CN108530405A - The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules - Google Patents
The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules Download PDFInfo
- Publication number
- CN108530405A CN108530405A CN201810429931.1A CN201810429931A CN108530405A CN 108530405 A CN108530405 A CN 108530405A CN 201810429931 A CN201810429931 A CN 201810429931A CN 108530405 A CN108530405 A CN 108530405A
- Authority
- CN
- China
- Prior art keywords
- nonmetallic
- reaction
- bonded
- alkene
- benzofuran
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C07D307/79—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Furan Compounds (AREA)
Abstract
The present invention provides the methods that addition C O in a kind of nonmetallic Louis acid catalysis olefin hydrocarbon molecules are bonded to benzofuran derivatives, include the following steps：Step 1 prepares alkene：Using phenol derivatives as raw material, by three-step reaction, the alkene as reaction substrate is obtained；Step 2 will be added nonmetallic lewis acid and toluene in reaction substrate that step 1 is prepared, the benzofuran derivatives be obtained by the reaction.The present invention is in reaction process at having used nonmetallic lewis acid to avoid pollution of the kish catalyst to product as catalyst, also eliminate troublesome post-processing.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly to a kind of synthetic method of benzofuran derivatives.
Background technology
Benzofuran compounds are a kind of natural organic-compounds being widely present in plant, such as in Radix Salviae Miltiorrhizae, hundred
In the medicinal plants such as portion, snowball, Chinese prickly ash.Benzofuran compounds have good antibacterial, anti-oxidant, antitumor, disease-resistant
The physiological activity such as poison, therefore can be used for selective adenosine A1 receptor antagonists, immunosuppressor etc..But because from natural production
Benzofuran compounds are extracted in object and cannot be satisfied the demand of people, therefore are just seemed very by artificial synthesis
It is important.
Alkene addition reaction is very important one kind chemical conversion reaction in organic synthesis and pharmaceutical chemistry.Direct addition
C-O keys to alkene be a kind of atom and all very economical efficient olefin functionalities method of step.Although alkene addition C-X (X
For hetero atom) it has been obtained for widely paying close attention to, but because the high stability of C-O keys, the direct addition C-O keys of alkene still fill
Full challenge.2012, Nakao seminars realized addition C-O in olefin hydrocarbon molecules using the Metal Palladium and boric acid catalyst of collaboration
Key, obtains benzofuran compounds, and reaction is carried out in 80 degrees Celsius of tetrahydrofuran solvents.Although reaction passes through alkene point
Addition C-O keys realize the synthesis of benzofuran in son, but apply transition metal palladium in the reaction.Transition is utilized in reaction
The high reaction activity of Metal Palladium realizes the activation of C-O keys, but it is one non-to dispel the residual of the transition metal in reaction system
Often difficult thing.Especially in medicine and daily necessities, there is very harsh requirement for the residue of transition metal.
So the synthesis for finding nonmetallic compound catalysis benzofuran compounds has important strategic importance.
Invention content
The object of the present invention is to provide addition C-O in a kind of nonmetallic Louis acid catalysis olefin hydrocarbon molecules to be bonded to benzo furan
It mutters the method for derivative, to solve the problems, such as of the existing technology to cause transition metal to remain using transition-metal catalyst.
To achieve the above object, the present invention uses following technical scheme：
A kind of method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules, packet
Include following steps：
Step 1 prepares alkene：Using phenol derivatives as raw material, by the three-step reaction as shown in following reaction equations, obtain
To the alkene as reaction substrate；Reaction equation is as follows：
Wherein R is H or OMe；
Nonmetallic lewis acid and toluene will be added in alkene that step 1 is prepared in step 2, is obtained by the reaction described
Benzofuran derivatives；Reaction equation is as follows：
The step 1 is specially：It is molten that potassium carbonate, methallyl chloride and compound 1 are added to the acetone stirred
In liquid, the mixture of formation is flowed back a night at room temperature, water is then added, then extracted with ether, collected organic layer simultaneously uses NaOH
Washing, uses MgSO4It is dried, is filtered and concentrated in vacuo to obtain intermediate compound 2；Intermediate compound 2 is dissolved
In n,N-Dimethylaniline or n,N-Dimethylformamide, mixture flows back at a temperature of 200-250 DEG C in nitrogen atmosphere
It 1-5 hours, is then cooled to room temperature, and is concentrated under reduced pressure, crude product is purified with rapid column chromatography, obtains the change of yellow oily
Close object 3；Under inert gas atmosphere, compound 3 is dissolved in solvent, is subsequently cooled to 0 DEG C, cyanogen bromide is added, then again
Triethylamine is added drop-wise in mixture, holds the mixture in 0 DEG C of lasting 3h, sediment is filtered through diatomite, and passes through hexane
It is repeatedly washed, then solvent is removed through rotary evaporation, obtain compound 4, as alkene.
