CN113200881A - Method for synthesizing beta-aminocarboxylate by using pentamethyl trichloro-cyclopentadienyl titanium and 4-hydroxybenzoic acid as catalysts - Google Patents
Method for synthesizing beta-aminocarboxylate by using pentamethyl trichloro-cyclopentadienyl titanium and 4-hydroxybenzoic acid as catalysts Download PDFInfo
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- CN113200881A CN113200881A CN202110413383.5A CN202110413383A CN113200881A CN 113200881 A CN113200881 A CN 113200881A CN 202110413383 A CN202110413383 A CN 202110413383A CN 113200881 A CN113200881 A CN 113200881A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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Abstract
The invention discloses a method for synthesizing beta-aminocarboxylate by the catalysis of pentamethyl trichloro-cyclopentadienyl titanium and 4-hydroxybenzoic acid, which comprises the step of reacting benzaldehyde compounds, aniline compounds and silicon-based ketene acetal to generate beta-aminocarboxylate under the conditions that pentamethyl trichloro-cyclopentadienyl titanium is used as a catalyst, 4-hydroxybenzoic acid is used as a ligand and ethanol is used as a solvent. The method has the advantages of mild reaction conditions, simple operation, short reaction time, single reaction product and high atom economy, and the beta-aminocarboxylate obtained by separating the product by simple column chromatography after the reaction is finished has wide biological activity and medicinal value.
Description
Technical Field
The invention belongs to the technical field of synthesis of beta-aminocarboxylate, and particularly relates to a method for synthesizing beta-aminocarboxylate by catalyzing pentamethyl trichloro-cyclopentadienyl titanium with 4-hydroxybenzoic acid.
Background
Beta-aminocarboxylate derivatives have a wide variety of pharmacological and biological properties, are widely found in natural products, and are, in addition, useful synthetic intermediates in organic chemistry and are widely used. Therefore, there has been extensive research into the synthesis of β -aminocarboxylate derivatives. Preparation of beta-aminocarboxylic acid estersThe classical method of (A) is a Mannich reaction synthesis method: and carrying out condensation reaction on one molecule of silylketene acetal, one molecule of aldehyde and one molecule of ammonia to obtain the beta-aminocarboxylic ester. Because of the medicinal and synthetic value of these compounds, many scientists around the world have endeavored to develop alternative synthetic methods that employ a wide variety of catalysts, including Lewis acid catalysts such as FeCl3、Sc(OTf)3、Mg(ClO4)2、InCl、Cu(OTf)2And the like. Bronsted acid catalysts such as synthetic phosphoric acid, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TfOH), L-proline, cellulose sulfate (CAS), Lactic Acid (LA), and the like. Of course, Lewis bases or Bronsted bases may also be used as catalysts in the synthesis reaction.
Although lewis acid has great application in catalyzing the synthesis of beta-aminocarboxylate, sometimes the lewis acid has the problems of harsh reaction conditions, poor reaction selectivity, low reaction efficiency, poor substrate applicability, environmentally-friendly solvent and the like. If the two acids can be combined, the advantages of the two acids are utilized to avoid the disadvantages of the two acids, the synthesis of the beta-aminocarboxylate derivative is realized through the synergistic effect of the Lewis acid and the Bronsted acid, the reaction efficiency and the selectivity of the reaction are further improved, the atom economy is improved, the simple, convenient, efficient and environment-friendly synthesis method is developed to synthesize the beta-aminocarboxylate derivative, more choices are provided for the synthesis method of the beta-aminocarboxylate derivative, and new development and prospects are brought to numerous fields.
Disclosure of Invention
The invention aims to provide a method for efficiently synthesizing beta-aminocarboxylate, which has the advantages of mild condition, simple operation, short reaction time, single reaction product, good substrate applicability and high efficiency.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: adding a benzaldehyde compound shown in a formula I, an aniline compound shown in a formula II and a silicon-based ketene acetal shown in a formula III into an organic solvent, adding pentamethyl trichloro-cyclopentadienyl titanium as a catalyst and adding 4-hydroxybenzoic acid as a ligand, reacting at room temperature for 10-12 hours, and separating and purifying a product to obtain a beta-amino carboxylic ester compound shown in a formula IV;
in the formula R1、R2Each independently represents H, halogen, C1～C4Alkyl radical, C1～C4Any one of alkoxy, nitro and hydroxyl.
In the above synthesis method, the molar ratio of the aniline compound, the ketene acetal, and the benzaldehyde compound is preferably 1:1:1.2 to 1.5.
