CN109665999A - The phenylacetic acid class compound and its synthetic method and application that a kind of meta position acyloxy replaces - Google Patents
The phenylacetic acid class compound and its synthetic method and application that a kind of meta position acyloxy replaces Download PDFInfo
- Publication number
- CN109665999A CN109665999A CN201811517030.4A CN201811517030A CN109665999A CN 109665999 A CN109665999 A CN 109665999A CN 201811517030 A CN201811517030 A CN 201811517030A CN 109665999 A CN109665999 A CN 109665999A
- Authority
- CN
- China
- Prior art keywords
- phenylacetic acid
- meta position
- class compound
- replaces
- synthetic method
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The phenylacetic acid class compound and its synthetic method that replace the invention discloses a kind of meta position acyloxy and application, the synthetic method for the phenylacetic acid class compound that the meta position acyloxy replaces is to utilize U- type template-policy, using pyrimidine as novel guiding basic mode plate, under catalysts conditions, realize the direct acetoxylation reaction of phenylacetic acid derivatives meta position, greatly simplify reaction process, reduce reaction cost, with reactivity height, selectivity is good, the advantages that wide application range of substrates, furthermore, by pyrimidine radicals template assemblies on drug molecule brufen, the meta position acetoxylation reaction of ibuprofen derivative equally may be implemented, new synthetic route is provided for the functionalization of drug molecule.
Description
Technical field
The benzene second that the present invention discloses the technical field for being related to Synthetic Organic Chemistry more particularly to a kind of meta position acyloxy replaces
Acid compounds and its synthetic method and application.
Background technique
Transition metal-catalyzed carbon-hydrogen bond activation reaction is to realize that one kind of carbon-carbon bond and carbon-heteroatom bond building is important
Means have the characteristics that atom economy type and step are succinct, in organic synthesis, drug because it is not necessarily to for substrate being functionalized in advance
Synthesis and natural products synthesis etc. are widely used.In recent years, researcher is mainly by aromatic compound
Middle introduce contains heteroatomic homing device, forms ring metal complex using the second third transition metal and heteroatomic coordination, with
Realize to highly selective and high reaction activity the carbon-hydrogen bond activation reaction of aromatic compound specific position.Wherein, most of to use
Transition metal palladium, rhodium, nickel, cobalt etc. are catalyst, carry out C-H bond reaction to the ortho position of guiding base, realize that carbon-carbon bond and carbon-are miscellaneous
The building of atom key.And by designing different homing device, participated in reaction using homing device synthesize it is a series of thick
The removing of homing device may be implemented under certain conditions in heterocyclic compound, and then will not influence the activity of substrate.
So far, there are more report and more deep research to guiding base ortho position carbon-hydrogen bond activation reaction, but
Less to the meta position of homing device, the report of the C-H bond functionalization of contraposition, mainly meta position carbon-hydrogen bond activation reacted
The Macrocyclic metal transition state energy formed in journey is higher, is not that very stable equal factors cause to react relatively difficult to achieve.And utilize transition
Metal catalytic realizes that the acetoxylation reaction of phenylacetic acid derivatives is even more to have not been reported.
Therefore, a kind of acetoxylation reaction using transition metal-catalyzed realization phenylacetic acid derivatives how is researched and developed, with
Remedy technology blank becomes people's urgent problem to be solved.
Summary of the invention
In consideration of it, the invention discloses a kind of phenylacetic acid class compound of meta position acyloxy substitution and its synthetic method and answering
With to make up the technological gap of the acetoxylation reaction of phenylacetic acid derivatives.
