CN112209847B - Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment - Google Patents
Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment Download PDFInfo
- Publication number
- CN112209847B CN112209847B CN202011137906.XA CN202011137906A CN112209847B CN 112209847 B CN112209847 B CN 112209847B CN 202011137906 A CN202011137906 A CN 202011137906A CN 112209847 B CN112209847 B CN 112209847B
- Authority
- CN
- China
- Prior art keywords
- reaction
- ionic liquid
- alcohol
- pressure
- ethyl
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/40—Acylated substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
-
- 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
- C07D307/02—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
- C07D307/56—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 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 ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing amide compounds by ionic liquid catalysis in a high-pressure environment. The method takes ionic liquid 1-ethyl-3-methylimidazolium acetate as a catalyst and a solvent, takes oxygen as an oxidant, and converts aromatic methanol or alkyl alcohol into an amide compound under high pressure and heating conditions. The synthesis method has the advantages that the cost of raw materials and technology is low; no toxic heavy metal catalyst is used, and the method is safe, low in toxicity, economical and environment-friendly compared with other traditional methods; the method has few steps and simple and convenient operation, is beneficial to large-scale synthesis, and has important significance for the synthesis and large-scale industrialization of the preparation of the amide compound.
Description
Technical Field
The invention relates to application of ionic liquid in catalytic amidation reaction under high pressure environment, in particular to the following steps: the imidazolium acetate ionic liquid is used as a catalyst, oxygen is used as an oxidant, and the aromatic methanol or alkyl alcohol is converted into an amide compound by combining oxidation and amidation reactions under high pressure and heating conditions.
Background
Amidation is one of the most important reactions in organic synthesis and chemical industry. Amide compounds are important components for synthesizing chemical intermediates and commodity chemicals, and have wide application in the aspects of biopharmaceuticals, material synthesis, medical diagnosis, food processing and the like. In practice, amides can generally be synthesized by condensation reactions between carboxylic acids and amines. Although this conventional process is well established, the synthesis process is often costly and inefficient in materials and environment in practice due to the need to handle corrosive acids and/or their derivatives and the large amount of condensation agents, additives and bases used to produce large amounts of undesirable by-products. Therefore, it is of great interest and background to develop a simple, efficient and economical process for the preparation of amides.
In recent years, the direct conversion of alcohols to amides has received increasing attention. The process avoids the use of harmful acids and their derivatives and eliminates the production of certain undesirable by-products, thereby significantly improving the overall reaction efficiency. In 2012, bantreil et al reported that the amide was obtained by reacting the hydrochloride of an alcohol and an amine at 80 ℃ for 4 hours with copper oxide as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing agent. The reaction produces by-product acid, the reduction of the amide yield due to the formation of by-products can be avoided by adding an excessive amount of alcohol, and the by-product acid can be easily removed in the post-treatment. The selectivity for amide formation is also quite good for reactions involving chiral starting materials. In 2013, ghosh et al proposed the synthesis of amides using iron salts as catalysts and air as oxidant. In the method, firstly, ferric nitrate and 2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) are combined to be used as a catalyst, oxygen in the air is used as an oxidant, and alcohol is oxidized to aldehyde; then the hydrochloride of the aldehyde and the amine reacts under the condition of taking tert-butyl hydroperoxide (TBHP) as an oxidizing agent and calcium carbonate as alkali to obtain the amide. The pure oxygen is used as the oxidant to effectively catalyze the reaction, but certain potential safety hazard exists. The reaction can be smoothly carried out by using oxygen in the air. However, when the reaction is carried out in air, the solvent in the reaction solution may be volatilized to the outside through an open system, which may cause damage to the environment and human body. In the same year, misletin and Madsen et al prepared amides by a one-pot reaction of an alcohol and an amine using rhodium as a catalyst. The by-product in the preparation method is only hydrogen, but is only suitable for the reaction of alcohol and amine without steric hindrance configuration. In 2015, hong et al used an N-heterocyclic carbene ruthenium complex as a catalyst, and synthesized an amide from an alcohol and an amine without adding a base. Researchers have found that the electronic effect of the alcohol and amine bearing groups involved in this reaction has a significant effect on the efficiency of the reaction. It can be seen that the conventional synthesis methods for directly converting alcohols into amides must use heavy metals as catalysts, and usually must be combined with additives to promote the reaction.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing an amide compound by ionic liquid catalysis in a high-pressure environment.
