CN109665999B - Meta-acyloxy substituted phenylacetic acid compound and synthesis method and application thereof - Google Patents
Meta-acyloxy substituted phenylacetic acid compound and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a meta-acyloxy substituted phenylacetic acid compound and a synthesis method and application thereof, wherein the synthesis method of the meta-acyloxy substituted phenylacetic acid compound utilizes a U-shaped template strategy, takes pyrimidine as a novel guide base template, realizes the direct acetoxylation reaction of the meta position of a phenylacetic acid derivative under the condition of a catalyst, greatly simplifies the reaction process, reduces the reaction cost, and has the advantages of high reaction activity, good selectivity, wide substrate application range and the like.
Description
Technical Field
The invention relates to the technical field of organic synthetic chemistry, in particular to a meta-acyloxy-substituted phenylacetic acid compound and a synthetic method and application thereof.
Background
The carbon-hydrogen bond activation reaction catalyzed by the transition metal is an important means for realizing the construction of carbon-carbon bonds and carbon-heteroatom bonds, has the characteristics of atom economy, simple steps and the like because a substrate does not need to be functionalized in advance, and is widely applied to the aspects of organic synthesis, pharmaceutical synthesis, natural product synthesis and the like. In recent years, researchers have realized highly selective and highly reactive carbon-hydrogen bond activation at specific positions of aromatic compounds mainly by introducing a heteroatom-containing directing group into the aromatic compounds and forming a ring metal complex by coordination of a second, third transition metal with the heteroatom. Wherein, most of transition metals such as palladium, rhodium, nickel, cobalt and the like are used as catalysts, and the carbon-hydrogen bond reaction is carried out on the ortho position of the guide group to realize the construction of carbon-carbon bonds and carbon-heteroatom bonds. And through designing different guide groups, a series of fused heterocyclic compounds are synthesized by utilizing the guide groups participating in the reaction, and the removal of the guide groups can be realized under certain conditions, so that the activity of a substrate cannot be influenced.
So far, there are many reports and more profound researches on the activation reaction of the carbon-hydrogen bond at the ortho position of the directing group, but there are few reports on the functionalization reaction of the carbon-hydrogen bond at the meta position and para position of the directing group, and mainly the transition state energy of the macrocyclic metal formed in the activation reaction process of the carbon-hydrogen bond at the meta position is high, and the reaction is difficult to realize due to factors such as poor stability and the like. The transition metal catalysis for the acetoxylation of phenylacetic acid derivatives is not reported.
Therefore, how to develop a method for realizing acetoxylation of phenylacetic acid derivatives by transition metal catalysis to make up for the technical gap is a problem to be solved urgently.
Disclosure of Invention
In view of this, the invention discloses a meta-acyloxy substituted phenylacetic acid compound, a synthesis method and an application thereof, so as to make up for the technical blank of acetoxylation reaction of phenylacetic acid derivatives.
The invention provides a method for acetoxylation of phenylacetic acid derivatives, which comprises the steps of taking phenylacetic acid derivatives shown in formula (I) as a raw material, taking iodobenzene acetate as an oxidant, reacting in a mixed solution consisting of a catalyst, a ligand, an additive and a solvent, and after the reaction is finished, pumping off the solvent by using a rotary evaporator to obtain a crude product;
performing column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate;
wherein R is one, two or three of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
r' is hydrogen, C1-C5One or both of an alkyl group and an aryl group.
The specific process of the acetoxylation reaction of the phenylacetic acid derivative comprises the following steps: vacuumizing a reactor, introducing nitrogen for replacement, sequentially adding a phenylacetic acid derivative, iodobenzene acetate, a catalyst, a ligand, an additive and a solvent into the reactor, heating for reaction for 12-24h, and after the reaction is finished, pumping off the solvent by using a rotary evaporator to obtain a crude product;
and carrying out column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate.
Preferably, the catalyst is a transition metal; preferably palladium acetate, dichloro (pentamethylcyclopentadienyl) rhodium (III) chloride dimer, dichloro (pentamethylcyclopentadienyl) iridium (III) chloride dimer or dichlorobis (4-methylisopropylphenyl) ruthenium (II).