One aspect of the present invention provides a kind of method of the acetoxylation reaction of phenylacetic acid derivatives, shown in formula (I)
Phenylacetic acid derivatives be raw material, using iodobenzene acetate as oxidant, in the mixed of catalyst, ligand, additive and solvent composition
It closes and is reacted in liquid, after reaction, take out solvent with Rotary Evaporators, obtain crude product；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is stone
The mixed solvent of oily ether and ethyl acetate；
Wherein, R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
The detailed process of the acetoxylation reaction of above-mentioned phenylacetic acid derivatives are as follows: reactor is vacuumized, nitrogen is passed through
Displacement, after phenylacetic acid derivatives, iodobenzene acetate, catalyst, ligand, additive and solvent are sequentially added in the reactor,
Heating reaction 12-24h takes out solvent with Rotary Evaporators, obtains crude product after reaction；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is stone
The mixed solvent of oily ether and ethyl acetate.
It is preferred that the catalyst is transition metal；Preferably palladium acetate, dichloro (pentamethylcyclopentadiene base) radium chloride
(III) dimer, dichloro (pentamethylcyclopentadiene base) iridium chloride (III) dimer or dichloro are bis- (4- isopropyl methyl phenyl)
Ruthenium (II).
Further preferably, the ligand is N- acetoglycocoll, N- acetylalanine, N- acetylvaline, N- acetophenone
One or both of alanine, N- Acetylleucine.
Further preferably, the additive is one or both of acetic acid, acetic anhydride.
Further preferably, the solvent is n,N-Dimethylformamide, dimethyl sulfoxide, methylene chloride, acetonitrile, Isosorbide-5-Nitrae-two
One or both of six ring of oxygen, 1,2- dichloroethanes, tetrahydrofuran, ethyl alcohol, methanol, trifluoroethanol and hexafluoroisopropanol.
Further preferably, the reaction temperature of the reaction is 20-140 DEG C.
Further preferably, the phenylacetic acid derivatives are 1:4 with the molar ratio of reacting of iodobenzene acetate.
It is the phenylacetic acid class compound that meta position acyloxy replaces by the product that the above method obtains, general structure is such as
Under:
Wherein, R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
The meta position acyloxy replace phenylacetic acid class compound can be used for relieving the pain, anti-inflammatory and antipyretic synthesis.
The method of the acetoxylation reaction of phenylacetic acid derivatives provided by the invention, using U- type template-policy, with phonetic
Pyridine is as novel guiding basic mode plate, under catalysts conditions, realizes the direct acetoxylation of phenylacetic acid derivatives meta position
Reaction greatly simplifies reaction process, reduces reaction cost, has high, good, wide application range of substrates of selectivity of reactivity etc. excellent
Point.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
The disclosure can be limited.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, for those of ordinary skill in the art
Speech, without creative efforts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the hydrogen spectrogram that the present invention discloses compound 3a in embodiment 1；
Fig. 2 is the carbon spectrogram that the present invention discloses compound 3a in embodiment 1；
Fig. 3 is the hydrogen spectrogram that the present invention discloses compound 3b in embodiment 2；
Fig. 4 is the carbon spectrogram that the present invention discloses compound 3b in embodiment 2；
Fig. 5 is the hydrogen spectrogram that the present invention discloses compound 3c in embodiment 3；
Fig. 6 is the carbon spectrogram that the present invention discloses compound 3c in embodiment 3；
Fig. 7 is the hydrogen spectrogram that the present invention discloses compound 3d in embodiment 4；
Fig. 8 is the carbon spectrogram that the present invention discloses compound 3d in embodiment 4.
Specific embodiment
The present invention is further explained with specific embodiment below, but be not intended to restrict the invention
Protection scope.
