CN113429285B - Method for synthesizing hydroxyacetone ester compounds based on methylene aziridine - Google Patents
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- CN113429285B CN113429285B CN202110991844.7A CN202110991844A CN113429285B CN 113429285 B CN113429285 B CN 113429285B CN 202110991844 A CN202110991844 A CN 202110991844A CN 113429285 B CN113429285 B CN 113429285B
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Abstract
The invention provides a method for synthesizing hydroxyacetone ester compounds based on methylene aziridine, which takes N-substituted methylene aziridine, carboxylic acid and water as raw materials to synthesize the hydroxyacetone ester compounds; the method avoids the use of a virulent metal catalyst, a strong oxidant and a halogenated reagent, and the reaction can be carried out at room temperature to prepare the hydroxyacetone ester compound with the yield of 70-95 percent; the method has the advantages of cheap and easily obtained starting raw materials, simple and convenient operation, mild conditions and no need of adding a catalyst.
Description
Technical Field
The invention relates to a method for preparing hydroxyacetone ester compounds, in particular to a method for synthesizing the hydroxyacetone ester compounds based on methylene aziridine, belonging to the technical field of chemical synthesis.
Background
The hydroxyacetone ester compounds are widely applied to the fields of medicines, pesticides, materials and the like, and the structures of the hydroxyacetone ester compounds are usually present in bioactive natural products and other functional molecules.
Conventional synthesis method for synthesizing hydroxyacetone ester compounds generally uses Pb (OAc)4、Tl(OAc)3And Mn (OAc)3Heavy metal with equal toxicityThe carboxylate of (2) is directly oxidized and coupled to prepare the compound, and the specific steps are as follows:
however, the method has the advantages of low yield, high reaction temperature and high toxicity of the catalyst.
In addition, the method for coupling different carboxylic acid compounds and ketone compounds by using iodine-containing compounds as catalysts is also a common synthetic method of hydroxyacetone ester compounds.
For example, Ochiai et al reported the reaction of ketones with acetic acid to form hydroxyacetone esters using iodobenzene as a catalyst and m-chloroperoxybenzoic acid (m-CPBA) as an oxidant (Journal of the American Chemical Society, 2005, 127: 12244-12245.); ishihara et al reported a method for preparing a hydroxyacetone ester using tetramethylammonium iodide (Bu4NI) to provide iodide ions for co-oxidation with t-butylhydroperoxide (TBHP) (Angewandte Chemie,2011,50: 5331-5334.); xujianhua group reported the use of potassium iodide as a catalyst and K2S2O8And K2HPO4Method for converting carboxylic acids and acetone into hydroxypropanone esters as mild oxidants (Organic)&Biomolecular Chemistry, 2016, 1-4.); and Zhang Petzel et al reported a 1, 2-dibromoethane-mediated synthesis method using potassium iodide as a catalyst (Chinese Chemical Letters, 2019, 59: 5331-5337.).
In the method, ketone is used as a raw material, an iodine-containing compound is required to be used as a catalyst, an oxidant or a halogenated reagent is required to be added, side reactions are increased, environmental pollution is caused, and the reaction temperature is usually high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing hydroxyacetone ester compounds, which realizes the following purposes:
the use of highly toxic metal catalysts, strong oxidants and halogenated reagents is avoided;
reducing the reaction temperature;
the reaction yield is improved.
The technical scheme adopted by the invention is as follows:
a method for synthesizing hydroxyacetone ester compounds based on methylene aziridine is used for synthesizing the hydroxyacetone ester compounds by taking N-substituted methylene aziridine, carboxylic acid and water as raw materials.
The following is a further improvement of the above technical solution:
the N-substituted methylene aziridine is one of N-benzyl-2-methylene aziridine, 1- (2, 2-dimethoxyethyl) -2-methylene aziridine and N-isopropyl-2-methylene aziridine.
The carboxylic acid is one of 3-phenyl propiolic acid, 3-naphthyl propiolic acid, p-methyl propiolic acid, p-fluorobenzene propiolic acid, butynoic acid, cinnamic acid and 2-furan acrylic acid.
The molar ratio of the N-substituted methylene aziridine to the carboxylic acid is (1.25-10): 1; the molar ratio of the N-substituted methylene aziridine to water is 1: (0.6-10).
Adding N-substituted methylene aziridine, carboxylic acid, water and a solvent, reacting for 24-48 hours at room temperature, removing the solvent after the reaction is finished, and purifying to obtain a product;
the purification method is to perform silica gel column chromatography on the residue after the solvent is removed, and the content of the residue is determined by the following steps of petroleum ether: ethyl acetate =10:1 (volume ratio) eluent washes the column to give the product.