More preferably, the ligand is one or two of N-acetyl glycine, N-acetyl alanine, N-acetyl valine, N-acetyl phenylalanine and N-acetyl leucine.
Further preferably, the additive is one or two of acetic acid and acetic anhydride.
More preferably, the solvent is one or two of N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydrofuran, ethanol, methanol, trifluoroethanol, and hexafluoroisopropanol.
Further preferably, the reaction temperature of the reaction is 20 to 140 ℃.
More preferably, the reaction molar ratio of the phenylacetic acid derivative to iodobenzene acetate is 1: 4.
The product obtained by the method is a meta-acyloxy substituted phenylacetic acid compound, and the structural general formula is as follows:
wherein R is one, two or three of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
r' is hydrogen, C1-C5One or both of an alkyl group and an aryl group.
The meta-acyloxy substituted phenylacetic acid compound can be used for synthesizing analgesic, anti-inflammatory and antipyretic drugs.
The method for acetoxylation of phenylacetic acid derivatives provided by the invention utilizes a U-shaped template strategy, uses pyrimidine as a novel guide base template, realizes direct acetoxylation of phenylacetic acid derivatives at meta position under the condition of a catalyst, greatly simplifies the reaction process, reduces the reaction cost, and has the advantages of high reaction activity, good selectivity, wide substrate application range and the like.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a hydrogen spectrum of compound 3a of example 1 of the present disclosure;
FIG. 2 is a carbon spectrum of Compound 3a of example 1 of the present disclosure;
FIG. 3 is a hydrogen spectrum of Compound 3b of example 2 of the present disclosure;
FIG. 4 is a carbon spectrum of compound 3b of example 2 of the present disclosure;
FIG. 5 is a hydrogen spectrum of compound 3c of example 3 of the present disclosure;
FIG. 6 is a carbon spectrum of compound 3c of example 3 of the present disclosure;
FIG. 7 is a hydrogen spectrum of Compound 3d of example 4 of the present disclosure;
FIG. 8 is a carbon spectrum of compound 3d of example 4 of the present disclosure.
Detailed Description
The present invention is further explained below with reference to specific embodiments, but is not intended to limit the scope of the present invention.
In view of the fact that the prior art has no report about acetoxylation of phenylacetic acid derivatives, the embodiment provides a method for acetoxylation of phenylacetic acid derivatives, which utilizes a U-shaped template strategy, takes pyrimidine as a novel guide base template, and realizes direct acetoxylation of the meta-position of the phenylacetic acid derivatives under the condition of a catalyst, thereby greatly simplifying the reaction process, in particular, the phenylacetic acid derivatives shown in formula (I) are taken as a raw material, iodobenzene acetate is taken as an oxidant, and the reaction is carried out in a mixed solution consisting of the catalyst, a ligand, an additive and a solvent, after the reaction is finished, the solvent is removed by a rotary evaporator, and a crude product is obtained;
performing column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate;
wherein, R is one, two or three of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I, and specifically comprises: m-alkyl, m-alkoxy, m-trifluoromethyl, m-cyano, m-nitro, m-F, m-Cl, m-Br, m-I, p-alkyl, p-alkoxy, p-trifluoromethyl, p-cyano, p-nitro, p-F, p-Cl, p-Br and p-I;
r' is hydrogen, C1-C5One of alkyl and arylOr both.
The concrete reaction operation process of the acetoxylation reaction of the phenylacetic acid derivative is as follows: vacuumizing a reactor, introducing nitrogen for replacement, sequentially adding a phenylacetic acid derivative, iodobenzene acetate, a catalyst, a ligand, an additive and a solvent into the reactor, heating for reaction for 12-24h, and after the reaction is finished, pumping off the solvent by using a rotary evaporator to obtain a crude product;
and carrying out column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate.