The amide of the present invention is a compound obtained by condensing an alkyl alcohol or an aromatic alcohol with an alkyl amine or an aromatic amine.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the method for preparing the amide compound by ionic liquid catalysis in a high-pressure environment comprises the following steps:
1) Dissolving reactant alcohol and amine in 1-ethyl-3-methylimidazolium acetate ionic liquid,
wherein the mole ratio of the reactants of alcohol, amine and imidazolium acetate ionic liquid is 1:0.5 to 2:6 to 8 percent of the total weight of the mixture,
the alcohol is any one of phenethyl alcohol, benzyl alcohol, n-amyl alcohol, cyclopropyl methanol, (p-methoxyphenyl) methanol, p-fluorobenzyl alcohol and furan methanol,
the amine is any one of N-phenylalamine, N-hexylamine, benzylamine, (4-methoxyl) 1-benzylamine, o-tolylmethylamine, (4-chlorphenyl) methylamine, (4- (trifluoromethyl) phenyl) methylamine, pyridine-3-methylamine, N-methyl-1-benzylamine, piperidine and 3-phenyl-N-propylamine,
2) In a high-pressure reaction kettle, applying pressure of at least 5.0Mpa to a reaction system under the condition of introducing oxygen;
3) Maintaining a high-pressure environment, continuously stirring for 4-48 hours until the reaction is sufficient, and heating to 110 ℃ under the premise of allowing the thermal stability of reactants and products to improve the reaction efficiency;
4) After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying to obtain a target amide product.
Preferably, the molar ratio of the reactant alcohol, amine and imidazolium acetate ionic liquid is 1.
Compared with the prior art, the method for preparing the amide compound by the ionic liquid under the high-pressure environment has the following innovation and advantages:
1. the synthesis method provided by the invention uses imidazolium acetate ionic liquid as a solvent and a catalyst at the same time, and is assisted by high pressure and air or pure oxygen to realize the conversion of alcohols to amides. The 1-ethyl-3-methylimidazolium acetate used has low cost. Oxygen is also a common readily available gas. The reaction kettle pressure of 5.0MPa is medium pressure, and is easy to realize in the chemical field, so the raw material and technology cost of the method is low;
2. the synthesis method provided by the invention realizes the conversion of alcohols into amides for the first time without the participation of dangerous chemicals or toxic reagents (such as heavy metals, peroxides and the like), so that the method is far safer, less toxic, economical and environment-friendly than other traditional methods;
3. the method only comprises two treatment operations of mixing, stirring and ventilating and pressurizing, has few steps and simple and convenient operation, is beneficial to large-scale synthesis, and has important significance for the synthesis and large-scale industrialization of the preparation of the amide compound.
Drawings
FIG. 1 is a high performance liquid chromatogram of 2-phenyl-N-p-phenylpropylacetamide synthesized by the method.
FIG. 2 is a high performance liquid chromatogram of N-hexyl-2-phenylacetamide synthesized by the method.
FIG. 3 is a high performance liquid chromatogram of N-benzyl-2-phenylacetamide synthesized by the present method.
FIG. 4 is a high performance liquid chromatogram of N- (4-methoxybenzyl) -2-phenylacetamide synthesized by the present method.
FIG. 5 is a high performance liquid chromatogram of N- (2-methylbenzyl) -2-phenylacetamide synthesized by the present method.
FIG. 6 is a high performance liquid chromatogram of N- (4-chlorobenzyl) -2-phenylacetamide synthesized by the present method.
FIG. 7 is a high performance liquid chromatogram of 2-phenyl-N- (4- (trifluoromethyl) benzyl) acetamide synthesized by the present method.
FIG. 8 is a high performance liquid chromatogram of 2-phenyl-N- (pyridin-3-ylmethyl) acetamide synthesized by this method.
FIG. 9 is a high performance liquid chromatogram of N-benzyl-N-methyl-2-phenylacetamide synthesized by the present method.
FIG. 10 is a high performance liquid chromatogram of piperidine-N-phenethyl-1-amide synthesized by the present method.
FIG. 11 is a high performance liquid chromatogram of N-N-phenylpropylbenzamide synthesized by the present method.
FIG. 12 is a high performance liquid chromatogram of N-N-phenylpropyl valeramide synthesized by the method.
FIG. 13 is a high performance liquid chromatogram of N-N-phenylpropylcyclopropanecarboxamide synthesized by the present method.
FIG. 14 is a high performance liquid chromatogram of N-N-phenylpropyl-p-methoxybenzamide synthesized by the present method.
FIG. 15 is a high performance liquid chromatogram of N-N-phenylpropyl-p-fluorobenzamide synthesized by the present method.
FIG. 16 is a high performance liquid chromatogram of N-N-phenylpropyl-2-furancarboxamide synthesized by the present method.
Detailed Description
The experimental materials, reagents and the like used in the following examples can be obtained commercially or by known experimental methods.
In the following examples, purification and qualitative and quantitative analysis of target products or intermediates were carried out by electrospray mass spectrometry, HPLC and NMR. In the electron spray mass spectrometry, a target product or an intermediate product is dissolved in a mixed solvent of acetonitrile and water, and the mixture is diluted by 10 to 100 times according to a proper proportion and is used forAnd (4) mass spectrometry. In the high performance liquid chromatography, a Jasco PU2080 system equipped with a C18 analytical column was used, and water (A) containing 0.1% trifluoroacetic acid and an aqueous 95% acetonitrile solution (B) containing 0.1% trifluoroacetic acid were used as mobile phases at a flow rate of 1.0mL/min. The measured retention time is determined by comparison with a standard. 1 H NMR and 13 c NMR spectra were obtained by BrukerrARX-500 ( 1 H：500MHz， 13 C:125 MHz). Chemical shifts (. Delta.) are expressed in parts per million (ppm) and the residual deuterated chloroform signal corresponds to 1 H NMR, at δ 7.27 ppm; for the 13 C NMR, at δ 77.23 ppm.
