of adjacent riodoxol under palladium chtalyst and intramolecular Heck reaction (Bioorg.Med.Chem.Lett.2005,15,4313).But these two kinds of methods all exist that the reaction times is longer, yield is lower and use the shortcomings such as precious metal catalyst.
Summary of the invention
The object of the invention is to overcome the shortcoming existed in prior art, a kind of method preparing different Aurone compound through Intra-molecular condensation that reaction times is short, yield is higher is provided.
Object of the present invention is achieved through the following technical solutions:
A kind of method preparing different Aurone compound through Intra-molecular condensation, for raw material with E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds (structural formula 1), under catalyzer and part effect, under the existence and microwave reaction condition of alkali, in solvent, react for some time; After having reacted, reaction solution is poured into water, is acidified to pH=3 ~ 4, extraction, dry, be spin-dried for solvent, purifying, obtain different Aurone compound (structural formula 2).
The chemical equation that the present invention relates to is as follows:
In formula 1, formula 2, the substituent R of A ring
1can be, but not limited to is single or multiple H, OH, OCH
3; The substituent R of B ring
2can be, but not limited to is single or multiple F, Cl, Br, OCH
3, OH, CF
3, NO
2.
Described catalyzer can be, but not limited to be neutralized verdigris (Cu (OAc)
2), cupric oxide (CuO), ventilation breather (Cu
2(OH)
2cO
3), copper hydroxide (Cu (OH)
2), copper sulfate (CuSO
4), cupric sulfate pentahydrate (CuSO
45H
2o), Red copper oxide (Cu
2o), cuprous iodide (CuI), cuprous chloride (CuCl), cuprous bromide (CuBr), thiophene-2-carboxylic acid cuprous (CuTc), preferred catalyst is Red copper oxide.
Described part can be, but not limited to be DMAP (DMAP), Tetramethyl Ethylene Diamine (TMEDA), oxine (Oxine), 1, the adjacent phenanthroline (1 of 10-, 10-phen), glycine (Glycine), preferred part is the adjacent phenanthroline of 1,10-.
Described alkali can be, but not limited to be triethylene diamine (DABCO), Tripotassium phosphate (K
3pO
4), sodium carbonate (Na
2cO
3), sodium bicarbonate (NaHCO
3), sodium acetate (NaOAc), sodium ethylate (C
2h
5ona), pyridine (Pyridine), triethylamine (Et
3n) etc., preferred bases is triethylamine.
Described solvent can be, but not limited to be dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), polyoxyethylene glycol-200 (PEG-400), PEG-4000 (PEG-400), preferred solvent is PEG-4000.
The ratio of the amount of substance of described E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds, catalyzer, part, alkali is 1:(0.05 ~ 0.3): (0.05 ~ 0.3): (1 ~ 3), the ratio of the amount of substance of preferred E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds, catalyzer, part, alkali is 1:0.2:0.2:2.
Described temperature of reaction is 130 ~ 150 DEG C, and preferable reaction temperature is 140 DEG C.
The described reaction times is 2 ~ 30 minutes, and the preferred reaction time is 2 ~ 20 minutes.
The present invention compared with prior art tool has the following advantages and effect:
(1) raw material of the present invention is easy to get, and the aromatic formaldehyde of the fragrant acetic acid that raw material E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds replaces by 2-bromine and replacement prepares through Perkin condensation reaction.
(2) quick and high efficient reaction of the present invention, adopts the mode of microwave heating, can in 2-30 minute complete reaction, and aftertreatment is easy, and reaction solution is through acidifying, and extraction, dry, column chromatography gets final product purifying.
(3) yield of the present invention is higher, can reach 89%.
Embodiment
Below in conjunction with embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
The synthesis of embodiment 1:E-3-(3,4-dimethoxy benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(3 successively, 4-Dimethoxyphenyl) vinylformic acid (3mmol, 1.1370g), Red copper oxide (0.6mmol, 0.0859g), 1,10-phen (0.6mmol, 0.1189g), Et
3n (6mmol, 0.6072g), 20mLPEG-400, stir, and under microwave condition, controls temperature of reaction 140 DEG C, react 20 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining faint yellow solid 0.7965g, is E-3-(3,4-dimethoxy benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one, yield 89%.