In view of in the prior art, the temporary not no report about the acetoxylation reaction of phenylacetic acid derivatives, this embodiment party
Case provides a kind of method of the acetoxylation reaction of phenylacetic acid derivatives, and this method utilizes U- type template-policy, with pyrimidine
As novel guiding basic mode plate, under catalysts conditions, the direct acetoxylation for realizing phenylacetic acid derivatives meta position is anti-
It answers, greatly simplifies reaction process, specifically, being oxidation with iodobenzene acetate using phenylacetic acid derivatives shown in formula (I) as raw material
Agent is reacted in the mixed liquor of catalyst, ligand, additive and solvent composition, after reaction, is taken out with Rotary Evaporators
Solvent obtains crude product；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is stone
The mixed solvent of oily ether and ethyl acetate；
Wherein, R be one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three,
Specifically include: alkyl, alkoxy, m-trifluoromethyl, cyano, nitro, F, Cl, Br, I, to alkyl, right
Alkoxy, to trifluoromethyl, to cyano, to nitro, to F, to Cl, to Br and to I；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
The specific operation process of the acetoxylation reaction of above-mentioned phenylacetic acid derivatives is as follows: reactor being taken out true
Sky is passed through nitrogen displacement, phenylacetic acid derivatives, iodobenzene acetate, catalyst, ligand, addition is sequentially added in the reactor
After agent and solvent, heating reaction 12-24h takes out solvent with Rotary Evaporators, obtains crude product after reaction；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is stone
The mixed solvent of oily ether and ethyl acetate.
Wherein, catalyst is transition metal, preferably are as follows: palladium acetate, dichloro (pentamethylcyclopentadiene base) radium chloride (III)
Dimer, dichloro (pentamethylcyclopentadiene base) iridium chloride (III) dimer or bis- (the 4- isopropyl methyl phenyl) rutheniums of dichloro
(II), the dosage of the catalyst is the 10% of phenylacetic acid derivatives molal quantity.
Ligand is that N- acetoglycocoll, N- acetylalanine, N- acetylvaline, N-acetylphenylalanine, N- acetyl are bright
One or both of propylhomoserin.
Additive is one or both of acetic acid, acetic anhydride, wherein dosage is phenylacetic acid derivatives molal quantity
400%.
Solvent is N,N-dimethylformamide, dimethyl sulfoxide, methylene chloride, acetonitrile, 1,4- dioxane, 1,2- dichloro
One or both of ethane, tetrahydrofuran, ethyl alcohol, methanol, trifluoroethanol and hexafluoroisopropanol, wherein every mM anti-
Answer 5-20 milliliters of object phenylacetic acid derivatives solvent.
In above-mentioned meta position process or acetoxylation, the reaction temperature for heating reaction is 20-140 DEG C.
In above-mentioned meta position process or acetoxylation, phenylacetic acid derivatives are 1:4 with the molar ratio of reacting of iodobenzene acetate.
Wherein, phenylacetic acid derivatives shown in formula (I) can be used any method and prepare, as long as meeting its general structure
It is required that the following are preparation method of the present invention, it is specifically as follows when reaction:
Specifically the preparation method is as follows: step 1: reactor vacuumize is passed through nitrogen displacement, sequentially add 5- Bromopyrimidine,
2- hydroxyl phenyl boric acid, palladium acetate, seven water potassium phosphates and isopropanol；After 80 DEG C of stirring 10-12h, it is sudden that salt water is added into reactor
It goes out reaction, products therefrom is extracted with ethyl acetate and is evaporated under reduced pressure, and obtained crude product obtains 2- (5- pyrimidine through silica gel column chromatography
Base) phenol.Step 2: 2- (5- pyrimidine radicals) phenol, aryl-acyl chlorides, triethylamine, DCE are added into reaction vessel；Stirring at normal temperature,
Products therefrom is extracted with ethyl acetate and is evaporated under reduced pressure, and obtained crude product obtains phenylacetic acid derivatives formula through silica gel column chromatography
(Ⅰ)。
It is the phenylacetic acid class compound that meta position acyloxy replaces by the product that the above method obtains, general structure is such as
Under:
Wherein, R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
The meta position acyloxy replace phenylacetic acid class compound can be used for relieving the pain, anti-inflammatory and antipyretic synthesis.
During the experiment, cloth equally may be implemented by pyrimidine radicals template assemblies on drug molecule brufen in inventor
The meta position acetoxylation of ibuprofen derivative is reacted, and it is drug that the template of miazines guiding base can remove in a mild condition
The function dough of molecule provides new synthetic route, and meta position with higher selectivity.