Example 8978 Synthesis of zxft 8978-para-phenylpropyl-phenylacetamide.
0.122g of phenethyl alcohol and 0.135g of n-phenylalanyl amine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, under the condition of introducing oxygen, the pressure of 5.0MPa is applied, the temperature is heated to 110 ℃, and the stirring is continued for 24 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product 2-phenyl-N-p-phenylpropyl acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is 2-phenyl-N-p-phenylpropyl acetamide, and the total yield is 94.42% (M/z [ M + H ]) as confirmed by mass spectrum, high performance liquid chromatography (figure 1) and nuclear magnetic resonance spectrum analysis] + ＝254.15437, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.30,7.30,7.29,7.29,7.28,7.28,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.21,7.21,7.21,7.21,7.20,7.20,7.19,7.19,7.19,7.19,6.62,6.62,6.61,3.51,3.51,3.50,3.21,3.20,3.19,3.18,3.18,3.17,2.65,2.65,2.65,2.64,2.63,2.63,2.62,2.62,2.62,1.81,1.80,1.80,1.79,1.79,1.78,1.77,1.77,1.76. 13 C NMR(125MHz,Chloroform-d)δ171.26,141.85,136.03,129.34,129.18,128.63,128.51,127.76,126.72,43.77,39.87,33.31,30.12)。
As a control group, 0.122g phenethyl alcohol and 0.135g N-phenylalanyl amine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium trifluoroacetate ionic liquid, 1-ethyl-3-methylimidazolium bisulfate ionic liquid, 1-ethyl-3-methylimidazolium fluoroborate ionic liquid, 1-ethyl-3-methylimidazolium dicyandiamide ionic liquid, 1-octyl-3-methylimidazolium acetate ionic liquid, tetrabutylammonium acetate ionic liquid, and 20% ammonium acetate dimethyl sulfoxide solution, respectively, and the pressure of 5.0MPa was applied under the condition of introducing oxygen, heating was performed to 110 ℃, and stirring was continued for 48 hours, so that the target product, 2-phenyl-N-paraphenylpropylacetamide, was not obtained, i.e., all the yields were 0% (see Table 1).
TABLE 1
Based on the above control experiment, it is known that the 1-ethyl-3-methylimidazolium acetate ionic liquid has a very specific catalytic effect on amidation reaction.
Example 8978 Synthesis of zxft 8978-hexyl-2-phenylacetamide.
0.122g of phenethyl alcohol and 0.101g of n-hexylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, under the condition of introducing oxygen, the pressure of 5.0MPa is applied, the temperature is increased to 110 ℃, and the stirring is continued for 12 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N-hexyl-2-phenyl acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the target is confirmed by mass spectrometry, high performance liquid chromatography (FIG. 2) and nuclear magnetic resonance spectrum analysisThe product is N-hexyl-2-phenyl acetamide, the total yield is 83.02% (M/z [ M + H ]] + ＝220.16478, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.30,7.30,7.29,7.29,7.28,7.28,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.21,7.21,7.20,7.20,6.65,6.64,6.63,3.51,3.51,3.50,3.18,3.17,3.17,3.16,3.16,3.15,1.50,1.49,1.49,1.48,1.48,1.47,1.47,1.46,1.46,1.45,1.33,1.33,1.32,1.32,1.32,1.32,1.31,1.30,1.30,1.30,1.30,1.29,1.29,1.29,1.29,1.28,1.28,1.28,1.27,1.27,1.26,1.26,1.26,0.90,0.90,0.90,0.89,0.89,0.89,0.89,0.88,0.88,0.88. 13 C NMR(125MHz,Chloroform-d)δ170.85,136.03,129.34,129.18,127.76,43.78,39.91,30.86,29.01,26.48,22.14,14.07)。
Example 8978 Synthesis of zxft 8978-benzyl-2-phenylacetamide.
0.122g of phenethyl alcohol and 0.107g of benzylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, under the condition of introducing oxygen, the pressure of 5.0MPa is applied, the temperature is increased to 110 ℃, and the stirring is continued for 8 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N-benzyl-2-phenyl acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is N-benzyl-2-phenyl acetamide, and the total yield is 93.51% (M/z [ M + H ]) after the analysis and confirmation of mass spectrum, high performance liquid chromatography (figure 3) and nuclear magnetic resonance spectrum] + ＝256.12572, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.31,7.30,7.30,7.29,7.29,7.29,7.29,7.29,7.28,7.28,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.20,7.20,7.20,7.19,7.18,7.18,7.18,7.17,7.17,7.17,7.16,7.16,7.16,6.86,6.85,6.85,6.84,6.84,6.83,4.41,4.41,4.41,4.40,4.40,4.40,3.78,3.50,3.50,3.50. 13 C NMR(125MHz,Chloroform-d)δ171.75,158.96,135.73,132.22,129.34,129.29,129.18,127.76,113.92,55.32,43.87,41.98)。
Example 8978 Synthesis of zxft 8978- (4-methoxybenzyl) -2-phenylacetamide.