The solvent is one of ethanol, tetrahydrofuran, acetonitrile and dichloromethane.
The molar volume ratio of the N-substituted methylene aziridine to the solvent is 1 mmol: (0-3) mL.
The hydroxy acetone ester compounds are 2-oxypropyl-3-phenyl propiolate, 2-oxypropyl-3-naphthyl propiolate, 2-oxypropyl-3-p-methylphenyl propiolate, 2-oxypropyl-3-p-fluorophenyl propiolate, 2-oxypropyl butynoate, 2-oxypropyl-3-phenylacrylate and 2-oxypropyl-3-furylacrylate.
On the basis of the technical scheme, the method can be divided into two situations of adding a solvent or not adding the solvent according to different water solubility of raw materials.
When the solvent is added: the molar ratio of the N-substituted methylene aziridine to water is 1: (0.6-1); the molar volume ratio of the N-substituted methylene aziridine to the solvent is 1 mmol: (1-3) mL.
When no solvent was added: adding excessive water, wherein part of water participates in the reaction, and part of water is used as a solvent, and the N-substituted methylene aziridine is required to be limited to be N-benzyl-2-methylene aziridine, wherein the molar ratio of the N-substituted methylene aziridine to the water is 1: 10.
the above scheme can realize the yield of the product of 70-95%.
Further preferred solutions are as follows:
the N-substituted methylene aziridine is one of N-benzyl-2-methylene aziridine and N-isopropyl-2-methylene aziridine.
The carboxylic acid is one of cinnamic acid and 2-furan acrylic acid.
The molar ratio of the N-substituted methylene aziridine to the carboxylic acid is 1.25: 1; the molar ratio of the N-substituted methylene aziridine to water is 1: (0.8-1).
Adding N-substituted methylene aziridine, carboxylic acid, water and a solvent, reacting for 48 hours at room temperature, removing the solvent after the reaction is finished, and purifying to obtain a product;
the purification method is to perform silica gel column chromatography on the residue after the solvent is removed, and the content of the residue is determined by the following steps of petroleum ether: ethyl acetate =10:1 (volume ratio) eluent washes the column to give the product.
The solvent is dichloromethane.
The molar volume ratio of the N-substituted methylene aziridine to the solvent is 1 mmol: 3 mL.
The products are 2-oxopropyl-3-phenylacrylate and 2-oxopropyl-3-furanacrylate.
The preferred technical scheme can realize the yield of the product of 90-95%.
The N-substituted methylene aziridine is a ternary cyclic compound which has rich chemical properties but exists relatively stably.
The invention has the following beneficial effects:
the method for synthesizing the hydroxyacetone ester compound takes N-substituted methylene aziridine as a raw material, avoids using a virulent metal catalyst, a strong oxidant and a halogenated reagent, and can react at room temperature to prepare the hydroxyacetone ester compound with the yield of 70-95%.
Drawings
FIG. 1 is a 1H NMR chart of 3a prepared in example 1;
FIG. 2 is a 13C NMR chart of 3a prepared in example 1;
FIG. 3 is a 1H NMR chart of 3b prepared in example 2;
FIG. 4 is a 13C NMR chart of 3b prepared in example 2;
FIG. 5 is a 1H NMR chart of 3c prepared in example 3;
FIG. 6 is a 13C NMR chart of 3C prepared in example 3;
FIG. 7 is a 1H NMR chart of 3d prepared in example 4;
FIG. 8 is a 13C NMR chart of 3d prepared in example 4;
FIG. 9 is a 1H NMR chart of 3e prepared in example 5;
FIG. 10 is a 13C NMR chart of 3e prepared in example 5;
FIG. 11 is a 1H NMR chart of 3f prepared in example 6;
FIG. 12 is a 13C NMR chart of 3f prepared in example 6;
FIG. 13 is a 1H NMR chart of 3g prepared in example 7;
FIG. 14 is a 13C NMR chart of 3g prepared in example 7.
Detailed Description
Example 1
The reaction was carried out in a 10ml reaction tube, and 0.6mmol of N-benzyl-2-methyleneaziridine (1 a), 0.4mmol of 3-phenylpropionic acid (2 a), 0.6mmol of water and 0.6ml of ethanol were added to react at 25 ℃ for 24 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (volume ratio) eluent washes the column to give the product 2-oxopropyl-3-phenylpropionate (3 a) in 85% isolated yield. The product was in the form of a white solid.