In the synthesis method, the addition amount of the pentamethyl trichlorotitanocene is preferably 1 to 5 percent of the molar amount of the aniline compound, and the addition amount of the 4-hydroxybenzoic acid is preferably 2 to 10 percent of the molar amount of the aniline compound.
In the above synthesis method, the organic solvent is preferably any one of ethanol, methanol and ethylene glycol.
The invention has the following beneficial effects:
the invention makes benzaldehyde compound react with aniline compound and silicon-based ketene acetal to generate beta-amino carboxylic ester under the condition that pentamethyl trichloro-cyclopentadienyl titanium is used as catalyst and 4-hydroxybenzoic acid is used as ligand. The method has the advantages of mild reaction conditions, simple operation, short reaction time, single reaction product and high atom economy, and the beta-aminocarboxylate obtained by separating the product by simple column chromatography after the reaction is finished has wide biological activity and medicinal value.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Synthesis of methyl 2, 2-dimethyl-3-phenyl-3- (2-hydroxy) phenylamino propionate
A20 mL reaction flask was charged with 0.0545g (0.5mmol) of o-aminophenol, 71. mu.L (0.7mmol) of benzaldehyde, 102. mu.L (0.5mmol) of silylketene acetal, 0.0125g (0.05mmol) of titanocene dichloride, 0.0181g (0.1mmol) of p-hydroxybenzoic acid and 0.5mL of ethanol, stirred at room temperature for 12 hours, stopped, cooled to room temperature naturally, rotary evaporated to remove ethanol, and separated by a silica gel column (eluent was a mixture of ethyl acetate and petroleum ether at a volume ratio of 1: 10) to obtain methyl 2, 2-dimethyl-3-phenyl-3- (2-hydroxy) phenylaminopropionate with a yield of 93%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1HNMR(400MHz,CDCl3)δ7.36–7.23(m,5H),6.78–6.48(m,3H),6.43(d,J ＝6.9Hz,1H),5.73(s,1H),4.98(s,1H),4.62(s,1H),3.73(s,3H),1.29(s,3H),1.26(s, 3H)；13C NMR(101MHz,CDCl3)δ177.82,144.37,139.06,135.63,128.42,127.99, 127.48,121.11,118.05,114.34,114.10,64.69,52.29,47.44,24.42,20.10.
example 2
Synthesis of methyl 2, 2-dimethyl-3- (4-nitro) phenyl-3- (2-hydroxy) phenylamino propionate
In example 1, benzaldehyde used was replaced with equimolar 4-nitrobenzaldehyde, and the other steps were the same as in example 1 to obtain methyl 2, 2-dimethyl-3- (4-nitro) phenyl-3- (2-hydroxy) phenylamino propionate in a yield of 66%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(400MHz,CDCl3)δ8.17(d,J＝8.6Hz,2H),7.51(d,J＝8.6Hz,2H), 7.28(s,1H),6.72(d,J＝7.6Hz,1H),6.64(t,J＝7.5Hz,1H),6.56(t,J＝7.4Hz,1H),6.29 (d,J＝7.7Hz,1H),5.46(s,1H),5.14(s,1H),4.69(s,1H),3.73(s,3H),1.32(s,3H),1.28 (s,4H),1.26(s,4H).；13C NMR(101MHz,CDCl3)δ176.63,147.36,143.68,134.96, 129.20,123.2,121.28,118.15,114.37,113.00,64.21,52.40,47.09,29.66,24.15,20.61.
example 3
Synthesis of methyl 2, 2-dimethyl-3-p-chlorophenyl-3- (2-hydroxy) phenylamino propionate
In example 1, the benzaldehyde used was replaced with 4-chlorobenzaldehyde and the other steps were the same as in example 1 to obtain methyl 2, 2-dimethyl-3-p-chlorophenyl-3- (2-hydroxy) phenylamino propionate in a yield of 89%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(400MHz,CDCl3)δ7.27(t,J＝3.2Hz,4H),6.72(d,J＝7.5Hz,1H), 6.66(t,J＝7.4Hz,1H),6.56(t,J＝7.3Hz,1H),6.36(d,J＝7.7Hz,1H),4.57(s,1H),3.72 (s,3H),1.28(s,3H),1.24(s,3H)；13C NMR(101MHz,CDCl3)δ177.38,144.08,137.78, 135.37,133.24,129.70,128.24,121.2,118.07,114.36,113.68,64.11,52.33,47.27,24.29, 20.24.
example 4
Synthesis of methyl 2, 2-dimethyl-3-phenyl-3- (2-hydroxy-4-chloro) phenylamino propionate
In example 1, the o-aminophenol used was replaced with 2-amino-4-chlorophenol, and the other steps were the same as in example 1 to give methyl 2, 2-dimethyl-3-phenyl-3- (2-hydroxy-4-chloro) phenylaminopropionate in a yield of 84%.