0.122g of phenethyl alcohol and 0.137g of (4-methoxy) 1-benzylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, under the condition of introducing oxygen, a pressure of 5.0MPa was applied, the mixture was heated to 110 ℃, and stirring was continued for 4 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N- (4-methoxybenzyl) -2-phenylacetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is N- (4-methoxybenzyl) -2-phenylacetamide confirmed by mass spectrometry, high performance liquid chromatography (figure 4) and nuclear magnetic resonance spectrum analysis, and the total yield is 96.89% (M/z [ M + H ]] + ＝256.12442, 1 H NMR(500MHz,Chloroform-d)δ7.34,7.34,7.33,7.32,7.32,7.32,7.31,7.30,7.30,7.29,7.29,7.28,7.28,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.25,7.24,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.20,7.20,7.19,7.18,4.39,4.39,4.38,4.38,4.37,4.37,3.50,3.50,3.50. 13 C NMR(125MHz,Chloroform-d)δ171.75,138.97,135.73,129.34,129.18,128.50,127.76,127.70,127.64,44.01,41.98)。
Example 8978 Synthesis of zxft 8978- (2-methylbenzyl) -2-phenylacetamide.
0.122g of phenethyl alcohol and 0.121g of o-tolylmethylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, and under the condition of introducing oxygen, a pressure of 5.0MPa was applied, the temperature was raised to 110 ℃, and stirring was continued for 24 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N- (2-methylbenzyl) -2-phenyl acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is N- (2-methylbenzyl) -2-phenyl acetamide and the total yield is 80.54% (M/z [ M + H ] through mass spectrum, high performance liquid chromatography (figure 5) and nuclear magnetic resonance spectrum analysis] + ＝240.13284, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.31,7.30,7.30,7.29,7.29,7.29,7.29,7.29,7.28,7.28,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.21,7.20,7.20,7.20,7.16,7.15,7.15,7.14,7.14,7.13,7.13,7.12,7.11,7.11,7.11,7.11,7.11,7.10,7.10,7.10,7.10,7.09,7.09,7.09,7.09,7.09,4.48,4.47,4.47,3.50,3.50,3.50,2.37. 13 C NMR(125MHz,Chloroform-d)δ171.67,138.49,136.99,135.73,130.25,129.34,129.18,128.32,127.76,127.27,126.68,42.89,41.98,19.36)。
Example 8978 Synthesis of zxft 8978- (4-chlorobenzyl) -2-phenylacetamide.
0.122g of phenethyl alcohol and 0.141g of (4-chlorophenyl) methylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, and under the condition of introducing oxygen, the pressure is applied under 5.0MPa, the temperature is heated to 110 ℃, and the stirring is continued for 48 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N- (4-chlorobenzyl) -2-phenyl acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the target product is N- (4-chlorobenzyl) -2-phenyl acetamide and the total yield is 41.01% (M/z [ M + H ] after the analysis of mass spectrum, high performance liquid chromatography (figure 6) and nuclear magnetic resonance spectrum confirms] + ＝260.08302, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.30,7.30,7.29,7.29,7.29,7.28,7.28,7.27,7.27,7.27,7.26,7.26,7.25,7.25,7.25,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.20,7.20,7.20,7.19,7.18,4.41,4.41,4.40,4.40,4.40,4.39,3.50,3.50,3.50. 13 C NMR(125MHz,Chloroform-d)δ171.75,137.57,135.73,133.65,131.12,129.38,129.34,129.18,127.76,43.93,41.98)。
Example 8978 Synthesis of zxft 8978-phenyl-N- (4- (trifluoromethyl) benzyl) acetamide.