The present invention is further illustrated with specific embodiment below.
Embodiment 1
Reactor, which vacuumizes, is passed through nitrogen displacement three times, sequentially adds 0.2mmol (58.0mg) phenylacetic acid derivatives (1a),
0.8mmol (257.58mg) iodobenzene acetate (2), 0.02mmol (4.48mg) Pd (OAc)2, 0.05mmol (5.86mg) Ac-Gly-
OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, 100 DEG C of stirrings are for 24 hours.After reaction, it is taken out with Rotary Evaporators molten
Agent, crude product are chromatographed by column, and eluant, eluent is petroleum ether: ethyl acetate=3:1 mixed solvent obtains acetoxyl group between 35.5mg
Substituted phenylacetic acid derivatives 3a, separation yield 51%.
The characterize data of compound 3a is as follows:
1H NMR(400MHz,CDCl3)δ9.15(s,1H),8.71(s,2H),7.50-7.45(m,1H),7.41-7.36
(m, 2H), 7.32 (t, J=8.0Hz, 1H), 7.21-7.19 (m, 1H), 7.03 (dd, J=7.9,2.0Hz, 2H), 6.94 (t, J
=2.0Hz, 1H), 3.70 (s, 2H), 2.31 (s, 3H)13C NMR(100MHz,CDCl3)δ169.4,169.0,157.6,
156.3,150.9,147.9,134.0,131.1,130.5,130.4,129.8,127.9,127.0,126.6,123.2,
122.4,120.8,40.9,21.2.HRMS(ESI):calcd for C20H16N2O4([M+H]+)349.1183,found
(349.1192. referring to Fig. 1, Fig. 2).
Embodiment 2
Reactor, which vacuumizes, is passed through nitrogen displacement three times, sequentially adds 0.2mmol (64.02mg) phenylacetic acid derivatives
(1b), 0.8mmol (257.58mg) iodobenzene acetate (2), 0.02mmol (4.48mg) Pd (OAc)2, 0.05mmol (5.86mg)
Ac-Gly-OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, 100 DEG C of stirrings are for 24 hours.After reaction, Rotary Evaporators are used
Solvent is taken out, crude product is chromatographed by column, and eluant, eluent is petroleum ether: ethyl acetate=3:1 mixed solvent obtains second between 41.6mg
The phenylacetic acid derivatives 3b that acyloxy replaces, separation yield 55%.
The characterize data of compound 3b is as follows:
1H NMR(400MHz,CDCl3)δ9.18(s,1H),8.75(s,2H),7.49-7.45(m,1H),7.38-7.36
(m, 2H), 7.23 (d, J=8.0Hz, 1H), 7.00 (dd, J=8.8,2.8Hz, 1H), 6.88 (d, J=2.8Hz, 1H), 6.83
(d, J=8.9Hz, 1H), 3.78 (s, 3H), 3.70 (s, 2H), 2.28 (s, 3H)13C NMR(100MHz,CDCl3)δ169.9,
169.3,157.4,156.4,155.1,148.0,143.8,131.3,130.5,130.3,127.7,126.8,124.0,
123.3,122.6,121.6,110.9,55.8,35.9,21.1.HRMS(ESI):calcd for C21H18N2O5([M+H]+)
379.1288, found 379.1297. (see Fig. 3, Fig. 4).
Embodiment 3
Reactor, which vacuumizes, is passed through nitrogen displacement three times, sequentially adds 0.2mmol (60.8mg) phenylacetic acid derivatives (1c),
0.8mmol (257.58mg) iodobenzene acetate (2), 0.02mmol (4.48mg) Pd (OAc)2, 0.05mmol (5.86mg) Ac-Gly-
OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, 100 DEG C of stirrings are for 24 hours.After reaction, it is taken out with Rotary Evaporators molten
Agent, crude product are chromatographed by column, and eluant, eluent is petroleum ether: ethyl acetate=3:1 mixed solvent obtains acetoxyl group between 39.1mg
Substituted phenylacetic acid derivatives 3c, separation yield 54%.