The obtained product is subjected to Bruker Avance type superconducting Fourier transformThe leaf digital nuclear magnetic resonance spectrometer is characterized, and the characterization data is as follows:1H NMR(400MHz,CDCl3)δ7.25–7.08(m,5H),6.92–6.84(m,2H),6.38– 6.25(m,2H),4.81(s,1H),4.34(s,1H),3.55(s,3H),1.19(s,3H),1.07(s,3H)；13C NMR (151MHz,CDCl3)δ176.99,145.56,138.81,128.90,128.21,127.68,121.89,114.53, 64.63,52.17,46.97,24.70,20.75.
example 5
Synthesis of methyl 2, 2-dimethyl-3- (4-tert-butyl) phenyl-3- (2-hydroxy) phenylamino propionate
In example 1, the benzaldehyde used was replaced with 4-tert-butylbenzaldehyde and the other steps were the same as in example 1 to give methyl 2, 2-dimethyl-3- (4-tert-butyl) phenyl-3- (2-hydroxy) phenylamino propionate in a yield of 89%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(400MHz,CDCl3)δ7.23(d,J＝8.1Hz,2H),7.16(d,J＝8.1Hz,2H), 6.73(d,J＝7.5Hz,1H),6.66(t,J＝7.4Hz,1H),6.56(t,J＝7.3Hz,1H),6.46(d,J＝7.7 Hz,1H),4.59(s,1H),3.72(s,3H),1.26(s,3H),1.25(d,J＝2.0Hz,6H),1.24(s,3H)；13C 13C NMR(101MHz,CDCl3)δ177.90,147.82,144.37,136.15,135.70,128.21,125.95, 121.03,117.90,114.18,64.28,52.19,47.48,33.60,24.41,23.89,19.91.
example 6
Synthesis of methyl 2, 2-dimethyl-3- (3-bromo) phenyl-3- (2-hydroxy) phenylamino propionate
In example 1, the benzaldehyde used was replaced with equimolar 3-bromobenzaldehyde and the other steps were the same as in example 1 to give methyl 2, 2-dimethyl-3- (3-bromo) phenyl-3- (2-hydroxy) phenylamino propionate in a yield of 90%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(400MHz,CDCl3)δ7.48(s,1H),7.39(d,J＝7.8Hz,1H),7.34–7.22 (m,1H),7.18(t,J＝7.8Hz,1H),6.73(d,J＝7.6Hz,1H),6.68(t,J＝7.5Hz,1H),6.57(t, J＝7.4Hz,1H),6.39(d,J＝7.7Hz,1H),4.55(s,1H),3.72(s,3H),1.29(s,3H),1.25(s, 3H)；13C NMR(101MHz,CDCl3)δ177.26,143.95,141.85,135.32,131.27,130.63, 129.55,126.94,122.27,121.18,117.98,114.31,113.39,64.19,52.32,47.28,24.19,20.30.
example 7
Synthesis of methyl 2, 2-dimethyl-3-phenyl-3- (2-methoxy) phenylamino propionate
In example 1, the o-aminophenol used was replaced with an equimolar amount of 2-methoxyaniline, and the other steps were the same as in example 1 to obtain methyl 2, 2-dimethyl-3-phenyl-3- (2-methoxy) phenylaminopropionate in a yield of 89%.
The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.17(d,J＝4.4Hz,4H),7.11(dt,J＝7.5,3.6Hz, 1H),6.57–6.52(m,2H),6.39–6.34(m,2H),4.39(d,J＝6.5Hz,2H),3.54(s,3H),3.54 (s,3H),1.15(s,3H),1.07(s,3H)；13C NMR(101MHz,CDCl3)δ176.07,150.86,140.17, 138.31,127.31,126.92,126.34,113.64,64.12(s),54.56,50.99,46.06,23.44,19.37。
Claims (4)
1. a method for synthesizing beta-aminocarboxylate by the catalysis of pentamethyl trichloro-titanocene and 4-hydroxybenzoic acid is characterized in that: adding a benzaldehyde compound shown in a formula I, an aniline compound shown in a formula II and a silicon-based ketene acetal shown in a formula III into an organic solvent, adding pentamethyl trichloro-cyclopentadienyl titanium as a catalyst and adding 4-hydroxybenzoic acid as a ligand, reacting at room temperature for 10-12 hours, and separating and purifying a product to obtain a beta-amino carboxylic ester compound shown in a formula IV;
in the formula R1、R2Each independently represents H, halogen, C1～C4Alkyl radical, C1～C4Any one of alkoxy, nitro and hydroxyl.