0.122g of phenethyl alcohol and 0.175g of (4- (trifluoromethyl) phenyl) methylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, and under the condition of introducing oxygen, the pressure of 5.0MPa is applied, the temperature is increased to 110 ℃, and the stirring is continued for 48 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product 2-phenyl-N- (4- (trifluoromethyl) benzyl) acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is 2-phenyl-N- (4- (trifluoromethyl) benzyl) acetamide, and the total yield is 42.60% (M/z [ M + H ] after the analysis of mass spectrum, high performance liquid chromatography (figure 7) and nuclear magnetic resonance spectrum] + ＝294.11214, 1 H NMR(500MHz,Chloroform-d)δ7.60,7.59,7.59,7.58,7.58,7.58,7.42,7.42,7.42,7.41,7.41,7.41,7.40,7.40,7.40,7.40,7.31,7.30,7.30,7.29,7.29,7.29,7.29,7.29,7.28,7.28,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.21,7.20,7.20,7.19,7.18,4.41,4.41,4.40,4.40,4.40,4.39,3.50,3.50,3.50. 13 C NMR(125MHz,Chloroform-d)δ171.75,139.09,135.73,129.66,129.40,129.34,129.18,129.14,128.89,128.87,128.86,128.84,128.82,127.76,127.38,125.93,125.90,125.87,125.84,125.23,123.09,120.95,44.59,41.98)。
Example 8978 Synthesis of zxft 8978-phenyl-N- (pyridin-3-ylmethyl) acetamide.
0.122g of phenethyl alcohol and 0.108g of pyridin-3-ylmethylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, and under the condition of introducing oxygen, a pressure of 5.0MPa was applied, the temperature was heated to 110 ℃ and stirring was continued for 24 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product 2-phenyl-N- (pyridine-3-ylmethyl) acetamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is 2-phenyl-N- (pyridine-3-ylmethyl) acetamide, and the total yield is 74.04% (M/z [ M + H ])] + ＝227.11237, 1 H NMR(500MHz,Chloroform-d)δ8.55,8.55,8.55,8.54,8.47,8.46,8.46,8.46,8.45,7.70,7.70,7.69,7.69,7.68,7.68,7.35,7.34,7.32,7.31,7.30,7.30,7.30,7.29,7.29,7.29,7.28,7.28,7.28,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.22,7.22,7.21,7.21,7.21,7.20,7.20,7.20,4.41,4.40,3.50,3.50,3.50. 13 C NMR(125MHz,Chloroform-d)δ171.75,148.75,148.38,135.73,135.22,134.13,129.34,129.18,127.76,123.27,41.98,41.81)。
Example 8978 Synthesis of zxft 8978-benzyl-N-methyl-2-phenylacetamide.
0.122g of phenethyl alcohol and 0.121g N-methyl-1-benzylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, under the condition of introducing oxygen, the pressure of 5.0MPa is applied, the temperature is increased to 110 ℃, and the stirring is continued for 48 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-benzyl-N-methyl-2-phenylacetamide. The reaction formula is as follows:
the obtained target product is N-benzyl-N-methyl-2-phenyl acetamide, and the total yield is 21.42% (M/z [ M + H ]) through mass spectrum, high performance liquid chromatography (figure 9) and nuclear magnetic resonance spectrum analysis and confirmation] + ＝240.13251, 1 H NMR(500MHz,Chloroform-d)δ7.32,7.32,7.32,7.31,7.30,7.30,7.30,7.29,7.29,7.29,7.28,7.27,7.27,7.27,7.27,7.26,7.26,7.26,7.26,7.26,7.25,7.25,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,4.48,4.48,4.48,3.58,3.58,3.58,2.87. 13 C NMR(125MHz,Chloroform-d)δ171.45,138.05,135.58,128.74,128.70,128.40,128.18,127.79,127.32,53.13,41.25,34.42)。
Example 10 synthesis of piperidine-N-phenethyl-1-amide.
0.122g of phenethyl alcohol and 0.085g of piperidine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, and under the condition of introducing oxygen, the pressure of 5.0MPa was applied, the temperature was increased to 110 ℃, and the stirring was continued for 48 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product piperidine-N-phenethyl-1-amide. The reaction formula is as follows:
the obtained target product is piperidine-N-phenethyl-1-amide and the total yield is 15.38% (M/z [ M + H ]) after the analysis and confirmation of mass spectrum, high performance liquid chromatography (figure 10) and nuclear magnetic resonance spectrum] + ＝240.13227, 1 H NMR(500MHz,Chloroform-d)δ7.31,7.30,7.30,7.29,7.29,7.29,7.28,7.28,7.27,7.27,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,3.64,3.63,3.63,3.50,3.50,3.49,3.48,3.44,3.44,3.43,3.43,1.66,1.65,1.65,1.65,1.64,1.64,1.63,1.63,1.62,1.62,1.61,1.61,1.60,1.60,1.60,1.60,1.59,1.59,1.58,1.58,1.58,1.58,1.57,1.57,1.56,1.56,1.56,1.55. 13 C NMR(125MHz,Chloroform-d)δ170.40,135.41,128.70,128.40,127.31,45.49,40.69,25.53,24.25)。
Example 11 synthesis of N-n-phenylpropylbenzamide.
