CN108047177B - Method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step - Google Patents
Method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step Download PDFInfo
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- CN108047177B CN108047177B CN201711376129.2A CN201711376129A CN108047177B CN 108047177 B CN108047177 B CN 108047177B CN 201711376129 A CN201711376129 A CN 201711376129A CN 108047177 B CN108047177 B CN 108047177B
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 23
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- -1 phenoxyamide compound Chemical class 0.000 claims abstract description 31
- 150000001907 coumarones Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZSHNFLCNZCPFAB-UHFFFAOYSA-N 3-bromoprop-2-ynoic acid Chemical compound OC(=O)C#CBr ZSHNFLCNZCPFAB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 10
- UOKZUTXLHRTLFH-UHFFFAOYSA-N o-phenylhydroxylamine Chemical class NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JFJODJVMRSQHPG-UHFFFAOYSA-N 2-(4-methylphenoxy)acetamide Chemical compound CC1=CC=C(OCC(N)=O)C=C1 JFJODJVMRSQHPG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PMNXYEIHZHINAN-UHFFFAOYSA-N 2-(4-ethylphenoxy)acetamide Chemical compound CCC1=CC=C(OCC(N)=O)C=C1 PMNXYEIHZHINAN-UHFFFAOYSA-N 0.000 description 1
- AOPRXJXHLWYPQR-UHFFFAOYSA-N 2-phenoxyacetamide Chemical compound NC(=O)COC1=CC=CC=C1 AOPRXJXHLWYPQR-UHFFFAOYSA-N 0.000 description 1
- ANCDHBXLDURTHN-UHFFFAOYSA-N 2-phenoxypropanamide Chemical compound NC(=O)C(C)OC1=CC=CC=C1 ANCDHBXLDURTHN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 206010062016 Immunosuppression Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007116 intermolecular coupling reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step, which is characterized in that a phenoxyamide compound and bromopropiolate are subjected to catalytic reaction in an organic solvent environment to obtain a 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound. The raw materials used in the method are cheap and easy to obtain, the reaction can be carried out at room temperature, and the treatment process is simple, so that the method is easy to operate and produce in a large scale. Almost no waste gas and waste are generated in the reaction process, and the environment-friendly and atomic economy is high. 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds are synthesized for the first time by the method in one step, and a new thought is provided for molecular biology research.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and relates to a method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step.
Background
As it is known that all proteins in an organism are composed of 20 natural amino acids, which are basic tools and optimal points for protein research, scientists indirectly research the precise structure, action targets and action mechanisms of proteins by the arrangement and functional groups of the amino acids in the proteins, and further seek to realize artificial repair and modification of the proteins. However, the only 20 natural amino acids have a limited number of functional groups, and thus cannot meet the requirements of chemical and biological scientific research and application on protein structure and function. Therefore, the artificial synthesis of various unnatural amino acids with different groups and functions becomes an important means for molecular biological research, wherein the beta-dehydrogenized unnatural amino acid is a class of unnatural amino acids with more applications. Benzofuran compounds occur in many natural plants and possess a variety of biological activities. Some substituted benzofurans compounds have good physiological activities of resisting tumor, virus, fungus, oxidation, immunosuppression and the like. Since the isolation of such compounds from natural products is limited, the construction of this structure has become one of the hot spots in organic synthesis.
The benzofuran unnatural amino acid is synthesized by combining the scientific research and application advantages of the unnatural amino acid and the physiological activity characteristics of the benzofuran compound. Has important application prospect in molecular biology research. The processes for the synthesis of benzofuran compounds have been reported and developed mainly focusing on the synthesis of 2-position or 2, 3-position substituted benzofuran compounds by transition metal catalyzed intramolecular or intermolecular coupling reactions, these 2-and 3-position substituents being generally limited to a portion of the aryl and alkyl groups. The chemical synthesis of benzofuran unnatural amino acids, i.e., benzofuran derivatives substituted with amino and carboxyl groups at the 2, 3-positions, respectively, has been reported to be difficult, and related biological studies are limited.
The prior method for synthesizing benzofuran derivatives usually uses functionalized starting materials, and some reaction substrates are more complex in structure and difficult to obtain; expensive metal catalysts are needed in the reaction process, and higher temperature is generally needed to ensure that the reaction conditions are harsh; the synthesized benzofuran compounds have limited kinds, and benzofuran substituted by both amino group and carboxyl group cannot be obtained. (Furstner, a.and Davies, p.w. j.am.chem.soc.,2005,127,15024.)
Disclosure of Invention
The first problem to be solved by the invention is to overcome the defects in the prior art and provide a method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step, which has mild conditions and simple post-treatment and is suitable for industrial production.
In order to solve the technical problems, the invention provides a method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step, which comprises the following steps: the phenoxyamide compound (formula 1) and the bromo-propiolic acid ester (formula 2) are subjected to catalytic reaction in an organic solvent environment to obtain a 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (formula 3);
wherein,
r ═ 4-methyl, 4-ethyl, 4-isopropyl, 6-methyl, 6-ethyl, 3, 5-dimethyl, 4-fluoro, 4-chloro-6-methyl, 5-methyl, 3-methyl, 5-bromo, 3-bromo,
4-
3-chloro-6-
R1Methyl, ethyl, isopropyl, tert-butoxy;
R2＝-COOEt,-COOMe。
in a preferred technical scheme of the invention, the reaction system is carried out under the catalytic action of sodium methoxide.
In a preferred technical scheme of the present invention, the reaction system is performed in an ethyl acetate solvent, that is, the organic solvent is ethyl acetate.