The characterize data of compound 3c is as follows:
1H NMR(400MHz,CDCl3)δ9.12(s,1H),8.70(s,2H),7.50-7.46(m,1H),7.40-7.33
(m, 2H), 7.21 (dd, J=8.1,0.8Hz, 1H), 6.83 (s, 2H), 6.72 (s, 1H), 3.65 (s, 2H), 2.33 (s, 3H),
2.29(s,3H).13C NMR(100MHz,CDCl3)δ169.8,169.1,157.2,156.3,150.7,147.8,140.2,
133.6,131.2,130.5,130.4,127.7,127.5,127.0,123.2,121.5,119.4,40.9,21.3,
21.1.HRMS(ESI):calcd for C21H18N2O4([M+H]+) 363.1339, found 363.1348. (see Fig. 5, Fig. 6).
Embodiment 4:
Reactor vacuumize is passed through nitrogen displacement three times, sequentially add 0.2mmol (64.02mg) phenylacetic acid derivatives (1d,
0.8mmol (257.58mg) iodobenzene acetate (2), 0.02mmol (4.48mg) Pd (OAc)2, 0.05mmol (5.86mg) Ac-Gly-
OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, 100 DEG C of stirrings are for 24 hours.After reaction, it is taken out with Rotary Evaporators molten
Agent, crude product are chromatographed by column, and eluant, eluent is petroleum ether: ethyl acetate=3:1 mixed solvent obtains acetoxyl group between 36.3mg
Substituted phenylacetic acid derivatives 3d, separation yield 48%.
The characterize data of compound 3d is as follows:
1H NMR(400MHz,CDCl3)δ9.15(s,1H),8.71(s,2H),7.48-7.45(m,1H),7.40-7.35
(m, 2H), 7.22-7.19 (m, 1H), 6.59 (t, J=2.0Hz, 1H), 6.57 (t, J=2.0Hz, 1H), 6.54 (t, J=
1.6Hz,1H),3.78(s,3H),3.65(s,2H),2.30(s,3H).13C NMR(100MHz,CDCl3)δ169.3,168.9,
160.6,157.6,156.3,151.7,147.9,134.6,131.1,130.5,130.4,127.9,127.0,123.2,
114.8,112.5,106.9,55.5,41.1,21.2.HRMS(ESI):calcd for C21H18N2O5([M+H]+)
379.1288, found 379.1295. (see Fig. 7, Fig. 8).
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are wanted by right
It asks and points out.
It should be understood that the invention is not limited to the content being described above, can without departing from the scope into
Row various modifications and change.The scope of the present invention is limited only by the attached claims.
Claims (10)
1. the phenylacetic acid class compound that a kind of meta position acyloxy replaces, which is characterized in that its general structure is as follows:
Wherein, R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
2. a kind of synthetic method for the phenylacetic acid class compound that meta position acyloxy as described in claim 1 replaces, which is characterized in that
Using phenylacetic acid derivatives shown in formula (I) as raw material, using iodobenzene acetate as oxidant, in catalyst, ligand, additive and molten
It is reacted in the mixed liquor of agent composition, after reaction, takes out solvent with Rotary Evaporators, obtain crude product；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is petroleum ether
With the mixed solvent of ethyl acetate；
Wherein, R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br, I, two or three；
R ' is hydrogen, C1-C5One or both of alkyl and aryl.
3. the synthetic method for the phenylacetic acid class compound that meta position acyloxy replaces according to claim 2, which is characterized in that tool
Body synthesis step is as follows:
Reactor is vacuumized, be passed through nitrogen displacement, sequentially added in the reactor phenylacetic acid derivatives, iodobenzene acetate,
After catalyst, ligand, additive and solvent, heating reaction 12-24h takes out solvent with Rotary Evaporators, obtains after reaction
Obtain crude product；
The crude product is subjected to column chromatography, obtains product, wherein eluant, eluent used in the column chromatography procedure is petroleum ether
With the mixed solvent of ethyl acetate.