0.108g of benzyl alcohol and 0.135g of 3-phenyl-n-propylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under a pressure of 5.0MPa with introduction of oxygen and stirred continuously for 12 hours. After the reaction is finished, the high pressure is removed and the heating is stopped, the reaction product is extracted from the mixture obtained by the reaction by methyl acetate, and the target product N-N-phenylpropylbenzamide is obtained by separation and purification by high performance liquid chromatography. The reaction formula is as follows:
the obtained target product is N-N-phenylpropylbenzamide, and the total yield is 87.32% (M/z [ M + H ]) determined by mass spectrometry, high performance liquid chromatography (FIG. 11) and nuclear magnetic resonance spectroscopy] + ＝240.13225, 1 H NMR(500MHz,Chloroform-d)δ7.87,7.86,7.85,7.80,7.79,7.79,7.79,7.78,7.77,7.77,7.77,7.54,7.54,7.54,7.53,7.52,7.52,7.51,7.51,7.51,7.46,7.45,7.45,7.44,7.44,7.43,7.42,7.42,7.42,7.42,7.28,7.27,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.21,7.21,7.21,7.21,7.21,7.20,7.20,7.20,7.20,7.20,7.19,7.19,7.19,7.19,3.41,3.41,3.40,3.39,3.38,2.67,2.67,2.67,2.66,2.66,2.65,2.64,2.64,2.64,1.93,1.92,1.92,1.91,1.91,1.90,1.90,1.89,1.88. 13 C NMR(125MHz,Chloroform-d)δ168.33,141.86,135.03,132.00,128.63,128.59,128.51,127.14,126.72,39.54,33.31,30.05)。
Example 12 Synthesis of N-n-phenylpropyl valeramide.
0.088g of n-pentanol and 0.135g of 3-phenyl n-propylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under a pressure of 5.0MPa with introduction of oxygen, and stirred continuously for 4 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-N-phenylpropyl valeramide. The reaction formula is as follows:
the target product is obtained by mass spectrometry, high performance liquid chromatography (figure 12) and nuclear magnetic resonance spectrum analysisN-N-phenylpropyl valeramide, with a total yield of 93.66% (M/z [ M + H ]] + ＝220.17316, 1 H NMR(500MHz,Chloroform-d)δ7.28,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.21,7.21,7.21,7.21,7.21,7.20,7.20,7.20,7.20,7.19,7.19,7.19,7.19,6.62,6.61,6.61,3.21,3.20,3.20,3.19,3.18,3.17,2.65,2.65,2.65,2.64,2.63,2.63,2.62,2.62,2.62,2.20,2.18,2.17,1.81,1.80,1.80,1.79,1.79,1.78,1.78,1.77,1.76,1.60,1.59,1.58,1.57,1.57,1.57,1.56,1.56,1.55,1.54,1.41,1.40,1.40,1.38,1.37,1.35,1.35,1.34,0.93,0.92,0.90. 13 C NMR(125MHz,Chloroform-d)δ174.63,141.85,128.63,128.51,126.72,39.57,36.15,33.31,30.13,27.23,21.87,13.82)。
Example 13 synthesis of N-n-phenylpropylcyclopropanecarboxamide.
0.072g of cyclopropylmethanol and 0.135g of 3-phenyl-n-propylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under an oxygen-fed pressure under 5.0MPa, and stirred continuously for 24 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-N-phenylpropylcyclopropanecarboxamide. The reaction formula is as follows:
the target product is N-N-phenylpropylcyclopropane formamide confirmed by mass spectrum, high performance liquid chromatography (figure 13) and nuclear magnetic resonance spectrum analysis, and the total yield is 65.30% (M/z [ M + H ]] + ＝204.13263, 1 H NMR(500MHz,Chloroform-d)δ7.28,7.27,7.27,7.27,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.21,7.21,7.21,7.21,7.21,7.20,7.20,7.20,7.20,7.20,7.19,7.19,7.19,7.19,6.98,6.97,6.96,3.16,3.15,3.15,3.14,3.14,3.13,2.65,2.65,2.65,2.64,2.63,2.63,2.62,2.62,2.62,2.42,2.41,2.40,2.39,2.38,1.81,1.80,1.80,1.79,1.79,1.78,1.77,1.77,1.76,0.82,0.81,0.81,0.80,0.80,0.79,0.79,0.78,0.78,0.78,0.77,0.77,0.77,0.76,0.76,0.74,0.74,0.73,0.73,0.73,0.72,0.72,0.72,0.71,0.71,0.71,0.70,0.70,0.69,0.69,0.68. 13 C NMR(125MHz,Chloroform-d)δ175.80,141.85,128.63,128.51,126.72,38.00,33.31,30.12,16.60,8.71)。
Example 14 synthesis of n-phenylpropyl-p-methoxybenzamide.