1H NMR (300 MHz, DMSO-d6) δ= 7.77 (d, J = 16.0 Hz, 1H), 7.57 – 7.50 (m, 2H), 7.44 – 7.31 (m, 3H), 4.99 (s, 2H), 2.13 (s, 3H); 13C NMR (300 MHz, DMSO-d6) δ = 200.37, 165.38; HRMS calcd for C12H10O3 [M+H]+ 202.0630; found 202.0627。
Example 2
The reaction was carried out in a 10ml reaction tube, and 0.6mmol of 1- (2, 2-dimethoxyethyl) -2-methyleneaziridine (1 b), 0.3mmol of 3-naphthylpropiolic acid (2 b), 0.4mmol of water and 1ml of tetrahydrofuran were added to react at 25 ℃ for 48 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: the column was washed with an eluent of ethyl acetate =10:1 (volume ratio) to give the product 2-oxopropyl-3-naphthylpropiolate (3 b) in 75% isolated yield as a colorless oil.
1H NMR (400 MHz, DMSO-d6) δ = 8.43 (s, 1H), 8.02 (t, J = 8.8 Hz, 3H), 7.71 – 7.61 (m, 3H), 5.02 (s, 2H), 2.15 (s, 3H); 13C NMR (101 MHz, DMSO-d6) δ = 201.20, 152.80, 134.88, 134.08, 132.72, 129.30, 128.96, 128.72, 128.38, 128.35, 127.82, 115.87, 87.73, 80.66, 70.07, 26.30; HRMS calcd for C16H12O3 [M+Na]+ 275.0786; found 275.0672。
Example 3
The reaction was carried out in a 10mL reaction tube, and 1mmol of N-benzyl-2-methyleneaziridine (1 a), 0.1mmol of p-methamphetamine (2 c), 1mmol of water, 3mL of acetonitrile were added and reacted at 25 ℃ for 48 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (volume ratio) eluent washes the column to give the product 2-oxopropyl-3-p-methylphenyl propiolate (3 c) in 80% isolated yield. The product was a colorless oil.
1H NMR (400 MHz, CDCl3) δ = 7.51 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 4.78 (s, 2H), 2.39 (s, 3H), 2.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ = 200.70, 153.25, 141.72, 133.18, 129.44, 116.16, 88.77, 79.49, 77.35, 77.03, 76.71, 69.11, 26.15, 21.78; HRMS calcd for C13H12O3 [M+Na]+ 239.0786; found 239.0669。
Example 4
The reaction was carried out in a 10ml reaction tube, and 0.6mmol of N-benzyl-2-methyleneaziridine (1 a), 0.4mmol of p-fluoropropargonic acid (2 d), 6mmol of water were added to react at 25 ℃ for 24 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (vol) eluent washes the column to give the product 2-oxopropyl-3-p-fluorophenylpropiolate (3 d) in 75% isolated yield. The product was a colorless oil.
1H NMR (400 MHz, CDCl3) δ = 7.62 (dd, J = 7.8, 5.6 Hz, 2H), 7.09 (t, J = 8.4 Hz, 2H), 4.80 (s, 2H), 2.22 (s, 3H); 13C NMR (101 MHz, CDCl3) δ = 200.38, 165.37, 162.85, 153.00, 135.51, 135.42, 116.35, 116.13, 87.06, 79.72, 69.15, 26.11; HRMS calcd for C12H9FO3 [M+H]+ 221.0536; found 221.0681。
Example 5
The reaction was carried out in a 10mL reaction tube, and 1.0 mmol of N-benzyl-2-methyleneaziridine (1 a), 0.5mmol of butynoic acid (2 e), 0.6mmol of water, 2mL of tetrahydrofuran were added and reacted at 25 ℃ for 24 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (vol) eluent washes the column to give the product 2-oxopropyl butynoate (3 e) in 70% isolated yield. The product was in the form of a yellow oil.
1H NMR (400 MHz, CDCl3) δ = 4.71 (s, 2H), 2.19 (s, 3H), 2.03 (s, 3H); 13C NMR (101 MHz, CDCl3) δ = 200.60, 152.72, 87.62, 71.61, 68.95, 26.07, 3.91; HRMS calcd for C7H8O3 [M+Na]+ 163.0473; found 163.0272。
Example 6
The reaction was carried out in a 10mL reaction tube, and 1.0 mmol of N-isopropyl-2-methyleneaziridine (1 c), 0.8mmol of cinnamic acid (2 f), 1.0 mmol of water, 3mL of dichloromethane were added and reacted at 25 ℃ for 48 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (vol) eluent washes the column to give the product 2-oxopropyl-3-phenylacrylate (3 f) in 95% isolated yield. The product was in the form of a yellow oil.