In the preferable technical scheme of the invention, the amount of the sodium methoxide is 2 times of that of the phenoxyamide compound.
In the preferable technical scheme of the invention, the amount of the bromopropiolate added is 2 times of that of the phenoxyamide compound.
In a preferred embodiment of the present invention, the reaction is carried out at normal temperature and pressure.
In the reaction method, 10ml of Ethyl Acetate (EA) is added into every 1mmol of raw materials to be used as a solvent, and the reaction time is 6-12 hours.
22 different substituted 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds are synthesized by the method, and are shown in the following table 1: where the letters below each compound are their classification designations, the percentage figures are the yield:
TABLE 1
After different substituted phenols are obtained through a known method to obtain phenoxyamide compounds, the phenoxyamide compounds react with bromopropiolate in an ethyl acetate solvent under the action of sodium methoxide at room temperature to obtain the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds with high efficiency. By the method, a plurality of benzofuran beta-dehydrogenation unnatural amino acid compounds are synthesized in one step.
The reaction condition is that 1mmol of phenoxyamide substrate and 2mmol of sodium methoxide are dissolved in 10ml of ethyl acetoacetate solvent, then 2mmol of bromopropiolate is added, and a plurality of 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds can be obtained after reaction for 6-12h at room temperature;
the method starts from simple and easily-obtained starting materials, and economically and efficiently synthesizes the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound under mild conditions. The phenoxy amide compound is obtained by taking phenol as a raw material in one step, and reacts with bromopropiolate at room temperature to obtain the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound in one step. Only a certain amount of sodium methoxide needs to be added in the reaction, so that the reaction yield is high and the adaptability is good. Only a small amount of sodium bromide is generated in the process, and almost no other byproducts are generated, so that the atom economy is high, and the concept of green chemistry is met.
The raw materials used in the method are cheap and easy to obtain, the reaction can be carried out at room temperature, and the treatment process is simple, so that the method is easy to operate and produce in a large scale. Almost no waste gas and waste are generated in the reaction process, and the environment-friendly and atomic economy is high. 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds are synthesized for the first time by the method in one step, and a new thought is provided for molecular biology research.
Detailed Description
For the sake of understanding, the present invention will be described in detail below by way of specific examples. It is to be expressly understood that the description is illustrative only and is not intended as a definition of the limits of the invention. Many variations and modifications of the present invention will be apparent to those skilled in the art in light of the teachings of this specification.
Example 1
Dissolving 1mmol of phenoxyamide substrate (phenoxyacetamide) and 2mmol of sodium methoxide in 10ml of ethyl acetate solvent, adding 2mmol of bromopropiolate (3-bromopropiolate), and reacting at room temperature for 6-12h to obtain 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (2-acetamido-3-ethyl formate benzofuran 4a), wherein the yield is 92 mmol.
Example 2
Dissolving 1mmol of phenoxyamide substrate (4-methylphenoxyacetamide) and 2mmol of sodium methoxide in 10ml of ethyl acetate solvent, adding 2mmol of bromopropiolate (3-bromopropiolate), and reacting at room temperature for 6-12h to obtain the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (5-methyl-2-acetamido-3-ethyl formate benzofuran 4b), wherein the yield is 0.87 mmol.
Example 3
Dissolving 1mmol of phenoxyamide substrate (4-ethylphenoxyacetamide) and 2mmol of sodium methoxide in 10ml of ethyl acetate solvent, adding 2mmol of bromopropiolate (3-ethyl bromopropiolate), and reacting at room temperature for 6-12h to obtain 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (5-ethyl-2-acetamido-3-ethyl formate benzofuran 4c), wherein the yield is 75 mmol.
Example 4
Dissolving 1mmol of phenoxyamide substrate (phenoxypropionamide) and 2mmol of sodium methoxide in 10ml of ethyl acetate solvent, adding 2mmol of bromopropiolate (3-bromopropiolate), and reacting for 6-12h at room temperature to obtain the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (2-propionylamino-3-ethyl formate benzofuran 4m), wherein the yield is 88 mmol.
Example 5
Dissolving 1mmol of phenoxyamide substrate (4-methylphenoxyacetamide) and 2mmol of sodium methoxide in 10ml of ethyl acetate solvent, adding 2mmol of bromopropiolate (3-methyl bromopropiolate), and reacting at room temperature for 6-12h to obtain the 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compound (5-methyl-2-acetamido-3-methyl formate benzofuran 4s), wherein the yield is 0.92 mmol.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. The method for synthesizing benzofuran beta-dehydrogenation unnatural amino acid in one step is characterized in that phenoxyamide compounds and bromopropiolate are subjected to catalytic reaction in an ethyl acetate solvent environment under the catalytic action of sodium methoxide to obtain 2-amino, 3-carboxyl substituted benzofuran beta-dehydrogenation unnatural amino acid compounds;
wherein, R is 4-methyl, 4-ethyl, 4-isopropyl, 6-methyl, 6-ethyl, 4-fluoro, 4-chloro, 5-methyl, 5-bromo,
R1methyl, ethyl, isopropyl, tert-butoxy;
R2＝-Et,-Me。
2. the synthesis method of claim 1, wherein the amount of sodium methoxide is 2 times of that of phenoxyamide compound.
3. The synthesis method according to claim 1, wherein the amount of the bromopropiolate added is 2 times of that of the phenoxyamide compound.
4. The method of claim 1, wherein the reaction is carried out at ambient temperature and pressure.
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