1HNMR(400MHz,DMSO-d
6)δ10.35(s,1H),7.74(d,J＝8.4Hz,1H),7.55(s,1H),7.41(dd,J＝1.6,8.0Hz,1H),7.36(d,J＝1.6Hz,1H),7.13(d,J＝8.4Hz,1H),6.67(d,J＝2.0Hz,1H),6.60(dd,J＝2.0,8.4Hz,1H),3.85(s,3H),3.81(s,3H)；
13CNMR(100MHz,DMSO-d
6)δ169.0,159.9,154.9,150.5,148.4,136.6,126.3,123.4,123.3,118.7,112.7,112.6,111.5,111.0,98.4,55.5,55.4。
The synthesis of embodiment 2:E-3-(3,5-dimethoxy benzene methene base) cumarone-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(2-bromophenyl)-3-(3 successively, 5-Dimethoxyphenyl) vinylformic acid (3mmol, 1.0896g), Red copper oxide (0.3mmol, 0.0430g), 1,10-phen (0.3mmol, 0.0595g), Et
3n (3mmol, 0.3036g), 20mLPEG-400, stir, and under microwave condition, controls temperature of reaction 130 DEG C, react 30 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.3811g, is E-3-(3,5-dimethoxy benzene methene base) cumarone-2 (3H)-one, yield 45%.
1HNMR(400MHz,DMSO-d
6)δ7.81(s,1H),7.78(d,J＝7.6Hz,1H),7.45(t,J＝7.6Hz,1H),7.31(d,J＝8.0Hz,1H),7.19(t,J＝7.6Hz,1H),6.95(d,J＝2.0Hz,2H),6.68(t,J＝2.0Hz,1H),3.80(s,6H)；
13CNMR(100MHz,DMSO-d
6)δ168.0,160.6,153.8,140.8,135.2,131.3,124.0,122.8,121.7,121.2,111.2,107.2,102.8,55.4。
The synthesis of embodiment 3:E-3-(3,5-dimethoxy benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(3 successively, 5-Dimethoxyphenyl) vinylformic acid (3mmol, 1.1370g), copper sulfate (0.9mmol, 0.1437g), DMAP (0.9mmol, 0.1100g), DABCO (9mmol, 1.0096g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 150 DEG C, react 2 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.5996g, is E-3-(3,5-dimethoxy benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one, yield 67%.
1HNMR(400MHz,DMSO-d
6)δ10.44(s,1H),7.62(d,J＝8.4Hz,1H),7.53(s,1H),6.90(d,J＝2.0Hz,2H),6.67(d,J＝2.0Hz,1H),6.63(t,J＝2.0Hz,1H),6.59(dd,J＝2.0,8.4Hz,1H),3.79(s,6H)；
13CNMR(100MHz,DMSO-d
6)δ168.6,160.4,160.4,155.3,135.7,135.6,123.9,121.4,112.1,111.2,106.8,102.1,98.4,55.2。
The synthesis of embodiment 4:E-6-hydroxyl-3-(4-hydroxyl-3,5-dimethoxy benzene methene base) cumarone-2-(3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-hydroxyl-3 successively, 5-Dimethoxyphenyl) vinylformic acid (3mmol, 1.1856g), cupric sulfate pentahydrate (0.6mmol, 0.1498g), TMEDA (0.6mmol, 0.0698g), Tripotassium phosphate (6mmol, 1.2736g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 145 DEG C, react 4 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining faint yellow solid 0.5563g, is E-6-hydroxyl-3-(4-hydroxyl-3,5-dimethoxy benzene methene base) cumarone-2-(3H)-one, yield 59%.