Among them, the catalyst is a transition metal, preferably: palladium acetate, dichloro (pentamethylcyclopentadienyl) rhodium (III) chloride dimer, dichloro (pentamethylcyclopentadienyl) iridium (III) chloride dimer or dichlorobis (4-methylisopropylphenyl) ruthenium (II), the catalyst being used in an amount of 10% by moles with respect to the phenylacetic acid derivative.
The ligand is one or two of N-acetyl glycine, N-acetyl alanine, N-acetyl valine, N-acetyl phenylalanine and N-acetyl leucine.
The additive is one or two of acetic acid and acetic anhydride, wherein the dosage is 400 percent of the mole number of the phenylacetic acid derivative.
The solvent is one or two of N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydrofuran, ethanol, methanol, trifluoroethanol and hexafluoroisopropanol, wherein 5-20 ml of the solvent is used for each millimole of the phenylacetic acid derivative serving as the reactant.
In the above-mentioned meta-acetoxylation method, the reaction temperature of the heating reaction is 20 to 140 ℃.
In the m-acetoxylation method, the reaction molar ratio of the phenylacetic acid derivative to the iodobenzene acetate is 1: 4.
The phenylacetic acid derivative shown in the formula (I) can be prepared by any method as long as the requirement of the structural general formula is met, and the following preparation method adopted by the invention is specifically used as follows:
the preparation method comprises the following steps: the method comprises the following steps: vacuumizing the reactor, introducing nitrogen for replacement, and sequentially adding 5-bromopyrimidine, 2-hydroxyphenylboronic acid, palladium acetate, potassium phosphate heptahydrate and isopropanol; stirring at 80 deg.C for 10-12h, adding saline water into the reactor to quench reaction, extracting the obtained product with ethyl acetate, distilling under reduced pressure, and subjecting the obtained crude product to silica gel column chromatography to obtain 2- (5-pyrimidinyl) phenol. Step two: adding 2- (5-pyrimidinyl) phenol, aryl acyl chloride, triethylamine and DCE into a reaction vessel; stirring at normal temperature, extracting the obtained product with ethyl acetate, distilling under reduced pressure, and performing silica gel column chromatography on the obtained crude product to obtain the phenylacetic acid derivative shown in formula (I).
The product obtained by the method is a meta-acyloxy substituted phenylacetic acid compound, and the structural general formula is as follows:
wherein R is one, two or three of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
r' is hydrogen, C1-C5One or both of an alkyl group and an aryl group.
The meta-acyloxy substituted phenylacetic acid compound can be used for synthesizing analgesic, anti-inflammatory and antipyretic drugs.
In the experimental process, the inventor assembles a pyrimidinyl template on the drug molecule ibuprofen, so that the meta-acetoxylation reaction of the ibuprofen derivative can be realized, the template of the pyrimidine guiding group can be removed under mild conditions, a new synthetic route is provided for the functionalization of the drug molecule, and the meta-selectivity is higher.
The invention is further illustrated by the following specific examples.
Example 1
The reactor was evacuated and purged with nitrogen three times, and 0.2mmol (58.0mg) of the phenylacetic acid derivative (1a), 0.8mmol (257.58mg) of iodobenzene acetate (2), 0.02mmol (4.48mg) of Pd (OAc) were added successively20.05mmol (5.86mg) Ac-Gly-OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, stirring at 100 ℃ for 24 h. After the reaction was completed, the solvent was removed by a rotary evaporator, and the crude product was subjected to column chromatography using a mixed solvent of petroleum ether and ethyl acetate 3:1 as an eluent to give 35.5mg of m-acetoxy-substituted phenylacetic acid derivative 3a in an isolated yield of 51%.
Characterization data for compound 3a are 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 (see fig. 1, 2).
Example 2
The reactor was evacuated and purged with nitrogen three times, and 0.2mmol (64.02mg) of phenylacetic acid derivative (1b), 0.8mmol (257.58mg) of iodobenzene acetate (2), 0.02mmol (4.48mg) of Pd (OAc) were added successively20.05mmol (5.86mg) Ac-Gly-OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, stirred at 100 ℃ for 24 h. After the reaction was completed, the solvent was removed by a rotary evaporator, and the crude product was subjected to column chromatography using a mixed solvent of petroleum ether and ethyl acetate 3:1 as an eluent to give 41.6mg of m-acetoxy-substituted phenylacetic acid derivative 3b in an isolated yield of 55%.