The solvent is anhydrous hexane and diethyl ether according to volume ratio 5:2 mixture.
Alkene, nonmetallic lewis acid and the toluene mixing that step 1 is prepared, are placed in closed container, 90
At DEG C reaction 12~for 24 hours；After reaction, it is cooled to room temperature, ether is used in combination to dilute；It is finally concentrated with diatomite, column chromatography is pure
Change product, product is obtained after drying.
In the step 2, nonmetallic lewis acid is B (C6F5)3。
Advantageous effect：The present invention is in reaction process at having used nonmetallic lewis acid to pass through Louis as catalyst
The complexing of acid and cyano in reaction substrate extracts the electronics in O-C keys, weakens the chemical bond strength of O-C keys.To make
Alkene is easy to carry out to the addition of O-C keys, obtains target product benzofuran derivatives.Lewis acidic this activation mode and
Transition metal is different, but realizes the same effect of transition metal.Meanwhile avoiding dirt of the metallic catalyst to reaction system
Dye, also eliminates troublesome post-processing.
Description of the drawings
Fig. 1 is the HNMR spectrograms for the raw material olefin that embodiment 1 obtains；
Fig. 2 is the raw material olefin that embodiment 1 obtains13CNMR spectrograms；
Fig. 3 is the HNMR spectrograms for the final product benzofuran derivatives A that embodiment 1 obtains；
Fig. 4 is the final product benzofuran derivatives A's that embodiment 1 obtains13CNMR spectrograms；
Fig. 5 is the HNMR spectrograms for the raw material olefin that embodiment 2 obtains；
Fig. 6 is the raw material olefin that embodiment 2 obtains13CNMR spectrograms；
Fig. 7 is the HNMR spectrograms for the final product benzofuran derivatives B that embodiment 2 obtains；
Fig. 8 is the final product benzofuran derivatives B's that embodiment 2 obtains13CNMR spectrograms；
Specific implementation mode
Further explanation is done to the present invention with reference to embodiment.
Embodiment 1
The present embodiment synthesizes benzofuran derivatives A, includes the following steps：
(1) alkene is prepared：
Reaction equation is：
20.0 milliliters that 12 grams of potassium carbonate, 8.6mL methallyl chlorides and 7.6 grams of phenol (compound 1) are added to are just
In the acetone soln of stirring, the mixture of formation is flowed back a night at room temperature, 100 milliliters of water are added later, then ether extracts
It takes (12 × 10ml).Collected organic layer is washed with the NaOH (3x80mL) of a concentration of 2M, uses MgSO4It is dried, filters and true
Sky is concentrated to give 4.8 grams of intermediate compounds 2, can be used directly, and need not purify.
4.8 g of compound 2 are dissolved in 4.0mL n,N-Dimethylaniline, mixture flows back 5 in 205 DEG C of nitrogen atmosphere
Hour.It is cooled to room temperature, 400 milliliters of diethyl ether are added, reaction mixture is cleaned with the HCl (3x200ml) of a concentration of 1M.Water layer
It is further extracted with diethyl ether (3x200ml).Organic layer is cleaned with water and brine.Then in MgSO4Upper drying, and under reduced pressure
Concentration.Crude product rapid column chromatography (SiO2,PET/EtOAc 30:1-5:1) it purifies, obtains 1.48 grams of centres of yellow oily
Product 2- (2- methacrylics) phenol, i.e. compound 3.
1.48 grams of 2- (2- methacrylics) phenol is dissolved in the mixing of anhydrous hexane and diethyl ether under an argon atmosphere
In object, wherein the volume ratio of anhydrous hexane and diethyl ether is 5：2；Mixed reaction solution is cooled to 0 DEG C, then once
Property be added 1.27 grams of cyanogen bromides；Then, 1.21 grams of triethylamines are added drop-wise in reaction mixture；Reaction mixture is maintained at 0
DEG C continue 3h, sediment is filtered by one layer of diatomite, and is repeatedly washed by hexane.It is removed by rotary evaporation molten
Agent obtains crude product, i.e. compound 4；1H NMR(400MHz,CDCl3)δ1.72(s,3H),3.34(s,2H),4.60(s,1H),
4.84 (s, 1H), 7.24-7.27 (m, 2H), 7.33 (dd, J=6.2,3.3Hz, 1H), 7.45 (d, J=8.3Hz, 1H)；13C
NMR(100MHz,CDCl3)δ22.3,37.4,109.0,112.6,114.5,126.8,128.0,128.3,131.9,142.6,
151.3。
The purity of crude product can be used for the catalysis reaction of next step, without further purification.In this step, all operations
It must all be carried out in draughty draught cupboard, because the toxicity of cyanogen bromide is very strong, cyaniding can be generated in hydrolytic process
Hydrogen.