1HNMR(400MHz,DMSO-d
6)δ10.33(s,1H),9.31(s,1H),7.81(d,J＝8.8Hz,1H),7.53(s,1H),7.11(s,2H),6.67(d,J＝2.0Hz,1H),6.62(dd,J＝2.4,8.8Hz,1H),3.82(s,6H)；
13CNMR(100MHz,DMSO-d
6)δ169.2,159.8,154.9,147.7,137.4,123.8,123.4,118.0,112.8,111.0,110.0,107.5,98.4,55.8。
The synthesis of embodiment 5:E-3-(4-hydroxy 3-methoxybenzene methene base) cumarone-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(2-bromophenyl)-3-(4-hydroxy 3-methoxybenzene base) vinylformic acid (3mmol successively, 1.0475g), cuprous iodide (0.3mmol, 0.0571g), oxine (0.3mmol, 0.0435g), sodium carbonate (6mmol, 0.6359g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 140 DEG C, 20 minutes reaction times.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.4990g, is E-3-(4-hydroxy 3-methoxybenzene methene base) cumarone-2 (3H)-one, yield 62%.
1HNMR(400MHz,DMSO-d
6)δ10.10(s,1H),7.95(d,J＝7.6Hz,1H),7.79(s,1H),7.38-7.44(m,3H),7.29(d,J＝8.0Hz,1H),7.20(td,J＝0.8,7.6Hz,1H),6.97(d,J＝8.0Hz,1H),3.84(s,3H)；
13CNMR(100MHz,DMSO-d
6)δ168.8,153.3,150.1,147.6,142.2,130.4,124.7,124.7,124.0,122.3,121.9,117.6,115.8,114.1,111.0,55.7。
The synthesis of embodiment 6:E-3-(4-hydroxyl-3-phenetole methene base)-6-hydroxyl benzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-hydroxyl-3-ethoxyl phenenyl) vinylformic acid (3mmol successively, 1.1376g), cuprous chloride (0.6mmol, 0.0594g), glycine (0.6mmol, 0.0450g), sodium bicarbonate (6mmol, 0.5041g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 140 DEG C, react 6 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.6622g, is E-3-(4-hydroxyl-3-phenetole methene base)-6-hydroxyl benzofuran-2 (3H)-one, yield 74%.
1HNMR(400MHz,DMSO-d
6)δ10.30(s,1H),9.85(s,1H),7.74(d,J＝8.4Hz,1H),7.51(s,1H),7.29-7.32(m,2H),6.95(d,J＝8.0Hz,1H),6.59-6.69(m,2H),4.07(q,J＝8.0Hz,2H),1.37(t,J＝8.0Hz,3H)；
13CNMR(100MHz,DMSO-d
6)δ169.4,159.9,154.9,149.5,146.8,137.4,125.1,123.9,123.4,117.9,115.8,114.8,112.9,111.1,98.5,63.8,14.7。
The synthesis of embodiment 7:E-6-hydroxyl-3-(4-trifluoromethylbenzene methene base) cumarone-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-trifluoromethyl) vinylformic acid (3mmol successively, 1.1615g), cuprous bromide (0.6mmol, 0.0861g), 1,10-phen (0.6mmol, 0.1189g), sodium acetate (6mmol, 0.4922g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 135 DEG C, 8 minutes reaction times.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.4410g, is E-6-hydroxyl-3-(4-trifluoromethylbenzene methene base) cumarone-2 (3H)-one, yield 48%.
1HNMR(400MHz,DMSO-d
6)δ10.33(s,1H),8.21(d,J＝8.4Hz,2H),7.88(s,1H),7.82(d,J＝8.0Hz,2H),7.67(d,J＝8.0Hz,1H),6.66(dd,J＝2.0,8.4Hz,1H),6.61(d,J＝2.0Hz,1H)。
The synthesis of embodiment 8:E-3-(4-fluorobenzene methene base)-6-hydroxyl benzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-fluorophenyl) vinylformic acid (3mmol successively, 1.0114g), thiophene-2-carboxylic acid cuprous (0.6mmol, 0.1144g), 1,10-phen (0.6mmol, 0.1189g), pyridine (8mmol, 0.6328g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 130 DEG C, react 6 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining faint yellow solid 0.3536g, is E-3-(4-fluorobenzene methene base)-6-hydroxyl benzofuran-2 (3H)-one, yield 46%.