0.138g (p-methoxyphenyl) methanol and 0.135g 3-phenyl-n-propylamine were dissolved in 1.00mL 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under a pressure of 5.0MPa with introduction of oxygen and stirring was continued for 24 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-N-phenylpropyl-p-methoxybenzamide. The reaction formula is as follows:
the target product is N-N-phenylpropyl-p-methoxybenzamide, and the total yield is 73.46% (M/z [ M + H ] after mass spectrum, high performance liquid chromatography (FIG. 14) and nuclear magnetic resonance spectrum analysis] + ＝270.14402, 1 H NMR(500MHz,Chloroform-d)δ8.01,8.00,7.99,7.84,7.84,7.83,7.82,7.82,7.81,7.28,7.27,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.21,7.21,7.21,7.21,7.21,7.20,7.20,7.20,7.19,7.19,7.19,7.19,6.96,6.96,6.96,6.95,6.94,6.94,3.83,3.42,3.41,3.41,3.40,3.40,3.39,2.67,2.67,2.67,2.66,2.66,2.65,2.64,2.64,2.64,1.93,1.92,1.92,1.91,1.91,1.90,1.90,1.89,1.88. 13 C NMR(125MHz,Chloroform-d)δ168.49,162.54,141.86,130.39,128.63,128.51,126.72,126.60,112.56,55.32,39.54,33.31,30.05)。
Example 15 synthesis of n-phenylpropyl-p-fluorobenzamide.
0.126g of p-fluorobenzyl alcohol and 0.135g of 3-phenyl-n-propylamine were dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under a pressure of 5.0MPa with introduction of oxygen, and stirred continuously for 24 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-N-phenylpropyl-p-fluorobenzamide. The reaction formula is as follows:
the target product is N-N-phenylpropyl-p-fluorobenzamide and the total yield is 68.85% (M/z [ M + H) confirmed by mass spectrum, high performance liquid chromatography (FIG. 15) and nuclear magnetic resonance spectrum analysis] + ＝258.12149, 1 H NMR(500MHz,Chloroform-d)δ8.04,8.03,8.02,7.94,7.93,7.93,7.93,7.92,7.92,7.92,7.92,7.91,7.91,7.91,7.90,7.28,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.21,7.21,7.21,7.20,7.19,7.19,7.19,7.19,3.42,3.41,3.40,3.39,2.67,2.67,2.67,2.66,2.66,2.65,2.64,2.64,2.64,1.93,1.92,1.92,1.91,1.91,1.90,1.90,1.89,1.88. 13 C NMR(125MHz,Chloroform-d)δ168.47,165.87,163.85,141.86,130.87,130.84,130.22,130.16,128.63,128.51,126.72,115.97,115.81,39.54,33.31,30.05)。
Example 16 Synthesis of N-n-phenylpropyl-2-furancarboxamide.
0.098g of furfuryl alcohol and 0.135g of 3-phenyl-n-propylamine are dissolved in 1.00mL of 1-ethyl-3-methylimidazolium acetate ionic liquid, heated to 110 ℃ under a pressure of 5.0MPa with aeration of oxygen, and stirred continuously for 48 hours. After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying by using a high performance liquid chromatography to obtain the target product N-N-phenylpropyl-2-furancarboxamide. The reaction formula is as follows:
the obtained target product is N-N-phenylpropyl-2-furancarboxamide and the total yield is 62.07% (M/z [ M + C) confirmed by mass spectrum, high performance liquid chromatography (FIG. 16) and nuclear magnetic resonance spectrum analysisH] + ＝230.11011, 1 H NMR(500MHz,Chloroform-d)δ7.87,7.86,7.85,7.63,7.63,7.63,7.28,7.27,7.27,7.26,7.26,7.26,7.25,7.25,7.24,7.24,7.24,7.23,7.23,7.23,7.22,7.22,7.21,7.21,7.21,7.20,7.20,7.19,7.19,7.19,7.19,6.56,6.55,6.55,6.54,3.37,3.36,3.35,3.34,3.34,3.33,2.67,2.67,2.67,2.66,2.66,2.65,2.64,2.64,2.64,1.93,1.92,1.92,1.91,1.91,1.90,1.90,1.89,1.88. 13 C NMR(125MHz,Chloroform-d)δ161.32,148.21,145.21,141.86,128.63,128.51,126.72,115.67,112.65,39.27,33.31,30.02)。
The present invention is illustrated in detail by the examples given above, but the present invention is not limited to the details given above, which means that the present invention is not limited to the details given above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are included in the scope of protection and disclosure of the present invention.
Claims (2)
1. The method for preparing the amide compound under the catalysis of the ionic liquid in the high-pressure environment is characterized by comprising the following steps of:
1) Dissolving reactant alcohol and amine in 1-ethyl-3-methylimidazolium acetate ionic liquid,
wherein the mole ratio of the reactant alcohol, amine and 1-ethyl-3-methylimidazolium acetate ionic liquid is 1:0.5 to 2:6~8 of the formula,
the alcohol is any one of phenethyl alcohol, benzyl alcohol, n-amyl alcohol, cyclopropyl methanol, (p-methoxyphenyl) methanol, p-fluorophenyl methanol and furan methanol,
the amine is n-phenylalamine, n-hexylamine, benzylamine, (4-methoxy) 1-benzylamine, o-tolylmethylamine, (4-chlorophenyl) methylamine, (4- (trifluoromethyl) phenyl) methylamine, pyridin-3-ylmethylamine,N-any one of methyl-1-benzylamine, piperidine, 3-phenyl-n-propylamine;
2) In a high-pressure reaction kettle, applying pressure of at least 5.0Mpa to a reaction system under the condition of introducing oxygen;
3) Maintaining a high-pressure environment, and continuously stirring for 4-48 hours until the reaction is complete, wherein the reaction efficiency is improved by heating to 110 ℃;
4) After the reaction is finished, removing high pressure and stopping heating, extracting a reaction product from a mixture obtained by the reaction by using methyl acetate, and separating and purifying to obtain a target amide product.
2. The method according to claim 1, wherein the molar ratio of the reactant alcohol, amine and 1-ethyl-3-methylimidazolium acetate ionic liquid is 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011137906.XA CN112209847B (en) | 2020-10-22 | 2020-10-22 | Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011137906.XA CN112209847B (en) | 2020-10-22 | 2020-10-22 | Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112209847A CN112209847A (en) | 2021-01-12 |
| CN112209847B true CN112209847B (en) | 2022-12-23 |
Family
ID=74054743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011137906.XA Active CN112209847B (en) | 2020-10-22 | 2020-10-22 | Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112209847B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084586A (en) * | 2017-12-25 | 2018-05-29 | 桐城市祥泰塑业有限公司 | A kind of ion liquid modified plastic fireproof plate and preparation method thereof |
-
2020
- 2020-10-22 CN CN202011137906.XA patent/CN112209847B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084586A (en) * | 2017-12-25 | 2018-05-29 | 桐城市祥泰塑业有限公司 | A kind of ion liquid modified plastic fireproof plate and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| An efficient, eco-friendly and sustainable tandem oxidative amidation of alcohols with amines catalyzed by heteropolyanion-based ionic liquids via a bifunctional catalysis process;Fu Renzhong等;《Tetrahedron》;20161104;第72卷;8319-8326 * |
| Direct oxidative amidation of aldehydes with amines catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions via a dualcatalysis process;Fu Renzhong等;《Organic & Biomolecular Chemistry》;20161231;第14卷;1784-1793 * |
| Microwave-assisted heteropolyanion-based ionic liquids catalyzed transamidation of non-activated carboxamides with amines under solvent-free conditions;Fu Renzhong等;《Tetrahedron》;20141027;第70卷;9492-9499 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112209847A (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108424375B (en) | Process for producing perfluoronitrile | |
| Yu et al. | Controllable access to multi-substituted imidazoles via palladium (ii)-catalyzed C–C coupling and C–N condensation cascade reactions | |
| CN110526801A (en) | Method for oxidizing cycloalkane by cobalt (II) porphyrin/copper (II) porphyrin salt concerted catalysis | |
| CN109053471A (en) | A kind of synthetic method of [60] fullerene cyclopentene derivatives | |
| CN112920066A (en) | Alpha-substituted-alpha-amino acid ester compound and preparation method thereof | |
| CN109134172B (en) | Ligand-regulated method for selectively synthesizing Z-and E-olefin by catalyzing alcohol hydrogen-donating iridium | |
| CN112209847B (en) | Method for preparing amide compound under catalysis of ionic liquid in high-pressure environment | |
| CN108610226B (en) | Method for preparing amide compound by using manganese oxide to catalyze amine oxidation | |
| CN102827015B (en) | Preparation method of 5-aminolevulinic acid (ALA) hydrochloride | |
| CN111072642B (en) | Preparation method of 5-succinimide chromone compound | |
| CN110922385A (en) | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde | |
| CN107915653B (en) | Method for preparing amide by catalyzing ester and amine to react | |
| CN106883206A (en) | Method for synthesizing coumarin by catalyzing (E) -o-hydroxycinnamaldehyde derivative with aza-carbene | |
| CN109232350A (en) | A method of preparing N-Boc-3- pyrrolidine formaldehyde | |
| CN105330550B (en) | A kind of preparation method of optically active 1 cyclohexylethylamine | |
| Liu et al. | Visible‐Light Enabled Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via C− O Bond Cleavage | |
| Tang et al. | Silver (i)-catalyzed addition of pyridine-N-oxides to alkynes: a practical approach for N-alkenoxypyridinium salts | |
| CN108383754B (en) | Preparation method and application of aryl oxime ester compound | |
| CN112939902A (en) | Preparation process of raw material furan for preparing 2-acetylfuran | |
| CN115353486B (en) | Method for synthesizing amide by catalyzing air oxidation alcohol and heteroaromatic amine with copper | |
| CN105001176B (en) | A kind of preparation method of 2 oxazolinone derivant | |
| CN114671781B (en) | Method for converting arylbenzylamine into arylnitrile compound | |
| CN110256387B (en) | Preparation method of medical intermediate | |
| EP1154972B1 (en) | Method and composition for hydroxylation of aromatic substrates | |
| Pappas et al. | Phenyl esters, preferred reagents for mono-acylation of polyamines in the presence of water |
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 |