2. The method for synthesizing beta-aminocarboxylate by the catalysis of pentamethyl trichlorotitanocene and 4-hydroxybenzoic acid according to claim 1, wherein the method comprises the following steps: the molar ratio of the aniline compound to the ketene acetal to the benzaldehyde compound is 1:1: 1.2-1.5.
3. The method for synthesizing beta-aminocarboxylate by the catalysis of pentamethyl trichlorotitanocene and 4-hydroxybenzoic acid according to claim 1, wherein the method comprises the following steps: the addition amount of the pentamethyl trichlorocyclopentadienyl titanium is 1 to 5 percent of the molar amount of the aniline compound, and the addition amount of the 4-hydroxybenzoic acid is 2 to 10 percent of the molar amount of the aniline compound.
4. The method for synthesizing beta-aminocarboxylate by the catalysis of pentamethyl trichlorotitanocene and 4-hydroxybenzoic acid according to claim 1, wherein the method comprises the following steps: the organic solvent is any one of ethanol, methanol and glycol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003261490A (en) * | 2002-03-11 | 2003-09-16 | Japan Science & Technology Corp | NEW CHIRAL ZIRCONIUM CATALYST AND METHOD FOR PRODUCING OPTICALLY ACTIVE ANTI-alpha-METHYL-beta-AMINOCARBONYL COMPOUND |
| JP2008068167A (en) * | 2006-09-12 | 2008-03-27 | Nissan Chem Ind Ltd | New chiral zirconium catalyst and manufacturing method of optical activity beta-aminocarbonyl compound using the same |
| CN103467321A (en) * | 2013-09-16 | 2013-12-25 | 陕西师范大学 | Method for preparing beta-amino-carbonyl compound |
| CN104140374A (en) * | 2014-07-21 | 2014-11-12 | 陕西师范大学 | Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode |
| CN105085582A (en) * | 2015-08-18 | 2015-11-25 | 陕西师范大学 | Isoligand cyclopentadiene-titanium coordination compound crystal and application thereof in preparing beta-amino carbonyl compounds |
-
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- 2021-04-16 CN CN202110413383.5A patent/CN113200881A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003261490A (en) * | 2002-03-11 | 2003-09-16 | Japan Science & Technology Corp | NEW CHIRAL ZIRCONIUM CATALYST AND METHOD FOR PRODUCING OPTICALLY ACTIVE ANTI-alpha-METHYL-beta-AMINOCARBONYL COMPOUND |
| JP2008068167A (en) * | 2006-09-12 | 2008-03-27 | Nissan Chem Ind Ltd | New chiral zirconium catalyst and manufacturing method of optical activity beta-aminocarbonyl compound using the same |
| CN103467321A (en) * | 2013-09-16 | 2013-12-25 | 陕西师范大学 | Method for preparing beta-amino-carbonyl compound |
| CN104140374A (en) * | 2014-07-21 | 2014-11-12 | 陕西师范大学 | Method for synthesizing beta-amidogen carbonyl compound through poly-aminophenol and titanocene dichloride in heterogeneous catalysis mode |
| CN105085582A (en) * | 2015-08-18 | 2015-11-25 | 陕西师范大学 | Isoligand cyclopentadiene-titanium coordination compound crystal and application thereof in preparing beta-amino carbonyl compounds |
Non-Patent Citations (6)
| Title |
|---|
| JING WANG ET AL.: "Synthesis of air-stable mixed bis-carboxylate titanocene complexes and their catalytic behaviors in cross-aldol and Mannich reactions", 《TRANSIT MET CHEM 》 * |
| NINGBO LI ET AL.: "Strong Lewis acid air-stable cationic titanocene perfluoroalkyl(aryl)sulfonate complexes as highly effcient and recyclable catalysts for C-C bond forming reactions", 《DALTON TRANS.》 * |
| YA WU ET AL.: "Solvent strategy for unleashing the Lewis acidity of titanocene dichloride for rapid Mannich reactions", 《RSC ADV.》 * |
| YUNYUN WANG ET AL.: "Organometallic titanocene complex as highly efficient bifunctional catalyst for intramolecular Mannich reaction", 《APPL ORGANOMETAL CHEM. 》 * |
| 张雅文等: "直接不对称催化Mannich反应", 《有机化学》 * |
| 马晶军 等: "有机催化不对称Mannich反应", 《化学进展》 * |
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