(2) benzofuran derivatives A is prepared：
Reaction equation is：
A micro reaction bulb is taken, magnetic stirrer is added, is put into a glove box full of nitrogen.In reaction bulb
In sequentially add the nonmetallic lewis acid B (C of 4,511 milligrams of 173 milligrams of compounds that step 1 prepares6F5)3With 5mL toluene.
With the tight reaction bulb of teflon seal cap, then taken out from glove box；Reaction bulb is heated to react for 24 hours at 90 DEG C；
After reaction, it is cooled to room temperature, is diluted with 10.0 milliliters of ether；Pass through TLC thin-layer chromatographic analysis (1:4EtOAc/
Hexanes) initial reactant completely consumes；Solution after reaction is concentrated with diatomite, with rapid column chromatography (1:9→
1:4 ether/hexanes) purified product, it is 147 milligrams of yellow solids to obtain product, and yield 85%, as product benzofuran derive
Object A.1H-NMR(300MHz,CDCl3) δ 1.67 (s, 3H), 2.71 (d, J=16.5Hz, 1H), 2.77 (d, J=16.5Hz, 1H),
3.14 (d, J=16.4Hz, 1H), 3.23 (d, J=16.4Hz, 1H), 6.79 (d, J=7.8Hz, 1H), 6.89 (td, J=7.5,
1.0Hz,1H),7.13–7.18(m,2H)；13C NMR(75MHz,CDCl3)δ25.9,29.7,41.2,84.6,110.0,
116.8,121.1,125.2,128.6,157.9。
Embodiment 2
The present embodiment synthesizes benzofuran derivatives B, includes the following steps：
(1) alkene is prepared：
Reaction equation is：
12 grams of potassium carbonate, 8.0mL methallyl chlorides and 8.0 grams of p methoxy phenols (compound 1) are added to 16.0
In the acetone soln of milliliter stirring, the mixture of formation is flowed back a night at room temperature, 100 milliliters of water are added later, then use second
Ether extracts (12 × 10ml).Collected organic layer is washed with the NaOH (3x80mL) of a concentration of 2M, uses MgSO4It is dried, filters
And 8.1 grams of intermediate compounds 2 are concentrated in vacuo to obtain, it can be used directly, need not purify.
8.0 grams of intermediate products 2 are dissolved in 35mLN, in dinethylformamide DMF solvent, mixture nitrogen at 240 DEG C
It flows back 80 minutes under microwave condition in atmosphere.It is cooled to room temperature, and is concentrated under reduced pressure.Crude product rapid column chromatography (SiO2,
PET/EtOAc 30:1-15:1) it purifies, obtains intermediate product 6.5 grams of 2- (2- methacrylics) -4- methoxyl groups of yellow oily
Phenol (i.e. compound 3).
1.8 grams of 2- (2- methacrylics) -4- metoxyphenols are dissolved in anhydrous hexane and diethyl under an argon atmosphere
In the mixture of ether, wherein the volume ratio of anhydrous hexane and diethyl ether is 5：2；Mixed reaction solution is cooled to 0 DEG C,
Then 1.27 grams of cyanogen bromides are added at one time；Then, 1.21 grams of triethylamines are added drop-wise in reaction mixture；By reaction mixture
It is maintained at 0 DEG C of lasting 3h, sediment is filtered by one layer of diatomite, and is repeatedly washed by hexane.Pass through rotary evaporation
Solvent is removed, crude product, i.e. compound 4 are obtained；1H NMR(300MHz,CDCl3)δ1.72(s,3H),3.31(s,2H),3.80
(s, 3H), 4.65 (s, 1H), 4.86 (s, 1H), 6.72-6.82 (m, 2H), 7.35 (d, J=9.3Hz, 1H)；13C NMR
(75MHz,CDCl3)δ22.2,37.6,55.6,109.6,112.5,112.8,115.8,116.9,129.3,142.4,145.4,
157.8。
The purity of crude product can be used for the catalysis reaction of next step, without further purification.In this step, all operations
It must all be carried out in draughty draught cupboard, because the toxicity of cyanogen bromide is very strong, cyaniding can be generated in hydrolytic process
Hydrogen.