4. the synthetic method for the phenylacetic acid class compound that the meta position acyloxy according to Claims 2 or 3 replaces, feature exist
In the catalyst is transition metal；Preferably palladium acetate, dichloro (pentamethylcyclopentadiene base) radium chloride (III) dimer,
Dichloro (pentamethylcyclopentadiene base) iridium chloride (III) dimer or bis- (the 4- isopropyl methyl phenyl) rutheniums (II) of dichloro.
5. the synthetic method for the phenylacetic acid class compound that the meta position acyloxy according to Claims 2 or 3 replaces, feature exist
In the ligand is N- acetoglycocoll, N- acetylalanine, N- acetylvaline, N-acetylphenylalanine, the bright ammonia of N- acetyl
One or both of acid.
6. the synthetic method for the phenylacetic acid class compound that the meta position acyloxy according to Claims 2 or 3 replaces, feature exist
In the additive is one or both of acetic acid, acetic anhydride.
7. the synthetic method for the phenylacetic acid class compound that the meta position acyloxy according to Claims 2 or 3 replaces, feature exist
In the solvent is n,N-Dimethylformamide, dimethyl sulfoxide, methylene chloride, acetonitrile, Isosorbide-5-Nitrae-dioxane, 1,2- dichloro
One or both of ethane, tetrahydrofuran, ethyl alcohol, methanol, trifluoroethanol and hexafluoroisopropanol.
8. the synthetic method for the phenylacetic acid class compound that meta position acyloxy replaces according to claim 3, which is characterized in that institute
The reaction temperature for stating reaction is 20-140 DEG C.
9. the synthetic method for the phenylacetic acid class compound that the meta position acyloxy according to Claims 2 or 3 replaces, feature exist
In the phenylacetic acid derivatives are 1:4 with the molar ratio of reacting of iodobenzene acetate.
10. a kind of application for the phenylacetic acid class compound that meta position acyloxy as described in claim 1 replaces, which is characterized in that use
In relieve the pain, anti-inflammatory and antipyretic synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811517030.4A CN109665999B (en) | 2018-12-12 | 2018-12-12 | Meta-acyloxy substituted phenylacetic acid compound and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811517030.4A CN109665999B (en) | 2018-12-12 | 2018-12-12 | Meta-acyloxy substituted phenylacetic acid compound and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109665999A true CN109665999A (en) | 2019-04-23 |
| CN109665999B CN109665999B (en) | 2022-05-20 |
Family
ID=66143707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811517030.4A Active CN109665999B (en) | 2018-12-12 | 2018-12-12 | Meta-acyloxy substituted phenylacetic acid compound and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109665999B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382910A (en) * | 2017-07-17 | 2017-11-24 | 辽宁石油化工大学 | A kind of difluoromethyl aldehyde hydrazone compounds and preparation method thereof |
-
2018
- 2018-12-12 CN CN201811517030.4A patent/CN109665999B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382910A (en) * | 2017-07-17 | 2017-11-24 | 辽宁石油化工大学 | A kind of difluoromethyl aldehyde hydrazone compounds and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| ANIRUDDHA DEY ET AL.,: ""Accessing Remote meta- and para-C(sp2)−H Bonds with Covalently Attached Directing Groups"", 《ANGEWANDTE CHEMIE》 * |
| BERA, M. , ET AL.: ""Meta-Selective Arene C-H Bond Olefination of Arylacetic Acid Using a Nitrile-Based Directing Group"", 《ORGANIC LETTERS》 * |
| DASHNOW, AN-SHNM, AND JN-QUANYU.: ""Activation of remote meta-C–H bonds assisted by an end-on template"", 《NATURE》 * |