1H NMR (400 MHz, CDCl3) δ = 7.80 (d, 1H), 7.54 (m, 2H),7.40 (m, 3H), 6.52 (d, 1H), 4.78 (s, 2H), 2.21 (s, 3H); 13C NMR (101 MHz, CDCl3) δ = 201.90, 166.11, 146.30, 134.15, 130.64, 128.96, 128.27, 117.79, 68.42, 26.18; HRMS calcd for C7H8O3 [M+Na]+ 163.0473; found 163.0272。
Example 7
The reaction was carried out in a 10mL reaction tube, and 1.0 mmol of N-benzyl-2-methyleneaziridine (1 a), 0.8mmol of 2-furanacrylic acid (2 g), 0.8mmol of water, 3mL of dichloromethane were added to react at 25 ℃ for 48 hours. After the reaction, the solvent was evaporated by a rotary evaporator, and the residue was subjected to silica gel column chromatography using petroleum ether: ethyl acetate =10:1 (vol) eluent washes the column to give the product 2-oxopropyl-3-furanacrylate (3 g) in 90% isolated yield. The product was in the form of a yellow oil.
1H NMR (400 MHz, CDCl3) 1H NMR (CDCl3, δ): 7.48 (d, 1H), 7.47–7.48 (m, 1H), 6.63 (d, 1H), 6.46 (dd, 1H), 6.37 (d, 1H), 4.73 (s, 2H), 2.17 (s, 3H); 13C NMR (101 MHz, CDCl3) δ = 202.1, 166.2, 150.8, 145.2, 132.4, 115.6, 114.4, 112.5, 68.4, 26.2; HRMS calcd for C10H10O4 [M+H]+ 195.0579; found 195.0572。
Claims (5)
1. A method for synthesizing hydroxy acetone ester compounds based on methylene aziridine is characterized in that: synthesizing a hydroxyacetone ester compound by using N-substituted methylene aziridine, carboxylic acid and water as raw materials;
the N-substituted methylene aziridine is one of N-benzyl-2-methylene aziridine, 1- (2, 2-dimethoxyethyl) -2-methylene aziridine and N-isopropyl-2-methylene aziridine;
the carboxylic acid is one of 3-phenyl propiolic acid, 3-naphthyl propiolic acid, p-methyl propiolic acid, p-fluorobenzene propiolic acid, butynoic acid, cinnamic acid and 2-furan acrylic acid;
the hydroxy acetone ester compounds are 2-oxypropyl-3-phenyl propiolate, 2-oxypropyl-3-naphthyl propiolate, 2-oxypropyl-3-p-methylphenyl propiolate, 2-oxypropyl-3-p-fluorophenyl propiolate, 2-oxypropyl butynoate, 2-oxypropyl-3-phenylacrylate and 2-oxypropyl-3-furylacrylate.
2. The method for synthesizing the hydroxyacetone ester compound based on the methylene aziridine as claimed in claim 1, wherein: the molar ratio of the N-substituted methylene aziridine to the carboxylic acid is (1.25-10): 1; the molar ratio of the N-substituted methylene aziridine to water is 1: (0.6-10).
3. The method for synthesizing the hydroxyacetone ester compound based on the methylene aziridine as claimed in claim 1, wherein: the method comprises the steps of adding N-substituted methylene aziridine, carboxylic acid, water and a solvent, and reacting for 24-48 hours at room temperature.
4. The method for synthesizing the hydroxyacetone ester compound based on the methylene aziridine as claimed in claim 3, wherein: the solvent is one of ethanol, tetrahydrofuran, acetonitrile and dichloromethane.
5. The method for synthesizing the hydroxyacetone ester compound based on the methylene aziridine as claimed in claim 3, wherein: the molar volume ratio of the N-substituted methylene aziridine to the solvent is 1 mmol: (0-3) mL.
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Non-Patent Citations (3)
| Title |
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| Cationic Pd(II)-Catalyzed Enantioselective Cyclization of Aroylmethyl 2-Alkynoates Initiated by Carbopalladation of Alkynes with Arylboronic Acids;Juan Song et al.;《ORGANIC LETTERS》;20070620;第9卷(第15期);第2947-2950页 * |
| Iodobenzene-Catalyzed α-Acetoxylation of Ketones. In Situ Generation of Hypervalent (Diacyloxyiodo)benzenes Using m-Chloroperbenzoic Acid;Masahito Ochiai et al.;《J. AM. CHEM. SOC.》;20050816;第127卷(第35期);第12244-12245页 * |
| KI-catalyzed α-acyloxylation of acetone with carboxylic acids;Ya-Dong Wu et al.;《Org. Biomol. Chem.》;20160525;第14卷;第5936-5939页 * |
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