1HNMR(400MHz,DMSO-d
6)δ10.41(s,1H),7.81(dd,J＝5.6,8.4Hz,2H),7.58(s,1H),7.55(d,J＝8.4Hz,1H),7.37(t,J＝8.8Hz,2H),6.66(d,J＝2.0Hz,1H),6.56(dd,J＝2.0,8.4Hz,1H)；
13CNMR(100MHz,DMSO-d
6)δ168.7,162.7(
1J
C-F＝247.6Hz),160.6,155.4,134.9,131.9(
3J
C-F＝8.6Hz),130.5(
4J
C-F＝2.5Hz),123.7,121.2,116.0(
2J
C-F＝22.0Hz),112.2,111.3,98.6。
The synthesis of embodiment 9:E-3-(2,4 dichloro benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(3,4-dichlorophenyl) vinylformic acid (3mmol, 1.1641g), neutralized verdigris (0.6mmol successively, 0.1198g), 1,10-phen (0.6mmol, 0.1189g), triethylamine (6mmol, 0.6071g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 140 DEG C, react 6 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining faint yellow solid 0.5897g, is E-3-(2,4 dichloro benzene methene base)-6-hydroxyl benzofuran-2 (3H)-one, yield 64%.
1HNMR(400MHz,DMSO-d
6)δ10.52(s,1H),7.85(d,J＝2.0Hz,1H),7.84(d,J＝8.4Hz,1H),7.60(dd,J＝2.0,8.4Hz,1H),7.45(s,1H),7.22(d,J＝8.8Hz,1H),6.67(d,J＝2.0Hz,1H),6.53(dd,J＝2.0,8.4Hz,1H)；
13CNMR(100MHz,DMSO-d
6)δ168.1,161.2,155.7,135.1,134.1,131.3,131.2,129.7,129.5,127.9,124.2,123.9,111.7,111.6,98.6。
The synthesis of embodiment 10:E-3-(4-hydroxybenzene methene base)-5-Methoxvbenzofuran-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-5-p-methoxy-phenyl of 2-)-3-(4-hydroxy phenyl) vinylformic acid (3mmol successively, 1.0475g), cupric oxide (0.6mmol, 0.0477g), 1,10-phen (0.6mmol, 0.1189g), triethylamine (6mmol, 0.6071g), 20mL methyl-sulphoxide, stir, under microwave condition, control temperature of reaction 140 DEG C, react 6 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.6616g, is E-3-(4-hydroxybenzene methene base)-5-Methoxvbenzofuran-2 (3H)-one, yield 76%.
1HNMR(400MHz,DMSO-d
6)δ10.41(s,1H),7.77(s,1H),7.73(d,J＝8.4Hz,2H),7.35(d,J＝2.4Hz,1H),7.21(d,J＝8.8Hz,1H),6.96-7.00(m,3H),3.73(s,3H)；
13CNMR(100MHz,DMSO-d
6)δ169.0,160.5,155.4,147.4,142.0,135.1,132.5,124.2,115.8,115.6,111.4,107.4,104.6,55.5。
The synthesis of embodiment 11:E-6-hydroxyl-3-(4-bromobenzene methene base) cumarone-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-bromophenyl) vinylformic acid (3mmol successively, 1.1942g), ventilation breather (0.6mmol, 0.1327g), 1,10-phen (0.6mmol, 0.1189g), triethylamine (6mmol, 0.6071g), 20mLPEG-400, stir, under microwave condition, control temperature of reaction 150 DEG C, react 6 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.6565g, is E-6-hydroxyl-3-(4-bromobenzene methene base) cumarone-2 (3H)-one, yield 69%.