| JIONG YANG: ""Transition metal catalyzed meta-C–H functionalization of aromatic compounds"", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| STEPAN, A. , ET AL.: ""Pd(II)-catalyzed ortho- or meta-C-H olefination of phenol derivatives"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109665999B (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | The Pyridyldiisopropylsilyl Group: A Masked Functionality and Directing Group for Monoselective ortho‐Acyloxylation and ortho‐Halogenation Reactions of Arenes | |
| Fu et al. | Nickel‐Catalyzed Difluoromethylation of Arylboronic Acids with Bromodifluoromethane | |
| Ito et al. | Efficient Preparation of New Rhodium‐and Iridium‐[Bis (oxazolinyl)‐3, 5‐dimethylphenyl] Complexes by C H Bond Activation: Applications in Asymmetric Synthesis | |
| Mikami et al. | A highly efficient asymmetric Suzuki–Miyaura coupling reaction catalyzed by cationic chiral palladium (II) complexes | |
| Sajith et al. | Exploration of copper and amine-free Sonogashira cross coupling reactions of 2-halo-3-alkyl imidazo [4, 5-b] pyridines using tetrabutyl ammonium acetate as an activator under microwave enhanced conditions | |
| Hsieh et al. | Asymmetric synthesis of indolines bearing a benzylic quaternary stereocenter through intramolecular arylcyanation of alkenes | |
| CN109535084B (en) | Meta-alkenyl phenylacetic acid compound and synthesis method and application thereof | |
| Chai et al. | Asymmetric allylation of aldehydes with allyltrichlorosilane using aza-paracyclophane-oxazoline-N-oxide catalysts | |
| Komatsuda et al. | Ring-opening fluorination of bicyclic azaarenes | |
| Kelkar et al. | Selectivity behavior in catalytic oxidative carbonylation of alkyl amines | |
| Khatravath et al. | Recent Advancements in Development of Radical Silylation Reactions | |
| CN110204481B (en) | Polysubstituted nitrogen-containing aromatic heterocyclic compound and preparation method and application thereof | |
| Toullec et al. | Au2O3 as a stable and efficient catalyst for the selective cycloisomerization of γ-acetylenic carboxylic acids to γ-alkylidene-γ-butyrolactones | |
| CN112301370B (en) | Electrochemical synthesis method of 1, 3-dimethyl-3-difluoroethyl-2-oxindole compound | |
| CN109810125A (en) | The preparation method of chiral copper complex and preparation method thereof, chiral unsaturated beta-nitro alpha-hydroxy esters | |
| CN109665999A (en) | The phenylacetic acid class compound and its synthetic method and application that a kind of meta position acyloxy replaces | |
| Jiang et al. | Efficient Iron-Catalyzed Tsuji-Trost Coupling Reaction of Aromatic Allylic Amides through a sp³-Carbon-Nitrogen Breaking | |
| Lee et al. | Palladium-catalyzed allylic substitution using in situ generated allylindium reagents | |
| CN105294499B (en) | A kind of preparation method of carbon imidodicarbonic diamide class compound | |
| Kazmierski et al. | 2, 2′-Bipyridine: An Efficient Ligand in the Cobalt-Catalyzed Synthesis of Organozinc Reagents from Aryl Chlorides and Sulfonates | |
| Lu et al. | Chiral N-thiophosphoryl imine-induced diastereoselective aza-Morita–Baylis–Hillman reaction | |
| CN105198806B (en) | A kind of method using aromatic amine, diketone synthesis of quinoline derivatives | |
| CN112194559B (en) | Synthesis method of chiral and achiral 2,2' -dihalogenated biaryl compound | |
| Moreno-Manas et al. | Suzuki cross-couplings on aryl (heteroaryl) bromides and chlorides with bulky aliphatic phosphines/Pd (0)-triolefinic macrocyclic catalyst | |
| CN110590679A (en) | Method for catalytic synthesis of 5-substituted barbituric acid derivative by rare earth chloride |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |