CN105085458A - Synthesis method of coumarin derivatives - Google Patents
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
The invention relates to a synthesis method of coumarin derivatives disclosed as Formula (III), which comprises the following steps: in a nitrogen atmosphere, adding compounds disclosed as Formula (I), compounds disclosed as Formula (II), a catalyst, an accelerator and an assistant into an organic solvent, stirring to react at 70-90 DEG C for 5-8 hours, and carrying out after-treatment to obtain the compounds disclosed as Formula (III), wherein R1 and R2 are respectively and independently selected from H, C1-C6 alkyl group or halogen; R3 and R4 are respectively and independently selected from C1-C6 alkyl group, unsubstituted phenyl group or phenyl group with substituent group (C1-C6 alkoxy group or halogen). Under the combined selection and synergic actions of the catalyst, accelerator, assistant and organic solvent, the high-yield target product can be obtained. The coumarin derivatives have wide industrial application value and production potential in the field of organic synthesis and especially the field of drug intermediate synthesis.
Description
Technical field
The present invention relates to a kind of synthetic method of fused ring compound, relate more particularly to a kind of synthetic method of coumarin derivatives, belong to especially medicine intermediate synthesis field, organic chemical synthesis field.
Background technology
In organic chemistry and medicine intermediate synthesis technical field, tonka bean camphor structure is the basic structure fragment of many natural products and medical compounds, and it gives these compounds biological activity widely.In addition, coumarin derivatives also can be used for preparing among luminous organic material or molecular device.
The effect so important just because of perfume (or spice) bucket chlorins compound and application potential, therefore, the novel method for synthesizing of research and development coumarin kind compound is very significant thing.
Traditional coumarins synthetic method is Pechmann reaction, also can adopt the condensation reaction method of strong acid or strong base catalyst.In addition, the synthetic method of metal catalysis in recent years also more report, illustratively as follows:
JiaChengguo etc. (" NewMethodforPreparationofCoumarinsandQuinolinonesviaPd-C atalyzedIntramolecularHydroarylationofC-CTripleBonds ", J.Org, Chem., 2000,65,7516-7522) to prepare its reaction formula of method of tonka bean camphor as follows for the intramolecular reaction that reports a kind of palladium chtalyst:
BarryM.Trost etc. (" AtomEconomy.Palladium-CatalyzedFormationofCoumarinsbyAdd itionofPhenolsandAlkynoatesviaaNetC-HInsertion ", J.Am.Chem.Soc., 2003,125,4518-4526) report a kind of palladium chtalyst building-up reactions by phenolic compound and alkynyl ester compound, its reaction formula is as follows:
KotaSasano etc. (" Palladium (II)-CatalyzedDirectCarboxylationofAlkenylC-HBondswithCO2 ", J.Am.Chem.Soc., 2013,135,10954-10957) report the building-up reactions of the palladium chtalyst that a kind of carbonic acid gas participates in, its reaction formula is as follows:
In order to expand new reaction type, the present inventor on the basis of existing technology, studied by a large amount of scientific experiment and aim to provide a kind of method that cyclization prepares coumarin derivatives, it adopts multiple elements design reaction system greatly to promote the smooth enforcement of catalyzed reaction, and achieve significant technique effect, show application prospect extremely widely.
Summary of the invention
In order to seek the novel method for synthesizing of coumarin derivatives, present inventor has performed deep research and exploration, after having paid enough creative works, thus completing the present invention.
Specifically, technical scheme of the present invention and content relate to the synthetic method of coumarin derivatives shown in a kind of following formula (III), described method comprises: under nitrogen atmosphere, following formula (I) compound, following formula (II) compound, catalyzer, promotor and auxiliary agent is added in organic solvent, then stirring reaction 5-8 hour at 70-90 DEG C, then through aftertreatment, described formula (III) compound is obtained
Wherein, R
1, R
2be selected from H, C independently of one another
1-C
6alkyl or halogen;
R
3, R
4be selected from C independently of one another
1-C
6alkyl, not replace or with substituent phenyl, described substituting group is C
1-C
6alkoxy or halogen.
In described synthetic method of the present invention, described C
1-C
6the implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
In described synthetic method of the present invention, described C
1-C
6alkoxyl group refers to " C defined above
1-C
6alkyl " be connected with O atom after group.
In described synthetic method of the present invention, the implication of described halogen refers to haloid element, non-exclusively such as can be F, Cl, Br or I.
In described synthetic method of the present invention, described catalyzer is ruthenium compound and Bu
2the mixture of SnIH (dibutyl iodine tin hydride), wherein ruthenium compound and Bu
2the mol ratio of SnIH is 1:3.
Wherein, described ruthenium compound is any one in ruthenocene, triphenylphosphine ruthenium chloride, four carbonyl diurethane chlorination two rutheniums or hydroxy chloride ruthenium, most preferably is triphenylphosphine ruthenium chloride.
In described synthetic method of the present invention, described promotor is organocopper compound, and it is selected from venus crystals (Cu (OAc)
2), copper trifluoromethanesulfcomposite (Cu (OTf)
2), acetylacetone copper (Cu (acac)
2) or trifluoroacetic acid copper (Cu (TFA)
2) in any one, most preferably be acetylacetone copper (Cu (acac)
2).
In described synthetic method of the present invention, described auxiliary agent is any one in 1-ethyl-3-methylimidazole acetate or 1-ethyl-3-methylimidazole trifluoroacetate, most preferably is 1-ethyl-3-methylimidazole trifluoroacetate.
In described synthetic method of the present invention, described organic solvent is the mixture of Isosorbide-5-Nitrae-dioxane and DMSO (dimethyl sulfoxide (DMSO)); Wherein, the volume ratio of Isosorbide-5-Nitrae-dioxane and DMSO is 1:2-3, such as, can be 1:2,1:2.5 or 1:3.
In described synthetic method of the present invention, the consumption of described organic solvent is not particularly limited, those skilled in the art can select suitable consumption, reacting balance is such as made to carry out, or aftertreatment is easy to the amount of carrying out, this belongs to ordinary skill in the art means, and this is no longer going to repeat them.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and formula (II) compound is 1:1.4-2, in non-limiting manner such as can 1:1.4,1:1.6,1:1.8 or 1:2.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and catalyzer is 1:0.08-0.14, i.e. the mole dosage of described formula (I) compound and the ruthenium compound of the described catalyzer of composition and Bu
2the ratio of total mole dosage of SnIH is 1:0.08-0.14, such as, can be 1:0.08,1:0.1,1:0.12 or 1:0.14.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and promotor is 1:0.2-0.3, such as, can be 1:0.2,1:0.25 or 1:0.3.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and auxiliary agent is 1:0.1-0.15, such as, can be 1:0.1,1:0.12,1:0.14 or 1:0.15.
In described synthetic method of the present invention, the aftertreatment that reaction terminates is specific as follows: after reaction terminates, by reaction mixture filtered while hot, filtrate naturally cools to room temperature, then adds deionized water and fully vibrate, add chloroform more fully to extract 2-3 time, merge organic phase, concentrating under reduced pressure, crosses silica gel flash column chromatography by gained residue, with volume ratio be the mixed solvent of the ethyl acetate of 1:2 and acetone as elutriant, thus obtain described formula (III) compound.
In sum, the invention provides a kind of synthetic method of coumarin derivatives, the method by the comprehensive selection of catalyzer, promotor, auxiliary agent and organic solvent with collaborative, thus high yield can obtain object product, in synthesis field, organic synthesis field especially medicine intermediate, there are industrial application value and production potential widely.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
Under room temperature, under nitrogen atmosphere, (be 1 of volume ratio 1:2 to appropriate organic solvent, the mixture of 4-dioxane and DMSO) in, add 100mmol above formula (I) compound, 140mmol above formula (II) compound, 8mmol catalyzer (be the Bu of 2mmol triphenylphosphine ruthenium chloride and 6mmol
2the mixture of SnIH), 20mmol accelerant C u (acac)
2with 10mmol auxiliary agent 1-ethyl-3-methylimidazole trifluoroacetate; Then 70 DEG C are warming up to and stirring reaction 8 hours at such a temperature;
After reaction terminates, by reaction mixture filtered while hot, filtrate naturally cools to room temperature, then adds deionized water and fully vibrate, then adds chloroform and fully extract 2-3 time, merge organic phase, concentrating under reduced pressure, crosses silica gel flash column chromatography by gained residue, is that the mixed solvent of the ethyl acetate of 1:2 and acetone is as elutriant with volume ratio, thus obtaining above formula (III) compound, productive rate is 97.6%.
1HNMR(CDCl
3,400MHz):δ2.29(s,3H),6.99(s,1H),7.08-7.16(m,4H),7.18-7.22(m,3H),7.28-7.37(m,5H)。
Embodiment 2
Under room temperature, under nitrogen atmosphere, (be 1 of volume ratio 1:2.5 to appropriate organic solvent, the mixture of 4-dioxane and DMSO) in, add 100mmol above formula (I) compound, 170mmol above formula (II) compound, 11mmol catalyzer (be the Bu of 2.75mmol triphenylphosphine ruthenium chloride and 8.25mmol
2the mixture of SnIH), 25mmol accelerant C u (acac)
2with 12mmol auxiliary agent 1-ethyl-3-methylimidazole trifluoroacetate; Then 80 DEG C are warming up to and stirring reaction 6 hours at such a temperature;
After reaction terminates, by reaction mixture filtered while hot, filtrate naturally cools to room temperature, then adds deionized water and fully vibrate, then adds chloroform and fully extract 2-3 time, merge organic phase, concentrating under reduced pressure, crosses silica gel flash column chromatography by gained residue, is that the mixed solvent of the ethyl acetate of 1:2 and acetone is as elutriant with volume ratio, thus obtaining above formula (III) compound, productive rate is 97.3%.
1HNMR(CDCl
3,400MHz):δ6.88-6.96(m,2H),7.02-7.13(m,6H),7.18-7.24(m,2H),7.45(d,J＝8.4Hz,1H),7.56-7.59(m,1H)。
Embodiment 3
Under room temperature, under nitrogen atmosphere, (be 1 of volume ratio 1:3 to appropriate organic solvent, the mixture of 4-dioxane and DMSO) in, add 100mmol above formula (I) compound, 200mmol above formula (II) compound, 14mmol catalyzer (be the Bu of 3.5mmol triphenylphosphine ruthenium chloride and 10.5mmol
2the mixture of SnIH), 30mmol accelerant C u (acac)
2with 15mmol auxiliary agent 1-ethyl-3-methylimidazole trifluoroacetate; Then 90 DEG C are warming up to and stirring reaction 5 hours at such a temperature;
After reaction terminates, by reaction mixture filtered while hot, filtrate naturally cools to room temperature, then adds deionized water and fully vibrate, then adds chloroform and fully extract 2-3 time, merge organic phase, concentrating under reduced pressure, crosses silica gel flash column chromatography by gained residue, is that the mixed solvent of the ethyl acetate of 1:2 and acetone is as elutriant with volume ratio, thus obtaining above formula (III) compound, productive rate is 97.2%.
1HNMR(CDCl
3,400MHz):δ3.77(s,3H),3.82(s,3H),6.73-6.76(m,2H),6.83-6.89(m,2H),7.04-7.08(m,4H),7.17-7.23(m,1H),7.27-7.31(m,1H),7.39-7.45(m,1H),7.48-7.53(m,1H)。
Embodiment 4
Under room temperature, under nitrogen atmosphere, to appropriate organic solvent (for volume ratio 1:2.5 Isosorbide-5-Nitrae-
The mixture of dioxane and DMSO) in, add 100mmol above formula (I) compound, 160mmol above formula (II) compound, 10mmol catalyzer (be the Bu of 2.5mmol triphenylphosphine ruthenium chloride and 7.5mmol
2the mixture of SnIH), 25mmol accelerant C u (acac)
2with 12mmol auxiliary agent 1-ethyl-3-methylimidazole trifluoroacetate; Then 75 DEG C are warming up to and stirring reaction 6 hours at such a temperature;
After reaction terminates, by reaction mixture filtered while hot, filtrate naturally cools to room temperature, then adds deionized water and fully vibrate, then adds chloroform and fully extract 2-3 time, merge organic phase, concentrating under reduced pressure, crosses silica gel flash column chromatography by gained residue, is that the mixed solvent of the ethyl acetate of 1:2 and acetone is as elutriant with volume ratio, thus obtaining above formula (III) compound (" n-Bu " is normal-butyl), productive rate is 97.4%.
1HNMR(CDCl
3,400MHz):δ0.98(t,J＝7.2Hz,3H),1.02(t,J＝7.2Hz,3H),1.44-1.62(m,8H),2.65(t,J＝8.0Hz,2H),2.83(t,J＝8.0Hz,2H),7.25-7.33(m,2H),7.44-7.48(m,1H),7.59(dd,J
1＝8.0Hz,J
2＝1.2Hz,1H)。
Embodiment 5-24
Embodiment 5-8: except replacing with except ruthenocene by the triphenylphosphine ruthenium chloride in catalyzer, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 5-8.
Embodiment 9-12: except being replaced with by the triphenylphosphine ruthenium chloride in catalyzer except four carbonyl diurethane chlorination two rutheniums, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 9-12.
Embodiment 13-16: except replacing with except hydroxy chloride ruthenium by the triphenylphosphine ruthenium chloride in catalyzer, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 13-16.
Embodiment 17-20: except catalyzer being replaced with one-component triphenylphosphine ruthenium chloride that consumption is the total consumption sum of original two kinds of components, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 17-20.
Embodiment 21-24: except catalyzer is replaced with the one-component Bu that consumption is the total consumption sum of original two kinds of components
2outside SnIH, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment and obtains embodiment 21-24.
The results are shown in following table 1.
Table 1
"--" represents not exist.
As can be seen here, in ruthenium compound, triphenylphosphine ruthenium chloride has best effect.Also can find out to only have and use triphenylphosphine ruthenium chloride and Bu simultaneously
2during the composite catalyst of SnIH, just can obtain excellent technique effect of the present invention; And when being used alone triphenylphosphine ruthenium chloride or Bu
2during SnIH, productive rate all will be caused to have significant reduction, be especially used alone Bu
2during SnIH, productive rate sharply reduces.Demonstrate triphenylphosphine ruthenium chloride and Bu thus
2unique concerted catalysis effect can be played between SnIH.
Embodiment 25-40
Embodiment 25-28: except promotor is replaced with Cu (OAc)
2outward, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 25-28.
Embodiment 29-32: except promotor is replaced with Cu (OTf)
2outward, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 29-32.
Embodiment 33-36: except promotor is replaced with Cu (TFA)
2outward, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 33-36.
Embodiment 37-40: except dispensing promotor, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 37-40.
The results are shown in following table 2.
Table 2
"--" represents not exist.
As can be seen here, acetylacetone copper (Cu (acac)
2) there is best facilitation effect, other copper compound all causes product decrease to some degree, and when not making used additives, productive rate reduces more obvious, this demonstrate that acetylacetone copper (Cu (acac)
2) there is beyond thought promotion synergy.
Embodiment 41-48
Embodiment 41-44: except auxiliary agent being replaced with 1-ethyl-3-methylimidazole acetate, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 41-44.
Embodiment 45-48: except dispensing auxiliary agent, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 45-48.
The results are shown in following table 3.
Table 3
"--" represents not exist.
As can be seen here, the existence of auxiliary agent can significantly improve products collection efficiency, and 1-ethyl-3-methylimidazole trifluoroacetate has best auxiliaring effect.
Embodiment 49-56
Embodiment 49-52: except organic solvent being replaced with one-component Isosorbide-5-Nitrae-dioxane, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 49-52.
Embodiment 53-56: except being replaced with by organic solvent except one-component DMSO, other operation is all constant, thus is repeated embodiment 1-4, obtains embodiment 53-56.
The results are shown in following table 4.
Table 4
As can be seen here, when using single solvent, productive rate decrease to some degree, this proves the two-pack organic solvent only having use Isosorbide-5-Nitrae-dioxane and DMSO, just can obtain excellent effect of the present invention.
In sum, the invention provides a kind of synthetic method of coumarin derivatives, the method by the comprehensive selection of catalyzer, promotor, auxiliary agent and organic solvent with collaborative, thus high yield can obtain object product, in synthesis field, organic synthesis field especially medicine intermediate, there are industrial application value and production potential widely.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the synthetic method of coumarin derivatives shown in a following formula (III), described method comprises: under nitrogen atmosphere, following formula (I) compound, following formula (II) compound, catalyzer, promotor and auxiliary agent is added in organic solvent, then stirring reaction 5-8 hour at 70-90 DEG C, then through aftertreatment, obtain described formula (III) compound
Wherein, R
1, R
2be selected from H, C independently of one another
1-C
6alkyl or halogen;
R
3, R
4be selected from C independently of one another
1-C
6alkyl, not replace or with substituent phenyl, described substituting group is C
1-C
6alkoxy or halogen.
2. the method for claim 1, is characterized in that: described catalyzer is ruthenium compound and Bu
2the mixture of SnIH, wherein ruthenium compound and Bu
2the mol ratio of SnIH is 1:3.
3. synthetic method as claimed in claim 2, is characterized in that: described ruthenium compound is any one in ruthenocene, triphenylphosphine ruthenium chloride, four carbonyl diurethane chlorination two rutheniums or hydroxy chloride ruthenium, most preferably is triphenylphosphine ruthenium chloride.
4. the synthetic method as described in any one of claim 1-3, is characterized in that: described promotor is organocopper compound, and it is selected from venus crystals (Cu (OAc)
2), copper trifluoromethanesulfcomposite (Cu (OTf)
2), acetylacetone copper (Cu (acac)
2) or trifluoroacetic acid copper (Cu (TFA)
2) in any one, most preferably be acetylacetone copper (Cu (acac)
2).
5. the synthetic method as described in any one of claim 1-4, it is characterized in that: described auxiliary agent is any one in 1-ethyl-3-methylimidazole acetate or 1-ethyl-3-methylimidazole trifluoroacetate, most preferably is 1-ethyl-3-methylimidazole trifluoroacetate.
6. the synthetic method as described in any one of claim 1-5, is characterized in that: described organic solvent is the mixture of Isosorbide-5-Nitrae-dioxane and DMSO (dimethyl sulfoxide (DMSO)); Wherein, the volume ratio of Isosorbide-5-Nitrae-dioxane and DMSO is 1:2-3.
7. the synthetic method as described in any one of claim 1-6, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:1.4-2.
8. the synthetic method as described in any one of claim 1-7, is characterized in that: the mol ratio of described formula (I) compound and catalyzer is 1:0.08-0.14.
9. the synthetic method as described in any one of claim 1-8, is characterized in that: the mol ratio of described formula (I) compound and promotor is 1:0.2-0.3.
10. the synthetic method as described in any one of claim 1-9, is characterized in that: the mol ratio of described formula (I) compound and auxiliary agent is 1:0.1-0.15.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710215226.7A CN106957294A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of medicine intermediate coumarin derivatives |
| CN201710215202.1A CN106946826A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
| CN201710215214.4A CN106977481A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of coumarin derivatives |
| CN201710215223.3A CN106957293A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of coumarin derivatives |
| CN201510514922.9A CN105085458B (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of coumarin derivatives |
| CN201710215217.8A CN106957292A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of medicine intermediate coumarin derivatives |
| CN201710215222.9A CN106916132A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
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| CN201510514922.9A CN105085458B (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of coumarin derivatives |
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| CN201710215217.8A Division CN106957292A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of medicine intermediate coumarin derivatives |
| CN201710215202.1A Division CN106946826A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
| CN201710215222.9A Division CN106916132A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
| CN201710215226.7A Division CN106957294A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of medicine intermediate coumarin derivatives |
| CN201710215214.4A Division CN106977481A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of coumarin derivatives |
| CN201710215223.3A Division CN106957293A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of coumarin derivatives |
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| CN201710215217.8A Withdrawn CN106957292A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of medicine intermediate coumarin derivatives |
| CN201710215223.3A Withdrawn CN106957293A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of coumarin derivatives |
| CN201710215222.9A Withdrawn CN106916132A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
| CN201710215202.1A Withdrawn CN106946826A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
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| CN201710215223.3A Withdrawn CN106957293A (en) | 2015-08-20 | 2015-08-20 | The synthetic method of coumarin derivatives |
| CN201710215222.9A Withdrawn CN106916132A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
| CN201710215202.1A Withdrawn CN106946826A (en) | 2015-08-20 | 2015-08-20 | A kind of synthetic method of medicine intermediate coumarin derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106432049A (en) * | 2016-09-27 | 2017-02-22 | 李纪焕 | Benzo-succinimide compound synthesis method |
| CN106432050A (en) * | 2016-09-27 | 2017-02-22 | 李纪焕 | Improved synthesis method for imine compound |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109369597B (en) * | 2018-12-28 | 2022-11-29 | 陕西师范大学 | Synthetic method of isocoumarin compound |
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| CN1986503A (en) * | 2006-12-28 | 2007-06-27 | 上海交通大学 | Iron catalyzed styrene derivative synthesizing process with active arene and alkyne |
| CN103408554A (en) * | 2013-07-31 | 2013-11-27 | 西安交通大学 | Hypertensive activity reducing pyrrole coumarins compound and preparation method thereof |
| US20140296232A1 (en) * | 2011-09-29 | 2014-10-02 | Massachusetts General Hospital | Compounds for the treatment of mycobacterial infections |
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2015
- 2015-08-20 CN CN201510514922.9A patent/CN105085458B/en not_active Expired - Fee Related
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- 2015-08-20 CN CN201710215223.3A patent/CN106957293A/en not_active Withdrawn
- 2015-08-20 CN CN201710215222.9A patent/CN106916132A/en not_active Withdrawn
- 2015-08-20 CN CN201710215202.1A patent/CN106946826A/en not_active Withdrawn
- 2015-08-20 CN CN201710215226.7A patent/CN106957294A/en not_active Withdrawn
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| CN1986503A (en) * | 2006-12-28 | 2007-06-27 | 上海交通大学 | Iron catalyzed styrene derivative synthesizing process with active arene and alkyne |
| US20140296232A1 (en) * | 2011-09-29 | 2014-10-02 | Massachusetts General Hospital | Compounds for the treatment of mycobacterial infections |
| CN103408554A (en) * | 2013-07-31 | 2013-11-27 | 西安交通大学 | Hypertensive activity reducing pyrrole coumarins compound and preparation method thereof |
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| YINGWEI ZHAO等: "Access to Coumarins by Rhodium-Catalyzed Oxidative Annulation of Aryl Thiocarbamates with Internal Alkynes", 《ORGANIC LETTERS》 * |
| YUEWEN LI等: "Copper-Catalyzed Direct Trifluoromethylation of Propiolates:Construction of Trifluoromethylated Coumarins", 《ORGANIC LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432049A (en) * | 2016-09-27 | 2017-02-22 | 李纪焕 | Benzo-succinimide compound synthesis method |
| CN106432050A (en) * | 2016-09-27 | 2017-02-22 | 李纪焕 | Improved synthesis method for imine compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106957294A (en) | 2017-07-18 |
| CN105085458B (en) | 2017-04-05 |
| CN106946826A (en) | 2017-07-14 |
| CN106957292A (en) | 2017-07-18 |
| CN106957293A (en) | 2017-07-18 |
| CN106977481A (en) | 2017-07-25 |
| CN106916132A (en) | 2017-07-04 |
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