1HNMR(400MHz,DMSO-d
6)δ10.46(s,1H),7.75(d,J＝8.4Hz,2H),7.71(d,J＝8.4Hz,2H),7.56(d,J＝8.0Hz,1H),7.55(s,1H),6.67(d,J＝2.4Hz,1H),6.56(dd,J＝8.4,2.4Hz,1H)；
13CNMR(100MHz,DMSO-d
6)δ168.7,160.8,155.5,134.5,133.2,131.9,131.3,123.9,123.3,121.8,112.2,111.4,98.6。
The synthesis of embodiment 12:E-6-hydroxyl-3-(4-oil of mirbane methene base) cumarone-2 (3H)-one
In 50mL microwave reaction bottle, add E-2-(the bromo-4-hydroxy phenyl of 2-)-3-(4-nitrophenyl) vinylformic acid (3mmol successively, 1.0925g), copper hydroxide (0.6mmol, 0.0585g), 1,10-phen (0.6mmol, 0.1189g), triethylamine (6mmol, 0.6071g), 20mL polyoxyethylene glycol-200, stir, under microwave condition, control temperature of reaction 150 DEG C, react 20 minutes.After having reacted, pour in 200mL water, be acidified to pH=4 with dilute hydrochloric acid, with 30mL extraction into ethyl acetate 3 times, merge organic layer, organic over anhydrous dried over mgso.Be spin-dried for solvent, column chromatography purification.Obtaining yellow solid 0.3909g, is E-6-hydroxyl-3-(4-oil of mirbane methene base) cumarone-2 (3H)-one, yield 46%.
1HNMR(400MHz,DMSO-d
6)δ10.58(s,1H),8.37(d,J＝8.4Hz,2H),7.99(d,J＝8.4Hz,2H),7.65(s,1H),7.52(d.J＝8.4Hz,1H),6.68(d,J＝2.0Hz,1H),6.57(dd,J＝8.4,2.0Hz,1H)；
13CNMR(100MHz,DMSO-d
6)δ168.3,161.4,156.0,147.5,140.8,132.7,130.5,124.4,124.0,124.0,111.9,111.6,98.7。
Claims (7)
1. prepare the method for different Aurone compound through Intra-molecular condensation for one kind, it is characterized in that: be for raw material with E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds, under catalyzer and part effect, under the existence and microwave reaction condition of alkali, in solvent, react for some time; After having reacted, reaction solution is poured into water, is acidified to pH=3 ~ 4, extraction, dry, be spin-dried for solvent, purifying, obtain different Aurone compound.
2. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: described catalyzer is that neutralized verdigris, cupric oxide, ventilation breather, copper hydroxide, copper sulfate, cupric sulfate pentahydrate, Red copper oxide, cuprous iodide, cuprous chloride, cuprous bromide or thiophene-2-carboxylic acid are cuprous.
3. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: described part is DMAP, Tetramethyl Ethylene Diamine, oxine, 1,10-adjacent phenanthroline or glycine.
4. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: described alkali is triethylene diamine, Tripotassium phosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium ethylate, pyridine or triethylamine.
5. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: described solvent is dimethyl sulfoxide (DMSO), DMF, polyoxyethylene glycol-200 or PEG-4000.
6. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: the ratio of the amount of substance of E-2-(2-bromo aryl)-3-aromatic substituted acrylic acid compounds, catalyzer, part, alkali is 1:(0.05 ~ 0.3): (0.05 ~ 0.3): (1 ~ 3).
7. the method preparing different Aurone compound through Intra-molecular condensation according to claim 1, is characterized in that: temperature of reaction is 130 ~ 150 DEG C, and the reaction times is 2 ~ 30 minutes.
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| CN106748672A (en) * | 2016-11-16 | 2017-05-31 | 广州中大南沙科技创新产业园有限公司 | A kind of preparation method of trans adjacent hydroxy diaryl ethylene compounds |
| CN106748672B (en) * | 2016-11-16 | 2019-09-17 | 广州中大南沙科技创新产业园有限公司 | A kind of preparation method of trans- adjacent hydroxy diaryl ethylene compounds |
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