Characterization data for compound 3b are 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, 4).
Example 3
The reactor was evacuated and purged with nitrogen three times, and 0.2mmol (60.8mg) of phenylacetic acid derivative (1c), 0.8mmol (257.58mg) of iodobenzene acetate (2), 0.02mmol (4.48mg) of Pd (OAc) were added successively20.05mmol (5.86mg) Ac-Gly-OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, stirring at 100 ℃ for 24 h. After the reaction was completed, the solvent was removed by a rotary evaporator, and the crude product was subjected to column chromatography using a mixed solvent of petroleum ether and ethyl acetate 3:1 as an eluent to give 39.1mg of m-acetoxy-substituted phenylacetic acid derivative 3c in an isolated yield of 54%.
Characterization data for compound 3c are 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, 6).
Example 4:
the reactor was evacuated and purged with nitrogen three times, and 0.2mmol (64.02mg) of a phenylacetic acid derivative (1d, 0.8mmol (257.58mg) of iodobenzene acetate (2), 0.02mmol (4.48mg) of Pd (OAc))20.05mmol (5.86mg) Ac-Gly-OH, 0.8mmol (81.7mg) acetic anhydride, 1mL HFIP, stirring at 100 ℃ for 24 h. After the reaction was completed, the solvent was removed by a rotary evaporator, and the crude product was subjected to column chromatography using a mixed solvent of petroleum ether and ethyl acetate 3:1 as an eluent to give 36.3mg of m-acetoxy-substituted phenylacetic acid derivative 3d in an isolated yield of 48%.
Characterization data for compound 3d are 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, 8).
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to what has been described above, but is capable of numerous modifications and variations without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (4)
1. A synthetic method of meta-acyloxy substituted phenylacetic acid compounds is characterized in that phenylacetic acid derivatives shown in a formula (I) are used as raw materials, iodobenzene acetate is used as an oxidant, the reaction is carried out in a mixed solution composed of a catalyst, a ligand, an additive and a solvent, after the reaction is finished, the solvent is removed by a rotary evaporator, and a crude product is obtained; wherein the catalyst is palladium acetate, the ligand is N-acetylglycine, the additive is acetic anhydride, and the solvent is hexafluoroisopropanol;
performing column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate; the structural general formula of the product is as follows:
wherein R is one of alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
r' is hydrogen, C1-C5One of an alkyl group and an aryl group.
2. The method for synthesizing the meta-acyloxy-substituted phenylacetic acid compound according to claim 1, which comprises the following steps:
vacuumizing a reactor, introducing nitrogen for replacement, sequentially adding a phenylacetic acid derivative, iodobenzene acetate, a catalyst, a ligand, an additive and a solvent into the reactor, heating for reaction for 12-24h, and after the reaction is finished, pumping off the solvent by using a rotary evaporator to obtain a crude product;
and carrying out column chromatography on the crude product to obtain a product, wherein an eluant used in the column chromatography process is a mixed solvent of petroleum ether and ethyl acetate.
3. The method for synthesizing m-acyloxy-substituted phenylacetic acids according to claim 2, wherein the reaction temperature is 20-140 ℃.
4. The method for synthesizing the meta-acyloxy-substituted phenylacetic acid compound according to claim 1 or 2, wherein the reaction molar ratio of the phenylacetic acid derivative to iodobenzene acetate is 1: 4.
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| "Accessing Remote meta- and para-C(sp2)−H Bonds with Covalently Attached Directing Groups";Aniruddha Dey et al.,;《Angewandte Chemie》;20181129;10820-10843 * |
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| "Meta-Selective Arene C-H Bond Olefination of Arylacetic Acid Using a Nitrile-Based Directing Group";Bera, M. , et al.;《Organic Letters》;20141013;第16卷(第21期);5760-5763 * |
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