(2) benzofuran derivatives B is prepared：
Reaction equation is：
A micro reaction bulb is taken, magnetic stirrer is added, is put into a glove box full of nitrogen.In reaction bulb
In sequentially add 204 milligrams of alkene, the 511 milligrams of nonmetallic lewis acid B (C that step 1 prepares6F5)3With 5mL toluene.With
The tight reaction bulb of teflon seal cap, then takes out from glove box；Reaction bulb is heated to react for 24 hours at 90 DEG C；Instead
It after answering, is cooled to room temperature, is diluted with 10.0 milliliters of ether；Pass through TLC thin-layer chromatographic analysis (1:4EtOAc/hexanes)
Initial reactant completely consumes；Solution after reaction is concentrated with diatomite, with rapid column chromatography (1:9→1:4 ether/
Hexane) purified product, product is 177 milligrams of red solids, yield 88%, as product benzofuran derivatives B.1H NMR
(300MHz,CDCl3) 1.65 (s, 3H), 2.72 (s, 2H), 3.11 (d, J=16.0Hz, 1H), 3.20 (d, J=16.0Hz,
1H),3.75(s,3H),6.68–6.75(m,3H)；13C NMR(75MHz,CDCl3)δ26.0,29.6,41.4,56.9,85.5,
111.3,116.7,117.2,121.8,126.3,144.6,146.2。
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (5)
1. a kind of method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules, special
Sign is：Include the following steps：
Step 1 prepares alkene：Using phenol derivatives as raw material, by the three-step reaction as shown in following reaction equations, made
For the alkene of reaction substrate；Reaction equation is as follows：
Wherein R is H or OMe；
Step 2 will be added nonmetallic lewis acid and toluene in alkene that step 1 is prepared, the benzo be obtained by the reaction
Furan derivatives；Reaction equation is as follows：
2. addition C-O is bonded to benzofuran and spreads out in nonmetallic Louis acid catalysis olefin hydrocarbon molecules according to claim 1
The method of biology, it is characterised in that：The step 1 is specially：Potassium carbonate, methallyl chloride and compound 1 are added to just
In the acetone soln of stirring, the mixture of formation is flowed back a night at room temperature, water is then added, then extracted with ether, collected
Organic layer is simultaneously washed with NaOH, uses MgSO4It is dried, is filtered and concentrated in vacuo to obtain intermediate compound 2；Is produced from centre
Compounds 2 are dissolved in n,N-Dimethylaniline or n,N-Dimethylformamide, mixture nitrogen at a temperature of 200-250 DEG C
Atmosphere encloses middle reflux 1-5 hours, is then cooled to room temperature, and be concentrated under reduced pressure, and crude product is purified with rapid column chromatography, is obtained
The compound 3 of yellow oily；Under inert gas atmosphere, compound 3 is dissolved in solvent, is subsequently cooled to 0 DEG C, bromine is added
To change cyanogen, then triethylamine is added drop-wise in mixture again, holds the mixture in 0 DEG C of lasting 3h, sediment is filtered through diatomite,
And repeatedly washed by hexane, then solvent is removed through rotary evaporation, obtain compound 4, as alkene.
3. in nonmetallic Louis acid catalysis olefin hydrocarbon molecules according to claim 2 addition C-O be bonded to benzofuran and
The method of its derivative, it is characterised in that：The solvent is anhydrous hexane and diethyl ether according to volume ratio 5:2 mixture.
4. in nonmetallic Louis acid catalysis olefin hydrocarbon molecules according to claim 1 addition C-O be bonded to benzofuran and
The method of its derivative, it is characterised in that：The step 2 is specially：Alkene that step 1 is prepared, nonmetallic Louis
This acid and toluene mixing, be placed in closed container, at 90 DEG C react 12~for 24 hours；After reaction, it is cooled to room temperature, and
It is diluted with ether；It is finally concentrated with diatomite, column chromatography purified product obtains product after drying.
5. addition C-O is bonded to benzofuran in nonmetallic Louis acid catalysis olefin hydrocarbon molecules according to claim 1 or 4
And its method of derivative, it is characterised in that：In the step 2, nonmetallic lewis acid is B (C6F5)3。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810429931.1A CN108530405A (en) | 2018-05-08 | 2018-05-08 | The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules |
| PCT/CN2019/087153 WO2019214749A1 (en) | 2018-05-08 | 2019-05-16 | Method for synthesizing benzofuran derivative by means of non-metal lewis acid catalyzing addition of c-o bond within olefin molecule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810429931.1A CN108530405A (en) | 2018-05-08 | 2018-05-08 | The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108530405A true CN108530405A (en) | 2018-09-14 |
Family
ID=63476625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810429931.1A Pending CN108530405A (en) | 2018-05-08 | 2018-05-08 | The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108530405A (en) |
| WO (1) | WO2019214749A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019214749A1 (en) * | 2018-05-08 | 2019-11-14 | 南京晓庄学院 | Method for synthesizing benzofuran derivative by means of non-metal lewis acid catalyzing addition of c-o bond within olefin molecule |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2855340B2 (en) * | 1988-06-10 | 1999-02-10 | 武田薬品工業株式会社 | 2-substituted coumaran derivatives |
| WO2006000902A1 (en) * | 2004-06-25 | 2006-01-05 | Pfizer Products Inc. | Dihydrobenzofuran compounds and uses thereof |
| TWI477497B (en) * | 2009-03-10 | 2015-03-21 | Takeda Pharmaceutical | Benzofuran derivatives |
| CN108530405A (en) * | 2018-05-08 | 2018-09-14 | 南京晓庄学院 | The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules |
-
2018
- 2018-05-08 CN CN201810429931.1A patent/CN108530405A/en active Pending
-
2019
- 2019-05-16 WO PCT/CN2019/087153 patent/WO2019214749A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019214749A1 (en) * | 2018-05-08 | 2019-11-14 | 南京晓庄学院 | Method for synthesizing benzofuran derivative by means of non-metal lewis acid catalyzing addition of c-o bond within olefin molecule |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019214749A1 (en) | 2019-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109422684A (en) | A method of synthesis 6- methyl phenanthridines class compound | |
| Pàmies et al. | Copper-catalysed asymmetric conjugate addition of organometallic reagents to enones using S, O-ligands with a xylofuranose backbone | |
| CN110305054A (en) | A kind of preparation method of disubstituted benzene vinyl derivatives | |
| CN108530405A (en) | The method that addition C-O is bonded to benzofuran derivatives in nonmetallic Louis acid catalysis olefin hydrocarbon molecules | |
| Yuan et al. | Reaction of aldimines and difluoroenoxysilane, an unexpected protocol for the synthesis of 2, 2-difluoro-3-hydroxy-1-ones | |
| CN112457276B (en) | Method for synthesizing butylphthalide | |
| Carlsen et al. | Studies toward the AB ring system of the tetrapetalone natural products | |
| Marco-Contelles et al. | Synthesis of chiral, densely functionalized medium-sized rings from carbohydrate precursors via regioselective exo/endo-primary alkyl radical cyclizations | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN102942511A (en) | Preparation method of cyclopentadiene | |
| CN109651385A (en) | A kind of preparation method of pyrans [3,2-a] carbazole compound | |
| CN107188792B (en) | Synthetic method of 2,4' -dihydroxy benzophenone compound | |
| CN106748953B (en) | A kind of synthetic method of pyrrolin -3- formic ether compounds | |
| CN104945231B (en) | Method for synthesizing 1,4-diketone compound by using 2-halogenated cyclopentanone as raw material | |
| CN108299297A (en) | A kind of novel 6- alkyl phenanthridines and derivative and preparation method thereof | |
| CN108191736B (en) | 2, 3-disubstituted indole derivatives and preparation method thereof | |
| CN109942432B (en) | Triaryl methanol compound and synthetic method thereof | |
| CN105884724B (en) | A kind of preparation method of benzofuran compounds | |
| CN113173908A (en) | Preparation method of thiophene compound | |
| CN106083688B (en) | A kind of synthetic method of 3- methyl-1-p-toluenesulfonyl tetrahydropyrrole compound | |
| CN106243073B (en) | A kind of 2-H 1-benzopyran derivatives and its synthetic method | |
| CN103936753B (en) | Natural products Daldinin and the like total synthesis method | |
| CN110128231A (en) | A kind of preparation method of diaryl acetylene compound | |
| CN104327025A (en) | Preparation method of 4-aryltetralin lactone derivatives | |
| CN109422673A (en) | A method of synthesis indole ketone compound containing iodine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180914 |
|
| RJ01 | Rejection of invention patent application after publication |